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Sample records for acrylonitrile butadiene rubber-polyvinyl

  1. Modification of PVC compounds with butadiene-acrylonitrile elastomers

    J. Stabik

    2006-04-01

    Full Text Available Purpose: The purpose of the paper is to present the research programme on influence of acrylonitrile-butadiene copolymers on properties of plasticized polyvinylchloride as window gaskets material.Design/methodology/approach: Short literature review concerning application of modified PVC as gasket material was presented. In experimental part two types of acrylonitrile-butadiene copolymers were used as elastomeric plasticizers. Compounds with fifteen different levels of modifiers content (up to 25% by weight were prepared and tested. Additionally three commercial compounds were tested as reference formulations. The following test were performed: Shore hardness, short-term and long-term elastic recovery, tensile strength, elongation at break and migration of plasticizers from gasket material to unplasticized PVC.Findings: Application of acrylonitrile-butadiene copolymers as PVC modifier enhanced many properties essential for window gasket materials such as long-term and short term elastic recovery, tensile strength and elongation at break. At the same time addition of these elastomers did not change migration of other plasticizers contained in gasket material. Obtained results indicated that among tested compounds best properties as gasket material exhibited plasticized PVC with 23% of acrylonitrile-butadiene copolymer Chemigum P83. Reference commercial compounds exhibited worse performance properties than compounds with this acrylonitrile-butadiene copolymer. Practical implications: Research programme allowed to elaborate plasticized PVC compounds modified with acrylonitrile-butadiene copolymer that can be industrially applied for PVC window gaskets.Originality/value: Obtained results are of scientific and practical value. Research programme allowed to investigate the influence of elastomeric modifiers on plasticized PVC properties. Research results are also of practical importance.

  2. 21 CFR 177.1020 - Acrylonitrile/butadiene/sty-rene co-polymer.

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Acrylonitrile/butadiene/sty-rene co-polymer. 177... SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances.../butadiene/sty-rene co-polymer. Acrylonitrile/butadiene/styrene copolymer identified in this section may...

  3. Equivalent lifetime prediction of acrylonitrile butadiene rubber for thermal aging

    Thermal degradation of acrylonitrile butadiene rubber(NBR), which is used for O-ring material as elastomeric sealed diaphragm valve in the nuclear power plants, is examined. The thermal degradation is accelerated at 130 .deg. C by arrhenius exploit method using the activation energy calculated by thermogravimetric analysis. The weight loss temperature and glass transition temperature are verified for thermally aged NBR. The relationship between dynamic mechanical properties and elongation at break are also investigated. The threshold valued of thermally aged NBR is a ten year in the change of elongation at break

  4. Recycling of Chrome Tanned Leather Dust in Acrylonitrile Butadiene Rubber

    El-Sabbagh, Salwa H.; Mohamed, Ola A.

    2010-06-01

    Concerns on environmental waste problem caused by chrome tanned leather wastes in huge amount have caused an increasing interest in developing this wastes in many composite formation. This leather dust was used as filler in acrylonitrile butadiene rubber (NBR) before treatment and after treatment with ammonia solution and sod. formate. Different formulations of NBR/ leather dust (untreated-treated with ammonia solution—treated with sod. formate) composites are prepared. The formed composite exhibit a considerable improvement in some of their properties such as rheometric characteristics especially with composites loaded with treated leather dust. Tensile strength, modulus at 100% elongation, hardness and youngs modulus were improved then by further loading start to be steady or decrease. Cross linking density in toluene were increased by incorporation of leather dust treated or untreated resulting in decreases in equilibrium swelling. Distinct increase in the ageing coefficient of both treated and untreated leather with drop in NBR vulcanizates without leather dust. Addition of leather dust treated or untreated exhibit better thermal stability.

  5. Chrome-tanned leather shavings as a filler of butadiene-acrylonitrile rubber.

    Przepiórkowska, A; Chrońska, K; Zaborski, M

    2007-03-01

    The noxious wastes from the tanning industry such as chrome-tanned leather shavings were used as the only filler of rubber mixes containing carboxylated butadiene-acrylonitrile rubber (XNBR) or butadiene-acrylonitrile rubber (NBR), and a dispersing agent Limanol PEV (Schill & Seilacher). The best form addition of leather powder to the rubber mixes is mixed the waste protein with zinc oxide. The leather powder added to the rubber mixes improves the mechanical properties: tensile strength (T(s)), elongation at break (epsilon(b)) and increase the cross-linking density of carboxylated XNBR and NBR rubber mixes. Satisfactory results of these studies are presented in this work. PMID:16942836

  6. The effect of unsaturated polyester resin from recycled PET as compatibilizer for styrene-butadiene (SBR)/ acrylonitrile-butadiene

    Unsaturated polyester resin (UPR) from recycled PET flakes was prepared by depolymerization with propylene glycol and poly esterified with adipic acid. The effect of addition of 5, 10 and 15 phr of unsaturated polyester resin (UPR) on the compatibility and physicomechanical properties of styrene-butadiene rubber (SBR) and acrylonitrile-butadiene rubber (NBR) blends were studied. DSC, TGA, MDR, FTIR and chemical methods were used to determine the degree of compatibility. The mechanical and physical properties of the blends were found to improve with addition of 10 phr UPR for SBR/NBR blend. (author)

  7. Electromechanical responses of poly(3-thiopheneacetic acid/acrylonitrile-butadiene rubbers

    2008-12-01

    Full Text Available Acrylonitrile-butadiene rubber (NBR and blends of poly(3-thiopheneacetic acid/ acrylonitrile-butadiene rubber, P3TAA/NBR, were fabricated, and the electrorheological properties, dielectric, and electrical conductivities were investigated . The electrorheological properties were determined under an oscillatory shear mode in a frequency range of 0.1 to 100 rad/s at various electric field strengths, from 0 to 2 kV/mm, at a fixed 27°C to observe the effects of acrylonitrile content (ACN in the rubber systems and the conductive particle concentration in the blends. For the pure rubber systems, the storage modulus response (ΔG′ is linearly dependent on its dielectric constant (ε′, and increases with the ACN content. For the NBR/P3TAA blends, the storage modulus response varies nonlinearly with the dielectric constant. The bending responses of the rubbers and the blends were investigated in a vertical cantilever fixture. For the pure rubber system, the bending angle and the dielectrophoresis force vary linearly with electric field strength. For the blend system, the bending angle and the dielectrophoresis force vary nonlinearly with electric field strength.

  8. Novel in situ coordinated cerium salt/acrylonitrile-butadiene rubber composite

    A novel rubber composite of acrylonitrile-butadiene rubber (NBR) filled with cerium salt particles was vulcanized via in situ coordination for the first time. The resulting materials exhibit good mechanical properties. Curing characteristics analysis, differential scanning calorimetry, X-ray photoelectron spectroscopy, tensile testing, and an equilibrium swelling method were used for the characterization of the composite. The results in this paper indicate that the composite is a kind of elastomer based on the in situ coordination crosslinking interactions between the nitrile groups (–CN) of NBR and cerium ions. The mechanical properties of vulcanized cerium salt/ NBR rubber are altered when changing the sorts of cerium salt. Moreover, these materials show good irradiation resistance because of the introduction of the cerium salt. -- Highlights: ► Cerium salts were firstly used to vulcanize the acrylonitrile-butadiene rubber. ► Cerium salts act as not only crosslink agents but also reinforcing fillers in the matrix. ► These materials show good irradiation resistance and mechanical properties at same time.

  9. Certification of mercury in acrylonitrile butadiene styrene by using isotope dilution mass spectrometry

    Under the framework of a co-certification system for the development of Certified Reference Materials (CRMs) among China, Japan and Korea, the 1st co-certification campaign of mercury in acrylonitrile butadiene styrene (ABS) for Japanese CRMs was taken. In this campaign isotope dilution mass spectrometry (IDMS) was used. First, all abundances of Hg in spike 202Hg, CRM and ABS were analyzed by MC-ICP-MS before the certification. Then the concentrations of 202Hg and Hg in ABS were determined with IDMS by Q-ICP-MS. A new procedure to reduce memory effect was used. first, dilute with 5 μg/g Au solution for 1 min; then, 5 μg/g EDTA solution for 2 min. The results accord to each other very well and this implies that the co-certification system can run swimmingly. (authors)

  10. Flame Retardant Effects of Nano-Clinoptilolite on AcrylonitrileButadiene-Styrene (ABS Nano-Composite

    Aboulfazl Barati

    2012-01-01

    Full Text Available In recent years, intumescent technology has found a place in polymer science as a method of providing flame retardance to polymeric materials. On heating, fire-retardant intumescent material restricts the action of the heat flux or flame. The proposed mechanism is based on charred layer acting as physical barrier, which slows down heat and mass transfer between the gas and the condensed phases. In this paper, the flammability of intumescent fire-retardant acrylonitrile-butadiene-styrene (ABS matrix composites consisting of hydromagnesite (HMg as an acid source and blowing agent, pentaerythritol (PER as a carbonisation agent and natural zeolite (clinoptilolite rich, Kansar Shargh as a synergistic agent were examined. The flammability of composites was characterized by limiting oxygen index (LOI measurement and horizontal burning tests. A synergistic effect in flame retardancy was observed when natural zeolites were used in combination with HMg and PER.

  11. Structures and Properties Characterization of Acrylonitrile-butadiene-styrene/Organo-palygorskite Clay Composites

    ZHANG Zhe; CHANG Ying; XU Jian; WU Zhancui; MA Hengchang; LEI Ziqiang

    2012-01-01

    Palygorskite (PGS) and vinyl tris-(2-methoxyethoxy) silane (KH-172) modified palygorskite (OPGS) were used to prepare acrylonitrile-butadiene-styrene (ABS)/clay composites.Thermal stability of the composites was evaluated by using thermogravimetric analysis (TGA).The morphology of the fractured surface and the degree of dispersion of the clay in the ABS matrix were observed by scanning electron microscopy (SEM).X-ray diffraction (XRD) analysis results showed the variation of the crystal structure.Measurements of the tensile properties of the ABS/clay composites proved that the ABS/OPGS composited material represented the most excellent tensile property,because of good compatibility and dispersion of ABS with OPGS.

  12. Ionizing radiation effect study by electron beam on acrylonitrile butadiene styrene - ABS terpolymer

    The great advantage in the researches involving development has as objective to increase significantly the quality of the products. The ABS (acrylonitrile, butadiene, styrene) resins are terpolymers formed by an elastomer and two thermoplastics amorphous components. The three different monomeric units from the terpolymer ABS contribute separately to the material characteristics exhibited. The molecular stiffness originating from polystyrene and the benzene ring hanging on the chain is responsible for the flexion module ABS. The acrylonitrile and the styrene incorporated butadiene exercises strong influence in the resistance to the impact because it reduces the bonding among them. The engineering use of this terpolymer became important due their mechanical properties and mainly, for the responses of this to tensions or deformations applied. The polymeric materials, when submitted to the ionizing radiation are modified by the transference of energy to these materials, introducing excitation and ionization of the molecules, generating chemical reactions that can produce permanent modifications in the polymeric physicochemical structure. The induced modifications can result in the polymeric material degradation or crosslinking, which can result in the improvement of some properties. This work has, as objective, to study the electron beam ionizing radiation effect, at different doses, in the properties of the polymer ABS. The studied properties were: tensile strength at break, elongation at break, Izod impact strength, flexural strength, melt flow index, Vicat softening temperature and the thermic distortion temperature. Also researches on Differential Scanning Calorimetry (DSC) and Thermogravimetric Analyses (TGA) were accomplished. From the experimental results, it was showed that for doses until 500 kGy, at 22.6 kGy/s dose rate, in the presence of air, the crosslinking process of ABS prevails. (author)

  13. Carboxyl-terminated butadiene-acrylonitrile-toughened epoxy/carboxyl-modified carbon nanotube nanocomposites: Thermal and mechanical properties

    H. F. Xie; Wang, Y. T.; Wang, C. S.; H. Y. Yin; Wang, L.L.; R. S. Cheng

    2012-01-01

    Carboxyl-modified multi-walled carbon nanotubes (MWCNT–COOHs) as nanofillers were incorporated into diglycidyl ether of bisphenol A (DGEBA) toughened with carboxyl-terminated butadiene-acrylonitrile (CTBN). The carboxyl functional carbon nanotubes were characterized by Fourier-transform infrared spectroscopy and thermogravimetric analysis. Furthermore, cure kinetics, glass transition temperature (Tg), mechanical properties, thermal stability and morphology of DGEBA/CTBN/MWCNT–COOH...

  14. Zinc chelates as new activators for sulphur vulcanization of acrylonitrile-butadiene elastomer

    2009-04-01

    Full Text Available The goal of this work was to apply several zinc chelates as activators for sulphur vulcanization of acrylonitrilebutadiene elastomer (NBR, in order to find alternatives for the conventionally used zinc oxide. In this article, we discuss the effects of different zinc complexes on the cure characteristics, crosslinks distribution in the elastomer network and mechanical properties of acrylonitrile-butadiene rubber. Zinc chelates seem to be good substitutes for zinc oxide as activators for sulphur vulcanization of NBR rubber, without detrimental effects on the crosslinking process and physical properties of the obtained vulcanizates. Moreover, application of zinc complexes allows to reduce the amount of zinc ions in rubber compounds by 40% compared to conventionally crosslinked vulcanizates with zinc oxide. It is a very important ecological goal since zinc oxide is classified as toxic to aquatic species and its amount in rubber products must be reduced below 2.5% at least. From a technological point of view it is a very important challenge.

  15. The physical and degradation properties of starch-graft-acrylonitrile/carboxylated nitrile butadiene rubber latex films.

    Misman, M A; Azura, A R; Hamid, Z A A

    2015-09-01

    Starch-graft-acrylonitrile (ANS) is compounded with carboxylated nitrile butadiene rubber (XNBR) latex. The control XNBR and the ANS/XNBR latex films were prepared through a coagulant dipping process. The films were subjected to ageing and soil burial procedures. For the biodegradation experiment, the surface of the film was assessed after the 2nd, 4th and 8th week of soil burial. The ANS, XNBR, and ANS/XNBR colloidal stability were determined with a Malvern Zetasizer. For the dipped latex films, the mechanical, morphological and thermal properties were analyzed. The addition of ANS into the XNBR latex increased the stability of the colloidal dispersions, decreased the latex film tensile strength, but increased the elongation at break due to the bipolar interaction of the ANS and XNBR particles. The ANS/XNBR latex films aged faster than the control films while the morphological analysis showed the existence of a starch crystal region and the formation of microbial colonies on the surfaces of the films. Based on the TGA-DTA curves, a higher ΔT was observed for the ANS/XNBR latex films signifying high thermal energy needed for the film to thermally degrade. PMID:26005134

  16. Method for the separation of high impact polystyrene (HIPS) and acrylonitrile butadiene styrene (ABS) plastics

    Jody, Bassam J.; Arman, Bayram; Karvelas, Dimitrios E.; Pomykala, Jr., Joseph A.; Daniels, Edward J.

    1997-01-01

    An improved method is provided for separating acrylonitrile butadiene styrene (ABS) and high impact polystyrene (HIPS) plastics from each other. The ABS and HIPS plastics are shredded to provide a selected particle size. The shredded particles of the ABS and HIPS plastics are applied to a solution having a solution density in a predefined range between 1.055 gm/cm.sup.3 and 1.07 gm/cm.sup.3, a predefined surface tension in a range between 22 dynes/cm to 40 dynes/cm and a pH in the range of 1.77 and 2.05. In accordance with a feature of the invention, the novel method is provided for separating ABS and HIPS, two solid thermoplastics which have similar densities by selectively modifying the effective density of the HIPS using a binary solution with the appropriate properties, such as pH, density and surface tension, such as a solution of acetic acid and water or a quaternary solution having the appropriate density, surface tension, and pH.

  17. An investigation on chloroprene-compatibilized acrylonitrile butadiene rubber/high density polyethylene blends

    Khalil Ahmed

    2015-11-01

    Full Text Available Blends of acrylonitrile butadiene rubber/high density polyethylene (NBR/HDPE compatibilized by Chloroprene rubber (CR were prepared. A fixed quantity of industrial waste such as marble waste (MW, 40 phr was also included. The effect of the blend ratio and CR on cure characteristics, mechanical and swelling properties of MW-filled NBR/HDPE blends was investigated. The results showed that the MW-filled NBR/HDPE blends revealed an increase in tensile strength, tear, modulus, hardness and cross-link density for increasing weight ratio of HDPE. The minimum torque (ML and maximum torque (MH of blends increased with increasing weight ratio of HDPE while scorch time (ts2 cure time (tc90, compression set and abrasion loss of blends decreased with increasing weight ratio of HDPE. The blends also showed a continuous reduction in elongation at break as well as swelling coefficient with increasing HDPE amount in blends. MW filled blends based on CR provided the most encouraging balance values of overall properties.

  18. Microstrueture and Properties of Fluoroelastomer/Butadiene-Acrylonitrile Rubber Interpenetrating Polymer Networks

    CHEN Chunming; XIONG Chuanxi; YANG Jian; DONG Lijie

    2008-01-01

    Interpenetrating polymer networks(IPNs)based on fluoroelastomer/butadiene-acrylonitrile rubber(FKM/NBR)by molten blending at a high temperature and chemical cross-linking of two components were prepared.The influence of the two networks component on the mechanical properties and thermostabilities was studied.The experimental results show that the mechanical properties of the IPNs are superior to those of the individual FKM and NBR networks due to forming the case of interpenetrating and intercross-linking between the two networks,the mechanical properties and thermal resistance exhibit higher values when 80/20(w/w)FKM and NBR is blended and respectively cured simultaneously.The co-continuous morphology of the IPNs in the blends of 80/20(w/w)FKM/NBR is found by transmission electron microscopy(TEM),the differential scanning calorimetry(DSC)determination shows that the blends of 80/20(w/w)FKM/NBR have better compatibility,and the glass transition temperature of the elastomer is -21.5℃.

  19. Latex stage blending of multiwalled carbon nanotube in carboxylated acrylonitrile butadiene rubber: Mechanical and electrical properties

    Highlights: ► MWCNT can act as a reinforcing filler in XNBR at very low concentration. ► SEM and XRD analysis confirm uniform distribution of nanotube in the matrix. ► Mechanical properties showed considerable improvement. ► Thermal stability of the composite is marginally improved. -- Abstract: Multiwalled carbon nanotube (MWCNT) was dispersed in sodium dodecyl benzene sulphonate (SDBS) by sonication. The dispersed MWCNT (0.05–0.3 gm) was incorporated in carboxylated acrylonitrile butadiene rubber (XNBR) latex. Mechanical, electrical and thermal properties of these composites were studied. Mechanical properties of the composites increased up to an optimum concentration and then decreased. Dielectric properties of the composites were studied in the S band (frequency range 2–4 GHz) by Cavity Perturbation method. Direct current (DC) electrical conductivity shows a percolation behaviour and conductivity increased by about 10 orders of magnitude. Thermal studies were conducted using Differential Scanning Calorimetry (DSC) and Thermo Gravimetric Analysis (TGA). As expected with the very small concentration of multiwalled carbon nanotube, glass transition temperature (Tg) and thermal stability of the composite showed a marginal increase. Composites were characterized by Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and Scanning electron microscope (SEM) analysis.

  20. Modification of dicyanate ester resin by liquid carboxyl-terminated butadiene acrylonitrile copolymer

    Bisphenol A dicyanate ester (BADCy) was modified with liquid carboxyl-terminated butadiene acrylonitrile (LCTBN). The cured BADCy resin was formed through the cyclotrimerization of cyanate functional groups into triazine rings, and there was the chemical reaction between BADCy and LCTBN. Mechanical performance indicated that the introduction of LCTBN into BADCy resin improved the impact strength with maintenance in flexural strength. Scanning electron microscopy (SEM) showed that the pure resin had a smooth glassy fracture surface, whereas cured blends containing LCTBN showed rougher fracture surfaces, and exhibited enhanced impact resistance. The TEM observation showed that the two phases in the cured resins exhibit a good interaction adhesion. Thermograms of BADCy modified with LCTBN showed the little reduction of heat deflection temperature, and a reduction in thermal stability temperature by 30 K. Dynamic mechanical analysis (DMA) showed that the pure BADCy had higher storage modulus (E') values than that of the BADCy modified with LCTBN, whereas the loss modulus (E'') was lower, and that the glass transition temperature (Tg) of modified BADCy was 229 deg. C and lower than that (249 deg. C) of pure BADCy resin.

  1. Crack initiation and propagation on the polymeric material ABS (Acrylonitrile Butadiene Styrene, under ultrasonic fatigue testing

    G. M. Domínguez Almaraz

    2015-10-01

    Full Text Available Crack initiation and propagation have been investigated on the polymeric material ABS (Acrylonitrile Butadiene Styrene, under ultrasonic fatigue testing. Three controlled actions were implemented in order to carry out fatigue tests at very high frequency on this material of low thermal conductivity, they are: a The applying load was low to limit heat dissipation at the specimen neck section, b The dimensions of testing specimen were small (but fitting the resonance condition, in order to restraint the temperature gradient at the specimen narrow section, c Temperature at the specimen neck section was restrained by immersion in water or oil during ultrasonic fatigue testing. Experimental results are discussed on the basis of thermo-mechanical behaviour: the tail phenomenon at the initial stage of fatigue, initial shear yielding deformation, crazed development on the later stage, plastic strain on the fracture surface and the transition from low to high crack growth rate. In addition, a numerical analysis is developed to evaluate the J integral of energy dissipation and the stress intensity factor K, with the crack length

  2. Carbon nanotube buckypaper reinforced acrylonitrile-butadiene-styrene composites for electronic applications.

    Díez-Pascual, Ana M; Gascón, David

    2013-11-27

    Novel acrylonitrile-butadiene-styrene (ABS) nanocomposites reinforced with pristine or functionalized single- or multiwalled carbon nanotube buckypaper (BP) sheets were manufactured via hot-compression and vacuum infiltration. Their morphology, thermal, mechanical, and electrical properties were comparatively investigated. Scanning electron microscopy and thermogravimetric analysis showed that the infiltration process leads to better BP impregnation than the hot-press technique. BPs made from functionalized or short nanotubes form compact networks that hamper the penetration of the matrix chains, whereas those composed of pristine tubes possess large pores that facilitate the polymer flow, resulting in composites with low degree of porosity and improved mechanical performance. Enhanced thermal and electrical properties are found for samples incorporating functionalized BPs since dense networks lead to more conductive pathways, and a stronger barrier effect to the diffusion of degradation products, thus better thermal stability. According to dynamic mechanical analysis these composites exhibit the highest glass transition temperatures, suggesting enhanced filler-matrix interactions as corroborated by the Raman spectra. The results presented herein demonstrate that the composite performance can be tailored by controlling the BP architecture and offer useful insights into the structure-property relationships of these materials to be used in electronic applications, particularly for EMI shielding and packaging of integrated circuits. PMID:24171494

  3. Study of the Effect of Grafted Antioxidant on the Acrylonitrile-Butadiene Copolymer Properties

    Abdulaziz Ibrahim Al-Ghonamy

    2010-01-01

    Full Text Available The grafting of ADPEA onto natural rubber was executed with UV radiation. Benzoyl peroxide was used to initiate the free-radical grafting copolymerization. Natural rubber-graft-N-(4-aminodiphenylether acrylamide (NR-g-ADPEA was characterized with an IR technique. The paper aims interested to determine the crosslinking density by using the ultrasonic technique. The ultrasonic velocities of both longitudinal and shear waves were measured in thermoplastic discs of NBR vulcanizates as a function of aging time. Ultrasonic velocity measurements were taken at 2 MHz ultrasonic frequency using the pulse echo method. We studied the effect of aging on the mechanical properties, crosslinking density, and the swelling and extraction phenomena for acrylonitrile-butadiene copolymer (NBR vulcanizates, which contained the prepared NR-g-ADPEA and a commercial antioxidant, N-isopropyl-N−-phenyl-p-phenylenediamine. The prepared antioxidant enhanced both the mechanical properties of the NBR vulcanizates and the permanence of the ingredients in these vulcanizates.

  4. Influence of metal coordination on conductivity behavior in poly(butadiene-acrylonitrile)-CoCl2 system

    The metal complex formation and the electrical properties of amorphous solid polymer electrolytes, based on poly(butadiene-acrylonitrile) copolymer (PBAN) and CoCl2, have been studied over the homogeneity region of the system limited by the CoCl2 concentration of 1.89 mol kg-1. It has been found that ionic conductivity is carried out by the unipolar anion transfer at lower CoCl2 concentrations (up to 0.10 mol kg-1). As the CoCl2 concentration increases, electronic conductivity appears in addition to ionic conductivity, and the former becomes dominant, starting from 0.38 mol kg-1. It has been shown that the nature of charge carriers is determined by the composition of metal complexes formed by CoCl2 and the macromolecular solvent PBAN. At lower concentrations, the [Co2L2Cl4]0 dimers are the predominant species (L being macromolecule side groups C≡N), and their dissociation is followed by the formation of mobile Cl- anions and immobile binuclear [Co2Cl3]+ complexes. As CoCl2 concentration increases, polynuclear [ConL2Cl2n]0 (n > 2) complexes appear (L being C≡N and C=C groups of PBAN). Specific features of chemical bonds in π-complexes of transition metals result in the appearance of electronic charge carriers. The abrupt increase in conductivity observed at the highest CoCl2 concentration is connected with the formation of a percolation network of polynuclear [ConL2Cl2n]0 complexes

  5. The effects of electron beam irradiation on the thermal properties, fatigue life and natural weathering of styrene butadiene rubber/recycled acrylonitrile-butadiene rubber blends

    Research highlights: → Addition of TMPTA helps to align polymer chains through crosslinking. → Improvement in fatigue life of irradiated blends due to formation of irradiation-induced crosslinks. → Excessive crosslinking caused reduction of tensile properties of irradiated SBR/NBRr blends. -- Abstract: The effects of electron beam (EB) irradiation on the thermal properties, fatigue life and natural weathering of styrene butadiene rubber/recycled acrylonitrile-butadiene rubber (SBR/NBRr) blends were investigated. The SBR/NBRr blends were prepared at 95/5, 85/15, 75/25, 65/35, or 50/50 blend ratios with and without the presence of a 3 part per hundred rubber (phr) of polyfunctional monomer, trimethylolpropane triacrylate (TMPTA). Results indicate that the crystallisation temperature (Tc) observed in polymeric blends is due to the alignment of polymer chains forming a semi-crystalline phase. Addition of TMPTA helps to align polymer chains through crosslinking. More crosslinking occurred between polymer blends with the help of TMPTA, upon irradiation. The improvement in fatigue life can also be associated with the stabilisation of SBR/NBRr blends upon irradiation and irradiation-induced crosslinking, which was accomplished with relatively low radiation-induced oxidative degradation in the presence of TMPTA. The tensile properties of both blends decreased over the periods of environmental exposure due to the effect of polymer degradation. After 6 months, the irradiated SBR/NBRr blends could not retain better retention [mainly with 25, 35 or 50 phr of recycled acrylonitrile-butadiene rubber (NBRr) particles] due to the samples becoming brittle over the long period of outdoor exposure.

  6. Fabrication of Acrylonitrile-Butadiene-Styrene Nanostructures with Anodic Alumina Oxide Templates, Characterization and Biofilm Development Test for Staphylococcus epidermidis.

    Camille Desrousseaux

    Full Text Available Medical devices can be contaminated by microbial biofilm which causes nosocomial infections. One of the strategies for the prevention of such microbial adhesion is to modify the biomaterials by creating micro or nanofeatures on their surface. This study aimed (1 to nanostructure acrylonitrile-butadiene-styrene (ABS, a polymer composing connectors in perfusion devices, using Anodic Alumina Oxide templates, and to control the reproducibility of this process; (2 to characterize the physico-chemical properties of the nanostructured surfaces such as wettability using captive-bubble contact angle measurement technique; (3 to test the impact of nanostructures on Staphylococcus epidermidis biofilm development. Fabrication of Anodic Alumina Oxide molds was realized by double anodization in oxalic acid. This process was reproducible. The obtained molds present hexagonally arranged 50 nm diameter pores, with a 100 nm interpore distance and a length of 100 nm. Acrylonitrile-butadiene-styrene nanostructures were successfully prepared using a polymer solution and two melt wetting methods. For all methods, the nanopicots were obtained but inside each sample their length was different. One method was selected essentially for industrial purposes and for better reproducibility results. The flat ABS surface presents a slightly hydrophilic character, which remains roughly unchanged after nanostructuration, the increasing apparent wettability observed in that case being explained by roughness effects. Also, the nanostructuration of the polymer surface does not induce any significant effect on Staphylococcus epidermidis adhesion.

  7. Study of the radiation-induced crosslinking of a butadiene-acrylonitrile polymer in the presence of N-para-bromophenylmaleimide

    Mixtures of butadiene-acrylonitrile copolymer with N-para-bromophenyl-maleimide (crosslinking sensitizer) were irradiated by exposure to the γ radiation of a 60Co source. The kinetics of crosslinking was evaluated as a function of composition, dose rate and temperature. The experimental measurements were carried out by infrared spectroscopy and magnetic resonance

  8. Study on Exothermic Oxidation of Acrylonitrile-butadiene-styrene (ABS Resin Powder with Application to ABS Processing Safety

    Jenq-Renn Chen

    2010-08-01

    Full Text Available Oxidative degradation of commercial grade ABS (Acrylonitrile-butadiene-styrene resin powders was studied by thermal analysis. The instabilities of ABS containing different polybutadiene (PB contents with respect to temperature were studied by Differential Scanning Calorimeter (DSC. Thermograms of isothermal test and dynamic scanning were performed. Three exothermic peaks were observed and related to auto-oxidation, degradation and oxidative decomposition, respectively. Onset temperature of the auto-oxidation was determined to be around 193 °C. However, threshold temperature of oxidation was found to be as low as 140 °C by DSC isothermal testing. Another scan of the powder after degeneration in air showed an onset temperature of 127 °C. Reactive hazards of ABS powders were verified to be the exothermic oxidation of unsaturated PB domains, not the SAN (poly(styrene-acrylonitrile matrix. Heat of oxidation was first determined to be 2,800 ± 40 J per gram of ABS or 4,720 ± 20 J per gram of PB. Thermal hazards of processing ABS powder are assessed by adiabatic temperature rise at process conditions. IR spectroscopy associated with heat of oxidation verified the oxidative mechanism, and these evidences excluded the heat source from the degradation of SAN. A specially prepared powder of ABS without adding anti-oxidant was analyzed by DSC for comparing the exothermic behaviors. Exothermic onset temperatures were determined to be 120 °C and 80 °C by dynamic scanning and isothermal test, respectively. The assessment successfully explained fires and explosions in an ABS powder dryer and an ABS extruder.

  9. 21 CFR 177.1050 - Acrylonitrile/styrene copoly-mer modified with butadiene/styrene elastomer.

    2010-04-01

    .... (e) Accelerated extraction end test. The modified copolymer shall yield acrylonitrile monomer not in... room temperature. A sample of the extracting solvent is then withdrawn and analyzed for acrylonitrile... Acrylonitrile Monomer in Acrylonitrile-Containing Polymers and Food Simulating Solvents,” which is...

  10. Carboxyl-terminated butadiene-acrylonitrile-toughened epoxy/carboxyl-modified carbon nanotube nanocomposites: Thermal and mechanical properties

    H. F. Xie

    2012-09-01

    Full Text Available Carboxyl-modified multi-walled carbon nanotubes (MWCNT–COOHs as nanofillers were incorporated into diglycidyl ether of bisphenol A (DGEBA toughened with carboxyl-terminated butadiene-acrylonitrile (CTBN. The carboxyl functional carbon nanotubes were characterized by Fourier-transform infrared spectroscopy and thermogravimetric analysis. Furthermore, cure kinetics, glass transition temperature (Tg, mechanical properties, thermal stability and morphology of DGEBA/CTBN/MWCNT–COOHs nanocomposites were investigated by differential scanning calorimetry (DSC, dynamic mechanical analysis (DMA, universal test machine, thermogravimetric analysis and scanning electron microscopy (SEM. DSC kinetic studies showed that the addition of MWCNT–COOHs accelerated the curing reaction of the rubber-toughened epoxy resin. DMA results revealed that Tg of rubber-toughened epoxy nanocomposites lowered with MWCNT–COOH contents. The tensile strength, elongation at break, flexural strength and flexural modulus of DGEBA/CTBN/MWCNT-COOHs nanocomposites were increased at lower MWCNT-COOH concentration. A homogenous dispersion of nanocomposites at lower MWCNT–COOH concentration was observed by SEM.

  11. Isolation of the ε-caprolactam denitrifying bacteria from a wastewater treatment system manufactured with acrylonitrile-butadiene-styrene resin

    ε-Caprolactam has high COD and toxicity, so its discharge to natural water and soil systems may lead to an adverse environmental effect on water quality, endangering public health and welfare. This investigation attempts to isolate ε-caprolactam denitrifying bacteria from a wastewater treatment system manufactured with acrylonitrile-butadiene-styrene (ABS) resin. The goal is to elucidate the effectiveness of isolated pure strain and ABS mixed strains in treating ε-caprolactam from synthetic wastewater. The results reveal that Paracoccus versutus MDC-3 was isolated from the wastewater treatment system manufactured with ABS resin. The ABS mixed strains and P. versutus MDC-3 can consume up to 1539 mg/l ε-caprolactam to denitrify from synthetic wastewater. Complete ε-caprolactam removal depended on the supply of sufficient electron acceptors (nitrate). Strain P. versutus MDC-3, Hyphomicrobium sp. HM, Methylosinus pucelana and Magnetospirillum sp. CC-26 are related closely, according to the phylogenetic analyses of 16S rDNA sequences

  12. Isolation of the {epsilon}-caprolactam denitrifying bacteria from a wastewater treatment system manufactured with acrylonitrile-butadiene-styrene resin

    Wang, C.-C. [Department of Environmental Engineering, Hungkuang University, Shalu, Taichung 433, Taiwan (China)]. E-mail: chunchin@sunrise.hk.edu.tw; Lee, C.-M. [Department of Environmental Engineering, National Chung Hsing University, Taichung 402, Taiwan (China)

    2007-06-25

    {epsilon}-Caprolactam has high COD and toxicity, so its discharge to natural water and soil systems may lead to an adverse environmental effect on water quality, endangering public health and welfare. This investigation attempts to isolate {epsilon}-caprolactam denitrifying bacteria from a wastewater treatment system manufactured with acrylonitrile-butadiene-styrene (ABS) resin. The goal is to elucidate the effectiveness of isolated pure strain and ABS mixed strains in treating {epsilon}-caprolactam from synthetic wastewater. The results reveal that Paracoccus versutus MDC-3 was isolated from the wastewater treatment system manufactured with ABS resin. The ABS mixed strains and P. versutus MDC-3 can consume up to 1539 mg/l {epsilon}-caprolactam to denitrify from synthetic wastewater. Complete {epsilon}-caprolactam removal depended on the supply of sufficient electron acceptors (nitrate). Strain P. versutus MDC-3, Hyphomicrobium sp. HM, Methylosinus pucelana and Magnetospirillum sp. CC-26 are related closely, according to the phylogenetic analyses of 16S rDNA sequences.

  13. Isolation of the epsilon-caprolactam denitrifying bacteria from a wastewater treatment system manufactured with acrylonitrile-butadiene-styrene resin.

    Wang, Chun-Chin; Lee, Chi-Mei

    2007-06-25

    epsilon-Caprolactam has high COD and toxicity, so its discharge to natural water and soil systems may lead to an adverse environmental effect on water quality, endangering public health and welfare. This investigation attempts to isolate epsilon-caprolactam denitrifying bacteria from a wastewater treatment system manufactured with acrylonitrile-butadiene-styrene (ABS) resin. The goal is to elucidate the effectiveness of isolated pure strain and ABS mixed strains in treating epsilon-caprolactam from synthetic wastewater. The results reveal that Paracoccus versutus MDC-3 was isolated from the wastewater treatment system manufactured with ABS resin. The ABS mixed strains and P. versutus MDC-3 can consume up to 1539mg/l epsilon-caprolactam to denitrify from synthetic wastewater. Complete epsilon-caprolactam removal depended on the supply of sufficient electron acceptors (nitrate). Strain P. versutus MDC-3, Hyphomicrobium sp. HM, Methylosinus pucelana and Magnetospirillum sp. CC-26 are related closely, according to the phylogenetic analyses of 16S rDNA sequences. PMID:17161908

  14. Reclamation of post-consumer plastics for development of polycarbonate and acrylonitrile butadiene styrene based nanocomposites with nanoclay

    Zicans, Janis; Meri, Remo Merijs; Ivanova, Tatjana; Berzina, Rita; Saldabola, Ruuta; Maksimov, Robert

    2016-05-01

    Suitability of recycled acrylonitrile-butadiene-styrene (R-ABS) and recycled polycarbonate (R-PC) for the development of polymer matrix nanocomposites with organically modified nanoclay (OMMT) is evaluated in comparison to virgin polymers (V-ABS and V-PC) based systems. The influence of OMMT content on the structure as well as calorimetric, mechanical and thermal properties of virgin and recycled polymers containing systems is revealed. Increase in stiffness and strength of virgin and recycled polymers based systems is observed along with rising nanoclay content. However, it is observed that reinforcing efficiency of clays on the R-ABS containing systems is reduced to certain extent in comparison to those, based on virgin polymers. It is shown, that in the presence of OMMT approximation of glass transition temperatures of both polymeric components is observed, which can testify about certain improvement of compatibility between PC and ABS. Increment of the modulus of elasticity and yield strength of the nanocomposites is associated with anisodiametric shape of OMMT, as well as with intercalation of polymer within the interlaminar space of the clay nanoparticles. It is also demonstrated that addition of nanoclay improves thermogravimetric behavior of the investigated compositions. Consequently, it is suggested that nanoclays can be used as promising functional additives and replace halogenated flame-retardants, without reducing mechanical properties of the composites.

  15. Effect of different curing systems on the mechanical and physico-chemical properties of acrylonitrile butadiene rubber vulcanizates

    Graphical abstract: The stress -strain behavior of NBr demonstrates a remarkable dependance on the applied curing system. Research highlights: → The cross-link density greatly affect the mechanical properties of vulcanizates. → Hardness, Young's modulus, and tensile modulus increased by increasing the cross-link density. → The radiation/coagent cured system gave higher results in thermal stability and thermal ageing than those of the sulfur cured system. -- Abstract: In the present study, the effect of different curing systems including sulfur, dicumyl peroxide, dicumyl peroxide/coagent and radiation/coagent on the mechanical and physico-chemical properties of acrylonitrile butadiene rubber (NBR) was studied. In order to correlate, the effect of curing systems on rubber, the comparison was carried out at comparable value of volume fraction of rubber in swollen gel (Vr) for NBR vulcanizates. Mechanical properties like tensile strength, elongation at break, modulus, Young's modulus, tearing strength and abrasion loss of vulcanizates have been followed up for comparison. In addition, physico-chemical properties like swelling ratio, soluble fraction, and cross-link density were investigated. On the other hand, the effects of fuel, thermogravimetric analysis, and thermal ageing have been studied.

  16. FINITE ELEMENT SIMULATION FOR YIELD STRESS OF HARD POLY(VINYL CHLORIDE)/ACRYLONITRILE-BUTADIENE-STYRENE BLENDS AT DIFFERENT CROSSHEAD SPEEDS

    Pei-hua Du; Jie Yu; Peng-fei Lin; Yi-hu Song; Qiang Zneng

    2011-01-01

    Hard poly(vinyl chloride) (PVC)/acrylonitrile-butadiene-styrene (ABS) blends were prepared using injectionmolding and influence of crosshead speed on mechanical properties was examined.Based on morphology parameters obtained from transmission electron microscopy photography and the material parameters from true stress-strain curves of neat PVC and ABS,yield stresses of the blends at different crosshead speeds were simulated employing a two-dimensional nine-particle model based on the finite element analysis (FEA).The FEA results were compared with the experimental yielding stress and the good agreement validated the simulation approach.The FEA approach allowed establishing a yielding criterion related to local yielding of the interstitial matrix between ABS particles.

  17. Studies on blends of cycloaliphatic epoxy resin with varying concentrations of carboxyl terminated butadiene acrylonitrile copolymer I: Thermal and morphological properties

    Garima Tripathi; Deepak Srivastava

    2009-04-01

    Differential scanning calorimetric (DSC), thermogravimetric analysis (TGA) and dynamic mechanical analysis (DMA) of the blends of cycloaliphatic epoxy (CAE) resin toughened with liquid elastomer such as carboxyl terminated butadiene acrylonitrile copolymer (CTBN) have been carried out. Exothermal heat of reaction due to cross linking of the resin in the presence of diamino diphenyl sulphone (DDS, an amine hardener) showed a decreasing trend with increasing rubber concentration. Enhancement of thermal stability as well as lower mass loss of the epoxy–rubber blends with increasing rubber concentration have been observed in thermogravimetric analysis (TGA). Dynamic mechanical properties reflected a monotonic decrease in the storage modulus (′) with increasing rubber concentration. The loss modulus (″) and the loss tangent (tan ) values, however, showed an increasing trend with rise of temperature up to a maximum (peak) followed by a gradual fall in both cases.

  18. Preparation and Characterization of Carboxyl-terminated Poly (butadiene-co-acrylonitrile)-epoxy Resin Prepolymers for Fusion-bonded-epoxy Powder Coating

    LIU Jingcheng; JIA Xiuli; ZHANG Shengwen; LIU Ren; LIU Xiaoya

    2012-01-01

    Liquid carboxyl-terminated poly(butadiene-co-acrylonitrile)(CTBN)-epoxy resin(EP)prepolymers were prepared with different contents of CTBN.The chemical reactions between EP and CTBN were characterized by Fourier ransform infrared (FTIR) spectroscopy and gel permeation chromatography (GPC).The scanning electron micrograph (SEM) and dynamic mechanical analysis (DMA) of curing films showed phase separation,and the rubber particles were finely dispersed in the epoxy matrix.Mechanical properties analysis of curing films showed that impact strength and elongation at break increased significantly upon the addition of CTBN,indicating good toughness of the modified epoxy resins.Thermogravimetric analysis (TGA) showed that the incorporation of CTBN had little effect on the thermal stability of EP.Fusion-bondedepoxy (FBE) powder coatings modified with CTBN-EP prepolymers were prepared.The experimental results demonstrate the ability of CTBN-EP prepolymers,toughening technology to dramatically enhance the flexibility and impact resistance of FBE coatings without compromising other key properties such as corrosion protection.

  19. Effects of aminopropyltriethoxysilane (γ-APS) on tensile properties and morphology of polypropylene (PP), recycle acrylonitrile butadiene rubber (NBRr) and sugarcane bagasse (SCB) composites

    Santiagoo, Ragunathan; Omar, Latifah; Zainal, Mustaffa; Ting, Sam Sung; Ismail, Hanafi

    2015-07-01

    The performance of sugarcane baggase (SCB) treated with γ-APS filled polypropylene (PP)/recycled acrylonitrile butadiene rubber (NBRr) biocomposites were investigated. The composites with different filler loading ranging from 5 to 30 wt % were prepared using heated two roll mill by melt mixing at temperature of 180 °C. Tensile properties of the PP/NBRr/SCB composites which is tensile strength, Young Modulus and elongation at break were investigated. Increasing of treated SCB filler loading in PP/NBRr/SCB composites have increased the Young modulus however decreased the tensile strength and elongation at break of the PP/NBRr/SCB composites. From the results, γ-APS treated SCB composites shown higher tensile strength and Young Modulus but lower elongation at break when compared to the untreated SCB composites. This is due to the stronger bonding between γ-APS treated SCB with PP/NBRr matrices. These findings was supported by micrograph pictures from morphological study. SCB filler treated with γ-APS has improved the adhesion as well as gave strong interfacial bonding between SCB filler and PP/NBRr matrices which results in good tensile strength of PP/NBRr/SCB composites.

  20. Flame retardancy mechanisms of bisphenol A bis(diphenyl phosphate) in combination with zinc borate in bisphenol A polycarbonate/acrylonitrile-butadiene-styrene blends

    Bisphenol A polycarbonate/acrylonitrile-butadiene-styrene (PC/ABS) with and without bisphenol A bis(diphenyl phosphate) (BDP) and 5 wt.% zinc borate (Znb) were investigated. The pyrolysis was studied by thermogravimetry (TG), TG-FTIR and NMR, the fire behaviour with a cone calorimeter applying different heat fluxes, LOI and UL 94. Fire residues were examined with NMR. BDP affects the decomposition of PC/ABS and acts as a flame retardant in the gas and condensed phases. The addition of Znb results in an additional hydrolysis of PC. The fire behaviour is similar to PC/ABS, aside from a slightly increased LOI and a reduced peak heat release rate, both caused by borates improving the barrier properties of the char. In PC/ABS + BDP + Znb, the addition of Znb yields a borate network and amorphous phosphates. Znb also reacts with BDP to form alpha-zinc phosphate and borophosphates that suppress the original flame retardancy mechanisms of BDP. The inorganic-organic residue formed provides more effective flame retardancy, in particular at low irradiation in the cone calorimeter, and a clear synergy in LOI, whereas for more developed fires BDP + Znb become less effective than BDP in PC/ABS with respect to the total heat evolved.

  1. Three-dimensional Printed Acrylonitrile Butadiene Styrene Framework Coated with Cu-BTC Metal-organic Frameworks for the Removal of Methylene Blue

    Wang, Zongyuan; Wang, Jiajun; Li, Minyue; Sun, Kaihang; Liu, Chang-Jun

    2014-08-01

    Three-dimensional (3D) printing was applied for the fabrication of acrylonitrile butadiene styrene (ABS) framework. Functionalization of the ABS framework was then performed by coating of porous Cu-BTC (BTC = benzene tricarboxylic acid) metal-organic frameworks on it using a step-by-step in-situ growth. The size of the Cu-BTC particles on ABS was ranged from 200 nm to 900 nm. The Cu-BTC/ABS framework can take up most of the space of the tubular reactor that makes the adsorption effective with no need of stirring. Methylene blue (MB) can be readily removed from aqueous solution by this Cu-BTC/ABS framework. The MB removal efficiency for solutions with concentrations of 10 and 5 mg/L was 93.3% and 98.3%, respectively, within 10 min. After MB adsorption, the Cu-BTC/ABS composite can easily be recovered without the need for centrifugation or filtration and the composite is reusable. In addition the ABS framework can be recovered for subsequent reuse. A significant advantage of 3D-printed frameworks is that different frameworks can be easily fabricated to meet the needs of different applications. This is a promising strategy to synthesize new frameworks using MOFs and polymers to develop materials for applications beyond adsorption.

  2. Heat shrinkable behavior, physico-mechanical and structure properties of electron beam cross-linked blends of high-density polyethylene with acrylonitrile-butadiene rubber

    Reinholds, Ingars; Kalkis, Valdis; Merijs-Meri, Remo; Zicans, Janis; Grigalovica, Agnese

    2016-03-01

    In this study, heat-shrinkable composites of electron beam irradiated high-density polyethylene (HDPE) composites with acrylonitrile-butadiene rubber (NBR) were investigated. HDPE/NBR blends at a ratio of components 100/0, 90/10, 80/20, 50/50 and 20/80 wt% were prepared using a two-roll mill. The compression molded films were irradiated high-energy (5 MeV) accelerated electrons up to irradiation absorbed doses of 100-300 kGy. The effect of electron beam induced cross-linking was evaluated by the changes of mechanical properties, gel content and by the differences of thermal properties, detected by differential scanning calorimetry. The thermo-shrinkage forces were determined as the kinetics of thermorelaxation and the residual shrinkage stresses of previously oriented (stretched up to 100% at above melting temperature of HDPE and followed by cooling to room temperature) specimens of irradiated HDPE/NBR blends under isometric heating-cooling mode. The compatibility between the both components was enhanced due to the formation of cross-linked sites at amorphous interphase. The results showed increase of mechanical stiffness of composites with increase of irradiation dose. The values of gel fraction compared to thermorelaxation stresses increased with the growth of irradiation dose level, as a result of formation cross-linked sites in amorphous PP/NBR interphase.

  3. Laser transmission welding of Acrylonitrile-Butadiene-Styrene (ABS) using a tailored high power diode-laser optical fiber coupled system

    Rodríguez-Vidal, E.; Quintana, I.; Etxarri, J.; Otaduy, D.; González, F.; Moreno, F.

    2012-06-01

    Laser transmission welding (LTW) of polymers is a direct bonding technique which is already used in different industrial applications sectors such as automobile, microfluidic, electronic and biomedicine. This technique offers several advantages over conventional methods, especially when a local deposition of energy and minimum thermal distortions are required. In LTW one of the polymeric materials needs to be transparent to the laser wavelength and the second part needs to be designed to be absorbed in IR spectrum. This report presents a study of laser weldability of ABS (acrylonitrile/butadiene/styrene) filled with two different concentrations of carbon nanotubes (0.01% and 0.05% CNTs). These additives are used as infrared absorbing components in the laser welding process, affecting the thermal and optical properties of the material and, hence, the final quality of the weld seam. A tailored laser system has been designed to obtain high quality weld seams with widths between 0.4 and 1.0mm. It consists of two diode laser bars (50W per bar) coupled into an optical fiber using a non-imaging solution: equalization of the beam quality factor (M2) in the slow and fast axes by a pair of micro step-mirrors. The beam quality factor has been analyzed at different laser powers with the aim to guarantee a coupling efficiency to the multimode optical fiber. The power scaling is carried out by means of multiplexing polarization technique. The analysis of energy balance and beam quality is performed in two linked steps: first by means ray tracing simulations (ZEMAX®) and second, by validation. Quality of the weld seams is analyzed in terms of the process parameters (welding speed, laser power and clamping pressure) by visual and optical microscope inspections. The optimum laser power range for three different welding speeds is determinate meanwhile the clamping pressure is held constant. Additionally, the corresponding mechanical shear tests were carried out to analyze the

  4. Studies on the physico-mechanical and thermal characteristics of blends of DGEBA epoxy, 3,4 epoxy cyclohexylmethyl, 3',4'-epoxycylohexane carboxylate and carboxyl terminated butadiene co-acrylonitrile (CTBN)

    Toughening of blend of diglycidyl ether of bisphenol-A (DGEBA) and 3,4 epoxy cyclohexylmethyl, 3',4'-epoxycylohexane carboxylate, i.e. cycloaliphatic epoxy resin (CAE) with varying weight ratios (0-25 wt%) of carboxyl terminated butadiene acrylonitrile (CTBN) copolymer have been investigated. Fourier transform infrared (FTIR) spectroscopic analysis established that the interaction between oxirane groups of DGEBA, CAE and CTBN were responsible for characteristics peak shifts in the blends compared to their counterparts. Physico-mechanical properties of the prepared samples, e.g. tensile, flexural and impact strengths showed an optimum concentration of CTBN (15 wt%) into epoxy matrix, which offered maximum toughening. Thermal stability of the prepared samples was analyzed by dynamic thermogravimetric runs. Cross-sections of the cured samples which failed during impact testing have been critically studied through scanning electron microscopic (SEM) analysis to gain insight into the phase morphology

  5. Studies on the physico-mechanical and thermal characteristics of blends of DGEBA epoxy, 3,4 epoxy cyclohexylmethyl, 3',4'-epoxycylohexane carboxylate and carboxyl terminated butadiene co-acrylonitrile (CTBN)

    Tripathi, Garima [Department of Plastic Technology, H. B. Technological Institute, Kanpur 208002 (India); Srivastava, Deepak [Department of Plastic Technology, H. B. Technological Institute, Kanpur 208002 (India)], E-mail: deepak_sri92@rediffmail.com

    2008-11-25

    Toughening of blend of diglycidyl ether of bisphenol-A (DGEBA) and 3,4 epoxy cyclohexylmethyl, 3',4'-epoxycylohexane carboxylate, i.e. cycloaliphatic epoxy resin (CAE) with varying weight ratios (0-25 wt%) of carboxyl terminated butadiene acrylonitrile (CTBN) copolymer have been investigated. Fourier transform infrared (FTIR) spectroscopic analysis established that the interaction between oxirane groups of DGEBA, CAE and CTBN were responsible for characteristics peak shifts in the blends compared to their counterparts. Physico-mechanical properties of the prepared samples, e.g. tensile, flexural and impact strengths showed an optimum concentration of CTBN (15 wt%) into epoxy matrix, which offered maximum toughening. Thermal stability of the prepared samples was analyzed by dynamic thermogravimetric runs. Cross-sections of the cured samples which failed during impact testing have been critically studied through scanning electron microscopic (SEM) analysis to gain insight into the phase morphology.

  6. An Investigation on the Extraction and Quantitation of a Hexavalent Chromium in Acrylonitrile Butadiene Styrene Copolymer (ABS) and Printed Circuit Board (PCB) by Ion Chromatography Coupled with Inductively Coupled Plasma Atomic Emission Spectrometry

    A hexavalent chromium (Cr (VI)) is one of the hazardous substances regulated by the RoHS. The determination of Cr (VI) in various polymers and printed circuit board (PCB) has been very important. In this study, the three different analytical methods were investigated for the determination of a hexavalent chromium in Acrylonitrile Butadiene Styrene copolymer (ABS) and PCB. The results by three analytical methods were obtained and compared. An analytical method by UV-Visible spectrometer has been generally used for the determination of Cr (VI) in a sample, but a hexavalent chromium should complex with diphenylcarbazide for the detection in the method. The complexation did make an adverse effect on the quantitative analysis of Cr (VI) in ABS. The analytical method using diphenylcarbazide was also not applicable to printed circuit board (PCB) because PCB contained lots of irons. The irons interfered with the analysis of hexavalent chromium because those also could complex with diphenylcarbazide. In this study, hexavalent chromiums in PCB have been separated by ion chromatography (IC), then directly and selectively detected by inductively coupled plasma atomic emission spectrometry (ICP-AES). The quantity of Cr (VI) in PCB was 0.1 mg/kg

  7. Determination of Bound Acrylonitrile Content in Acrylonitrile-butadiene Rubber(NBR) by Infrared Spectroscopy Method%红外光谱法测定丁腈橡胶中的结合丙烯腈含量

    高杜娟; 黄世英; 赵家琳; 刘俊保

    2015-01-01

    Infrared spectrometry in this article was used to determinate the bound acrylonitrile content in nitrile rubber( NBR). In the process of experimenting,the sample preparation conditions were determined and the stand-ard values of seven substitute standard sample were confirmed by Kjeldahl method,through which the quantitative calculation formula was get. And finally,the results were compared with the method of element analysis.%本文采用红外光谱法测定丁腈橡胶( NBR)中的结合丙烯腈含量,确定了样品前处理条件,通过凯氏定氮法确定7个代用标准胶中结合丙烯腈含量的标准值,得出了结合丙烯腈含量的定量计算公式,测试结果与元素分析法进行了对比。

  8. Comparison of sodium naphthenate and air-ionization corona discharge as surface treatments for the ethylene-tetrafluoroethylene polymer (ETFE) to improve adhesion between ETFE and acrylonitrile-butadiene-styrene polymer (ABS) in the presence of a cyanoacrylate adhesive (CAA)

    This study compares two ethylene-tetrafluoroethylene (ETFE) surface activation treatments, namely chemical attack with a solution of sodium naphthenate and plasma erosion via air-ionization corona discharge in order to improve the adhesive properties of the ETFE. An experimental design was prepared for both treatments in order to assess the effect of the treatment characteristics on the tensile load needed to break the bond between the ETFE and the acrylonitrile-butadiene-styrene polymer (ABS) formed with a cyanoacrylate adhesive (CAA) applied between them. The reason for the selection of this problem is that both polymers are frequently used in the biomedical industry for their properties, and they need to be joined firmly in biomedical devices, and the cyanoacrylate adhesive is the adhesive traditionally used for fluoropolymers, in this case the ETFE, and the same CAA has also shown good adhesion with ABS. However, the strength of the bond for the triplet ETFE-CAA-ABS has not been reported and the improvement of the strength of the bond with surface treatments is not found in scholarly journals for modern medical devices such as stents and snares. Both treatments were compared based on the aforementioned design of experiments. The case where ETFE receives no surface treatment serves as the reference. The results indicated that the three factors evaluated (initial drying of the material, temperature of the chemical bath, and immersion time), and their interactions have no significant effect over the tensile load at failure (tensile strength) of the adhesive bond being evaluated. For the air-ionization corona discharge treatment, two factors were evaluated: discharge exposition time and air pressure. The results obtained from this experimental design indicate that there is no significant difference between the levels of the factors evaluated. These results were unexpected as the ranges used were representative of the maximum ranges permissible in manufacturing

  9. Comparison of sodium naphthenate and air-ionization corona discharge as surface treatments for the ethylene-tetrafluoroethylene polymer (ETFE) to improve adhesion between ETFE and acrylonitrile-butadiene-styrene polymer (ABS) in the presence of a cyanoacrylate adhesive (CAA)

    Lucía Johanning-Solís, Ana; Stradi-Granados, Benito A.

    2014-09-01

    This study compares two ethylene-tetrafluoroethylene (ETFE) surface activation treatments, namely chemical attack with a solution of sodium naphthenate and plasma erosion via air-ionization corona discharge in order to improve the adhesive properties of the ETFE. An experimental design was prepared for both treatments in order to assess the effect of the treatment characteristics on the tensile load needed to break the bond between the ETFE and the acrylonitrile-butadiene-styrene polymer (ABS) formed with a cyanoacrylate adhesive (CAA) applied between them. The reason for the selection of this problem is that both polymers are frequently used in the biomedical industry for their properties, and they need to be joined firmly in biomedical devices, and the cyanoacrylate adhesive is the adhesive traditionally used for fluoropolymers, in this case the ETFE, and the same CAA has also shown good adhesion with ABS. However, the strength of the bond for the triplet ETFE-CAA-ABS has not been reported and the improvement of the strength of the bond with surface treatments is not found in scholarly journals for modern medical devices such as stents and snares. Both treatments were compared based on the aforementioned design of experiments. The case where ETFE receives no surface treatment serves as the reference. The results indicated that the three factors evaluated (initial drying of the material, temperature of the chemical bath, and immersion time), and their interactions have no significant effect over the tensile load at failure (tensile strength) of the adhesive bond being evaluated. For the air-ionization corona discharge treatment, two factors were evaluated: discharge exposition time and air pressure. The results obtained from this experimental design indicate that there is no significant difference between the levels of the factors evaluated. These results were unexpected as the ranges used were representative of the maximum ranges permissible in manufacturing

  10. Polybenzoxazole-filled nitrile butadiene rubber compositions

    Gajiwala, Himansu M. (Inventor); Guillot, David G. (Inventor)

    2008-01-01

    An insulation composition that comprises at least one nitrile butadiene rubber (NBR) having an acrylonitrile content that ranges from approximately 26% by weight to approximately 35% by weight and polybenzoxazole (PBO) fibers. The NBR may be a copolymer of acrylonitrile and butadiene and may be present in the insulation composition in a range of from approximately 45% by weight to approximately 56% by weight of a total weight of the insulation composition. The PBO fibers may be present in a range of from approximately 3% by weight to approximately 10% by weight of a total weight of the insulation composition. A rocket motor including the insulation composition and a method of insulating a rocket motor are also disclosed.

  11. [Migrants from disposable gloves and residual acrylonitrile].

    Wakui, C; Kawamura, Y; Maitani, T

    2001-10-01

    Disposable gloves made from polyvinyl chloride with and without di(2-ethylhexyl) phthalate (PVC-DEHP, PVC-NP), polyethylene (PE), natural rubber (NR) and nitrile-butadiene rubber (NBR) were investigated with respect to evaporation residue, migrated metals, migrants and residual acrylonitrile. The evaporation residue found in n-heptane was 870-1,300 ppm from PVC-DEHP and PVC-NP, which was due to the plasticizers. Most of the PE gloves had low evaporation residue levels and migrants, except for the glove designated as antibacterial, which released copper and zinc into 4% acetic acid. For the NR and NBR gloves, the evaporation residue found in 4% acetic acid was 29-180 ppm. They also released over 10 ppm of calcium and 6 ppm of zinc into 4% acetic acid, and 1.68-8.37 ppm of zinc di-ethyldithiocarbamate and zinc di-n-butyldithiocarbamate used as vulcanization accelerators into n-heptane. The acrylonitrile content was 0.40-0.94 ppm in NBR gloves. PMID:11775358

  12. Computational Investigation of the Competition between the Concerted Diels-Alder Reaction and Formation of Diradicals in Reactions of Acrylonitrile with Non-Polar Dienes

    James, Natalie C.; Um, Joann M.; Padias, Anne B.; Hall, H. K.; Houk, K. N.

    2013-01-01

    The energetics of the Diels-Alder cycloaddition reactions of several 1,3-dienes with acrylonitrile, and the energetics of formation of diradicals, were investigated with density functional theory (B3LYP and M06-2X) and compared to experimental data. For the reaction of 2,3-dimethyl-1,3-butadiene with acrylonitrile, the concerted reaction is favored over the diradical pathway by 2.5 kcal/mol using B3LYP/6-31G(d); experimentally this reaction gives both cycloadduct and copolymer. The concerted ...

  13. Reinforcement of hydrogenated carboxylated nitrile-butadiene rubber by multi-walled carbon nanotubes

    Hydrogenated carboxylated acrylonitrile-butadiene rubber (HXNBR) and multi-walled carbon nanotubes (MWCNT) composites were prepared. The dispersion of MWCNT in HXNBR matrix was evaluated by field emission scanning electron microscopy. HXNBR/MWCNT composite had shorter scorch time and optimum curing time compared with that of unfilled HXNBR. The tensile strength and modulus of HXNBR/MWCNT composites increased with increasing MWCNT content. Mooney-Rivlin equation was used to describe the stress-strain behavior of unfilled HXNBR and the strain amplification factor was taken into account for HXNBR/MWCNT composites. The Mullins effect and dynamic mechanical properties of HXNBR/MWCNT composite were also investigated.

  14. 21 CFR 180.22 - Acrylonitrile copolymers.

    2010-04-01

    ..., distilled water, 8 percent or 50 percent ethanol, 3 percent acetic acid, and either n-heptane or an... conditions for the use of acrylonitrile copolymers have been, or soon will be, undertaken. Toxicity...

  15. Recycling cycle of materials applied to acrylonitrile-butadiene-styrene/policarbonate blends with styrene-butadiene-styrene copolymer addition

    Cândido, L. H. A.; Ferreira, D. B.; Júnior, W. Kindlein; Demori, R.; Mauler, R. S.

    2014-05-01

    The scope of this research is the recycling of polymers from mobile phones hulls discarded and the performance evaluation when they are submitted to the Recycling Cycle of Materials (RCM). The studied material was the ABS/PC blend in a 70/30 proportion. Different compositions were evaluated adding virgin material, recycled material and using the copolymer SBS as impact modifier. In order to evaluate the properties of material's composition, the samples were characterized by TGA, FTIR, SEM, IZOD impact strength and tensile strength tests. At the first stage, the presented results suggest the composition containing 25% of recycled material and 5% of SBS combines good mechanical performance to the higher content of recycled material and lower content of impact modifier providing major benefits to recycling plans. Five cycles (RCM) were applied in the second stage; they evidenced a decrease trend considering the impact strength. At first and second cycle the impact strength was higher than reference material (ABS/PC blend) and from the fourth cycle it was lower. The superiority impact strength in the first and second cycles can be attributed to impact modifier effect. The thermal tests and the spectrometry didn't show the presence of degradation process in the material and the TGA curves demonstrated the process stability. The impact surface of each sample was observed at SEM. The microstructures are not homogeneous presenting voids and lamellar appearance, although the outer surface presents no defects, demonstrating good moldability. The present work aims to assess the life cycle of the material from the successive recycling processes.

  16. Starch Modification by Graft Copolymerization of Acrylonitrile

    刘瑞贤; 李莉; 茹宗玲; 张黎明; 高建平; 田汝川

    2003-01-01

    The graft copolymerization of acrylonitrile (AN) onto starch under the initiation of potassium permanganate was investigated. The effect of various reaction conditions on the graft copolymerization was studied. The relationships between the grafting rate and the initiator concentration of potassium permanganate, monomer acrylonitrile and backbone starch, as well as reaction temperature were established. The oxidation reaction of starch with manganic ions and valence changes of manganic ions during the graft copolymerization were discussed. The results show that manganic ion Mn7+ underwent a series of valence changes during the graft copolymerization: Mn(Ⅶ) → Mn(Ⅳ) → Mn(Ⅲ) → Mn(Ⅱ). The grafting rate of the graft copolymerization of acrylonitrile onto starch is also given.

  17. Power Efficient, Restart-Capable Acrylonitrile-Butadiene-Styrene Arc Ignitor for Hybrid Rockets

    Whitmore, Stephen; Merkely, Daniel; Inkley, Nathan

    2014-01-01

    Because hybrid rocket propellant materials are individually chemically stable prior to mixing within the combustion chamber, these systems possess well-known safety advantages. Unfortunately, the relative stability of traditional hybrid propellants also makes hybrid systems difficult to ignite. Hybrid ignition has historically involved one of three means, 1) pyrotechnic charges, 2) plasma torch, and 3) electric spark plugs with bi-propellant injectors. All of these methods possess distinct di...

  18. Coconut shell powder as cost effective filler in copolymer of acrylonitrile and butadiene rubber.

    Keerthika, B; Umayavalli, M; Jeyalalitha, T; Krishnaveni, N

    2016-08-01

    Filler is one of the major additives in rubber compounds to enhance the physical properties. Even though numerous benefits obtained from agricultural by products like coconut shell, rice husk etc., still they constitute a large source of environmental pollution. In this investigation, one of the agricultural bye product coconut shell powder (CSP) is used as filler in the compounding KNB rubber. It shows the positive and satisfied result was achieved only by the use of filler Fast Extrusion Furnace (FEF) and coconut shell powder (CSP) which was used 50% in each. The effect of these fillers on the mechanical properties of a rubber material at various loading raging from 0 to 60PHP was studied. Mercaptodibanzothiazole disulphide (MBTS) was used as an accelerator. The result shows that presence of 25% and 50% of the composites has better mechanical properties like Hardness, Tensile strength, Elongation at break and Specific gravity when compared with other two combinations. Even though both 25% and 50% of composites shows good mechanical properties, 50% of CSP have more efficient than 25% of CSP. PMID:27060197

  19. A comparison of the characteristics of excimer and femtosecond laser ablation of acrylonitrile butadiene styrene (ABS)

    See, Tian Long; Liu, Zhu; Li, Lin; Zhong, Xiang Li

    2016-02-01

    This paper presents an investigation on the ablation characteristics of excimer laser (λ = 248 nm, τ = 15 ns) and femtosecond laser (λ = 800 nm, τ = 100 fs) on ABS polymer sheets. The laser-material interaction parameters (ablation threshold, optical penetration depth and incubation factor) and the changes in material chemical properties were evaluated and compared between the two lasers. The work shows that the ablation threshold and effective optical penetration depth values are dependent on the wavelength of laser beam (photon energy) and the pulse width. The ablation threshold value is lower for the excimer laser ablation of ABS (Fth = 0.087 J/cm2) than that for the femtosecond laser ablation of ABS (Fth = 1.576 J/cm2), demonstrating a more dominating role of laser wavelength than the pulse width in influencing the ablation threshold. The ablation depth versus the logarithmic scale of laser fluence shows two linear regions for the fs laser ablation, not previously known for polymers. The effective optical penetration depth value is lower for excimer laser ablation (α-1 = 223 nm) than that for femtosecond laser ablation (α-1 = 2917 nm). The ablation threshold decreases with increasing number of pulses (NOP) due to the chain scission process that shortens the polymeric chains, resulting in a weaker polymeric configuration and the dependency is governed by the incubation factor. Excimer laser treatment of ABS eliminates the Cdbnd C bond completely through the chain scission process whereas Cdbnd C bond is partially eliminated through the femtosecond laser treatment due to the difference in photon energy of the two laser beams. A reduction in the Cdbnd C bond through the chain scission process creates free radical carbons which then form crosslinks with each other or react with oxygen, nitrogen and water in air producing oxygen-rich (Csbnd O and Cdbnd O bond) and nitrogen-rich (Csbnd N) functional groups.

  20. Enhancement the Thermal Stability and the Mechanical Properties of Acrylonitrile-Butadiene Copolymer by Grafting Antioxidant

    Abdulaziz Ibrahim Al-Ghonamy

    2010-01-01

    Full Text Available Monomeric antioxidants are widely used as effective antioxidants to protect polymers against thermal oxidation. Low molecular weight antioxidants are easily lost from polymer through migration, evaporation, and extraction. Physical loss of antioxidants is considered to be major concern in the environmental issues and safety regulation as well as long life time of polymers. The grafting copolymerization of natural rubber and o-aminophenol was carried out by using two-roll mill machine. The prepared natural rubber-graft-o-Aminophenol, NR-graft-o-AP, was analysed by using Infrared and 1H-NMR Spectroscopy techniques. The thermal stability, mechanical properties, and ultrasonic attenuation coefficient were evaluated for NBR vulcanizates containing the commercial antioxidant, N-phenyl-β-naphthylamine (PBN, the prepared grafted antioxidant, NR-graft-o-AP, and the control vulcanizate. Results of the thermal stability showed that the prepared NR-graft-o-AP can protect NBR vulcanizate against thermal treatment much better than the commercial antioxidant, PBN, and control mix, respectively. The prepared grafted antioxidant improves the mechanical properties of NBR vulcanizate.

  1. Rubber-toughened polypropylene/acrylonitrile-co-butadiene-co-styrene blends: Morphology and mechanical properties

    Šlouf, Miroslav; Kolařík, Jan; Kotek, Jiří

    2007-01-01

    Roč. 47, č. 5 (2007), s. 582-592. ISSN 0032-3888 R&D Projects: GA ČR GP106/02/P029; GA ČR GA106/04/1051 Institutional research plan: CEZ:AV0Z40500505 Keywords : polymer blends * co-continuity * predictive models Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.272, year: 2007

  2. Curing characteristics and dynamic mechanical behaviour of reinforced acrylonitrile-butadiene/chlorosulfonated polyethylene rubber blends

    Markovic, G.; Marinovic-Cincovic, M.; Valentová, H.; Ilavský, Michal; Radovanovic, B.; Budinski-Simendic, J.

    2005-01-01

    Roč. 494, - (2005), s. 475-480. ISSN 0255-5476 Institutional research plan: CEZ:AV0Z40500505 Keywords : adhesion strength * crosslinking * CSM Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.399, year: 2005

  3. Acrylonitrile Potentiates Noise-Induced Hearing Loss in Rat

    Fechter, Laurence D.; Gearhart, Caroline; Shirwany, Najeeb A

    2003-01-01

    Acrylonitrile, one of the 50 most commonly produced industrial chemicals, has recently been identified as a promoter of noise-induced hearing loss (NIHL). This agent has the potential to produce oxidative stress through multiple pathways. We hypothesize that acrylonitrile potentiates NIHL as a consequence of oxidative stress. The objectives of this study were to characterize acrylonitrile exposure conditions that promote permanent NIHL in rats and determine the ability of this nitrile to prod...

  4. The influence of carbon black on curing kinetics and thermal aging of acrylonitrile–butadiene rubber

    Jaroslava Budinski-Simendić

    2009-10-01

    Full Text Available Elastomers based on a copolymer of butadiene and acrylonitrile (NBR have excellent oil resistance but are very sensitive for degradation at very high temperatures. The aim of this applicative contribution was to determine the effect of high abrasion furnace carbon black with primary particle size 46 nm on aging properties of elastomeric materials based on NBR as network precursor. The curing kinetics was determined using the rheometer with an oscillating disk, in which the network formation process is registered by the torque variation during time. The vulcanizates were obtained in a hydraulic press at 150 °C. The mechanical properties of elastomeric composites were determined before and after thermal aging in an air circulating oven. The reinforcing effect of the filler particles was assessed according to mechanical properties before and after aging.

  5. Catalytic Polymerization of Acrylonitrile by Khulays Bentonite

    Matar M. Al-Esaimi

    2007-04-01

    Full Text Available The aqueous polymerization of acrylonitrile (AN catalyzed with exchanged Khulays bentonite . The influence of various polymerization parameters ( e.g., concentrations of Potassium Persulfate (K2S2O8 and monomer , various of organic solvents, and different temperature has been investigated. It was found that the rate of polymerization of AN was found to be dependent on monomer concentration, initiator and temperature. The activation energy of polymerization was calculated .Thermal properties of the polymer were studied by TGA and DSC techniques. © 2007 CREC UNDIP. All rights reserved.Received: 5 February 2007; Received in revised: 19 April 2007; Accepted: 7 May 2007[How to Cite: M. M. Al-Esaimi. (2007. Catalytic Polymerization of Acrylonitrile by Khulays Bentonite. Bulletin of Chemical Reaction Engineering and Catalysis, 2 (2-3: 32-36.  doi:10.9767/bcrec.2.1.4.6-10][How to Link/DOI: http://dx.doi.org/10.9767/bcrec.2.1.4.6-10 || or local: http://ejournal.undip.ac.id/index.php/bcrec/article/view/4] 

  6. Gas-phase photocatalytic oxidation of acrylonitrile.

    Krichevskaya, Marina; Jõks, Svetlana; Kachina, Anna; Preis, Sergei

    2009-05-01

    Photocatalytic oxidation (PCO) of acrylonitrile (AN) on titanium dioxide in the gaseous phase was studied. AN readily undergoes photocatalytic degradation in a gas-solid system by using TiO(2) Degussa P25. The AN PCO volatile products, visible in the infrared spectra, included nitrogen dioxide, nitrous oxide, carbon dioxide, water, hydrogen cyanide and carbon monoxide. Longer contact time resulted in deeper oxidation of AN with decreasing hydrogen cyanide and increasing nitrogen dioxide content. The effect of temperature increasing from 60 to 130 degrees C was observed to be slightly negative in terms of AN degradation rate. However, the effect of increased temperature was noticeable in terms of the character and yields of the PCO products: HCN peaks diminished with growing peaks of NO(2). PMID:19424531

  7. Acrylonitrile characterization and high energetic photochemistry at Titan temperatures

    Toumi, A.; Piétri, N.; Chiavassa, T.; Couturier-Tamburelli, I.

    2016-05-01

    Laboratory infrared spectra of amorphous and crystalline acrylonitrile (C2H3CN) ices were recorded between 4000 and 650 cm-1. Heating up the acrylonitrile sample to 160 K shows details on the transition between amorphous and crystalline ice at ∼94 K. This molecule can be used as an indicator of the surface temperature of Titan since it is known also to be ∼94 K. The desorption energy of acrylonitrile was determined using two methods (IRTF and mass spectrometries) to be around 35 kJ mol-1. Solid phase acrylonitrile was irradiated with vacuum ultraviolet (VUV) light at low temperatures (20, 70, 95 and 130 K) using a microwave-discharge hydrogen flow lamp. Isoacrylonitrile, cyanoacetylene (HC3N), isocyanoacetylene (HC2NC), acetylene (C2H2) and hydrogen cyanide (HCN) were identified as photoproducts by using FTIR spectroscopy. The branching ratio of each pathway has been calculated for the different temperatures. We have estimated the acrylonitrile, HCN and HC3N νCtbnd N stretching band strengths to be respectively A = 3.98 ×10-18 , A = 1.38 ×10-18 and A = 2.92 ×10-18cmmolecule-1 .

  8. Radiation grafting of styrene and acrylonitrile to cellulose and polyethylene

    Hassanpour, S.

    1999-06-01

    Radiation induced graft polymerization is one of the best methods for obtaining material with new properties. In this work, radiation grafting of styrene, mixture of styrene and acrylonitrile to cellulose and polyethylene in the presence of methanol as a solvent by mutual method is discussed. At a low dose rate, high grafting yields were obtained from the two systems used, due to lesser termination of free radicals with the polymer growing radicals and recombination of primary radicals, resulting in a longer chain length of the grafted copolymer. In the system of styrene and acrylonitrile, comonomer technique was used and the styrene controlled the homopolymer formation during graft polymerization. Water uptake of cellulose decreased by increasing the grafting yields. Grafted cellulose can be molded to some extent and in a high percent of grafting, a new transparent material was obtained. By radiation grafting of styrene-acrylonitrile to low density polyethylene a high degree of crosslinking was observed.

  9. Commercial Application of the XYA-5 Catalyst in Acrylonitrile Unit

    Li Zhengguang

    2008-01-01

    The XYA-5 catalyst was first applied in commercial scale on an 80-kt/a acrylonitrile unit at the Daqing Refining and Chemical Company.Test results had shown that the once-through yield of acrylonitrile exceeded 80% with the unit consumption of propylene reaching 1032 kg on each ton of acryionitrile.The product quality could be easily put under control and the distribution of reaction products was reasonable with good cleaning performance and stability of the catalyst that was suitable for use on this commercial unit.

  10. Effect of amine-terminated butadiene-acrylonitrile/clay combinations on the structure and properties of epoxy nanocomposites

    Kelnar, Ivan; Rotrekl, Jakub; Kaprálková, Ludmila; Hromádková, Jiřina; Strachota, Adam

    2012-01-01

    Roč. 125, č. 5 (2012), s. 3477-3483. ISSN 0021-8995 R&D Projects: GA AV ČR IAA200500904 Institutional research plan: CEZ:AV0Z40500505 Keywords : epoxy nanocomposites * mechanical properties * microstructure Subject RIV: JI - Composite Materials Impact factor: 1.395, year: 2012

  11. Effect of winding layer and speed on kenaf/glass fiber hybrid reinforced acrylonitrile butadiene styrene (ABS) composites

    Khoni, Norizzahthul Ainaa Abdul; Sharifah Shahnaz S., B.; Ghazali, Che Mohd Ruzaidi

    2016-07-01

    The usage of natural fiber is becoming significant in composite industries due to their good performance. Single and continuous natural fibers have relatively high mechanical properties; especially their young modulus can be as high as glass fibers. Filament winding is a method to produce technically aligned composites which have high fibers content. The properties of filament winding can be tailored to meet the end product requirements. This research studied the compression properties of kenaf/glass fibers hybrid reinforced composites. Kenaf/glass fibers hybrid composite samples were fabricated by filament winding technique and their properties were compared with the properties of neat kenaf fiber and glass fibers composites. The kenaf/glass fiber hybrid composites exhibited higher strength compared to the neat glass fibers composites. Composites of helical pattern, which produced at low winding speed showed better compression resistance than hoop pattern winding, which produced at high winding speed. As predicted, kenaf composite showed highest water absorption; followed by kenaf/glass fiber hybrid composites while neat glass fiber has lowest water absorption capability.

  12. Application of gamma irradiation for incorporation of rubber powder in the formulations of acrylonitrile-butadiene rubber (NBR)

    Full text: Polymeric materials do not decompose easily, disposal of waste polymers is a major environmental problem of global character. Recycling is an economical alternative and environmentally recommended for polymers consumed and discarded by society. As regards the rubber in object, its natural decomposition is much slower due to their highly crosslinked, in three-dimensional networks, structures which makes it an infusible and insoluble material. Moreover, these three dimensional structures entails several problems for their recovery and reprocessing. The aim of this paper was to study the behavior of NBR rubber recycle. It was used rubber powder from industry. The powder was irradiated in master-batch composition and used directly in classical formulations for rubber vulcanization. The master-batch processed was irradiated at doses of 50, 100 and 150kGy in 60Co source at 5 kGy s-1 rate, at room temperature. Gamma radiation created active sites during devulcanization that promoted further integration of the rubber powder in formulations for commercial use. The processes were compared and their products were characterized by analytical methods of the physical properties such as tensile strength and elongation. The greatest change in the properties of polymeric materials by exposure to ionizing radiation resulted mainly of two main reactions occurring in the polymer molecule: chains scission (degradation) and crosslinking. Although these two processes occur simultaneously in all the polymers, the predominance of one or other effect depends mainly of the chemical structure of each polymer, and the irradiation conditions. In the results was observed the behavior of nitrile rubber under different doses and radiation improvement of the mechanical properties. (author)

  13. Application of gamma irradiation for incorporation of rubber powder in the formulations of acrylonitrile-butadiene rubber (NBR)

    Kiyan, Ludmila Y.P.; Parra, Duclerc Fernandes, E-mail: ludmilapozzo@gmail.com [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil). Centro de Quimica e Meio Ambiente (CQMA)

    2013-07-01

    Full text: Polymeric materials do not decompose easily, disposal of waste polymers is a major environmental problem of global character. Recycling is an economical alternative and environmentally recommended for polymers consumed and discarded by society. As regards the rubber in object, its natural decomposition is much slower due to their highly crosslinked, in three-dimensional networks, structures which makes it an infusible and insoluble material. Moreover, these three dimensional structures entails several problems for their recovery and reprocessing. The aim of this paper was to study the behavior of NBR rubber recycle. It was used rubber powder from industry. The powder was irradiated in master-batch composition and used directly in classical formulations for rubber vulcanization. The master-batch processed was irradiated at doses of 50, 100 and 150kGy in {sup 60}Co source at 5 kGy s{sup -1} rate, at room temperature. Gamma radiation created active sites during devulcanization that promoted further integration of the rubber powder in formulations for commercial use. The processes were compared and their products were characterized by analytical methods of the physical properties such as tensile strength and elongation. The greatest change in the properties of polymeric materials by exposure to ionizing radiation resulted mainly of two main reactions occurring in the polymer molecule: chains scission (degradation) and crosslinking. Although these two processes occur simultaneously in all the polymers, the predominance of one or other effect depends mainly of the chemical structure of each polymer, and the irradiation conditions. In the results was observed the behavior of nitrile rubber under different doses and radiation improvement of the mechanical properties. (author)

  14. Design and Synthesis of Transparent Poly (acrylonitrile butadiene-styrene) and Relationship Between Its Phase Construction and Transparency

    2006-01-01

    A series of transparent ABS(T-ABS) resins were prepared by emulsion in situ suspension polymerization. The influences of the particle size and the content of rubber particles on the transparency of T-ABS resins were studied by varying the size and content of rubber particles in a single model system( rubber particles with a uniform size). The optical properties of T-ABS resins were investigated in a mixed system of SBR/PB particles and a bi-modal particle system(rubber particles with two different sizes, 70 and 400 nm in diameter) of SBR particles. It was found that when the size of the smaller particles (70 nm) in the mixed system of SBR/PB particles was in the range of 50-100 nm in diameter, the T-ABS resins showed a better transparency. These results provide a flexible and practical process for the preparation of T-ABS resins with good optical and mechanical properties.

  15. Industrial emissions of 1,3-butadiene.

    Mullins, J A

    1990-01-01

    Sources of industrial emissions of 1,3-butadiene are discussed both by process (production, consumers) and type (equipment leaks, point sources). Quantification of the emissions are presented, as reported by the U.S. Environmental Protection Agency in 1986. The reported emissions attributed to equipment leaks (also known as fugitive emissions) range from about 50 to 95% of the total, depending on the specific production process used. The methods by which these emissions were estimated are dis...

  16. Polyacrylamide polymers derived from acrylonitrile without intermediate isolation

    Norton, C.J.; Falk, D.O.

    1977-04-05

    Hydrolyzed and neutralized acrylonitrile is polymerized in solution without isolation to produce a high molecular weight polyacrylamide useful for mobility control in secondary recovery of petroleum. The polyacrylamide optionally may be hydrolyzed, methylolated, and sulfomethylated to further enhance its water-thickening properties. This procedure reduces the cost of making polyacrylamide. (5 claims)

  17. Thermal Stability of Poly (acrylonitrile-methyl acrylate) Copolymers

    HAN Na; ZHANG Xing-xiang; WANG Xue-chen

    2008-01-01

    Poly (acrylonitrile-methyl acrylate) copolymer was synthesized by water depositing polymerization and has a typical feed ratio of 85/15. And then 1 - 3 wt% lauryl alcohol maleic anhydride (LAM) was adopted as stabilizer to mix with the acrylonitrile based copolymer. The mixtures were characterized by using Fourier Transform Infrared Spectroscopy (FTIR), Nuclear Magnetic Resonance (1H NMR ), Gel Permeation Chromatography ( GPC ), Differential Scanning Calorimetry (DSC), optic microscope and Ubbelohde viscosimetryr etc. The melting point (Tm) and glass transition temperature (Tg) of the 85/15 AN/MA copolymer mixed with LAM all decrease with the increase of stabilizer content. The lowest Tg and Tm were 116.1 ℃ and 209. 1℃ respectively at the heating rate of 100℃/min when the content of LAM is 2 wt%. The 85°/15 AN/MA copolymer mixed with 1 - 3 w t% LAM possess good thermal stability up to 30 min at 220 ℃.

  18. Study on irradiated polymerization of acrylonitrile by NMR

    Sup 13 C CP/MAS spectra and nuclear Overhauser effects (NOE) at room temperature have been measured for acrylonitrile (AN) in homophase irradiated polymerization. With the increase of radiation dose the chemical shift of cracking peaks and NOE are variation. This implies that the polymerized mechanism of AN were changed with the variation of irradiated doses and dose rate. There is the stronger affinity electron group (-CN) in acrylonitrile monomer. It may be polymerized by various ways and mechanism and be gained the polymer of difference structures and molecular weight of polyacrylonitrile (PAN). Starmicarbon and Starker obtained higher molecular weight of polyacrylonitrile by peroxysulfate-pyrosulfite in oxidation-reduction system. The superhigh molecular weight of PAN was synthesized chemically according to the method of Wu et. al. by suspension polymerization. In this paper we discussed that the relative concentrations of steric dyads and triads in the chain structure in PAN and the irradiation polymerized mechanism of acrylonitrile monomer in room temperature by different dose and dose rate

  19. NTP Toxicology and Carcinogenesis Studies of 1,3-Butadiene (CAS No. 106-99-0) in B6C3F1 Mice (Inhalation Studies).

    1984-08-01

    1,3-Butadiene is used as an intermediate in the production of elastomers, polymers, and other chemicals. Of the 1,3-butadiene used in 1978, 44% was used to manufacture styrene-butadiene rubber (a substitute for natural rubber, produced by copolymerization of 1,3-butadiene with styrene), and 19% was used to produce polybutane elastomer (a substance that increases resistance of tire products to wear, heat degradation, and blowouts). Chloroprene monomer, derived from 1,3-butadiene, is used exclusively to manufacture neoprene elastomers for non-tire and latex applications. Commercial nitrile rubber, used largely in rubber hoses, seals, and gaskets for automobiles, is a copolymer of 1,3-butadiene and acrylonitrile. Acrylonitrile- butadiene- styrene resins, usually containing 20%-30% 1,3-butadiene by weight, are used to make parts for automobiles and appliances. Other polymer uses include specialty polybutadiene polymers, thermoplastic elastomers, nitrile barrier resins, and K resins(R). 1,3-Butadiene is used as an intermediate in the production of a variety of industrial chemicals, including two fungicides, captan and captofol. It is approved by the U.S. Food and Drug Administration for use in the production of adhesives used in articles for packaging, transporting, or holding food; in components of paper and paperboard that are in contact with dry food; and as a modifier in the production of semigrid and rigid vinyl chloride plastic food-contact articles. No information was located on the levels of monomer or on its elution rate from any of the commercially available polymers. It is not known if unreacted 1,3-butadiene migrated from packaging materials. Male and female B6C3F1 mice were exposed to air containing 1,3-butadiene (greater than 99% pure) at concentrations of 0-8,000 ppm in 15-day and 14-week inhalation studies. In the 15-day studies, survival was unaffected by dose, and no pathologic effects were observed; slight decreases in mean body weight occurred at the

  20. Species difference in metabolism of inhaled butadiene

    Chronic exposure of B6C3F1 mice and Sprague-Dawley rats to butadiene (BD) produced a very high incidence of cancer in mice while the incidence in rats was much lower with different tissues affected. Studies at this institute indicate that for equivalent exposures, the blood BD epoxide concentrations in mice are 5-fold higher than in rats and > 10-fold higher than in Cynomolgus monkeys. In this study, the profiles of urinary metabolites of butadiene were determined in Cynomolgus monkeys, F344/N rats, Sprague Dawley rats, B6C3F1 mice and Syrian hamsters, species containing widely divergent hepatic epoxide hydrolase (EH) activities. Animals were exposed for 2 hr to 8,000 ppm [14C]BD and 24-hr urine samples were analyzed for metabolites. Two major urinary metabolites were identified, N-acetyl-S-(-1(or 2)-3-butene-2(or 1)-ol)cysteine (1) and N-acetyl-S-(-4-butane-1,2-diol)cysteine (2). Monkeys exposed by inhalation produced primarily metabolite 2, while rodent species produced 1-4 times as much of 1 compared to 2. The ratio of 2/1 formation was related to the hepatic epoxide hydrolase activity in different species. The high 2/1 ratio in monkeys was consistent with the lower blood epoxide levels in this species. If BD metabolism by humans is similar to that in the monkey, exposure of humans to BD may result in lower tissue concentrations of reactive metabolites than an equivalent exposure of rodents. This has important implications for assessing the risk to humans of BD exposure based on rodent studies

  1. Kinetic and equilibrium studies of acrylonitrile binding to cytochrome c peroxidase and oxidation of acrylonitrile by cytochrome c peroxidase compound I

    Chinchilla, Diana, E-mail: Diana_Chinchilla@yahoo.com; Kilheeney, Heather, E-mail: raindropszoo@yahoo.com; Vitello, Lidia B., E-mail: lvitello@niu.edu; Erman, James E., E-mail: jerman@niu.edu

    2014-01-03

    Highlights: •Cytochrome c peroxidase (CcP) binds acrylonitrile in a pH-independent fashion. •The spectrum of the CcP/acrylonitrile complex is that of a 6c–ls ferric heme. •The acrylonitrile/CcP complex has a K{sub D} value of 1.1 ± 0.2 M. •CcP compound I oxidizes acrylonitrile with a maximum turnover rate of 0.61 min{sup −1}. -- Abstract: Ferric heme proteins bind weakly basic ligands and the binding affinity is often pH dependent due to protonation of the ligand as well as the protein. In an effort to find a small, neutral ligand without significant acid/base properties to probe ligand binding reactions in ferric heme proteins we were led to consider the organonitriles. Although organonitriles are known to bind to transition metals, we have been unable to find any prior studies of nitrile binding to heme proteins. In this communication we report on the equilibrium and kinetic properties of acrylonitrile binding to cytochrome c peroxidase (CcP) as well as the oxidation of acrylonitrile by CcP compound I. Acrylonitrile binding to CcP is independent of pH between pH 4 and 8. The association and dissociation rate constants are 0.32 ± 0.16 M{sup −1} s{sup −1} and 0.34 ± 0.15 s{sup −1}, respectively, and the independently measured equilibrium dissociation constant for the complex is 1.1 ± 0.2 M. We have demonstrated for the first time that acrylonitrile can bind to a ferric heme protein. The binding mechanism appears to be a simple, one-step association of the ligand with the heme iron. We have also demonstrated that CcP can catalyze the oxidation of acrylonitrile, most likely to 2-cyanoethylene oxide in a “peroxygenase”-type reaction, with rates that are similar to rat liver microsomal cytochrome P450-catalyzed oxidation of acrylonitrile in the monooxygenase reaction. CcP compound I oxidizes acrylonitrile with a maximum turnover number of 0.61 min{sup −1} at pH 6.0.

  2. Preparation and Characterization of Acrylonitrile Copolymers by Emulsion Technique

    Acrylonitrile (AN) binary copolymers with styrene (St) and maleic acid (MA) of different compositions were prepared by free radical emulsion copolymerization using potassium persulfate and sodium bisulfite as a redox pair initiation system and sodium dodecyl benzene sulfonate as an emulsifier. Based on the copolymerization data of the (AN/St) and (AN/MA) in emulsion polymerization process, the reactivity ratios of the prepared copolymers were investigated by different methods. Thermogravimetric analysis and X-ray diffraction were studied to characterize the prepared copolymers. Physicomechanical properties of some copolymeric lattices films were also identified

  3. BIOMARKERS IN CZECH WORKERS EXPOSED TO 1,3-BUTADIENE: A TRANSITIONAL EPIDEMIOLOGIC STUDY

    All the biomarkers of exposure were correlated with the measurements of butadiene recorded by the air samplers. Although the correlation between hemoglobin adducts and exposure levels was strongest, urinary metabolites were also found to be very useful measures of butadiene...

  4. 46 CFR 154.1750 - Butadiene or vinyl chloride: Refrigeration system.

    2010-10-01

    ... 46 Shipping 5 2010-10-01 2010-10-01 false Butadiene or vinyl chloride: Refrigeration system. 154... and Operating Requirements § 154.1750 Butadiene or vinyl chloride: Refrigeration system. A refrigeration system for butadiene or vinyl chloride must not use vapor compression unless it: (a) Avoids...

  5. Structure and activity of tellurium-cerium oxide acrylonitrile catalysts

    Ammoxidation of propylene to acrylonitrile (ACN) was investigated over various silica-supported (Te,Ce)O catalysts at 360 and 4400C. The binary oxide system used consists of a single nonstoichiometric fluorite-type phase α-(Ce,Te)O2 up to about 80 mole% TeO2 and a tellurium-saturated solid solution β-(Ce,Te)O2 at higher tellurium concentrations. The ACN yield varies almost linearly with the tellurium content of (Ce,Te)O2. The β-(Ce,Te)O2 phase is the most active component of the system (propylene conversion and ACN selectivity at 440 C of 76.7 and 74%, respectively) and is slightly more selective to ACN than α-Te02. Tellurium reduces the overoxidation properties of cerium and selective oxidation occurs through Te(IV)-bonded oxygen

  6. BARRIER PROPERTY AND STRUCTURE OF ACRYLONITRILE/ACRYLIC COPOLYMERS

    YANG Zhenghua; LI Yuesheng

    1997-01-01

    A series of acrylonitrile (AN) copolymers with methyl acrylate (MA) or ethyl acrylate (EA) as comonomer (5-23 wt%) was prepared by free-radical copolymerization. The permeability coefficients of the copolymers to oxygen and carbon dioxide were measured at 1.0 MPa and at 30 ℃, and those to water vapor also measured at 100% relative humidity and at 30 ℃. All the AN/acrylic copolymers are semicrystalline. As the acrylate content increase, the permeability coefficients of the copolymers to oxygen and carbon dioxide are increased progressively, but those to water vapor are decreased progressively. The gas permeability coefficients of the polymers were correlated with free-volume fractions or the ratio of free volume to cohesive energy.

  7. Determination of potentially carcinogenic compounds in food : trace analysis of vinylchloride, vinylidenechloride, acrylonitrile, epichlorohydrin and diethylpyrocarbonate

    Lierop, van J.B.H.

    1979-01-01

    Toxicological evidence shows that some monomers present in packaging materials may be carcinogenic. These monomers, notably vinylchloride, vinylidenechloride, acrylonitrile and epichlorohydrin, may migrate from the packaging material into the food. Therefore, severe limits are set to the contents of

  8. On the catalytic gas phase oxidation of butadiene to furan

    Kubias, B.; Rodemerck, U. [Institut fuer Angewandte Chemie Berlin-Adlershof e.V., Berlin (Germany); Ritschl, F.; Meisel, M. [Humboldt-Universitaet, Berlin (Germany). Inst. fuer Chemie

    1998-12-31

    Applying the thermochemical selectivity criterion of Hadnett et al. It is shown that the selectivity of the furan formation is not limited by a too low strength of the C-H bonds in furan when compared with the C-H bond dissociation energy in the educt molecule butadiene. In the oxidation of butadiene on a CsH{sub 2}PMo{sub 12}O{sub 40} catalyst a maximum yield of 22 mol% furan has been obtained. To improve this comparatively low furan yield oxidation activity of the catalyst must be lowered to prevent the consecutive reaction to maleic anhydride. (orig.)

  9. Gender differences in the metabolism of 1,3-butadiene to butadiene diepoxide in Sprague-Dawley rats

    Thornton-Manning, J.R.; Dahl, A.R.; Bechtold, W.E. [and others

    1995-12-01

    1,3-Butadiene (BD), a gaseous compound used in the production of rubber, is a potent carcinogen in mice and a weak carcinogen in rats. The mechanism of BD-induced carcinogenicity is thought to involve genotoxic effects of its reactive epoxide metabolites butadiene monoepoxide (BDO) and butadiene diepoxide (BDO{sub 2}). Studies in our laboratory have shown that levels of the epoxides, particularly BDO{sub 2}, are greater in mice-the more sensitive species-than rats. While both epoxides are genotoxic in a number of assays, BDO{sub 2} is mutagenic in TK6 human lymphoblastoid cells at concentrations approximately 100-fold lower than BDO. Species differences in carcinogenicity of BD have posed a dilemma to investigators deciding which animal model is most appropriate for BD risk assessment.

  10. Grafting of acrylonitrile onto cellulosic material derived from bamboo (Dendrocalamus strictus

    2008-01-01

    Full Text Available Bamboo, a lignocellulosic biopolymer material, is of interest as feedstock for production of cellulose derivatives by chemical functionalization. Optimization of grafting of acrylonitrile onto cellulosic material (average Degree of Polymerization 816, isolated from bamboo (Dendrocalamus stictus was performed by varying the process parameters such as duration of soaking of cellulosic material in ceric ammonium nitrate solution, ceric ammonium nitrate concentration, polymerization time, temperature of reaction and acrylonitrile concentration to study their influence on percent grafting and grafting efficiency. Graft copolymerization of acrylonitrile onto cellulosic material derived from bamboo (Dendrocalamus strictus in heterogenous medium can be initiated effectively with ceric ammonium nitrate. The optimum reaction conditions obtained for grafting of acrylonitrile onto cellulosic material were: duration of dipping cellulosic material in ceric ammonium nitrate solution 1 hr, ceric ammonium nitrate concentration 0.02 M, acrylonitrile concentration 24.6 mol/anhydroglucose unit, temperature of reaction 40°C and polymerization time 4 hrs. The percent grafting for optimized samples is 210.3% and grafting efficiency is 97%. The characterization of the grafted products by means of FTIR and Scanning Electron Microscopy furnished the evidence of grafting of acrylonitrile onto the cellulosic material.

  11. 1,3-Butadiene: Biomarkers and application to risk assessment

    Swenberg, J. A.; Bordeerat, N. K.; Boysen, G.; Carro, S.; Georgieva, N. I.; Troutman, J. M.; Upton, P. B.; Albertini, R. J.; Vacek, P. M.; Walker, V. E.; Šrám, Radim; Goggin, M.; Tretyakova, N.

    2011-01-01

    Roč. 192, 1-2 (2011), s. 150-154. ISSN 0009-2797 Institutional research plan: CEZ:AV0Z50390512 Keywords : risk assessment * 1,3-butadiene * occupational exposure Subject RIV: DN - Health Impact of the Environment Quality Impact factor: 2.865, year: 2011

  12. Excited State Spectra and Dynamics of Phenyl-Substituted Butadienes

    Wallace-Williams, Stacie E.; Schwartz, Benjamin J.; Møller, Søren;

    1994-01-01

    A combination of steady-state and dynamic spectral measurements are used to provide new insights into the nature of the excited-state processes of all-trans-1,4-diphenyl-1,3-butadiene and several analogs: 1,4-diphenyl- 1,3-cyclopentadiene, 1,1,4,4-tetraphenylbutadiene, 1,2,3,4-tetraphenyl-1...

  13. The Formation and characteristics of Acrylonitrile/Urea Inclusion Compound

    Zou, Jun-Ting; Pang, Wen-Min; Shi, Lei; Lu, Fei

    2012-01-01

    The formation process and composition of the acrylonitrile/urea inclusion compounds (AN/UIC) with different aging times and AN/urea molar feed ratios are studied by differential scanning calorimetry (DSC) and X-ray diffraction (XRD). It is suggested that DSC could be one of the helpful methods to determine the guest/host ratio and the heat of decomposition. Meanwhile, the guest/host ratio and heat of deformation are obtained, which are 1.17 and 5361.53 J/mol, respectively. It is found that the formation of AN/UIC depends on the aging time. The formation process ends after enough aging time and the composition of AN/UIC becomes stable. It is suggested AN molecules included in urea canal lattice may be packed flat against each other. XRD results reveal that once AN molecules enter urea lattice, AN/UIC are formed, which possess the final structure. When AN molecules are sufficient, the content of AN/UIC increased as aging time prolonging until urea tunnels are saturated by AN.

  14. Selective Vulnerability of the Cochlear Basal Turn to Acrylonitrile and Noise

    B. Pouyatos

    2009-01-01

    Full Text Available Exposure to acrylonitrile, a high-production industrial chemical, can promote noise-induced hearing loss (NIHL in the rat even though this agent does not itself produce permanent hearing loss. The mechanism by which acrylonitrile promotes NIHL includes oxidative stress as antioxidant drugs can partially protect the cochlea from acrylonitrile+noise. Acrylonitrile depletes glutathione levels while noise can increase the formation of reactive oxygen species. It was previously noted that the high-frequency or basal turn of the cochlea was particularly vulnerable to the combined effects of acrylonitrile and noise when the octave band noise (OBN was centered at 8 kHz. Normally, such a noise would be expected to yield damage at a more apical region of the cochlea. The present study was designed to determine whether the basal cochlea is selectively sensitive to acrylonitrile or whether, by adjusting the frequency of the noise band, it would be possible to control the region of the auditory impairment. Rats were exposed to one of three different OBNs centered at different frequencies (4 kHz, 110 dB and 8 or 16 kHz at 97 dB for 5 days, with and without administration of acrylonitrile (50 mg/kg/day. The noise was set to cause limited NIHL by itself. Auditory function was monitored by recording distortion products, by compound action potentials, and by performing cochlear histology. While the ACN-only and noise-only exposures induced no or little permanent auditory loss, the three exposures to acrylonitrile+noise produced similar auditory and cochlear impairments above 16 kHz, despite the fact that the noise exposures covered 2 octaves. These observations show that the basal cochlea is much more sensitive to acrylonitrile+noise than the apical partition. They provide an initial basis for distinguishing the pattern of cochlear injury that results from noise exposure from that which occurs due to the combined effects of noise and a chemical

  15. An experimental Raman and theoretical DFT study on the self-association of acrylonitrile.

    Alía, Jose M; Edwards, Howell G M; Fawcett, W Ronald; Smagala, Thomas G

    2007-02-01

    The liquid structure of acrylonitrile (propenenitrile) has been investigated using Raman spectroscopy and density functional theory (DFT) ab initio calculations with the 6-311++G** basis set. Two different and complementary experimental approaches were undertaken: FT-Raman spectra of 13 acrylonitrile solutions in carbon tetrachloride (concentration range=0.25-12.0 mol.L-1) were studied in detail including principal component analysis (PCA) of the CN stretching band. Furthermore, dispersive Raman spectra of neat acrylonitrile were obtained at eight different temperatures from 238 up to 343 K. The complex and asymmetric acrylonitrile Raman CN stretching band can be decomposed into two components attributed to monomeric and self-associated forms. Ab initio results fully support this assignment and suggest that the self-associated complex is a nonplanar trimer held together by dipole-dipole interactions. At ambient temperature, the composition of acrylonitrile can be expressed as a mixture of 25% monomers and 75% trimers. Close to the boiling point, trimers still represent 65% of the liquid composition. The corresponding enthalpy of association was estimated to be -22+/-2 kJ.mol-1. PMID:17266219

  16. Biocompatibility of epoxidized styrene-butadiene-styrene block copolymer membrane

    Styrene-butadiene-styrene block copolymer (SBS) membrane was prepared by solution casting method and then was epoxidized with peroxyformic acid generated in situ to yield the epoxidized styrene-butadiene-styrene block copolymer membrane (ESBS). The structure and properties of ESBS were characterized with infrared spectroscopy, Universal Testing Machine, differential scanning calorimetry (DSC), and thermogravimetry analysis (TGA). The performances of contact angle, water content, protein adsorption, and water vapor transmission rate on ESBS membrane were determined. After epoxidation, the hydrophilicity of the membrane increased. The water vapor transmission rate of ESBS membrane is similar to human skin. The biocompatibility of ESBS membrane was evaluated with the cell culture of fibroblasts on the membrane. It revealed that the cells not only remained viable but also proliferated on the surface of the various ESBS membranes and the population doubling time for fibroblast culture decreased.

  17. A Study of the Fluorescence Response of Tetraphenyl-butadiene

    Jerry, R.; Winslow, L.(Massachusetts Institute of Technology, Cambridge, Massachusetts, 02139, U.S.A.); Bugel, L.; Conrad, J. M.

    2010-01-01

    Tetraphenyl-butadiene (TPB) is a widely used fluorescent wavelength-shifter. A common application is in liquid-argon-based particle detectors, where scintillation light is produced in the UV at 128 nm. In liquid argon experiments, TPB is often employed to shift the scintillation light to the visible range in order to allow detection via standard photomultiplier tubes. This paper presents studies on the stability of TPB with time under exposure to light. We also examine batch-to-batch variatio...

  18. Scintillation of thin tetraphenyl butadiene films under alpha particle excitation

    Pollmann, Tina; Kuźniak, Marcin

    2010-01-01

    The alpha induced scintillation of the wavelength shifter 1,1,4,4-tetraphenyl-1,3-butadiene (TPB) was studied to improve the understanding of possible surface alpha backgrounds in the DEAP dark matter search experiment. We found that vacuum deposited thin TPB films emit 882 +/-210 photons per MeV under alpha particle excitation. The scintillation pulse shape consists of a double exponential decay with lifetimes of 11 +/-5 ns and 275 +/-10ns.

  19. Conversion of 2,3-butanediol to butadiene

    Lilga, Michael A.; Frye, Jr, John G.; Lee, Suh-Jane; Albrecht, Karl O.

    2016-09-06

    A composition comprising 2,3-butanediol is dehydrated to methyl vinyl carbinol and/or 1,3-butadiene by exposure to a catalyst comprising (a) M.sub.xO.sub.y wherein M is a rare earth metal, a group IIIA metal, Zr, or a combination thereof, and x and y are based upon an oxidation state of M, or (b) M.sup.3.sub.a(PO.sub.4).sub.b where M.sup.3 is a group IA, a group IIA metal, a group IIIA metal, or a combination thereof, and a and b are based upon the oxidation state of M.sup.3. Embodiments of the catalyst comprising M.sub.xO.sub.y may further include M.sup.2, wherein M.sup.2 is a rare earth metal, a group IIA metal, Zr, Al, or a combination thereof. In some embodiments, 2,3-butanediol is dehydrated to methyl vinyl carbinol and/or 1,3-butadiene by a catalyst comprising M.sub.xO.sub.y, and the methyl vinyl carbinol is subsequently dehydrated to 1,3-butadiene by exposure to a solid acid catalyst.

  20. Performance of CTBN(carboxyl-terminated poly (butadiene-co-acrylonitrile))-EP(diglycidyl ether of bisphenol-A(DGEBA)) Prepolymers and CTBN-EP/polyetheramine (PEA) System

    SHI Minxian; HUANG Zhixiong; LI Yaming; YANG Guorui

    2009-01-01

    CTBN-EP prepolymers were synthesized from CTBN and epoxy resin under the catalysis of HTMAB.FTIR analyses indicate the formation of ester group between the carboxyl group of CTBN and the oxirane group of epoxy resin.The viscosity of modified prepolymer increases with CTBN content increasing,but the epoxy value of the prepolymer decreases greatly.DSC analyses verify that CTBN affects the curing process of CTBN-EP/PEA system.Mechanical testing presents the improved toughness of CTBN-EP/PEA curings for the decrease of tensile strength,flexural strength and compressive strength,and increase of impact strength and elongation-at-break with the CTBN content increasing.SEM micrographs show the rubber phase with many holes in diameter about 0.5-1.5μm is formed when CTBN content is lower than 10 phr.However,the pattern of SEM graph shows some stalactite-like strips when CTBN content is higher than 15 phr.Furthermore,the SEM image of 25 phr CTBN sample forms a kind of co-continuous structure.

  1. ABSORPTION OF CO2 AND SUBSEQUENT VISCOSITY REDUCTION OF AN ACRYLONITRILE COPOLYMER. (R829555)

    Acrylonitrile (AN) copolymers (AN content greater than about 85 mol%) are traditionally solution processed to avoid a cyclization and crosslinking reaction that takes place at temperatures where melt processing would be feasible. It is well known that carbon dioxide (CO

  2. New grafted copolymer of polystyrene with acrylonitrile using gamma-irradiation

    Commercial polystyrene aggregates were purified and grafted with acrylonitrile using gamma-irradiation. New copolymer was obtained, characterized and its properties were investigated. The results indicated that the best grafting percentage ratio could be obtained when the concentration of the ferrous ammonium sulphate (FAS) is about 0.25% and the monomer concentration is 80% at 1.5 Mrad dos

  3. New Star-Branched Poly(acrylonitrile) Architectures : ATRP Synthesis and Solution Properties

    Pitto, Valentina; Voit, Brigitte I.; Loontjens, Ton J.A.; Benthem, Rolf A.T.M. van

    2004-01-01

    Atom transfer radical polymerization (ATRP) has been chosen as ‘‘living’’/controlled free radical polymerization system to synthesize a number of novel poly(acrylonitrile) (PAN) architectures. The reaction conditions for the synthesis of linear samples with control over molar mass and molar mass dis

  4. Turbidimetric behavior of Butadiene Rubber (BR) solutions in toluene and dichloromethane after heating at open air

    This paper deals with the turbidimetric behavior of Butadiene Rubber BR solutions, a synthetic rubber, in two solvents (toluene and dichloromethane), after heating at open air till 180 Deg Celsius for optimal polymer cracking conditions. Concentration, solvent and temperature effects have been studied using methanol as precipitant. Butadiene rubber exhibits a high sensitivity to autoxidation with high tendency to reticulation.

  5. Development of a conductimetric biosensor using immobilised Rhodococcus ruber whole cells for the detection and quantification of acrylonitrile.

    Roach, P C J; Ramsden, D K; Hughes, J; Williams, P

    2003-10-30

    A conductimetric biosensor for the detection of acrylonitrile in solution was designed and characterised using whole cells of Rhodococcus ruber NCIMB 40757, which were immobilised into a disc of dimethyl silicone sponge (ImmobaSil). The biosensor described was capable of the detection and quantification of acrylonitrile in aqueous solution, having a linear response to concentrations between 2 and 50 mM (106-2650 ppm) acrylonitrile. The biosensor has been shown to be reproducible with respect to the data obtained over a number of days, and retains stability for a minimum period of at least 5 days before recalibration of the biosensor is required. PMID:14559001

  6. Pressure dependence of the Boson peak in poly(butadiene)

    Frick, B

    2002-01-01

    Variation of pressure and temperature in inelastic neutron scattering experiments allows us to separate density and thermal energy contributions. We summarise briefly the influence of pressure and temperature on the dynamic scattering law of the polymer glass former poly(butadiene) far below the glass transition. We also show the advantage of using a liquid-niobium pressure cell in such studies. The effect of pressure on the boson peak is to shift the peak towards higher energies and to reduce the low-frequency modes more strongly below the boson-peak maximum than above. A decrease in the Debye-Waller factor with increasing pressure is observed. (orig.)

  7. Carbon nanotubes as reinforcement of styrene-butadiene rubber

    This study reports an easy technique to produce cured styrene-butadiene rubber (SBR)/multi-walled carbon nanotubes (MWCNT) composites with a sulphur/accelerator system at 150 deg. C. Significant improvement in Young's modulus and tensile strength were achieved by incorporating 0.66 wt% of filler without sacrificing SBR elastomer high elongation at break. A comparison with carbon black filled SBR was also made. Field emission scanning electron microscopy was used to investigate dispersion and fracture surfaces. Results indicated that the homogeneous dispersion of MWCNT throughout SBR matrix and strong interfacial adhesion between oxidized MWCNT and the matrix are responsible for the considerable enhancement of mechanical properties of the composite

  8. Telomerization of butadiene with starch under mild conditions.

    Mesnager, Julien; Quettier, Claude; Lambin, Anne; Rataboul, Franck; Pinel, Catherine

    2009-01-01

    The design of industrial products based on bioresources is a challenging issue. Modification of starch, by hydrophobic chemical substituents, results in an innovative hydrophobic material. Herein, the hydrophobic part of the derivative, comprised of octadienyl chains, is introduced through catalytic butadiene telomerization. The process is efficiently conducted on starch in its granular form in an aqueous medium using hydrosoluble palladium complexes. After optimization, a turnover number (TON) of up to 550 was achieved in the presence of [(pi-allyl)PdCl](2) catalyst and, unusually, by using dimethylisosorbide as a cosolvent. PMID:19856380

  9. Pressure dependence of the Boson peak in poly(butadiene)

    Variation of pressure and temperature in inelastic neutron scattering experiments allows us to separate density and thermal energy contributions. We summarise briefly the influence of pressure and temperature on the dynamic scattering law of the polymer glass former poly(butadiene) far below the glass transition. We also show the advantage of using a liquid-niobium pressure cell in such studies. The effect of pressure on the boson peak is to shift the peak towards higher energies and to reduce the low-frequency modes more strongly below the boson-peak maximum than above. A decrease in the Debye-Waller factor with increasing pressure is observed. (orig.)

  10. Heck Arylation of Acrylonitrile with Aryl Iodides Catalyzed by a Silica-bound Arsine Palladium(0) Complex

    Ming Zhong CAI; Hong ZHAO; Rong Li ZHANG

    2005-01-01

    Acrylonitrile reacts with aryl iodides in the presence of tri-n-butylamine and a catalytic amount of a silica-bound arsine palladium(0) complex to afford stereoselectively (E)-cinnamonitriles in high yields.

  11. Dimedone-catalyzed Addition of Amines into Cyano Group: Facile Synthesis of Thiazol-2-yl Substituted E-Acrylonitriles

    朱伟军; 屠兴超; 冯惠; 屠蔓苏; 姜波; 吴飞跃; 屠树江

    2012-01-01

    An efficient dimedone-catalyzed synthesis of highly functionalized thiazol-2-yl substituted E-acrylonitrile derivatives has been established through two-step reaction of a-thiocyanate ketones with malononitrile and amines. The a-thiocyanate ketones were subjected with malononitrile to provide thiazol-2-ylidenemalononitrile derivatives, followed with various amines in the presence of dimedone to yield the final thiazol-2-yl substituted acrylonitrile derivatives.

  12. Mechanical property modification and morphology of poly(styrene-b-hydrogenated butadiene-b-styrene)/poly(hydrogenated butadiene) blends

    Baetzold, J.P.; Gancarz, I.; Quan, X.; Koberstein, J.T. (Univ. of Connecticut, Storrs, CT (United States))

    1994-09-12

    The mechanical properties and morphology of a series of triblock copolymer blends with midblock associating homopolymers of varying molecular weight (Mw) have been characterized. The symmetric triblock copolymer studied contains polystyrene endblocks and midblocks of hydrogenated poly(1,2-butadiene) and is mixed with hydrogenated poly (1,2-butadiene) homopolymers of Mw both below and above that of the copolymer midblock. The rubbery plateau modulus determined by dynamic mechanical spectroscopy increases with increasing Mw of the homopolymer at fixed overall homopolymer content. At fixed Mw, the composition dependence of the plateau modulus is complex and shows unusually synergistic behavior. For high Mw homopolymers the plateau modulus increases initially upon homopolymer addition. Small angle neutron scattering and TEM are employed to determine the morphological changes. In all cases, the blends exhibit a lamellar microphase structure, with homopolymer macrophases apparent at high homopolymer contents. The apparent homopolymer solubility limits are found to be inversely related to the homopolymer Mw. The results indicate that the lamellar repeat distance decreases upon addition of the lowest Mw homopolymer and that the microdomains swell in blends containing homopolymers with Mw similar to that of the midblock sequence and are unchanged for high Mw homopolymers with negligible solubility. The results suggest that the interesting mechanical response of the blends can be explained by consideration of the changes in their entanglement structure resulting from confinement of the homopolymer chains within the highly constrained environment of the midblock lamellae.

  13. Inhalation toxicity and carcinogenicity of 1,3-butadiene in Sprague-Dawley rats.

    Owen, P E; Glaister, J R

    1990-01-01

    A 2-year inhalation study was conducted in Sprague-Dawley rats with 1,3-butadiene. Groups of 110 male and 110 female rats inhaled 1,3-butadiene at 0, 1000, or 8000 ppm for 6hr/day, 5 days/week. Interim clinical pathology, neuromuscular, and histopathology investigations were carried out. The study terminated at 20 to 25% survival (105 weeks for females, 111 weeks for males). Following exposure to 1,3-butadiene there were no effects on hematology, blood chemistry, urine analysis, and neuromusc...

  14. Copolymerization of Indene with Acrylic Acid, Itaconic Acid and Acrylonitrile: Characterization and Reactivity Ratios

    Random copolymers of indene (In) with acrylic acid (AA), itaconic acid (IA) and acrylonitrile (AN) were synthesized by free radical polymerization in dioxane in the presence of azobisisobutyronitrile as an initiator at 60 degree C. The homopolymer of indene and acrylonitrile was prepared using K2MnO4 and sulphuric acid as an initiator, while acrylic acid and itaconic acid were prepared using K2S2O8 solution. The reactivity ratios of the monomers were calculated by different methods. X-ray diffraction as well as thermal analyses were studied. The latter was studied via thermogravimetric analysis and differential thermal analysis. The complexation with metal ions such as Cu+2 and Fe+2 was investigated. The copolymerization and the complexation processes were confirmed by FTIR spectroscopy. Also the activation energy of the prepared copolymers was determined

  15. Nitrilase-catalysed conversion of acrylonitrile by free and immobilized cells of Streptomyces sp.

    V K Nigam; A K Khandelwal; R K Gothwal; M K Mohan; B Choudhury; A S Vidyarthi; P Ghosh

    2009-03-01

    The biotransformation of acrylonitrile was investigated using thermophilic nitrilase produced from a new isolate Streptomyces sp. MTCC 7546 in both the free and immobilized state. Under optimal conditions, the enzyme converts nitriles to acids without the formation of amides. The whole cells of the isolate were immobilized in agar-agar and the beads so formed were evaluated for 25 cycles at 50°C. The enzyme showed a little loss of activity during reuse. Seventy-one per cent of 0.5 M acrylonitrile was converted to acid at 6 h of incubation at a very low density of immobilized cells, while 100% conversion was observed at 3 h by free cells.

  16. Detection of acrolein and acrylonitrile with a pulsed room temperature quantum cascade laser

    Manne, J.; Jäger, W.; Tulip, J.

    2010-06-01

    We investigated the use of a pulsed, distributed feedback quantum cascade laser centered at 957 cm-1 in combination with an astigmatic Herriot cell with 250 m path length for the detection of acrolein and acrylonitrile. These molecules have been identified as hazardous air-pollutants because of their adverse health effects. The spectrometer utilizes the intra-pulse method, where a linear frequency down-chirp, that is induced when a top-hat current pulse is applied to the laser, is used for sweeping across the absorption line. Up to 450 ns long pulses were used for these measurements which resulted in a spectral window of ~2.2 cm-1. A room temperature mercury-cadmium-telluride detector was used, resulting in a completely cryogen free spectrometer. We demonstrated detection limits of ~3 ppb for acrylonitrile and ~6 ppb for acrolein with ~10 s averaging time. Laser characterization and optimization of the operational parameters for sensitivity improvement are discussed.

  17. Ultrafine conducting fibers: metallization of poly(acrylonitrile-co-glycidyl methacrylate) nanofibers

    Menceloğlu, Yusuf Z.; Menceloglu, Yusuf Z.; Demir, Mustafa Muammer; Uğur, Gökçe; Ugur, Gokce; Gülgün, Mehmet Ali; Gulgun, Mehmet Ali

    2005-01-01

    Electrospun poly(glycidylmethacrylate) (PGMA) and poly(acrylonitrile-co-glycidyl methacrylate) (P(AN-GMA)) nanofibers were coated with monodisperse silver nanoparticles by using an electroless plating technique at ambient conditions. Oxirane groups on the surface of nanofibers were replaced with reducing agent, hydrazine. Surface modified nanofibers were allowed to react with ammonia solution of AgNO3. A redox reaction takes place and metallic silver nucleate on fibers surface. Parameters aff...

  18. Adsorption of Acrylonitrile on Some Soils and Minerals from Aqueous Solutions

    WUDE-YI; N.MATSUE; 等

    1993-01-01

    Equilibrium and kinetic studies have been made on the adsorption of acrylonitrile(CH2=CHCN) on three soils and four minerals from aqueous solutions.It was shown that the organic matter was the major factor affecting the adsorption process in the soils.The conformity of the equilibrium data to linear type(one soil) and Langmuir type(two soils) isotherms indicated that different mechanisms were involved in the adsorption.This behavior appears bo be related to the hydrophobicity of soil organic matter due to their composition and E4/E6 ratio of humic acids.The adsorption kinetics were also different among the soils,indicating the difference in porosity of organic matter among the soils,and the kinetics strongly affected the adsorption capacity of soils for acrylonitrile.Acrylonitrile was slightly adsorbed from aqueous solutions on pyrophyllite with electrically neutral and hydrophobic nature,and practically not on montmorillonite and kaolinite saturated with Ca.However,much higher adsorption occurred on the zeolitized coal ash,probably caused by high organic carbon content(107g/kg).

  19. Photodegradation Mechanisms of Tetraphenyl Butadiene Coatings for Liquid Argon Detectors

    Jones, B J P; Conrad, J M; Pla-Dalmau, A

    2013-01-01

    We report on studies of degradation mechanisms of tetraphenyl butadiene (TPB) coatings of the type used in neutrino and dark matter liquid argon experiments. Using gas chromatography coupled to mass spectrometry we have detected the ultraviolet-blocking impurity benzophenone (BP). We monitored the drop in performance and increase of benzophenone concentration in TPB plates with exposure to ultraviolet (UV) light, and demonstrate the correlation between these two variables. Based on the presence and initially exponential increase in the concentration of benzophenone observed, we propose that TPB degradation is a free radical-mediated photooxidation reaction, which is subsequently confirmed by displaying delayed degradation using a free radical inhibitor. Finally we show that the performance of wavelength-shifting coatings of the type envisioned for the LBNE experiment can be improved by 10-20%, with significantly delayed UV degradation, by using a 20% admixture of 4-tert-Butylcatechol.

  20. A Study of the Fluorescence Response of Tetraphenyl-butadiene

    Jerry, R; Bugel, L; Conrad, J M

    2010-01-01

    Tetraphenyl-butadiene (TPB) is a widely used fluorescent wavelength-shifter. A common application is in liquid-argon-based particle detectors, where scintillation light is produced in the UV at 128 nm. In liquid argon experiments, TPB is often employed to shift the scintillation light to the visible range in order to allow detection via standard photomultiplier tubes. This paper presents studies on the stability of TPB with time under exposure to light. We also examine batch-to-batch variations. We compare scintillation-grade TPB to 99% pure TPB response. In the 99% pure samples, we report a yellowing effect, and full degradation of the TPB emission-peak, upon extended exposure to light.

  1. Aging studies on thin tetra-phenyl butadiene films

    Acciarri, R.; Canci, N.; Cavanna, F.; Segreto, E.; Szelc, A. M.

    2013-10-01

    Tetra-Phenyl Butadiene (TPB) is the most commonly used compound to wave-shift the 128 nm scintillation light of liquid Argon down to the visible spectrum. We present a study on the loss of conversion efficiency of thin TPB films evaporated on reflective foils when exposed to light and atmosphere. The efficiency of the films is measured and monitored with a dedicated set-up that uses gaseous Argon excited by alpha particles to produce 128 nm photons and working at room temperature. In particular we performed a two years long exposure of the samples to lab diffuse light and atmosphere. We also performed more controlled aging tests to investigate the effect of storing samples in a inert atmosphere.

  2. Photodegradation mechanisms of tetraphenyl butadiene coatings for liquid argon detectors

    Jones, B. J. P.; VanGemert, J. K.; Conrad, J. M.; Pla-Dalmau, A.

    2013-01-01

    We report on studies of degradation mechanisms of tetraphenyl butadiene (TPB) coatings of the type used in neutrino and dark matter liquid argon experiments. Using gas chromatography coupled to mass spectrometry we have detected the ultraviolet-blocking impurity benzophenone. We monitored the drop in performance and increase of benzophenone concentration in TPB plates with exposure to ultraviolet (UV) light, and demonstrate the correlation between these two variables. Based on the presence and initially exponential increase in the concentration of benzophenone observed, we propose that TPB degradation is a free radical-mediated photooxidation reaction, which is subsequently confirmed by displaying delayed degradation using a free radical inhibitor. Finally we show that the performance of wavelength-shifting coatings of the type envisioned for the LBNE experiment can be improved by 10-20%, with significantly delayed UV degradation, by using a 20% admixture of 4-tert-Butylcatechol.

  3. γ irradiation of carboxylated styrene-butadiene rubber latex

    The crosslinking behavior of carboxylated styrene-butadiene rubber latex (CSBRL) by using gamma radiation with 2-ethyl hexyl acrylate (2-EHA) as crosslinking sensitizer has been studied in detail. In addition, the variation of the particle size and distribution of latex, chemical structure and thermal property of CSBRL with absorbed dose have been discussed. Also the radiation vulcanization mechanism of CSBRL has been suggested. The experiments showed that, the dose rate has small effect on the cross-link behavior of CSBRL, and the swelling ratio decreased rapidly with the increase of absorbed dose. Increasing the dose, the average molecular weight per crosslinked units (Mc) decreased and crosslinking density increased. When the dose is below 25 kGy, no significant changes in the particle size and distribution of latex were observed. The micro-FTIR analysis and DSC curves confirmed the existence of grafting reaction accompanying the crosslinking reaction during the gamma irradiation with 2-EHA as sensitizer

  4. Photodegradation mechanisms of tetraphenyl butadiene coatings for liquid argon detectors

    We report on studies of degradation mechanisms of tetraphenyl butadiene (TPB) coatings of the type used in neutrino and dark matter liquid argon experiments. Using gas chromatography coupled to mass spectrometry we have detected the ultraviolet-blocking impurity benzophenone. We monitored the drop in performance and increase of benzophenone concentration in TPB plates with exposure to ultraviolet (UV) light, and demonstrate the correlation between these two variables. Based on the presence and initially exponential increase in the concentration of benzophenone observed, we propose that TPB degradation is a free radical-mediated photooxidation reaction, which is subsequently confirmed by displaying delayed degradation using a free radical inhibitor. Finally we show that the performance of wavelength-shifting coatings of the type envisioned for the LBNE experiment can be improved by 10-20%, with significantly delayed UV degradation, by using a 20% admixture of 4-tert-Butylcatechol.

  5. Review of old chemistry and new catalytic advances in the on-purpose synthesis of butadiene.

    Makshina, Ekaterina V; Dusselier, Michiel; Janssens, Wout; Degrève, Jan; Jacobs, Pierre A; Sels, Bert F

    2014-11-21

    Increasing demand for renewable feedstock-based chemicals is driving the interest of both academic and industrial research to substitute petrochemicals with renewable chemicals from biomass-derived resources. The search towards novel platform chemicals is challenging and rewarding, but the main research activities are concentrated on finding efficient pathways to produce familiar drop-in chemicals and polymer building blocks. A diversity of industrially important monomers like alkenes, conjugated dienes, unsaturated carboxylic acids and aromatic compounds are thus targeted from renewable feedstock. In this context, on-purpose production of 1,3-butadiene from biomass-derived feedstock is an interesting example as its production is under pressure by uncertainty of the conventional fossil feedstock. Ethanol, obtained via fermentation or (biomass-generated) syngas, can be converted to butadiene, although there is no large commercial activity today. Though practised on a large scale in the beginning of the 20th century, there is a growing worldwide renewed interest in the butadiene-from-ethanol route. An alternative route to produce butadiene from biomass is through direct carbohydrate and gas fermentation or indirectly via the dehydration of butanediols. This review starts with a brief discussion on the different feedstock possibilities to produce butadiene, followed by a comprehensive summary of the current state of knowledge regarding advances and achievements in the field of the chemocatalytic conversion of ethanol and butanediols to butadiene, including thermodynamics and kinetic aspects of the reactions with discussions on the reaction pathways and the type of catalysts developed. PMID:24993100

  6. Ab initio investigation of the passivation effect of the acrylonitrile molecule on the Si(100)-(2 × 1) surface

    Usanmaz, D., E-mail: demetusanmaz@gmail.com [Physics Program, Middle East Technical University, Northern Cyprus Campus, Kalkanlı, Güzelyurt, KKTC, Mersin 10 (Turkey); Srivastava, G.P. [School of Physics, University of Exeter, Stocker Road, Exeter EX4 4QL (United Kingdom)

    2014-08-17

    Highlights: • Different bonding configurations of acrylonitrile molecule on the Si(2 × 1) surface based on reported experimental results have been investigated. • The acrylonitrile molecule has the minimum energy configuration at the on-top adsorption site. • The adsorption of the acrylonitrile molecule passivates the Si(2 × 1) surface both chemically as well as electronically. • The resulting surface structure is passivated both chemically as well as electronically. - Abstract: Based on pseudopotentials and the density functional theory, we have investigated the atomic geometry and electronic structure of the acrylonitrile molecule adsorbed on the Si(100)-(2 × 1) surface. By considering different bonding configurations based on reported experimental results, we have investigated several possible geometries. Our total energy results suggest that the acrylonitrile molecule has the minimum energy configuration at the on-top adsorbtion site. The electronic surface properties of the most stable structure have been discussed. Our results show that the adsorption of this molecule fully passivates the Si(001)(2 × 1) surface.

  7. Ion exchange membranes based on vinylphosphonic acid-co-acrylonitrile copolymers for fuel cells

    Žitka, Jan; Bleha, Miroslav; Schauer, Jan; Galajdová, Barbora; Paidar, M.; Hnát, J.; Bouzek, K.

    2015-01-01

    Roč. 56, č. 12 (2015), s. 3167-3173. ISSN 1944-3994. [International Conference on Membrane and Electromembrane Processes - MELPRO 2014. Prague, 18.05.2014-21.05.2014] R&D Projects: GA ČR(CZ) GPP106/12/P643 EU Projects: European Commission(XE) 608931 - MAT4BAT Institutional support: RVO:61389013 Keywords : vinylphosphonic acid * poly(vinylphosphonic acid-co-acrylonitrile) * ionic conductivity Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.173, year: 2014

  8. Modification of fiber properties through grafting of acrylonitrile to rayon by chemical and radiation methods

    Inderjeet Kaur; Neelam Sharma; Vandna Kumari

    2013-01-01

    Fibrous properties of rayon has been modified through synthesis of graft copolymers of rayon with acrylonitrile (AN) by chemical method using ceric ammonium nitrate (CAN/HNO3) as a redox initiator and gamma radiation mutual method. Percentage of grafting (Pg) was determined as a function of initiator concentration, monomer concentration, irradiation dose, temperature, time of reaction and the amount of water. Maximum percentage of grafting (160.01%) using CAN/HNO3 was obtained at [CAN] = 22.8...

  9. Gas permeability of polyvinyltrimethylsilane modified by irradiation-induced grafting of acrylonitrile

    Gas permeability and diffusion at 20-80 deg through homogeneous polyvinyltrimethylsilane membranes modified by acrylonitrile grafting have been studied. Coefficients of diffusion and permeability of all gases under study for the samples containing PAN are lower than for pure polymer. An increase of PAN content in membranes resuls in increasing of selectivity of permeability for He-CH4, He-N2, He-CO2, H2-CH4 gas pairs. The correlation of the coefficient of diffusion with the effective cross-section of gas molecules and of the coefficient of solubility with their strength constants of the Lennard-Jones potential is observed

  10. Autodetachment dynamics of acrylonitrile anion revealed by 2D electron impact spectra

    We have measured the elastic and vibrationally inelastic differential cross sections in acrylonitrile at the scattering angle of 135°. We have found out that the bands at 2.9 and 4.4 eV are shape resonances, while sharp structures in the region 0 -0.5 eV are either boomerang structure of a shape resonance or vibrational Feshbach resonances. We gain detailed view of the autodetachment dynamics from a 2D spectrum where cross section is plotted against the incident energy and the energy loss.

  11. Positron lifetime study of polycarbonate/poly(styrene-co-acrylonitrile) blends

    Čížek, J.; Motyčka, V.; Procházka, I.; Ilavský, Michal; Kolařík, Jan

    2001-01-01

    Roč. 363, č. 3 (2001), s. 340-342. ISSN 0255-5476. [International Conference on Positron Annihilation /12./. Munchen, 06.08.2000-12.08.2000] R&D Projects: GA ČR GA106/98/0700; GA AV ČR KSK2050602 Institutional research plan: CEZ:AV0Z4050913 Keywords : partial miscibility of polymers * polycarbonate/poly(styrene-co- acrylonitrile ) blends * positron lifetime spectroscopy Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.461, year: 2001

  12. Effect of strain on dielectric properties of poly(styrene-co-acrylonitrile)/polycarbonate blend

    Nedbal, J.; Valentová, H.; Ilavský, Michal

    Bratislava : Polymer Institute of the Slovak Academy of Sciences, 2003 - (Omastová, M.). s. 58 ISBN 80-968433-2-X. [Bratislava International Conference on Modified Polymers ModPol /18./. 05.10.2003-08.10.2003, Stará Lesná] R&D Projects: GA AV ČR IAA4112901 Grant ostatní: GA UK(CZ) 166/2001/B Institutional research plan: CEZ:AV0Z4050913 Keywords : dielectric properties * poly(styrene-co- acrylonitrile )/polycarbonate blends Subject RIV: BM - Solid Matter Physics ; Magnetism

  13. ION CONDUCTION IN COMPLEX OF ACRYLONITRILE-COPOLYMERIZED COMB POLYETHER WITH LITHIUM PERCHLORATE

    XU Kang; DENG Zhenghua; WAN Guoxiang

    1991-01-01

    Poly ( oligoether methacrylate- co- acrylonitrile ) s, P ( MEOn- AN ), with oligoether pendants of different lengths were synthesized and the ion conduction property of their Li-salt complexes was studied as the function of polymer structure. At proper copolymer composition, lithium concentration and pendant length, the ion conductivity reaches 7.0×10-5S/cm at ambient temperature, together with improved mechanical strength. The ion transport in the polymer media is assisted by segmental relaxation ,which is confirmed both by the consistency between ion conductivity and Tg and by the study of TSC.

  14. Onderzoek naar de mutagene werking van acrylonitril met microorganismen Drosophila melanogaster en L5178Y muize-lymfoomcellen

    Voogd CE; van der Stel JJ; Verharen HW; Kramers PGN; Mout HCA; Knaap AGAC; Langbroek PG

    1985-01-01

    Acrylonitril was mutageen bij 5 mmol/l in de fluctuatietest zonder metabolische activering ; in gasfase werd bij 0,5 mmol/l lucht een mutagene werking gevonden. Deze stof was ook mutageen in de Ames-test voor Salmonella typhimurium TA1535 (15 mmol/plaat) met metabolische activering doch niet met de stammen TA98 en TA100. In de gasfase werd in de Ames-test geen mutagene werking gevonden, groeiremming trad op bij ca. 0,1 mmol/l lucht. Met acrylonitril werd geen mutagene werking gevonden op Dros...

  15. [Carcinogenicity of acrylonitrile and evaluation of approaches to pathogenetic correction of acrylate toxicity and antitumorigenic anthracycline doxorubicin toxicity during chemotherapy].

    Tarskikh, M M; Shumbasov, M A; Kolesnikov, S I

    2013-01-01

    Statistical analysis within the 20-year period showed that approximately 49% of workers who were exposed to widespread industrial poison acrylonitrile subsequently died from malignancy of different localization. The conducted experimental investigations demonstrated that acrylonitrile with the subacute intoxication of animals, the anti-tumor antibiotic doxorubicin, their combination, interwoven tumor and tumor developed against the background the introduction of acrylate and subsequent treatment doxorubicin led to onset of free-radical reactions. These reactions by themselves might stimulate development of malignancy. This fact confirms the need for antioxidant tracking of chemotherapy of tumors in the similar clinical cases. PMID:23819331

  16. Secondary organic aerosol formation from the photooxidation of isoprene, 1,3-butadiene, and 2,3-dimethyl-1,3-butadiene under high NOx conditions

    D. R. Cocker III

    2011-02-01

    Full Text Available Secondary organic aerosol (SOA formation from atmospheric oxidation of isoprene has been the subject of multiple studies in recent years; however, reactions of other conjugated dienes emitted from anthropogenic sources remain poorly understood. SOA formation from the photooxidation of isoprene, isoprene-1-13C, 1,3-butadiene, and 2,3-dimethyl-1,3-butadiene is investigated for high NOx conditions. The SOA yield measured in the 1,3-butadiene/NOx/H2O2 irradiation system (0.089–0.178 was close to or slightly higher than that measured with isoprene under similar NOx conditions (0.077–0.103, suggesting that the photooxidation of 1,3-butadiene is a possible source of SOA in urban air. In contrast, a very small amount of SOA particles was produced in experiments with 2,3-dimethyl-1,3-butadiene. Off-line liquid chromatography – mass spectrometry analysis revealed oligoesters as the major SOA products observed from all dienes investigated. The oligoesters originate from the unsaturated aldehyde gas-phase diene reaction products, which undergo oligoester formation through heterogeneous oxidation under high NOx conditions. Oligoesters produced by the dehydration reaction between nitrooxypolyol and 2-methylglyceric acid monomer or its oligomer were also discovered in these experiments with isoprene as the starting diene. These oligomers are possible sources of the 2-methyltetrols found in ambient aerosol samples collected under high NOx conditions. Furthermore, in low-temperature experiments also conducted in this study, the SOA yield measured with isoprene at 278 K was 2–3 times as high as that measured at 300 K under similar concentration conditions. Although oligomerization plays an important role in SOA formation from isoprene photooxidation, the observed temperature dependence of SOA yield is largely explained by gas/particle partitioning of semi-volatile compounds.

  17. Photoinitiator grafted styrene-butadiene-styrene triblock copolymer

    Grafting of photoinitiator-4-maleimidobenzophenone (4-MBP) onto styrene-butadiene-styrene (SBS) triblock copolymer was carried out by free radical polymerization. The grafting ratio was evaluated by varying initiator concentrations, and the structure of grafted copolymer (SBS-g-MBP) was characterized by attenuated total reflectance infrared Fourier transform spectroscopy (ATR-FTIR), proton nuclear magnetic resonance (1H NMR) and X-ray photoelectron spectroscopy (XPS). The results confirmed that 4-MBP was successfully grafted onto the SBS backbone. Thermal gravimetric analyzer (TGA), dynamic mechanical thermal analysis (DMTA), scanning electron microscopy (SEM), and atomic force microscopy (AFM) were used to study the thermal properties and morphology of the SBS-g-MBP. From the data of TGA, the SBS-g-MBP had better thermal stability compared with that of SBS. DMTA testing indicated that the glass transition temperature (Tg) of SBS-g-MBP was higher than that of SBS. With the aid of SEM and AFM, the structure of micro-phase separation can be observed obviously. What is more, the aggregates become smaller compared with those of pure SBS. The experiment of UV-crosslinked SBS-g-MBP revealed that the gel fraction could be facilely controlled by adjusting grafting ratio and exposure time. The results suggested that this novel grafted copolymer could be attractive for its application in biomedical materials such as medical pressure-sensitive adhesive.

  18. High performance light-colored nitrile-butadiene rubber nanocomposites.

    Lei, Yanda; Guo, Baochun; Chen, Feng; Zhu, Lixin; Zhou, Wenyou; Jia, Demin

    2011-12-01

    High mechanical performance nitrile-butadiene rubber (NBR) with light color was fabricated by the method of in situ formation of zinc disorbate (ZDS) or magnesium disorbate (MDS). The in situ formed ZDS and its polymerization via internal mixing was confirmed by X-ray diffaraction. The mechanical properties, ageing resistance, morphology and the dynamic mechanical analysis were fully studied. It was found that with increasing loading of metallic disorbate both the curing rate and the ionic crosslink density was largely increased. The modulus, tensile strength and tear strength were largely increased. With a comparison between internal mixing and opening mixing, the mechanical performance for the former one was obviously better than the latter one. The high performance was ascribed to the finely dispersion nano domains with irregular shape and obscure interfacial structures. Except for the NBR vulcanizate with a high loading of MDS, the others' ageing resistance with incorporation of these two metallic disorbate was found to be good. Dynamic mechanical analysis (DMA) showed that, with increasing loading of metallic disorbate, the highly increased storage modulus above -20 degrees C, the up-shifted glass transition temperature (Tg) and the reduced mechanical loss were ascribed to strengthened interfacial interactions. PMID:22408977

  19. [Identification of migrants from nitrile-butadiene rubber gloves].

    Mutsuga, Motoh; Kawamura, Yoko; Wakui, Chiseko; Maitani, Tamio

    2003-04-01

    Polyvinyl chloride gloves containing di(2-ethylhexyl) phthalate are restricted for food contact use. In their place, disposable gloves made from nitrile-butadiene rubber (NBR) are used in contact with foodstuffs. Some unknown substances were found to migrate into n-heptane from NBR gloves. By GC/MS, HR-MS and NMR, their chemical structures were confirmed to be 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (used as a plasticizer), 4,4'-butylidenedi(6-tert-butyl-m-cresol), a mixture of styrenated phenols consisting of 2-(alpha-methylbenzyl)phenol, 4-(alpha-methylbenzyl)phenol, 2,6-di(alpha-methylbenzyl)phenol, 2,4-di(alpha-methylbenzyl)phenol and 2,4,6-tri(alpha-methylbenzyl)phenol (used as antioxidants), and 2,4-di-tert-butylphenol, which seems to a degradation product of antioxidant. Migration levels of these compounds were 1.68 micrograms/cm2 of 2,4-di-tert-butylphenol, 2.80 micrograms/cm2 of 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, 46.08 micrograms/cm2 of styrenated phenols and 4.22 micrograms/cm2 of 4,4'-butylidenedi(6-tert-butyl-m-cresol) into n-heptane, respectively. The content of total styrenated phenols was 6,900 micrograms/g in NBR gloves. PMID:12846157

  20. An estimation of photon scattering length in tetraphenyl-butadiene

    Stolp, D.; Dalager, O.; Dhaliwal, N.; Godfrey, B.; Irving, M.; Kazkaz, K.; Manalaysay, A.; Neher, C.; Stephenson, S.; Tripathi, M.

    2016-03-01

    Tetraphenyl-butadiene (TPB) is a wavelength shifting material that can absorb ultraviolet photons and emit blue photons. It is used in the detection of vacuum ultraviolet (VUV) photons, for which typical photo-sensors, such as most photomultiplier tubes (PMT) and silicon photomultipliers (SiPM), do not have any quantum efficiency. The secondary blue light is emitted isotropically, however, due to scattering within the material, its angular distribution upon exiting the material can not be easily predicted. Here we describe a procedure for estimating the scattering length of blue light in TPB, by measuring and modeling the angular distribution as a function of layer thickness. The experiment consists of shining 254nm light at various thicknesses of TPB deposited on fused silica, and measuring the intensity of blue light using SiPMs on either side of the sample. We simulate light propagation within the sample to estimate the light yield and compare that to the data, which allows us to estimate mean scattering length for photons in TPB to be in the range 2-3 μm, with some preference for a central value of 2.75 μm.

  1. Rich methane laminar flames doped with light unsaturated hydrocarbons. Part II: 1,3butadiene

    Gueniche, Hadj-Ali; Fournet, René; Battin-Leclerc, Frédérique

    2007-01-01

    In line with the study presented in the part I of this paper, the structure of a laminar rich premixed methane flame doped with 1,3-butadiene has been investigated. The flame contains 20.7% (molar) of methane, 31.4% of oxygen and 3.3% of 1,3-butadiene, corresponding to an equivalence ratio of 1.8, and a ratio C4H6 / CH4 of 16 %. The flame has been stabilized on a burner at a pressure of 6.7 kPa using argon as dilutant, with a gas velocity at the burner of 36 cm/s at 333 K. The temperature ranged from 600 K close to the burner up to 2150 K. Quantified species included usual methane C0-C2 combustion products and 1,3-butadiene, but also propyne, allene, propene, propane, 1,2-butadiene, butynes, vinylacetylene, diacetylene, 1,3-pentadiene, 2-methyl-1,3-butadiene (isoprene), 1-pentene, 3-methyl-1-butene, benzene and toluene. In order to model these new results, some improvements have been made to a mechanism previously developed in our laboratory for the reactions of C3-C4 unsaturated hydrocarbons. The main reacti...

  2. Sensitive detection of acrolein and acrylonitrile with a pulsed quantum-cascade laser

    Manne, J.; Lim, A.; Tulip, J.; Jäger, W.

    2012-05-01

    We report on spectroscopic measurements of acrolein and acrylonitrile at atmospheric pressure using a pulsed distributed feedback quantum-cascade laser in combination with intra- and inter-pulse techniques and compare the results. The measurements were done in the frequency region around 957 cm-1. In the inter-pulse technique, the laser is excited with short current pulses (5-10 ns), and the pulse amplitude is modulated with an external current ramp resulting in a ˜2.3 cm-1 frequency scan. In the intra-pulse technique, a linear frequency down-chirp during the pulse is used for sweeping across the absorption line. Long current pulses up to 500 ns were used for these measurements which resulted in a spectral window of ˜2.2 cm-1 during the down-chirp. These comparatively wide spectral windows facilitated the measurements of the relatively broad absorption lines (˜1 cm-1) of acrolein and acrylonitrile. The use of a room-temperature mercury-cadmium-telluride detector resulted in a completely cryogen-free spectrometer. We demonstrate ppb level detection limits within a data acquisition time of ˜10 s with these methodologies.

  3. Two-dimensional spectra of electron collisions with acrylonitrile and methacrylonitrile reveal nuclear dynamics

    Detailed experimental information on the motion of a nuclear packet on a complex (resonant) anion potential surface is obtained by measuring 2-dimensional (2D) electron energy loss spectra. The cross section is plotted as a function of incident electron energy, which determines which resonant anion state is populated, i.e., along which normal coordinate the wave packet is launched, and of the electron energy loss, which reveals into which final states each specific resonant state decays. The 2D spectra are presented for acrylonitrile and methacrylonitrile, at the incident energy range 0.095-1.0 eV, where the incoming electron is temporarily captured in the lowest π∗ orbital. The 2D spectra reveal selectivity patterns with respect to which vibrations are excited in the attachment and de-excited in the detachment. Further insight is gained by recording 1D spectra measured along horizontal, vertical, and diagonal cuts of the 2D spectrum. The methyl group in methacrylonitrile increases the resonance width 7 times. This converts the sharp resonances of acrylonitrile into boomerang structures but preserves the essence of the selectivity patterns. Selectivity of vibrational excitation by higher-lying shape resonances up to 8 eV is also reported

  4. Two-dimensional spectra of electron collisions with acrylonitrile and methacrylonitrile reveal nuclear dynamics

    Regeta, K., E-mail: khrystyna.regeta@unifr.ch; Allan, M., E-mail: michael.allan@unifr.ch [Department of Chemistry, University of Fribourg, Chemin du Musée 9, CH-1700 Fribourg (Switzerland)

    2015-05-14

    Detailed experimental information on the motion of a nuclear packet on a complex (resonant) anion potential surface is obtained by measuring 2-dimensional (2D) electron energy loss spectra. The cross section is plotted as a function of incident electron energy, which determines which resonant anion state is populated, i.e., along which normal coordinate the wave packet is launched, and of the electron energy loss, which reveals into which final states each specific resonant state decays. The 2D spectra are presented for acrylonitrile and methacrylonitrile, at the incident energy range 0.095-1.0 eV, where the incoming electron is temporarily captured in the lowest π{sup ∗} orbital. The 2D spectra reveal selectivity patterns with respect to which vibrations are excited in the attachment and de-excited in the detachment. Further insight is gained by recording 1D spectra measured along horizontal, vertical, and diagonal cuts of the 2D spectrum. The methyl group in methacrylonitrile increases the resonance width 7 times. This converts the sharp resonances of acrylonitrile into boomerang structures but preserves the essence of the selectivity patterns. Selectivity of vibrational excitation by higher-lying shape resonances up to 8 eV is also reported.

  5. Ultrasonic velocity and absorption study of binary mixtures of cyclohexane with acrylonitrile by interferometric method at different frequencies

    Pawar, N. R.; Chimankar, O. P.; Bhandakkar, V. D.; Padole, N. N.

    2012-12-01

    The ultrasonic velocity (u), absorption (α), density (ρ), and viscosity (η) has been measured at different frequencies (1MHz to 10MHz) in the binary mixtures of cyclohexane with acrylonitriile over the entire range of composition at temperature 303K. Vander Waal's constant (b), adiabatic compressibility (βa), acoustic impedance (Z), molar volume (V), free length (Lf), free volume, internal pressure, intermolecular radius and relative association have been also calculated. A special application for acrylonitrile is in the manufacture of carbon fibers. These are produced by paralysis of oriented poly acrylonitrile fibers and are used to reinforce composites for high-performance applications in the aircraft, defense and aerospace industries. Other applications of acrylonitrile are in the production of fatty amines, ion exchange resins and fatty amine amides used in cosmetics, adhesives, corrosion inhibitors and water-treatment resins. Cyclohexane derivatives can be used for the synthesis of pharmaceuticals, dyes, herbicides, plant growth regulator, plasticizers, rubber chemicals, nylon, cyclamens and other organic compounds. In the view of these extensive applications of acrylonitrile and cyclohexane in the engineering process, textile and pharmaceutical industries present study provides qualitative information regarding the nature and strength of interaction in the liquid mixtures through derive parameters from ultrasonic velocity and absorption measurement.

  6. Synthesis of diblock copolymers comprising poly(2-vinylpyridine-co-acrylonitrile) and polystyrene blocks by nitroxide-mediated radical polymerization

    Lokaj, Jan; Poláková, Lenka; Holler, Petr; Starovoytova, Larisa; Štěpánek, Petr; Diat, O.

    2007-01-01

    Roč. 105, č. 3 (2007), s. 1616-1622. ISSN 0021-8995 R&D Projects: GA ČR GESON/03/E001 Institutional research plan: CEZ:AV0Z40500505 Keywords : 2-vinylpyridine-acrylonitrile copolymers * nitroxide-mediated radical copolymerization * chain extension Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.008, year: 2007

  7. Synthesis and gas permeability of block copolymers composed of poly(styrene-co-acrylonitrile) and polystyrene blocks

    Lokaj, Jan; Brožová, Libuše; Holler, Petr; Pientka, Zbyněk

    2002-01-01

    Roč. 67, č. 2 (2002), s. 267-278. ISSN 0010-0765 R&D Projects: GA ČR GA203/99/0572 Institutional research plan: CEZ:AV0Z4050913 Keywords : azeotropic styrene- acrylonitrile copolymers * block copolymers * nitroxide-mediated copolymerization Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.848, year: 2002

  8. Ultrasonic velocity and absorption study of binary mixtures of cyclohexane with acrylonitrile by interferometric method at different frequencies

    The ultrasonic velocity (u), absorption (α), density (ρ), and viscosity (η) has been measured at different frequencies (1MHz to 10MHz) in the binary mixtures of cyclohexane with acrylonitriile over the entire range of composition at temperature 303K. Vander Waal's constant (b), adiabatic compressibility (βa), acoustic impedance (Z), molar volume (V), free length (Lf), free volume, internal pressure, intermolecular radius and relative association have been also calculated. A special application for acrylonitrile is in the manufacture of carbon fibers. These are produced by paralysis of oriented poly acrylonitrile fibers and are used to reinforce composites for high-performance applications in the aircraft, defense and aerospace industries. Other applications of acrylonitrile are in the production of fatty amines, ion exchange resins and fatty amine amides used in cosmetics, adhesives, corrosion inhibitors and water-treatment resins. Cyclohexane derivatives can be used for the synthesis of pharmaceuticals, dyes, herbicides, plant growth regulator, plasticizers, rubber chemicals, nylon, cyclamens and other organic compounds. In the view of these extensive applications of acrylonitrile and cyclohexane in the engineering process, textile and pharmaceutical industries present study provides qualitative information regarding the nature and strength of interaction in the liquid mixtures through derive parameters from ultrasonic velocity and absorption measurement.

  9. Evaporative emissions of 1,3-butadiene from petrol-fuelled motor vehicles

    Ye, Y.; Galbally, I. E.; Weeks, I. A.; Duffy, B. L.; Nelson, P. F.

    This study reports the identification and quantification of 1,3-butadiene in petrol and in the evaporative emissions from Australian light-duty passenger vehicles. The mass fraction of 1,3-butadiene in each of the different grades of any brand of Australian petrol was found to be relatively constant for a given marketing area. However, the mass fractions vary significantly between the different brands (or refineries) from 0.004±0.001% to 0.047±0.008%. The measurements of the evaporative emissions of 1,3-butadiene from in-service motor vehicles were performed using standard Australian Design Rule 37/00 (ADR 37/00) Sealed Housing Evaporative Determination (SHED) tests. For post-1985 catalyst equipped vehicles fuelled with unleaded petrol, average evaporative emissions of 1,3-butadiene were 9.4 (0.7-22) and 5.0 (0.1-23) mg per test for diurnal and hot soak SHED tests, respectively. The corresponding average evaporative emissions for the older, pre-1986 non-catalyst equipped vehicles fuelled with leaded petrol were 26.5 (11.7-45.4) and 9.2 (4.3-13.1) mg per test, respectively, about double the observed emissions from newer vehicles. For the complete vehicle set (all ages), the average mass fraction of 1,3-butadiene in the total hydrocarbon (sum of C 1-C 10 hydrocarbons) emission was 0.21±0.14% from the diurnal phase and was 0.11±0.06% from the hot-soak phase. Evaporative emissions were estimated to contribute about 4% (ranging from 1-15%) of the total (exhaust and evaporative) emissions of 1,3-butadiene from Australian motor vehicles.

  10. Rich premixed laminar methane flames doped by light unsaturated hydrocarbons. II. 1,3-Butadiene

    Gueniche, H.A.; Glaude, P.A.; Fournet, R.; Battin-Leclerc, F. [Departement de Chimie-Physique des Reactions, UMR 7630 CNRS, INPL-ENSIC, 1 rue Grandville, BP 20451, 54001 Nancy Cedex (France)

    2007-10-15

    In line with the study presented in Part I of this paper, the structure of a rich premixed laminar methane flame doped with 1,3-butadiene has been investigated. The flame contains 20.7% (molar) of methane, 31.4% of oxygen, and 3.3% of 1,3-butadiene, corresponding to an equivalence ratio of 1.8, and a C{sub 4}H{sub 6}/CH{sub 4} ratio of 16%. The flame has been stabilized on a burner at a pressure of 6.7 kPa using argon as dilutant, with a gas velocity at the burner of 36 cm/s at 333 K. The temperature ranged from 600 K close to the burner up to 2150 K. Quantified species included the usual methane C{sub 0}-C{sub 2} combustion products and 1,3-butadiene, but also propyne, allene, propene, propane, 1,2-butadiene, butynes, vinylacetylene, diacetylene, 1,3-pentadiene, 2-methyl-1,3-butadiene (isoprene), 1-pentene, 3-methyl-1-butene, benzene, and toluene. To model these new results, some improvements have been made to a mechanism previously developed in our laboratory for the reactions of C{sub 3}-C{sub 4} unsaturated hydrocarbons. The main reaction pathways of consumption of 1,3-butadiene and of formation of C{sub 6} aromatic species have been derived from flow rate analyses. In this case, the C{sub 4} route to benzene formation plays an important role in comparison to the C{sub 3} pathway. (author)

  11. Application of Lignin as Antioxidant in Styrene Butadiene Rubber Composite

    Liu, Shusheng; Cheng, Xiansu

    2010-11-01

    Lignin isolated from enzymatic hydrolyzed cornstalks (EHL) is a renewable natural polymer, and rubber is one of the most important polymer materials. The application of EHL in rubber industry is of great significance. The influence of EHL and antioxidant RD on the vulcanizing characteristics, thermal oxidative aging stability under free condition, and water extraction resistance of styrene-butadiene rubber (SBR) were investigated. The effect of EHL/antioxidant D composite antioxidant on the thermal oxidative ageing of SBR was also evaluated. Results showed that the protection of SBR from thermal oxidative aging by EHL/antioxidant D composite antioxidant was superior to that of antioxidant D. This is because EHL molecules have hindered phenol group and have excellent auxiliary antioxidant role with antioxidant D. Moreover, the influence of EHL on the vulcanizing characteristics of SBR compounds was better than that of antioxidant RD, and EHL can reduce the cure rate and increase the optimum cure time. It is because that the EHL molecules have hindered phenol group and methoxy group, which can form a special structure to capture free radical and terminate the chain reaction. The retained tensile strength of SBR compounds with EHL was similar to that of the samples with antioxidant RD, while the retained elongation at break of SBR compounds with EHL was higher than that of the samples with antioxidant RD. In addition, the SBR compounds with EHL have a good water extraction resistance property, which was similar to the samples with antioxidant RD. This is because EHL have large molecular weight, good stability and low solubility in water. In conclusion, due to the low price, abundant resources, non-toxic and pollution-free, etc., EHL will have broad application prospect.

  12. Azidated Ether-Butadiene-Ether Block Copolymers as Binders for Solid Propellants

    Cappello, Miriam; Lamia, Pietro; Mura, Claudio; Polacco, Giovanni; Filippi, Sara

    2016-07-01

    Polymeric binders for solid propellants are usually based on hydroxyl-terminated polybutadiene (HTPB), which does not contribute to the overall energy output. Azidic polyethers represent an interesting alternative but may have poorer mechanical properties. Polybutadiene-polyether copolymers may combine the advantages of both. Four different ether-butadiene-ether triblock copolymers were prepared and azidated starting from halogenated and/or tosylated monomers using HTPB as initiator. The presence of the butadiene block complicates the azidation step and reduces the storage stability of the azidic polymer. Nevertheless, the procedure allows modifying the binder properties by varying the type and lengths of the energetic blocks.

  13. Studies of plastic crystal gel polymer electrolytes based on poly(vinylidene chloride-co-acrylonitrile)

    Hambali, D.; Zainuddin, Z.; Supa'at, I.; Osman, Z.

    2016-02-01

    In this work, we have prepared systems of poly(vinylidene chloride-co-acrylonitrile) (PVdC-co-AN) based gel polymer electrolytes (GPEs) which are single plasticized-GPEs and double plasticized-GPEs. Both systems comprised plastic crystal succinonitrile SN to form plastic crystal gel polymer electrolyte (PGPE) films. The ionic conductivity of the PGPE films were analysed by means of a.c. impedance spectroscopy at room temperature as well as at the temperature range of 303 K to 353 K. The temperature dependence ionic conductivity was found to obey the VTF rule. To study the interactions among the constituents in the PGPEs, Fourier Transform Infrared Spectroscopy (FTIR) was carried out and hence, the complexation between them has also been confirmed.

  14. Quantitation of DNA Adducts Induced by 1,3-Butadiene

    Sangaraju, Dewakar; Villalta, Peter W.; Wickramaratne, Susith; Swenberg, James; Tretyakova, Natalia

    2014-07-01

    Human exposure to 1,3-butadiene (BD) present in automobile exhaust, cigarette smoke, and forest fires is of great concern because of its potent carcinogenicity. The adverse health effects of BD are mediated by its epoxide metabolites such as 3,4-epoxy-1-butene (EB), which covalently modify genomic DNA to form promutagenic nucleobase adducts. Because of their direct role in cancer, BD-DNA adducts can be used as mechanism-based biomarkers of BD exposure. In the present work, a mass spectrometry-based methodology was developed for accurate, sensitive, and precise quantification of EB-induced N-7-(1-hydroxy-3-buten-2-yl) guanine (EB-GII) DNA adducts in vivo. In our approach, EB-GII adducts are selectively released from DNA backbone by neutral thermal hydrolysis, followed by ultrafiltration, offline HPLC purification, and isotope dilution nanoLC/ESI+-HRMS3 analysis on an Orbitrap Velos mass spectrometer. Following method validation, EB-GII lesions were quantified in human fibrosarcoma (HT1080) cells treated with micromolar concentrations of EB and in liver tissues of rats exposed to sub-ppm concentrations of BD (0.5-1.5 ppm). EB-GII concentrations increased linearly from 1.15 ± 0.23 to 10.11 ± 0.45 adducts per 106 nucleotides in HT1080 cells treated with 0.5-10 μM DEB. EB-GII concentrations in DNA of laboratory rats exposed to 0.5, 1.0, and 1.5 ppm BD were 0.17 ± 0.05, 0.33 ± 0.08, and 0.50 ± 0.04 adducts per 106 nucleotides, respectively. We also used the new method to determine the in vivo half-life of EB-GII adducts in rat liver DNA (2.20 ± 0.12 d) and to detect EB-GII in human blood DNA. To our knowledge, this is the first application of nanoLC/ESI+-HRMS3 Orbitrap methodology to quantitative analysis of DNA adducts in vivo.

  15. Acrylonitrile-14C metabolism in rats: effect of the route of administration on the elimination of thiocyanate and other radioactive metabolites in urine and feces

    In Wistar rats, the elimination of the sum of radioactive metabolites of acrylonitrile-14C was not markedly influenced by the route of acrylonitrile administration. The elimination of thiocyanate, however, was significantly higher after oral (23% of the dose) than after intraperitoneal (4%), subcutaneous (4.6%), or intravenous (1.2%) administrations. The elimination of the sum of radioactive metabolites was highest in the first 4 hours after acrylonitrile administration and rapidly decreased whereas the excretion of thiocyanate reached the maximum between hours 8 and 14 after oral or intraperitoneal administration. Less than 1% of the radioactivity of the acrylonitrile-14C dose was eliminated in feces irrespective of the route of administration. (author)

  16. 75 FR 31713 - 2-Propenoic acid polymer, with 1,3-butadiene and ethenylbenzene; Tolerance Exemption

    2010-06-04

    ...,3- butadiene and ethenylbenzene, minimum number average molecular weight (in AMU) 9400 (CAS Reg. No..., minimum number average molecular weight (in AMU) 9400; CAS Reg. No. 25085-39-6. That notice included a... absorbing polymer with a number average molecular weight (MW) greater than or equal to 10,000...

  17. 40 CFR 80.55 - Measurement methods for benzene and 1,3-butadiene.

    2010-07-01

    ... Environmental Analysis, 55 Analytical Chemistry 14, at 2210-2218 (1983) (copies may be obtained from the...,3-butadiene. 80.55 Section 80.55 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) REGULATION OF FUELS AND FUEL ADDITIVES Reformulated Gasoline §...

  18. Polymer composites prepared from heat-treated starch and styrene-butadiene latex

    Thermoplastic starch/latex polymer composites were prepared using styrene–butadiene (SB) latex and heat-treated cornstarch. The composites were prepared in a compression mold at 130 °C, with starch content 20%. An amylose-free cornstarch, waxy maize, was used for this research and the heat treatment...

  19. Ternary Ag/MgO-SiO2 catalysts for the conversion of ethanol into butadiene.

    Janssens, Wout; Makshina, Ekaterina V; Vanelderen, Pieter; De Clippel, Filip; Houthoofd, Kristof; Kerkhofs, Stef; Martens, Johan A; Jacobs, Pierre A; Sels, Bert F

    2015-03-01

    Ternary Ag/Magnesia-silica catalysts were tested in the direct synthesis of 1,3-butadiene from ethanol. The influence of the silver content and the type of silica source on catalytic performance has been studied. Prepared catalysts were characterized by (29) Si NMR, N2 sorption, small-angle X-ray scattering measurements, XRD, environmental scanning electron microscopy with energy dispersive X-ray analysis (ESEM/EDX), FTIR spectroscopy of adsorbed pyridine and CO2 , temperature-programmed desorption of CO2 and UV/Vis diffuse reflectance spectroscopy. Based on these characterization results, the catalytic performance of the catalysts in the 1,3-butadiene formation process was interpreted and a tentative model explaining the role of the different catalytically active sites was elaborated. The balance of the active sites is crucial to obtain an active and selective catalyst to form 1,3-butadiene from ethanol. The optimal silver loading is 1-2 wt% on a MgO-silica support with a molar Mg/Si ratio of 2. The silver species and basic sites (Mg−O pairs and basic OH groups) are of prime importance in the 1,3-butadiene production, catalyzing mainly the ethanol dehydrogenation and the aldol condensation, respectively. PMID:25410420

  20. Blends of Styrene-Butadiene-Styrene Triblock Copolymer with Random Styrene-Maleic Anhydride Copolymers

    Piccini, Maria Teresa; Ruggeri, Giacomo; Passaglia, Elisa; Picchioni, Francesco; Aglietto, Mauro

    2002-01-01

    Blends of styrene-butadiene-styrene triblock copolymer (SBS) with random styrene-maleic anhydride copolymers (PS-co-MA), having different MA content, were prepared in a Brabender Plastigraph mixer. The presence of polystyrene (PS) blocks in the SBS copolymer and the high styrene content (93 and 86 w

  1. Covalent immobilization of glucose oxidase onto new modified acrylonitrile copolymer/silica gel hybrid supports.

    Godjevargova, Tzonka; Nenkova, Ruska; Dimova, Nedyalka

    2005-08-12

    New polymer/silica gel hybrid supports were prepared by coating high surface area of silica gel with modified acrylonitrile copolymer. The concentrations of the modifying agent (NaOH) and the modified polymer were varied. GOD was covalently immobilized on these hybrid supports and the relative activity and the amount of bound protein were determined. The highest relative activity and sufficient amount of bound protein of the immobilized GOD were achieved in 10% NaOH and 2% solution of modified acrylonitrile copolymer. The influence of glutaraldehyde concentration and the storage time on enzyme efficiency were examined. Glutaraldehyde concentration of 0.5% is optimal for the immobilized GOD. It was shown that the covalently bound enzyme (using 0.5% glutaraldehyde) had higher relative activity than the activity of the adsorbed enzyme. Covalently immobilized GOD with 0.5% glutaraldehyde was more stable for four months in comparison with the one immobilized on pure silica gel, hybrid support with 10% glutaraldehyde and the free enzyme. The effect of the pore size on the enzyme efficiency was studied on four types of silica gel with different pore size. Silica with large pores (CPC-Silica carrier, 375 A) presented higher relative activity than those with smaller pore size (Silica gel with 4, 40 and 100 A). The amount of bound protein was also reduced with decreasing the pore size. The effect of particle size was studied and it was found out that the smaller the particle size was, the greater the activity and the amount of immobilized enzyme were. The obtained results proved that these new polymer/silica gel hybrid supports were suitable for GOD immobilization. PMID:16080168

  2. Photoinitiated decomposition of substituted ethylenes: The photodissociation of vinyl chloride and acrylonitrile at 193 nm

    Blank, D.A.; Suits, A.G.; Lee, Y.T. [Lawrence Berkeley National Lab., CA (United States)] [and others

    1997-04-01

    Ethylene and its substituted analogues (H{sub 2}CCHX) are important molecules in hydrogen combustion. As the simplest {pi}-bonded hydrocarbons these molecules serve as prototypical systems for understanding the decomposition of this important class of compounds. The authors have used the technique of photofragment translational spectroscopy at beamline 9.0.2.1 to investigate the dissociation of vinyl chloride (X=Cl) and acrylonitrile (X=CN) following absorption at 193 nm. The technique uses a molecular beam of the reactant seeded in helium which is crossed at 90 degrees with the output of an excimer laser operating on the ArF transition, 193.3 nm. The neutral photoproducts which recoil out of the molecular beam travel 15.1 cm where they are photoionized by the VUV undulator radiation, mass selected, and counted as a function of time. The molecular beam source is rotatable about the axis of the dissociation laser. The authors have directly observed all four of the following dissociation channels for both systems: (1) H{sub 2}CCHX {r_arrow} H + C{sub 2}H{sub 2}X; (2) H{sub 2}CCHX {r_arrow} X + C{sub 2}H{sub 3}; (3) H{sub 2}CCHX {r_arrow} H{sub 2} + C{sub 2}HX; and (4) H{sub 2}CCHX {r_arrow} HX + C{sub 2}H{sub 2}. They measured translational energy distributions for all of the observed channels and measured the photoionization onset for many of the photoproducts which provided information about their chemical identity and internal energy content. In the case of acrylonitrile, selective product photoionization provided the ability to discriminate between channels 2 and 4 which result in the same product mass combination.

  3. Emission of 1,3-butadiene from petrol-driven motor vehicles

    Ye, Y.; Galbally, I. E.; Weeks, I. A.

    This study reports the measurement of 1,3-butadiene emissions from 30 petrol-driven vehicles from the Australian car fleet using the Australian Design Rule 37/00 vehicle test procedure. Six of the cars tested were not equipped with catalytic converters and used leaded petrol as fuel. The remaining 24 cars were fitted with catalytic converters and used unleaded petrol. 1,3-Butadiene in exhaust samples was found to degrade rapidly in SUMMA treated stainless steel canisters and the degradation followed first-order kinetics. The rate coefficient of the decay can be represented by a linear dependence on the concentration of nitrogen oxides in the exhaust ( r2 = 0.79, n = 43), and the gas-phase reaction of NO 2 and 1,3-butadiene may have a major role in this loss. The 1,3-butadiene concentrations used to estimate vehicle emissions were corrected for this loss using the decay rate constant either observed from replicate analyses or from the NO x concentrations in the samples. The measurements showed that 1,3-butadiene was emitted at a rate of 20.7 ± 9.2 mg km -1 from 6 non-catalyst vehicles. There was considerable scatter in the observations from catalyst equipped vehicles and we infer that this was due to the malfunction of the emission control devices on some vehicles. The 19 vehicles that appeared to have functioning catalyst emission control devices had an average emission rate of 2.1 ± 1.5 mg km -1. These emission rates are consistent with atmospheric observations and are much higher than those reported previously. We calculate that more than 90% of the 1,3-butadiene in engine exhaust comes from the common alkane and aromatic constituents of the fuel. A comparison of emissions in the different phases of the drive cycle indicates that current emission controls remove more than 90% of the 1,3-butadiene from the initial exhaust mixture.

  4. Secondary organic aerosol formation from the photooxidation of isoprene, 1,3-butadiene, and 2,3-dimethyl-1,3-butadiene under high NOx conditions

    D. R. Cocker III

    2011-07-01

    Full Text Available Secondary organic aerosol (SOA formation from atmospheric oxidation of isoprene has been the subject of multiple studies in recent years; however, reactions of other conjugated dienes emitted from anthropogenic sources remain poorly understood. SOA formation from the photooxidation of isoprene, isoprene-1-13C, 1,3-butadiene, and 2,3-dimethyl-1,3-butadiene is investigated for high NOx conditions. The SOA yield measured in the 1,3-butadiene/NOx/H2O2 irradiation system (0.089–0.178 was close to or slightly higher than that measured with isoprene under similar NOx conditions (0.077–0.103, suggesting that the photooxidation of 1,3-butadiene is a possible source of SOA in urban air. In contrast, a very small amount of SOA particles was produced in experiments with 2,3-dimethyl-1,3-butadiene. Off-line liquid chromatography – mass spectrometry analysis revealed that the signals of oligoesters comprise a major fraction (0.10–0.33 of the signals of the SOA products observed from all dienes investigated. The oligoesters originate from the unsaturated aldehyde gas phase diene reaction products; namely, semi-volatile compounds produced by the oxidation of the unsaturated aldehyde undergo particle-phase oligoester formation. Oligoesters produced by the dehydration reaction between nitrooxypolyol and 2-methylglyceric acid monomer or its oligomer were also characterized in these experiments with isoprene as the starting diene. These oligomers are possible sources of the 2-methyltetrols found in ambient aerosol samples collected under high NOx conditions. Furthermore, in low-temperature experiments also conducted in this study, the SOA yield measured with isoprene at 278 K was 2–3 times as high as that measured at 300 K under similar concentration conditions. Although oligomerization plays an important role in SOA formation from isoprene photooxidation, the observed temperature dependence of SOA yield is largely explained by gas/particle partitioning

  5. Synthesis and Thermal Properties of Acrylonitrile/Butyl Acrylate/Fumaronitrile and Acrylonitrile/Ethyl Hexyl Acrylate/Fumaronitrile Terpolymers as a Potential Precursor for Carbon Fiber

    Siti Nurul Ain Md Jamil

    2014-09-01

    Full Text Available A synthesis of acrylonitrile (AN/butyl acrylate (BA/fumaronitrile (FN and AN/EHA (ethyl hexyl acrylate/FN terpolymers was carried out by redox polymerization using sodium bisulfite (SBS and potassium persulphate (KPS as initiator at 40 °C. The effect of comonomers, BA and EHA and termonomer, FN on the glass transition temperature (Tg and stabilization temperature was studied using Differential Scanning Calorimetry (DSC. The degradation behavior and char yield were obtained by Thermogravimetric Analysis. The conversions of AN, comonomers (BA and EHA and FN were 55%–71%, 85%–91% and 76%–79%, respectively. It was found that with the same comonomer feed (10%, the Tg of AN/EHA copolymer was lower at 63 °C compared to AN/BA copolymer (70 °C. AN/EHA/FN terpolymer also exhibited a lower Tg at 63 °C when compared to that of the AN/BA/FN terpolymer (67 °C. By incorporating BA and EHA into a PAN system, the char yield was reduced to ~38.0% compared to that of AN (~47.7%. It was found that FN reduced the initial cyclization temperature of AN/BA/FN and AN/EHA/FN terpolymers to 228 and 221 °C, respectively, in comparison to that of AN/BA and AN/EHA copolymers (~260 °C. In addition, FN reduced the heat liberation per unit time during the stabilization process that consequently reduced the emission of volatile group during this process. As a result, the char yields of AN/BA/FN and AN/EHA/FN terpolymers are higher at ~45.1% and ~43.9%, respectively, as compared to those of AN/BA copolymer (37.1% and AN/EHA copolymer (38.0%.

  6. Morphology of polystyrene-block-poly(styrene-co-acrylonitrile) and polystyrene-block-poly(styrene-co-acrylonitrile-co-5-vinyltetrazole) diblock copolymers prepared by nitroxide-mediated radical polymerization and „click“ chemistry

    Gromadzki, Daniel; Lokaj, Jan; Černoch, Peter; Diat, O.; Nallet, F.; Štěpánek, Petr

    2008-01-01

    Roč. 44, č. 1 (2008), s. 189-199. ISSN 0014-3057 R&D Projects: GA ČR GESON/06/E005 Grant ostatní: Marie Curie Fellowship(EU) HPMT-CT-2001-00396 Institutional research plan: CEZ:AV0Z40500505 Keywords : polystyrene-block-poly(styrene-co- acrylonitrile -co-5-vinyltetrazole) * TEMPO * click chemistry Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.143, year: 2008

  7. Pre-irradiation induced emulsion co-graft polymerization of acrylonitrile and acrylic acid onto a polyethylene nonwoven fabric

    A pre-irradiation induced emulsion co-graft polymerization method was used to introduce acrylonitrile and acrylic acid onto a PE nonwoven fabric. The use of acrylic acid is meant to improve the hydrophilicity of the modified fabric. The kinetics of co-graft polymerization were studied. The existence of polyacrylonitrile (PAN) and poly(acrylic acid) (PAAc) graft chains was proven by Fourier transform infrared spectroscopy (FTIR) analysis. The existence of the nitrile groups in the graft chains indicates that they are ready for further amidoximation and adsorption of heavy metal ions. - Highlights: • Acrylonitrile and acrylic acid were co-grafted onto a PE nonwoven fabric. • Pre-irradiation induced emulsion graft polymerization technique is applied. • The existence of AAc resulted in the increased hydrophilicity of the grafted fabric

  8. Ion complex membranes of acrylonitrile copolymers having methacrylic acid and amphiphilic quaternized ammonium groups for uracil molecular imprinting

    Copolymers having methacrylic acid and amphiphilic quaternized ammonium groups were used for preparation of molecular imprinting membrane of uracil (URA) template. The imprinted polymeric membranes were prepared by phase inversion molecular imprinting by using poly(acrylonitrile-co-methylacrylic acid) [P(AN-co-MAA)] and poly(acrylonitrile-co-vinylbenzyl-stearyldimethylamine chloride) [P(AN-co-SMA)]. Evidence confirmed that both copolymers were mixed to form ion complex by electrostatic interaction between the methacrylic acid and the quaternized ammonium groups. The electrostatic networks of the resultant membranes made the membrane dense and useful for molecule recognition of the template. The imprinted membranes made of different mole ratio of their copolymer segments were examined in binding of URA and other analog molecules

  9. Antibacterial activity of poly(vinyl alcohol)-b-poly(acrylonitrile) based micelles loaded with silver nanoparticles.

    Bryaskova, Rayna; Pencheva, Daniela; Kyulavska, Mariya; Bozukova, Dimitriya; Debuigne, Antoine; Detrembleur, Christophe

    2010-04-15

    A new amphiphilic poly(vinyl alcohol)-b-poly(acrylonitrile) (PVOH-b-PAN) copolymer obtained by selective hydrolysis of well-defined poly(vinyl acetate)-b-poly(acrylonitrile) copolymer synthesized by cobalt mediated radical polymerization was used for the preparation of PVOH-b-PAN based micelles with embedded silver nanoparticles. The successful formation of silver loaded micelles has been confirmed by UV-vis, DLS and TEM analysis and their antibacterial activity against Escherichia coli (E. coli), Staphylococcus aureus (S. aureus), Pseudomonas aeruginosa (P. aeruginosa) and spore solution of Bacillus subtilis (B. subtilis) has been studied. PVOH-b-PAN based micelles with embedded silver nanoparticles showed a strong bactericidal effect against E. coli, S. aureus and P. aeruginosa and the minimum bactericidal concentration for each system (MBC) has been determined. PMID:20074742

  10. Enhanced photorefractive performance in CdSe quantum-dot-dispersed poly(styrene-co-acrylonitrile) polymers

    This paper reports on the enhanced photorefractive behavior of a CdSe quantum-dot-dispersed less expensive polymer of poly(styrene-co-acrylonitrile). The capability of CdSe quantum dots used as photosensitizers and the associated photorefractive performance are characterized through a photocurrent experiment and a two-beam coupling experiment, respectively. An enhanced two-beam coupling gain coefficient of 12.2 cm-1 at 46 V/μm was observed owning to the reduced potential barrier. The photorefractive performance per CdSe quantum dot is three orders of magnitude higher than that in the sample sensitized by trinitrofluorenone in poly(styrene-co-acrylonitrile), and almost ten times higher than that in the CdSe quantum-dot-sensitized poly(N-vinylcarbazole) polymers.

  11. Conversion of ethanol to 1,3-butadiene over Na doped ZnxZryOz mixed metal oxides

    Baylon, Rebecca A.; Sun, Junming; Wang, Yong

    2016-01-01

    Despite numerous studies on different oxide catalysts for the ethanol to 1,3-butadiene reaction, few have identified active sites (i.e., type of acidity) correlated to the catalytic performances. In this work, the type of acidity needed for ethanol to 1,3-butadiene conversion has been studied over Zn/Zr mixed oxide catalysts. Specifically, synthesis method, Zn/Zr ratio, and Na doping have been used to control the surface acid-base properties, as confirmed by characterizations such as NH3-TPD and IR-Py techniques. The 2000 ppm Na doped Zn1Zr10Oz-H with balanced base and weak Bronsted acid sites was found to give not only high selectivity to 1,3-butadiene (47%) at near complete ethanol conversion (97%), but also exhibited a much higher 1,3-butadiene productivity than other mixed oxides studied.

  12. Synthesis of novel N-, S-substituted-polyhalo-1, 3-butadienes and crystal structure of dibutadienyl homopiperazine

    Nahide Gulsah Deniz; Cemil Ibis

    2013-07-01

    Polyhalogenated-2-nitro-1, 3-butadienes are important synthetic precursors for a variety of polyfunctionalized bioactive heterocycles. Herein, we report the reactions of 1, 1, 3, 4, 4-pentachloro-2-nitro-1, 3-butadiene 1 and 4-bromo-1, 1, 3, 4-tetrachloro-2-nitro-1, 3-butadiene 2 with amino and thiol containing nucleophiles to obtain highly functionalized (E)-polyhalodiene-2-nitro-1, 3-butadiene derivatives. Most of these reactions were found to be highly selective resulting in good to high yields of the products. All new compounds have been characterized by nuclear magnetic resonance spectroscopy (NMR), mass spectrometry (MS) and Fourier transform infrared spectroscopy (FT-IR) spectroscopic data. Single crystal X-ray structure analysis of compound 8c is reported.

  13. Synthesis and quaternization of nitroxide-terminated poly(4-vinylpyridine-co-acrylonitrile) macroinitiators and related diblock copolymers

    Poláková, Lenka; Lokaj, Jan; Holler, Petr; Starovoytova, Larisa; Pekárek, Michal; Štěpánek, Petr

    -, 065 (2010), s. 1-10. ISSN 1618-7229 R&D Projects: GA ČR GESON/06/E005; GA ČR GA203/07/0659 Institutional research plan: CEZ:AV0Z40500505 Keywords : 4-vinylpyridine-acrylonitrile copolymers * block copolymers * nitroxide-mediated radical polymerization Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.574, year: 2010 http://www.e-polymers.org/journal/papers/lpolakova_240710.pdf

  14. Investigation of the cathodic electropolymerization of acrylonitrile, ethylacrylate and methylmethacrylate by coupled quartz crystal microbalance analysis and cyclic voltammetry

    Baute, Noëlle; Martinot, Lucien; Jérôme, Robert

    1999-01-01

    The cathodic electropolymerization of acrylonitrile (AN), ethylacrylate (EA) and methylmethacrylate (MMA), has been monitored for the first time by coupled electrochemical quartz crystal microbalance (QCM) and cyclic voltammetry analyses. These data have been compared to the previously published analyses for methacrylonitrile (MAN). At the potential Ep1 of the less cathodic of the two voltammetric peaks observed (peak I), the polymer formed is anchored firmly to the cathode even in a good sol...

  15. The Effect of Uncertainty in Exposure Estimation on the Exposure-Response Relation between 1,3-Butadiene and Leukemia

    George Maldonado

    2009-09-01

    Full Text Available Abstract: In a follow-up study of mortality among North American synthetic rubber industry workers, cumulative exposure to 1,3-butadiene was positively associated with leukemia. Problems with historical exposure estimation, however, may have distorted the association. To evaluate the impact of potential inaccuracies in exposure estimation, we conducted uncertainty analyses of the relation between cumulative exposure to butadiene and leukemia. We created the 1,000 sets of butadiene estimates using job-exposure matrices consisting of exposure values that corresponded to randomly selected percentiles of the approximate probability distribution of plant-, work area/job group-, and year specific butadiene ppm. We then analyzed the relation between cumulative exposure to butadiene and leukemia for each of the 1,000 sets of butadiene estimates. In the uncertainty analysis, the point estimate of the RR for the first non zero exposure category (>0–<37.5 ppm-years was most likely to be about 1.5. The rate ratio for the second exposure category (37.5–<184.7 ppm-years was most likely to range from 1.5 to 1.8. The RR for category 3 of exposure (184.7–<425.0 ppm-years was most likely between 2.1 and 3.0. The RR for the highest exposure category (425.0+ ppm-years was likely to be between 2.9 and 3.7. This range off RR point estimates can best be interpreted as a probability distribution that describes our uncertainty in RR point estimates due to uncertainty in exposure estimation. After considering the complete probability distributions of butadiene exposure estimates, the exposure-response association of butadiene and leukemia was maintained. This exercise was a unique example of how uncertainty analyses can be used to investigate and support an observed measure of effect when occupational exposure estimates are employed in the absence of direct exposure measurements.

  16. Clusters of acrylonitrile in methanol/ethanol: A structure-spectra correlation by quantum chemical and polarized Raman study

    Graphical abstract: Ab initio and DFT calculations were performed to obtain the ground state geometry of neat acrylonitrile (C2H3C≡N, Acr), self-associated dimer, trimer and their hydrogen bonded complexes with methanol (M) and ethanol (E) in gas phase. Polarized Raman study was made for neat Acr and its binary mixtures with M/E. The ν(C≡N) line profile of neat Acr was analyzed to two component bands as free and self-associated Acr, respectively. The dephasing of the ν(C≡N) mode as a function of concentration was explained in terms of two contributions, one arising from micro viscosity dependence and the other from concentration fluctuation. Research highlights: → This paper deals with the Polarized Raman spectroscopic study of acrylonitrile and its hydrogen bonded complex with methanol and ethanol. → Quantum chemical study of molecular interactions of acrylonitrile clusters with methanol and ethanol. → Peak position and linewidth variation of ν(C≡N) stretching of acrylonitrile with concentration. → Spectra-structure correlation. - Abstract: Ab initio and DFT calculations were performed to obtain the ground state geometry of neat acrylonitrile (C2H3C≡N, Acr), self-associated dimer, trimer and their hydrogen bonded complexes with methanol (M) and ethanol (E) in gas phase. Polarized Raman study was made for neat Acr and its binary mixtures with M/E. The ν(C≡N) line profile of neat Acr was analyzed to two component bands at 2228.7 and 2226.9 cm-1 and attributed to free and self-associated Acr, respectively. The calculated ν(C≡N) mode of self-associated dimer/trimer complex and hydrogen bonded complex were compared with the experimentally observed Raman spectra. The dephasing of the ν(C≡N) mode as a function of concentration was explained in terms of two contributions, one arising from micro viscosity dependence and the other from concentration fluctuation. The viscosity dependent contribution, however, dominates over the concentration

  17. Oxidative Dehydrogenation of Butane to Butadiene and Butene Using a Novel Inert Membrane Reactor

    2000-01-01

    The oxidative dehydrogenation of butane to butadiene and butene was studied using a conventional fixed-bed ractor (FBR), inert membrane reactor (IMR) and mixed inert membrane reactor (MIMR). When IMR and MIMR were employed, a ceramic membrane modified by partially coating with glaze was used to distribute oxygen to a fixed-bed of 24-V-Mg-O catalyst. The oxygen partial pressure in the catalyst bed could be decreased. The effect of feeding modes and operation conditions were investigated. The selectivity of C4 dehydrogenation products (butene and butadiene) was found to be higher in IMR than in FBR. The feeding mode with 20% of air mixing with butane in MIMR was found to be more efficient than the feeding mode with all air permeating through ceramic membrane. The MIMR gave the most smooth temperature profile along the bed.

  18. Activation of CO2 in reaction with butadiene catalyzed by palladium

    Studies on the fixation of CO2 by transition-metal complexes has stimulated the authors to research the catalytic activation of CO2 in reactions with monoolefins, alkynes, allene, butadiene, and isoprene. To develop highly efficient and selectively acting catalysts, capable of activating CO2 under mild conditions, the authors studied the reaction of CO2 with butadiene in a DMFA solution by the action of the catalytic system Pd(acac)2-PPh3, widely used in telomerization of 1,3-dienes with H2O. Under the reaction conditions, low-valence phosphonic complexes of palladium catalyze the oxidation of triphenylphosphine to triphenylphosphine oxide and the reduction of CO2 to CO

  19. Palladium-Catalyzed Telomerization of Butadiene with Polyols: From Mono to Polysaccharides

    Bouquillon, Sandrine; Muzart, Jacques; Pinel, Catherine; Rataboul, Franck

    The telomerization of butadiene with alcohols is an elegant way to synthesize ethers with minimal environmental impact since this reaction is 100% atom efficient. Besides telomerization of butadiene with methanol and water that is industrially developed, the modification of polyols is still under development. Recently, a series of new substrates has been involved in this reaction, including diols, pure or crude glycerol, protected or unprotected monosaccharides, as well as polysaccharides. This opens up the formation of new products having specific physicochemical properties. We will describe recent advances in this field, focusing on the reaction of renewable products and more specifically on saccharides. The efficient catalytic systems as well as the optimized reaction conditions will be described and some physicochemical properties of the products will be reported.

  20. Innovative Neutron Shielding Material Composing of Natural Rubber-Styrene Butadiene Rubber Blends Diboron Trioxide

    The optimized flexible and lightweight neutron shielding materials were designed using the Monte Carlo N-Particle (MCNP) code. The neutron shielding materials thickness for 10 mm and 100 mm were considered for the neutron shielding performance. Results indicated that 10 mm shielding material of rubber compound between natural rubber (NR) and styrene butadiene rubber (SBR) blend (1:1) compose with diboron trioxide 60 phr and 100 mm shielding material for 4 layers structure of rubber compound between natural rubber (NR) and styrene butadiene rubber (SBR) blend compose with diboron trioxide 10 phr and rubber compound with iron oxide 100 phr offered advantages on neutron shielding compared to other designs. Experimental for these shielding material results verified the correctness of the optimal design and fabrication. The designed shielding materials are highly suitable for applications in nuclear science and technology.

  1. Modification of poly(styrene-block-butadiene-block-styrene) [SBS] with phosphorus containing fire retardants

    Chernyy, Sergey; Ullah, Saif; Jomaas, Grunde;

    2015-01-01

    An elaborate survey of the chemical modification methods for endowing highly flammable SBS with increased fire resistant properties by means of chemical modification of the polymer backbone with phosphorus containing fire retardant species is presented. Optimal conditions for free radical addition...... of the Psingle bondH containing fire retardants to a double bonds of poly(butadiene) block of SBS were found, affording varied degree of the modification (0.2–21 mol%). Alternatively, a two-step procedure based on an epoxidation step followed by hydrolysis of the epoxides with phosphoric acid was...... developed resulting in 20 mol% of poly(butadiene) block modification. Based on TGA results, organophosporus-modified SBS was found to be amenable to charring – a property which correlated directly with the reduced flammability of the modified polymer observed in Cone Calorimetry tests. Furthermore...

  2. Gamma Radiation Shielding Properties of Styrene- Butadiene Rubber/Lead Oxide Composites

    Styrene-butadiene rubber/lead oxide composites were prepared as gamma-radiation shields. The composites were prepared with different concentrations of red lead oxide (Pb3O4). The assessment of the linear attenuation coefficient of the SBR/lead oxide composites for gamma -rays from 137Cs gamma -radiation point source was studied. The styrene-butadiene rubber/lead oxide composites can attain up to about 43% of the shielding capacity of pure lead. The incorporation of high concentrations of lead oxide and the effect of accumulative irradiation doses up to 3000 kGy on the physico-mechanical properties of the composites were studied. These led to hardening of the SBR rubber/lead oxide composites

  3. Genotoxicity of 1,3-butadiene and its epoxy intermediates.

    Walker, Vernon E; Walker, Dale M; Meng, Quanxin; McDonald, Jacob D; Scott, Bobby R; Seilkop, Steven K; Claffey, David J; Upton, Patricia B; Powley, Mark W; Swenberg, James A; Henderson, Rogene F

    2009-08-01

    Current risk assessments of 1,3-butadiene (BD*) are complicated by limited evidence of its carcinogenicity in humans. Hence, there is a critical need to identify early events and factors that account for the heightened sensitivity of mice to BD-induced carcinogenesis and to deter-mine which animal model, mouse or rat, is the more useful surrogate of potency for predicting health effects in BD-exposed humans. HEI sponsored an earlier investigation of mutagenic responses in mice and rats exposed to BD, or to the racemic mixture of 1,2-epoxy-3-butene (BDO) or of 1,2,3,4-diepoxybutane (BDO2; Walker and Meng 2000). In that study, our research team demonstrated (1) that the frequency of mutations in the hypoxanthine-guanine phosphoribosyl transferase (Hprt) gene of splenic T cells from BD-exposed mice and rats could be correlated with the species-related differences in cancer susceptibility; (2) that mutagenic-potency and mutagenic-specificity data from mice and rats exposed to BD or its individual epoxy intermediates could provide useful information about the BD metabolites responsible for mutations in each species; and (3) that our novel approach to measuring the mutagenic potency of a given chemical exposure as the change in Hprt mutant frequencies (Mfs) over time was valuable for estimating species-specific differences in mutagenic responses to BD exposure and for predicting the effect of BD metabolites in each species. To gain additional mode-of-action information that can be used to inform studies of human responses to BD exposure, experiments in the current investigation tested a new set of five hypotheses about species-specific patterns in the mutagenic effects in rodents of exposure to BD and BD metabolites: 1. Repeated BD exposures at low levels that approach the occupational exposure limit for BD workers (set by the U.S. Occupational Safety and Health Administration) are mutagenic in female mice. 2. The differences in mutagenic responses of the Hprt gene to BD

  4. HPRT Mutations in Lymphocytes from 1,3-Butadiene-Exposed Workers in China

    Liu, Shengxue; Ao, Lin; Du, Bing; Zhou, Yanhong; Yuan, Jian; Bai, Yang; Zhou, Ziyuan; Cao, Jia

    2007-01-01

    Background 1,3-Butadiene (BD) is an important industrial chemical and an environmental and occupational pollutant. The carcinogenicity of BD in rodents has been proved, but its carcinogenic and mutagenic molecular mechanism(s) are not fully elucidated in humans. Objectives In the present study, we compared the mutation frequencies and exon deletions of BD-exposed workers with that of control subjects in China to identify the characteristic mutations associated with BD exposure in the human HP...

  5. New Piperazine Derivatives Synthesized from Thio-Substituted Polyhalogeno-2-nitro-1,3-butadienes

    S. Goksin Aydinli; Cemil Ibis

    2010-01-01

    It is known that polyhalogeno-nitro-1,3-butadienes are important starting materials for the synthesis of polyfunctionalized bioactive heterocycles. Novel N,S-substituted nitrobutadienes (4a-j) were synthesized from the reaction of the monothio-substituted nitrodiene derivatives (2a) and (2b) with some piperazine derivatives. These new compounds are stable and the structures of these products were characterized by spectroscopic data. The structure of the novel N,S-substituted nitrodiene compou...

  6. Thermal Stability and Flammability of Styrene-Butadiene Rubber-Based (SBR) Ceramifiable Composites

    Rafał Anyszka; Dariusz M. Bieliński; Zbigniew Pędzich; Przemysław Rybiński; Mateusz Imiela; Mariusz Siciński; Magdalena Zarzecka-Napierała; Tomasz Gozdek; Paweł Rutkowski

    2016-01-01

    Ceramifiable styrene-butadiene (SBR)-based composites containing low-softening-point-temperature glassy frit promoting ceramification, precipitated silica, one of four thermally stable refractory fillers (halloysite, calcined kaolin, mica or wollastonite) and a sulfur-based curing system were prepared. Kinetics of vulcanization and basic mechanical properties were analyzed and added as Supplementary Materials. Combustibility of the composites was measured by means of cone calorimetry. Their t...

  7. Microstructural analysis of carbon nanomaterials produced from pyrolysis/combustion of Styrene-Butadiene-Rubber (SBR)

    Joner Oliveira Alves; Chuanwei Zhuo; Yiannis Angelo Levendis; Jorge Alberto Soares Tenório

    2011-01-01

    Styrene-Butadiene-Rubber (SBR) is a synthetic rubber copolymer used to fabricate several products. This study aims to demonstrate the use of SBR as feedstock for carbon nanomaterials (nanofibers and nanotubes) growth, and therefore to establish a novel process for destination of waste products containing SBR. A three stage electrically heated flow reactor was used. Small pellets of rubber were pyrolyzed at a temperature of 1000 ºC. The pyrolyzates were mixed with oxygen-containing gases and w...

  8. Performance Analysis of Styrene Butadiene Rubber-Latex on Cement Concrete Mixes.

    Er. Kapil Soni; Dr. Y. P Joshi

    2014-01-01

    To improve the performance of concrete, polymers are mixed with concrete. It has been observed that polymer-modified concrete (PMC) is more durable than conventional concrete due to superior strength and high durability. In this research, effect of Styrene-Butadiene Rubber (SBR) latex on compressive strength and flexural strength of concrete has been studied and also the optimum polymer (SBR-Latex) content for concrete is calculated. This research was carried out to establish t...

  9. Synthesis and mutagenesis of the butadiene-derived N3 2'-deoxyuridine adducts.

    Fernandes, Priscilla H; Hackfeld, Linda C; Kozekov, Ivan D; Hodge, Richard P; Lloyd, R Stephen

    2006-07-01

    1,3-Butadiene is a known carcinogen and mutagen that acts through a variety of metabolic intermediates that react with DNA, forming stable and unstable lesions on dG, dA, dC, and dT. The N3 2'-deoxyuridine adducts are a highly stable, stereoisomeric mixture of adducts derived from the reaction of cytosine with the monoepoxide metabolite of butadiene, followed by spontaneous deamination. In this study, the phosphoramidites and subsequent oligodeoxynucleotides containing the N3 2'-deoxyuridine adducts have been constructed and characterized. Using a single-stranded shuttle vector DNA, the mutagenic potential of these adducts has been tested following replication in mammalian cells. Replication past the N3 2'-deoxyuridine adducts was found to be highly mutagenic with an overall mutation yield of approximately 97%. The major mutations that were observed were C to T transitions and C to A transversions. In vitro, these adducts posed a complete block to both the Klenow fragment of Escherichia coli polymerase I and polymerase epsilon, while these lesions significantly blocked polymerase delta. These data suggested a possible involvement of bypass polymerases in the in vivo replication of these lesions. Overall, these findings indicate that the N3 2'-deoxyuridine adducts are highly mutagenic lesions that may contribute to butadiene-mediated carcinogenesis. PMID:16841966

  10. Inhalation developmental toxicology studies: Teratology study of 1,3-butadiene in mice: Final report

    Hackett, P.L.; Sikov, M.R.; Mast, T.J.; Brown, M.G.; Buschbom, R.L.; Clark, M.L.; Decker, J.R.; Evanoff, J.J.; Rommereim, R.L.; Rowe, S.E.; Westerberg, R.B.

    1987-11-01

    Maternal toxicity, reproductive performance and developmental toxicology were evaluated in CD-1 mice following whole-body, inhalation exposures to 0, 40, 200 and 1000 ppM of 1,3-butadiene. The female mice, which had mated with unexposed males were exposed to the chemical for 6 hours/day on 6 through 15 dg and sacrificed on 18 dg. Maternal animals were weighed prior to mating and on 0, 6, 11 and 18 dg; the mice were observed for mortality, morbidity and signs of toxicity during exposure and examined for gross tissue abnormalities at necropsy. Live fetuses were weighed and subjected to external, visceral and skeletal examinations to detect growth retardation and morphologic anomalies. Significant concentration-related decreases were detected in a number of maternal body weight measures. There was a significant concentration-related depression of fetal body weights and placental weights. Body weights of male fetuses of all exposed groups were significantly lower than values for control fetuses; weights of female fetuses were significantly depressed in the mice exposed to 200 and 1000 ppM. In the 200- and 1000-ppM exposure groups, weights of placentas of male fetuses were significantly decreased, but placental weights of female fetuses were significantly affected only in litters exposed to the highest 1,3-butadiene concentration. This exposure regimen produced significant signs of maternal toxicity at concentrations of 200 and 1000 ppM 1,3-butadiene.

  11. Atmospheric pressure plasma polymerization of 1,3-butadiene for hydrophobic finishing of textile substrates

    Atmospheric pressure plasma processing of textile has both ecological and economical advantages over the wet-chemical processing. However, reaction in atmospheric pressure plasma has important challenges to be overcome before it can be successfully used for finishing applications in textile. These challenges are (i) generating stable glow plasma in presence liquid/gaseous monomer, and (ii) keeping the generated radicals active in the presence of contaminants such as oxygen and air. In this study, a stable glow plasma was generated at atmospheric pressure in the mixture of gaseous reactive monomer-1,3-butadiene and He and was made to react with cellulosic textile substrate. After 12 min of plasma treatment, the hydrophilic surface of the cellulosic substrate turned into highly hydrophobic surface. The hydrophobic finish was found to be durable to soap washing. After soap washing, a water drop of 37 μl took around 250 s to get absorbed in the treated sample compared to 0. Both top and bottom sides of the fabric showed similar hydrophobic results in terms of water absorbency and contact angle. The results may be attributed to chemical reaction of butadiene with the cellulosic textile substrate. The surface characterization of the plasma modified samples under SEM and AFM revealed modification of the surface under <100 nm. The results showed that atmospheric pressure plasma can be successfully used for carrying out reaction of 1,3-butadiene with cellulosic textile substrates for producing hydrophobic surface finish.

  12. Preirradiation grafting of acrylonitrile onto polypropylene monofilament for biomedical applications: I. Influence of synthesis conditions

    Graft polymerization of acrylonitrile onto polypropylene (PP) monofilament was carried out by a preirradiation method using a 6Co gamma radiation source. The influence of synthesis conditions, such as preirradiation dose, reaction time, monomer concentration, reaction temperature and additives was determined. The grafting was considerably influenced by the instantaneous swelling of the monofilament in the reaction mixture during the course of the grafting process. The order of dependence of the rate of grafting on monomer concentration was found to be 1.04. The nature of the medium of the grafting and the additives had profound influence over the grafting reaction. The accelerative effects of solvent medium on the grafting were higher in methylethyl ketone (MEK) and dimethylformamide (DMF) as compared to methanol. At the same time, partial replacement of DMF with water led to acceleration in the grafting with peak maxima at 20% solvent composition. The addition of a small amount of sulfuric acid to the reaction mixture also resulted in a significant acceleration of the degree of grafting

  13. Nanostructured synthetic carbons obtained by pyrolysis of spherical acrylonitrile/divinylbenzene copolymers.

    Danish J Malik

    Full Text Available Novel carbon materials have been prepared by the carbonization of acrylonitrile (AN/divinylbenzene (DVB suspension porous copolymers having nominal crosslinking degrees in the range of 30-70% and obtained in the presence of various amounts of porogens. The carbons were obtained by pre-oxidation of AN/DVB copolymers at 250-350°C in air followed by pyrolysis at 850°C in an N(2 atmosphere. Both processes were carried out in one furnace and the resulting material needed no further activation. Resulting materials were characterized by XPS and low temperature nitrogen adsorption/desorption. It was found that maximum pyrolysis yield was ca. 50% depending on the oxidation conditions but almost independent of the crosslinking degree of the polymers. Porous structure of the carbons was characterized for the presence of micropores and macropores, when obtained from highly crosslinked polymers or polymers oxidized at 350°C and meso- and macropores in all other cases. The latter pores are prevailing in the structure of carbons obtained from less porous AN/DVB resins. Specific surface area (BET of polymer derived carbons can vary between 440 m(2/g and 250 m(2/g depending on the amount of porogen used in the synthesis of the AN/DVB polymeric precursors.

  14. AGET ATRP of acrylonitrile with ionic liquids as reaction medium without any additional ligand

    Atom transfer radical polymerization using activators generated by electron transfer (AGET ATRP) of acrylonitrile (AN) was carried out for the first time in 1-methylimidazolium acetate ([mim][AT]), 1-methylimidazolium propionate([mim][PT]), and 1-methylimidazolium butyrate ([mim][BT]), respectively. The polymerization was approached by using ascorbic acid (VC) as a reducing agent, ethyl 2-bromoisobutyrate (EBiB) as initiator, only FeBr3 as catalyst without any additional ligand. Kinetic studies showed that both AGET ATRP of AN in the absence of oxygen and in the presence of air proceeded in a well-controlled manner. Under the same conditions, the polymerization in the presence of air provided rather slower reaction rate and showed better control of molecular weight and its distribution than in the absence of oxygen. The sequence of the apparent polymerization rate constants of AGET ATRP of AN in three ionic liquids was kapp([mim][AT]) > kapp([mim][PT]) > kapp([mim][BT]). The living nature of the polymerization was confirmed by chain end analysis and block copolymerization of methyl methacrylate with polyacrylonitrile as macroinitiator. All the three ionic liquids and FeBr3 could be recycled and reused and had no effect on the living nature of polymerization.

  15. Kinetic studies of uranyl ion adsorption on acrylonitrile (AN) / polyethylene glycol (PEG) interpenetrating networks (IPN)

    The kinetics of the adsorption of uranyl ions on amidoximated acrylonitrile (AN)/ polyethylene glycol (PEG) interpenetrating network (IPNs) from aqueous solutions was studied as a function of time and temperature. Adsorption analyses were performed for definite uranyl ion concentrations of 1x10-2M and at four different temperatures as 290K, 298K, 308K and 318K. Adsorption time was increased from zero to 48 hours. Adsorption capacities of uranyl ions by PEG/AN IPNS were determined by gamma spectrometer. The results indicate that adsorption capacity increases linearly with increasing temperature. The max adsorption capacity was found as 602 mgu/g IPN at 308K. Adsorption rate was evaluated from the curve plotted of adsorption capacity versus time, for each temperature. Rate constants for uranyl ions adsorption on amidoximated ipns were calculated for 290K, 298K, 308K and 318K at the solution concentration of 1x10-2M . The results showed that as the temperature increases the rate constant increases exponentially too. The mean activation energy of uranyl ions adsorption was found as 34.6 kJ/mole by using arrhenius equation. (author)

  16. Regenerated thermosetting styrene-co-acrylonitrile sandwich composite panels reinforced by jute fibre: structures and properties

    Jinglong Li; Qin Peng; Anrong Zeng; Junlin Li; Xiaole Wu; Xiaofei Liu

    2016-02-01

    Jute fibres-reinforced sandwich regenerated composite panels were fabricated using industrial waste thermosetting styrene-co-acrylonitrile (SAN) foam scraps via compression moulding for the purpose of recycling waste SAN foam and obtaining high physical performance. The jute fibres were, respectively, treated by heat, sodium hydroxide (NaOH) solution (5.0 wt%), and N,N-dimethylacetamide (DMAc) in order to improve the mechanical properties of the composites. The structures and mechanical properties of the composites were studied. The SAN matrix got compact and some crystalline region formed in SAN matrix via compression moulding. The composite reinforced by DMAc-treated jute fibres performed optimum mechanical properties among the regenerated panels whose impact strength, flexural strength, and compressive strength were 19.9 kJ m−2, 41.7 MPa, and 61.0 MPa, respectively. Good interfacial bonding between DMAc-treated fibres and SAN matrix was verified by peel test and exhibited in SEM photographs. Besides, the water absorption of DMAc-treated fibres composite was lower than other SAN/jute fibre-reinforced sandwich composite panels.

  17. Covalent Immobilization of Lipase on Poly ( acrylonitrile-co-maleic acid) Ultrafiltration Hollow Fiber Membrane

    YE Peng; XU Zhi-kang; WU Jian; DENG Hong-tao; SETA Patrick

    2005-01-01

    Lipase from Candida rugosa was covalently immobilized on the surface of an ultrafiltration hollow fiber membrane fabricated from poly (acrylonitrile-co-maleic acid) (PANCMA) in which the carboxyl groups were activated with 1-ethyl-3-(dimethylaminopropyl) carbodiimide hydrochloride (EDC) and dicyclohexyl carbodiimide (DCC)/N-hydroxyl succinimide(NHS), respectively. The properties of the immobilized lipase were assayed and compared with those of the free enzyme. The maximum activities were observed in a relatively broader pH value range at high temperatures for the immobilized lipase compared to the free one. It was also found that the thermal and pH stabilities of lipase were improved upon immobilization and at 50 ℃ the thermal inactivation rate constant values are 2.1×10-2 for the free lipase, 3.2×10-3 for the immobilized lipase on the EDC-activated PANCMA membrane and 3.5×10-3 for the immobilized lipase on the DCC/NHS-activated PANCMA membrane, respectively.

  18. Preparation and evaluation of some investigated natural and acrylonitrile rubber vulcanizations for physiotherapeutic purposes

    A trial was made to design and prepare rubber article that can be used to reactivate, strengthen and reinforce the hand muscles and fingers which had suffered from trouble movement.The investigated rubber article was prepared from natural and acrylonitrile rubber formulations. These formulations were processed in the form of compounds which contain significant quantities of fillers as Hisil, CaCO3 and TiO2.The rheological characteristics and physicochemical properties of the vulcanizations were determined according to standard tests. It was found that it is possible to prepare the designated rubber article for the desired purpose. The test results show that the prepared rubber article has a good chemical resistant against acid, alkali, and salt. Also it possesses high resistance to deterioration and deformation. The prepared article has an ability to retain its elastic property after the action of compressive forces at 70 degree C for 24 hours.This was conformed with applied commercial hand exercise therapeutic article

  19. Optical properties of polycarbonate/styrene-co-acrylonitrile blends: effects of molecular weight of the matrix.

    Yi, Ping; Xiong, Ying; Guo, Shaoyun

    2015-12-01

    In this paper, the effects of the molecular weight of a polycarbonate (PC) matrix on the phase morphology and optical properties of a PC/styrene-co-acrylonitrile (SAN) blend were investigated. A scanning electron microscope is used to analyze the phase morphology of the blends, and Mie scattering theory is used to analyze the changing laws of the optical properties of PC/SAN blends with the increasing of PC molecular weight. Results show that the average particle diameter is not strongly changed with different PC molecular weight because the values of the viscosity ratios are very close to each other. But it is obvious that the number of large particles gradually reduced while small particles (especially dmolecular weight. And the increase in small particles will result in an increase in backward scattering so the transmittance of PC/SAN blends decreases with the increase of PC molecular weight. However, the balance of the scattering coefficients and the number concentration of particles eventually lead to the haze of the blends being very close, despite having different PC molecular weights. Meanwhile, the photographs of scattering patterns indicate that the PC/SAN blends whose component weight ratios are fixed at 70:30 have excellent antiglare properties, despite the changes in molecular weight of the PC matrix. PMID:26836652

  20. Peroxydisulfate initiated synthesis of potato starch-graft-poly(acrylonitrile under microwave irradiation

    2007-01-01

    Full Text Available Potato starch-graft-poly(acrylonitrile could be efficiently synthesized using small concentration of ammonium peroxydisulfate (0.0014M in aqueous medium under microwave irradiation. A representative microwave synthesized graft copolymer was characterized using Fourier Transform Infrared Spectroscopy, X-ray Diffraction, Scanning Electron Microscopy and Thermogravimetric Analysis. Under microwave conditions oxygen removal from the reaction vessel was not required and the graft copolymer was obtained in high yield using very small amount of ammonium peroxydisulfate, however using the same amount of ammonium peroxydisulfate (0.0014M on thermostatic water bath no grafting was observed up to 98°C (even in inert atmosphere. Raising the concentration of the initiator to 0.24 M resulted into 10% grafting at 50 °C but in inert atmosphere.The viscosity/shear stability of the grafted starch (aqueous solution and water/saline retention ability of the microwave synthesized graft copolymer were also studied and compared with that of the native potato starch.

  1. AGET ATRP of acrylonitrile with ionic liquids as reaction medium without any additional ligand

    Chen Hou, E-mail: lduchenhou@hotmail.com [School of Chemistry and Materials Science, Ludong University, Yantai 264025 (China); Liang Ying; Liu Delong; Tan Zhi; Zhang Shaohong; Zheng Meiling; Qu Rongjun [School of Chemistry and Materials Science, Ludong University, Yantai 264025 (China)

    2010-05-10

    Atom transfer radical polymerization using activators generated by electron transfer (AGET ATRP) of acrylonitrile (AN) was carried out for the first time in 1-methylimidazolium acetate ([mim][AT]), 1-methylimidazolium propionate([mim][PT]), and 1-methylimidazolium butyrate ([mim][BT]), respectively. The polymerization was approached by using ascorbic acid (VC) as a reducing agent, ethyl 2-bromoisobutyrate (EBiB) as initiator, only FeBr{sub 3} as catalyst without any additional ligand. Kinetic studies showed that both AGET ATRP of AN in the absence of oxygen and in the presence of air proceeded in a well-controlled manner. Under the same conditions, the polymerization in the presence of air provided rather slower reaction rate and showed better control of molecular weight and its distribution than in the absence of oxygen. The sequence of the apparent polymerization rate constants of AGET ATRP of AN in three ionic liquids was k{sub app}([mim][AT]) > k{sub app}([mim][PT]) > k{sub app}([mim][BT]). The living nature of the polymerization was confirmed by chain end analysis and block copolymerization of methyl methacrylate with polyacrylonitrile as macroinitiator. All the three ionic liquids and FeBr{sub 3} could be recycled and reused and had no effect on the living nature of polymerization.

  2. 国内外丙烯腈供需现状和发展趋势%Global Supply & Demand Situation and Developing Trend of Acrylonitrile

    吴宇红

    2012-01-01

    介绍了丙烯腈的国内外供需现状,分析了未来丙烯腈装置的投资计划及下游应用领域的需求情况,并预测了未来丙烯腈供需状况。估计到2015年全球丙烯腈产能将出现过剩,投资还需谨慎。%The global supply and demand situation of acrylinitrile was introduced.Based on anaysis of acrylinitrile plant investment plans and demand situation of downstream application filelds,the supply and demand situation of acrylonitrile in the future was predicted.It is predicted that global acrylonitrile capability would be surplus by 2015,so investment on acrylonitrile needs discretion.

  3. Uptake of one and two molecules of 1,3-butadiene by platinum bis(dithiolene): a theoretical study.

    Dang, Li; Ni, Shao Fei; Hall, Michael B; Brothers, Edward N

    2014-09-15

    Platinum bis(dithiolene) complexes have reactivity toward alkenes like nickel bis(dithiolene) complexes. We examined the uptake of 1,3-butadiene by platinum bis(dithiolene) [Pt(tfd)2] (tfd = S2C2(CF3)2) via a density functional theory study; both 1,2- and 1,4-additions of 1,3-butadiene to the ligands of Pt(tfd)2 to form both interligand and intraligand adducts were studied. For single 1,3-butadiene addition, direct 1,4-addition on interligand S-S, 1,2-addition on intraligand S-S, and 1,4-addition on intraligand S-C are all feasible at room temperature and are controlled by the symmetry of the highest occupied molecular orbital of 1,3-butadiene and the lowest unoccupied molecular orbital of Pt(tfd)2. However, the formation of the interligand S-S adduct through 1,4-addition of one molecule of cis-1,3-butadiene is the most favorable route, with a reaction barrier of 9.3 kcal/mol. The other two addition processes cannot compete with this one due to both higher reaction barriers and unstable adducts. Other possible pathways, such as formation of cis-interligand S-S adduct from 1,2-addition of one molecule of 1,3-butadiene via a twisted trans-interligand S-S adduct, have higher barriers. Our calculated results show that 1,4-addition of a single molecule of 1,3-butadiene on the interligand S-S gives the kinetically stable product by a one-step pathway. But of at least equal importance is the apofacial 1,4-addition of two molecules of 1,3-butadiene on the intraligand S-C of the same ligand on Pt(tfd)2, which yields the thermodynamically stable product, obtained via a short lifetime intermediate, the 1:1 intraligand S-C adduct, being formed through several pathways. The calculated results in this study well explain the experimental observation that 1:1 interligand S-S adduct was formed in a short time, and the intraligand S-C adduct from two molecules of cis-1,3-butadiene was accumulated in 20 h at 50° and characterized by X-ray crystallography. PMID:25184506

  4. Modification of fiber properties through grafting of acrylonitrile to rayon by chemical and radiation methods

    Inderjeet Kaur

    2013-11-01

    Full Text Available Fibrous properties of rayon has been modified through synthesis of graft copolymers of rayon with acrylonitrile (AN by chemical method using ceric ammonium nitrate (CAN/HNO3 as a redox initiator and gamma radiation mutual method. Percentage of grafting (Pg was determined as a function of initiator concentration, monomer concentration, irradiation dose, temperature, time of reaction and the amount of water. Maximum percentage of grafting (160.01% using CAN/HNO3 was obtained at [CAN] = 22.80 × 10−3 mol/L, [HNO3] = 112.68 × 10−2 mol/L and [AN] = 114.49 × 10−2 mol/L in 20 mL of water at 45 °C within 120 min while in case of gamma radiation method, maximum Pg (90.24% was obtained at an optimum concentration of AN of 76.32 × 10−2 mol/L using 10 mL of water at room temperature with total dose exposure of 3.456 kGy/h. The grafted fiber was characterized by FTIR, SEM, TGA and XRD studies. Swelling behavior of grafted rayon in different solvents such as water, methanol, ethanol, DMF and acetone was studied and compared with the unmodified rayon. Dyeing behavior of the grafted fiber was also investigated.

  5. Dynamic and kinetic aspects of the adsorption of acrylonitrile on Si(001)-2x1

    Using scanning tunnelling microscopy (STM), photoelectron and photoabsorption spectroscopies, we have examined how acrylonitrile (H2C=CH-C≡N) reacts with the Si(001)-2x1 surface for coverages ranging from ∼1012 molecules/cm2 to ∼1014 molecules/cm2. At 300 K, in the very low coverage regime (below 1013 molecules/cm2), filled- and empty-state STM images show that the molecule bridges, via its β carbon and nitrogen ends, two silicon dangling bonds, across the trench separating two dimer rows. A cumulative-double-bond unit (C=C=N) is formed. The 300 K STM image results from the dynamic flipping of the molecule between two equivalent equilibrium positions, which can be seen when the molecular motion is slowed down at 80 K. For coverages larger than 1013 molecules/cm2, for which STM does not show ordered adsorption any more, the adsorption kinetics were observed in real-time using valence band photoemission and resonant Auger yield, associated with N 1s x-ray absorption spectroscopy (NEXAFS). At 300 K, these techniques point to a situation more complex than the one explored by STM at very low coverage. Three species (cyano-bonded, vinyl-bonded, and cumulative-double-bond species) are detected. Their distribution does not vary with increasing coverage. All dimerization-related surface states are quenched at saturation. The uptake rates versus coverage relationship points to the presence of a mobile precursor. Finally, the paper discusses a possible mechanism leading to the formation of cross-trench C=C=N unit at low coverage, and the reasons why the product branching ratio changes with increasing coverage

  6. Nanofibrous poly(acrylonitrile-co-maleic acid) membranes functionalized with gelatin and chitosan for lipase immobilization.

    Ye, Peng; Xu, Zhi-Kang; Wu, Jian; Innocent, Christophe; Seta, Patrick

    2006-08-01

    Nanofibrous membranes with an average diameter of 100 and 180 nm were fabricated from poly(acrylonitrile-co-maleic acid) (PANCMA) by the electrospinning process. These nanofibrous membranes contain reactive groups which can be used to covalently immobilize biomacromolecules. Two natural macromolecules, chitosan and gelatin, were tethered on these nanofibrous membranes to fabricate dual-layer biomimetic supports for enzyme immobilization in the presence of 1-ethyl-3-(dimethyl-aminopropyl) carbodiimide hydrochloride (EDC)/N-hydroxyl succinimide (NHS). Lipase from Candida rugosa was then immobilized on these dual-layer biomimetic supports using glutaraldehyde (GA), and on the nascent PANCMA fibrous membrane using EDC/NHS as coupling agent, respectively. The properties of the immobilized lipases were assayed. It was found that there is an increase of the activity retention of the immobilized lipase on the chitosan-modified nanofibrous membrane (45.6+/-1.8%) and on the gelatin-modified one (49.7+/-1.8%), compared to that on the nascent one (37.6+/-1.8%). The kinetic parameters of the free and immobilized lipases, K(m) and V(max), were also assayed. In comparison with the immobilized lipase on the nascent nanofibrous membrane, there is an increase of the V(max) value for the immobilized lipases on the chitosan- and gelatin-modified nanofibrous membranes. Results also indicate that the pH and thermal stabilities of lipases increase upon immobilization. The residual activities of the immobilized lipases are 55% on the chitosan-modified nanofibrous membrane and 60% on the gelatin-modified one, after 10 uses. PMID:16584770

  7. Chitosan-tethered poly(acrylonitrile-co-maleic acid) hollow fiber membrane for lipase immobilization.

    Ye, Peng; Xu, Zhi-Kang; Che, Ai-Fu; Wu, Jian; Seta, Patrick

    2005-11-01

    A protocol was used to prepare a dual-layer biomimetic membrane as support for enzyme immobilization by tethering chitosan on the surface of poly(acrylonitrile-co-maleic acid) (PANCMA) ultrafiltration hollow fiber membrane in the presence of 1-ethyl-3-(dimethylaminopropyl) carbodiimide hydrochloride (EDC)/N-hydroxylsuccin-imide (NHS). The chemical change of the chitosan-modified PANCMA membrane surface was confirmed with Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Lipase from Candida rugosa was immobilized on this dual-layer biomimetic membrane using glutaraldehyde (GA), and on the nascent PANCMA membrane using EDC/NHS as coupling agent. The properties of the immobilized enzymes were assayed and compared with those of the free one. It was found that both the activity retention of the immobilized lipase and the amount of bound protein on the dual-layer biomimetic membrane (44.5% and 66.5 mg/m2) were higher than those on the nascent PANCMA membrane (33.9% and 53.7 mg/m2). The kinetic parameters of the free and immobilized lipases, Km and Vmax, were also assayed. The Km values were similar for the immobilized lipases, while the Vmax value of the immobilized lipase on the dual-layer biomimetic membrane was higher than that on the nascent PANCMA membrane. Results indicated that the pH and thermal stabilities of lipase increased upon immobilization. The residual activity of the immobilized lipase after 10 uses was 53% on the dual-layer biomimetic membrane and 62% on the nascent PANCMA membrane. PMID:15919112

  8. Microporous poly(acrylonitrile-methyl methacrylate) membrane as a separator of rechargeable lithium battery

    We studied microporous poly(acrylonitrile-methyl methacrylate), AMMA, membrane as the separator of Li/LiMn2O4 cell. The porous AMMA membrane was prepared by the phase inversion method with N,N-dimethylformamide (DMF) as the solvent and water as the non-solvent. We observed that morphology of the resulting membrane was strongly affected by the concentration of polymer solution: low concentration produced finger-like pores with dense skin on two surfaces of the membrane, while high concentration yielded open voids with dense layer on the other surface of the membrane. Regardless of their morphology, both membranes could be rapidly wetted by the liquid electrolyte (1.0 m LiBF4 dissolved in 1:3 wt.% mixture of ethylene carbonate (EC) and γ-butyrolactone (GBL)), and could be swollen at elevated temperatures, which resulted in the formation of a microporous gel electrolyte (MGE). It was shown that the resulting MGE not only had high ionic conductivity and but also had good compatibility with metal lithium even at 60 deg. C. Cyclic voltammetric test showed that the MGE had an electrochemical window of 4.9 V versus Li+/Li. At room temperature, the Li/MGE/LiMn2O4 cell showed excellent cycliability with a specific capacity of 121-125 mA h g-1 LiMn2O4. It was shown that even at 60 deg. C good mechanical strength of the MGE remained. Therefore, the MGE is suitable for the application of battery separator at elevated temperatures

  9. Pre-irradiation grafting of acrylonitrile onto chitin for adsorption of arsenic in water

    Radiation-induced grafting is an effective technique for preparation of novel materials. In this study, partially deacetylated chitin with deacetylation degree (DDA) of about 40% was graft-copolymerized with acrylonitrile (AN) by a γ-ray pre-irradiation method. The maximal grafting degree of AN onto pre-irradiated chitin at 25±1.2 kGy was 114% for AN concentration in dimethylformamide of 40% (v/v) at 70 °C for 8 h. The mixture ratio of 0.1 N NH2OH·HCl to 0.1 N NaOH was selected to be 7:3 (v/v) for amidoxime conversion of cyano-groups on grafted chitin (Chi-g-AN). The characteristics of modified chitin were depicted by the FT-IR spectra, BET area and SEM images. Adsorption equilibrium of As(III) onto Chi-g-AN converted amidoxime (Chi-g-AN-C) fits with the Langmuir model and the maximal adsorption capacity was 19.724 mg/g. The break-through times of As(III) on Chi-g-AN-C in column adsorption experiments increased with the increase in bed depths. - Highlights: • Partially deacetylated chitin was used for grafting AN by pre-irradiation. • The maximal grafting degree of AN onto chitin was 114%. • The cyano- of AN was converted into amidoxime to enhance adsorption. • The adsorption capacity of As(III) onto modified chitin was 19.724 mg/g. • Removal of arsenic in groundwater samples was tested by continuous adsorption

  10. Modeling contaminant transport and remediation at an acrylonitrile spill site in Turkey

    Şengör, S. Sevinç; Ünlü, Kahraman

    2013-07-01

    The August 1999 earthquake in Turkey damaged three acrylonitrile (AN) storage tanks at a plant producing synthetic fiber by polymerization. A numerical modeling study was carried out to analyze the groundwater flow and contaminant (AN) transport at the spill site. This study presents the application of a numerical groundwater model to determine the hydrogeological parameters of the site, where such data were not available during the field surveys prior to the simulation studies. The two- and three-dimensional transient flow and transport models were first calibrated using the first 266 days of observed head and concentration data and then verified using the remaining 540-day observed data set. Off-site migration of the contaminant plume was kept under control within the site boundaries owing to the favorable geology of the site, the characteristics of the local groundwater flow regime and the pumping operations. As expected, the applied pump-and-treat system was effective at high-permeability zones, but not fully effective at low-permeability zones. The results of long-term simulations for unconfined aquifer showed that the size of the plume in the high permeability zone shrank significantly due to the dilution by natural recharge. However, in the low permeability zone, it was not significantly affected. The study showed that accurate and sufficient data regarding the source characteristics, concentration and groundwater level measurements, groundwater pumping rates and their durations at each of the extraction points involved in the pump-and-treat system along with the hydrogeological site characterization are the key parameters for successful flow and transport model calibrations.

  11. Radiation grafting of acrylonitrile on ethylene-propylene diene terpolymer rubber. Optimization of grafting parameters and oil resistance properties

    Radiation induced grafting of acrylonitrile (ACN) on ethylene-propene diene terpolymer (EPDM) rubber film was investigated by mutual radiation grafting technique. Effect of experimental variables viz. radiation dose, dose rate, type of solvent and monomer content on extent of grafting was studied. From the kinetic studies a mathematical relation Rgα[M]0.7D0.68 showing non-linear relationship for rate of grafting with monomer concentration and dose was deduced. The grafted samples showed increased hardness and oil resistance. (author)

  12. SELECTIVE SEPARATION OF WATER—ETHANOL MIXTURE THROUGH COPOLYMERIC MEMBRANES.Ⅱ.ACRYLONITRILE AND MALEIC ANHYDRIDE COPOLYMERIC MEMBRANES

    ZHangFuyao; ZhangYifeng; 等

    1993-01-01

    Acrylonitrile(AN) and maleic anhydride(MA) copolymer has been synthesized by radical polymerization using ammonium persulfate and sodium bisulfite as initiator.The pervaporation properties of the copolymeric membranes prepared have been investigated for the first time. The dependences of pervaporation characteristics on coplymer composition,feed concentration and operating temperature have been studied.In order to improve the separation properties of the copolymeric membranes,the membranes were hydrolyzed with 10 wt% soldium hydroxide or potassium hydroxide aqueous solution.The hydrolyzed membranes containing more than 0.069MA mol fraction showed higher tensile strength and separation properties than the original membranes.

  13. Towards quantification of butadiene content in styrene-butadiene block copolymers and their blends with general purpose polystyrene (GPPS) and the relation between mechanical properties and NMR relaxation times

    The properties of styrene-butadiene-styrene (SBS) block copolymers do not only depend on the butadiene content and the degree of polymerisation but also on their chain architecture. In this contribution we present the results of a low-field time domain (TD) NMR study in which the transverse relaxation behaviour of different SBS block copolymers was analysed and correlated with findings from mechanical testing on pure and blended materials and transmission electron microscopy data which provide information on the microphase separation. The results indicate that while a straightforward determination of the butadiene content as in blended materials like ABS is not possible for these materials, the TD-NMR results correlate quite well with the mechanical performance of blends from SBS block copolymers with general purpose polystyrene (GPPS), i.e. industrial grade homopolymer polystyrene. Temperature-dependent experiments on pure and blended materials revealed a slight reduction in the softening temperature of the GPPS fraction in the blends

  14. Mutations induced by 1,3-butadiene metabolites, butadiene diolepoxide, and 1,2,3,4-diepoxybutane at the Hprt locus in CHO-K1 cells.

    Lee, Dong-Hyun; Kim, Tae-Ho; Lee, Sun-Young; Kim, Hyun-Jo; Rhee, Seung Keun; Yoon, ByoungSu; Pfeifer, Gerd P; Lee, Chong-Soon

    2002-12-31

    Butadiene (BD) is an important industrial chemical that is classified as a probable human carcinogen. Butadiene diolepoxide (BDE) and 1,2,3,4-diepoxybutane (DEB) are metabolites of carcinogenic BD and contain the DNA-reactive one and two epoxides, respectively. In this study, the mutation frequencies and mutation spectra that are induced by BDE and DEB have been investigated at the hprt locus in CHO-K1 cells. The BDE- and DEB-treated CHO-K1 cells were allowed to grow for several days, then seeded in a medium that contained 6-thioguanine in order to select the hprt mutants. BDE exhibited the mutagenic activity at concentrations that were approximately 100-times higher than DEB. The mutation spectra for BDE and DEB were determined by a reverse transcription-polymerase chain reaction of hprt mRNA, which was followed by automatic DNA sequencing of the PCR products. The mutational spectrum for BDE was exon deletions (16/41), G x C --> A x T transitions (11/41), and A x T --> G x C transitions (5/41). The mutational spectrum for DEB was exon deletions (15/39), G x C --> A x T transitions (11/39), and A x T --> T x A transversions (5/39). The most common base substitution that was induced by both BDE and DEB was G x C --> A x T transitions. The sites of the single base substitutions that were induced by BDE and DEB were guanine and adenine, which was consistent with the DNA adduct profiles. The high frequencies of the exon deletions by each metabolite occurred in the regions of exons 2, 3, or 4. These data indicate that BDE and DEB are mutagenic carcinogens by forming DNA adducts at the site of adenine and guanine, and inducing large exon deletions and single base substitutions. PMID:12521305

  15. Inhalation developmental toxicology studies of 1,3-butadiene in the rat: Final report

    Hackett, P.L.; Sikov, M.R.; Mast, T.J.; Brown, M.G.; Buschbom, R.L.; Clark, M.L.; Decker, J.R.; Evanoff, J.J.; Rommereim, R.L.; Rowe, S.E.; Westerberg, R.B.

    1987-11-01

    Maternal toxicity, reproductive performance and developmental toxicology were evaluated in Sprague-Dawley-derived rats during and following 6 hours/day, whole-body, inhalation exposures to 0, 40, 200, and 1000 ppM of 1,3-butadiene. The female rats (Ns = 24 to 28), which had mated with unexposed males, were exposed to the chemical from 6 through 15 dg and sacrificed on 20 dg. Maternal animals were weighed prior to mating and on 0, 6, 11, 16 and 20 dg; the rats were observed for mortality, morbidity and signs of toxicity during exposure and examined for gross tissue abnormalities at necropsy. Live fetuses were weighed and subjected to external, visceral and skeletal examinations to detect growth retardation and morphologic anomalies. There were no significant differences among treatment groups in maternal body weights or extragestational weights of rats exposed to 1,3-butadiene concentrations of 40 or 200 ppM, but, in animals exposed to 1000 ppM, significantly depressed body weight gains were observed during the first 5 days of exposure and extragestational weight gains tended to be lower than control values. These results, and the absence of clinical signs of toxicity, were considered to indicate that there was no maternal toxicity at exposure levels of 200 ppM or lower. The percentage of pregnant animals and the number of litters with live fetuses were unaffected by treatment. Under the conditions of this exposure regimen, there was no evidence for a teratogenic response to 1,3-butadiene exposure.

  16. Atmospheric pressure plasma polymerization of 1,3-butadiene for hydrophobic finishing of textile substrates

    Samanta, Kartick K; Jassal, Manjeet; Agrawal, Ashwini K, E-mail: ashwini@smita-iitd.co, E-mail: manjeet.jassal@smita-iitd.co [Smart and Innovative Textile Materials Group (SMITA), Department of Textile Technology, Indian Institute of Technology, Hauz Khas, New Delhi-110016 (India)

    2010-02-01

    Atmospheric pressure plasma processing of textile has both ecological and economical advantages over the wet-chemical processing. However, reaction in atmospheric pressure plasma has important challenges to be overcome before it can be successfully used for finishing applications in textile. These challenges are (i) generating stable glow plasma in presence liquid/gaseous monomer, and (ii) keeping the generated radicals active in the presence of contaminants such as oxygen and air. In this study, a stable glow plasma was generated at atmospheric pressure in the mixture of gaseous reactive monomer-1,3-butadiene and He and was made to react with cellulosic textile substrate. After 12 min of plasma treatment, the hydrophilic surface of the cellulosic substrate turned into highly hydrophobic surface. The hydrophobic finish was found to be durable to soap washing. After soap washing, a water drop of 37 {mu}l took around 250 s to get absorbed in the treated sample compared to < 1 s in the untreated samples. The plasma modified samples showed water contact angle of around 134{sup 0}. Both top and bottom sides of the fabric showed similar hydrophobic results in terms of water absorbency and contact angle. The results may be attributed to chemical reaction of butadiene with the cellulosic textile substrate. The surface characterization of the plasma modified samples under SEM and AFM revealed modification of the surface under <100 nm. The results showed that atmospheric pressure plasma can be successfully used for carrying out reaction of 1,3-butadiene with cellulosic textile substrates for producing hydrophobic surface finish.

  17. Magnetic properties of barium ferrite dispersed within polystyrene-butadiene-styrene block copolymers.

    Chipara, M; Skomski, R; Ali, N; Hui, D; Sellmyer, D J

    2009-06-01

    Magnetic properties of nanocomposite materials obtained by dispersing barium ferrite nanoparticles within polystyrene-butadiene-styrene block copolymer, in the temperature range, 300 to 500 K are reported. The temperature dependence of the magnetization at saturation, averaged uniaxial magnetocrystalline anisotropy, and coercive field of thick films are analyzed. A "matrix effect" was noticed within the glass transition range of the hard component (polystyrene) of the polymeric matrix. The reported modifications of the magnetic properties were assigned to the competition between the magnetic and mechanical reorientation of nanoparticles within the polymeric matrix. Such modifications were not observed in barium ferrite dispersed in cement. PMID:19504902

  18. Reinforcing styrene butadiene rubber with lignin-novolac epoxy resin networks

    Yu, P.; He, H; Jiang, C; Wang, D; Jia, Y.; Zhou, L.; D. M. Jia

    2015-01-01

    In this study, lignin-novolac epoxy resin networks were fabricated in the styrene butadiene rubber (SBR) matrix by combination of latex compounding and melt mixing. Firstly, SBR/lignin compounds were co-coagulated by SBR latex and lignin aqueous solution. Then the novolac epoxy resin (F51) was added in the SBR/lignin compounds by melt compounding method. F51 was directly cured by lignin via the ring-opening reaction of epoxy groups of F51 and OH groups (or COOH groups) of lignin during the cu...

  19. 1,3-Butadiene hydrogenation on pd-supported systems: geometric effects

    Souza P.R.N.

    2002-01-01

    Full Text Available A strong metal support interaction (SMSI effect was observed on Pd/Nb2O5 and Pd/TiO2 catalysts, and it produces small, exposed Pd ensembles. A decrease in the trans/cis 2-butene ratio was observed after reduction at 773 K. Selectivity changes were ascribed to the decoration model. Theoretical models were developed based on semi-empirical molecular-orbital calculations for 1,3-butadiene and Pd n clusters. Experimental results are in agreement with our theoretical model, which proposes a greater stabilization of the cisoid intermediate on small Pd ensembles.

  20. Improving compatibility of styrene-butadiene-styrene/polyamide 6 blends by radiation crosslinking of the SBS

    This work is aimed at improving compatibility of styrene-butadiene-styrene (SBS) copolymer / polyamide 6 (PA6) blends through radiation crosslinking of the blends by 60Co γ-rays, in which three-dimensional network structure is formed by the crosslinked SBS molecular chains. Micro-morphology, rheological properties, mechanical properties and water absorption of the PA6/SBS blend with different ratios irradiated to 100 kGy were characterized by relevant instrumental techniques. The results show that performance of the SBS/PA6 blends could be improved by radiation modification of the SBS copolymer. (authors)

  1. Self-Assembled Poly(butadiene)-b-Poly(ethylene oxide) Polymersomes as Paclitaxel Carriers

    Li, Shuliang; Byrne, Belinda; Welsh, JoEllen; Palmer, Andre F.

    2007-01-01

    In this work, self-assembled poly(butadiene)-b-poly(ethylene oxide) (PB-PEO) polymersomes (polymer vesicles) and worm micelles were evaluated as paclitaxel carriers. Paclitaxel was successfully incorporated into PB-PEO polymersomes and worm micelles. The loading capacity of paclitaxel inside PB-PEO colloids ranged from 6.7-13.7% w/w, depending on the morphology of copolymer colloids and the molecular weight of diblock copolymer. Paclitaxel loaded OB4 (PB219-PEO121) polymersome formulations we...

  2. STUDY ON STYRENE-BUTADIENE BLOCK COPOLYMER FOR THE MODIFICATION OF TIRE TREAD

    WANG Yan; CHEN Weijie; MU Ruifeng; WANG Yongwei; YU Fengnian; LIU Qing

    1996-01-01

    This paper mainly deals with the design and synthesis of a novel styrene-butadiene block copolymer. When this copolymer is used in the tread portion of tyres, it can improve wet skid resistance and reduce rolling resistance without sacrificing its general physicalmechanical properties. The visco-elastic curve of tire tread using the novel copolymer as its rubber portion was showed. Reactivity ratios for two monomers in the polymerizing system were calculated. The diagrams of differential, integral and finite difference calculi throughout the whole molecular chain were presented. The influence of the micro- and macro-structure of the copolymer chain on wet skid resistance and rolling resistance was discussed.

  3. Study Tensile Strength and Wear Rate for Unsaturated Polyester Resin and Nitrile butadiene Rubber Polymer Blend

    Entihaa G. Daway

    2015-06-01

    Full Text Available Binary polymer blend was prepared by mechanical mixing method of unsaturated polyester resin with Nitrile Butadiene Rubber (NBR with different weight ratios (0, 5, 10 and 15 % of (NBR. Tensile characteristics and wear rates of these blends were studied for all mixing ratios. The microstructure of fracture surfaces of the prepared samples were investigated by optical microscope. The results were showed that strain rates of the resin material increase after blending it with rubber while the ultimate tensile strength and Young’s modulus values of it will decrease. It is also noticed that the wear rate of resin decreases with increasing of (NBR content.

  4. Blends of Styrene-Butadiene-Styrene Triblock Copolymer with Random Styrene-Maleic Anhydride Copolymers

    Piccini, Maria Teresa; Ruggeri, Giacomo; Passaglia, Elisa; Picchioni, Francesco; Aglietto, Mauro

    2002-01-01

    Blends of styrene-butadiene-styrene triblock copolymer (SBS) with random styrene-maleic anhydride copolymers (PS-co-MA), having different MA content, were prepared in a Brabender Plastigraph mixer. The presence of polystyrene (PS) blocks in the SBS copolymer and the high styrene content (93 and 86 wt.-%, respectively) in the two kinds of used PS-co-MA samples afforded a good compatibility between the PS phases of the two polymers. On the other hand, the presence of polar anhydride groups allo...

  5. Studies on Macro—kinetics of Gas Phase Polymerization of Butadiene with Rare—earch Catalyst

    FANGDonyu; SUNJianzhong; 等

    2002-01-01

    The study of the kinetics of gas phase polymerization of butadiene with heterogeneous catalyst based on neodymium(Nd) was carried out.The effects of reaction temperature,reaction pressure,dispersing medium, and types of catalyst on kinetics of polymerization were investigated .A kinetic model with two kinds of active sites was proposed.The results show that the effects of the reaction temperature and the types of dispersing medium and catalyst on the kinetic performance of polymerization are significant,and that the combined model of first and second order decay of active site of catalyst can be used to describe the phenomena.

  6. Effect of solution-blended poly(styrene-co-acrylonitrile copolymer on crystallization of poly(vinylidene fluoride

    2010-05-01

    Full Text Available Effect of solution-blended poly(styrene-co-acrylonitrile (SAN copolymer on crystallization of poly(vinylidene fluoride (PVDF was investigated by Fourier transform infrared spectroscopy (FTIR, differential scanning calorimetry (DSC and wide angle X-ray diffraction (WAXD. Acrylonitrile segment in SAN copolymer was partially miscible with PVDF. Styrene segment in SAN reduced the copolymer’s polarity and its miscibility with PVDF. FTIR and WAXD tests both showed as-prepared PVDF was mainly β-phase. We employed an index Aβdivided by Xc, suggesting that blended SAN could decrease the content of β-phase of PVDF. By DSC, the smaller content of PVDF made the system more miscible so that the Tg,SAN of pure SAN decreased from 86.6 to 81.6°C of sample PVDF/SAN = 20/80; further increase PVDF to 50/50, the Tg,SAN had a relative increase to be 84.2°C. However, for SAN by melt molding, Tg,SAN increased with the increase of PVDF content, which might be due to the incorporation of SAN into inter-spacing of PVDF lamellae, because PVDF molecular chains had not enough mobility to retreat from the SAN’s embrace and crystallize despite of the exit of SAN.

  7. Fire and Gas Barrier Properties of Poly(styrene-co-acrylonitrile Nanocomposites Using Polycaprolactone/Clay Nanohybrid Based-Masterbatch

    S. Benali

    2008-01-01

    Full Text Available Exfoliated nanocomposites are prepared by dispersion of poly(ε-caprolactone (PCL grafted montmorillonite nanohybrids used as masterbatches in poly(styrene-co-acrylonitrile (SAN. The PCL-grafted clay nanohybrids with high inorganic content are synthesized by in situ intercalative ring-opening polymerization of ε-caprolactone between silicate layers organomodified by alkylammonium cations bearing two hydroxyl functions. The polymerization is initiated by tin alcoholate species derived from the exchange reaction of tin(II bis(2-ethylhexanoate with the hydroxyl groups borne by the ammonium cations that organomodified the clay. These highly filled PCL nanocomposites (25 wt% in inorganics are dispersed as masterbatches in commercial poly(styrene-co-acrylonitrile by melt blending. SAN-based nanocomposites containing 3 wt% of inorganics are accordingly prepared. The direct blend of SAN/organomodified clay is also prepared for sake of comparison. The clay dispersion is characterized by wide-angle X-ray diffraction (WAXD, atomic force microscopy (AFM, and solid state NMR spectroscopy measurements. The thermal properties are studied by thermogravimetric analysis. The flame retardancy and gas barrier resistance properties of nanocomposites are discussed both as a function of the clay dispersion and of the matrix/clay interaction.

  8. Dye-sensitized solar cell with poly(acrylic acid-co-acrylonitrile)-based gel polymer electrolyte

    Highlights: ► A nontoxic, easily synthesized poly(acrylic acid-co-acrylonitrile) showed suitable transmittance for dye-sensitized solar cell. ► A cell with relatively large active area fabricated with this polymer material showed acceptable efficiency. ► The gel polymer matrix affected the charge recombination, I3− diffusion, double layer capacitance, and electron lifetime in the cell. - Abstract: A non-conducting, nontoxic poly(acrylic acid-co-acrylonitrile) (PAA) was prepared and used as a supporting matrix for the electrolyte of dye-sensitized solar cells (DSSCs). DSSCs of active area 0.80 cm × 1.10 cm fabricated with PAA, 0.5 M LiI, 0.05 M I2, 0.5 M 3-tert-butylpyridine, and 0.1 M 1-methyl-3-propylimidazolium iodide in 3-methoxypropionitrile solvent showed an average solar energy conversion efficiency of 1.61% under simulated sunlight illumination of 100 mW cm−2, AM 1.5. The effects of the gel polymer matrix on the electrochemical properties of DSSCs were studied using the electrochemical impedance spectroscopy. Relative to the non-gel reference cells, the results showed a decrease in charge recombination, ionic diffusion, and double layer capacitance and an increase in electron lifetime. These results could play an important role in determining the future direction for the development of high-performance gel polymer electrolytes.

  9. The Protective Value of Hesperidin in Mitigating the Biochemical Perturbations and Trace Element alterations induced by Acrylonitrile in Rats

    N. M. Abdallah*, N. E. Amien**, M. R. Mohamed*, A. S. Nada**, M. A. Mohamed

    2013-07-01

    Full Text Available Objective: Acrylonitrile (a chemical pollutant has been reported to induce harmful effects in humans. Therefore, this study was designed to evaluate the protective effects of hesperidin, a natural bioflavonoid, against the toxicity induced by acrylonitrile (AN in rats. Material&Methods: This study includes determination of serum total scavenger capacity “TSC”, liver enzymes (aspartate transaminase “ASAT”, alanine transaminase “ALAT” and alkaline phosphatase “ALP”, total proteins, albumin, glucose, creatinine, urea and lipid profile. Moreover, liver and kidney homogenate glutathione content “GSH”, catalase, superoxide dismutase “SOD”, glutathione peroxidase “GPx”, malondialdehyde “MDA” and some minerals were estimated. Results: revealed that administration of AN (orally 50mg/ kg b.wt. induced alterations in TSC level as well as liver, kidney and lipid profiles. In addition, a decrease in GSH-content and catalase, SOD and GPx activities was observed with an increase in MDA levels in both liver and kidney. There was disturbance in certain minerals such as Cu, Zn, Fe, Se, Ca, Mg and Mn. Conclusion: particularly, Hesperidin administration (orally 200 mg/kg b.wt. ameliorates the oxidative stress induced by AN, consistent with the reported antioxidant activity of hesperidin

  10. Acrylonitrile potentiates hearing loss and cochlear damage induced by moderate noise exposure in rats

    The diversity of chemical and drugs that can potentiate noise-induced hearing loss (NIHL) has impeded efforts to predict such interactions. We have hypothesized that chemical contaminants that disrupt intrinsic antioxidant defenses hold significant risk for potentiating NIHL. If this is true, then acrylonitrile (ACN) would be expected to potentiate NIHL. ACN, one of the 50 most commonly used chemicals in the United States, is metabolized via two pathways that are likely to disrupt intrinsic reactive oxygen species (ROS) buffering systems: (1) it conjugates glutathione, depleting this important antioxidant rapidly; (2) a second pathway involves the formation of cyanide, which can inhibit superoxide dismutase. We hypothesized that moderate noise exposure, that does not produce permanent hearing loss by itself, could initiate oxidative stress and that ACN could render the inner ear more sensitive to noise by disrupting intrinsic antioxidant defenses. Temporary and persistent effects of ACN alone (50 mg/kg, sc 5 days), noise alone (95 or 97 dB octave band noise, 4 h/day for 5 days), or ACN in combination with noise were determined using distortion product otoacoustic emissions (DPOAEs) and compound action potential (CAP) amplitudes. Histopathological damage to hair cells resulting from these treatments was also investigated using surface preparations of the organ of Corti. Individually, neither ACN nor noise exposures caused any permanent hearing or hair cell loss; only a reversible temporary threshold shift was measured in noise-exposed animals. However, when given in combination, ACN and noise induced permanent threshold shifts (13-16 dB between 7 and 40 kHz) and a decrease in DPOAE amplitudes (up to 25 dB at 19 kHz), as well as significant outer hair cell (OHC) loss (up to 20% in the first row between 13 and 47 kHz). This investigation demonstrates that ACN can potentiate NIHL at noise levels that are realistic in terms of human exposure, and that the OHCs are the

  11. Thermodynamic calculations for molecules with asymmetric internal rotors--application to 1,3-butadiene.

    Wong, Bryan M; Raman, Sumathy

    2007-03-01

    We present quantum mechanical partition functions, free energies, entropies, and heat capacities of 1,3-butadiene derived from ab initio calculations. Our technique makes use of a reaction path-like Hamiltonian to couple all 23 vibrational modes to the large-amplitude torsion, which involves heavy asymmetric functional groups. Ab initio calculations were performed at the B3LYP, MP2, and CCSD(T) levels of theory and compared with experimental values as a reference case. By using the ab initio potentials and projected frequencies, simple perturbative expressions are presented for computing the couplings of all the vibrational modes to the large-amplitude torsion. The expressions are particularly suited for programming in the new STAR-P software platform which automatically parallelizes our codes with distributed memory via a familiar MATLAB interface. Using the efficient parallelization scheme of STAR-P, we obtain thermodynamic properties of 1,3-butadiene for temperatures ranging from 50 to 500 K. The free energies, entropies, and heat capacities obtained from our perturbative formulas are compared with conventional approximations and experimental values found in thermodynamic tables. PMID:17226834

  12. Selective dispersion of different organoclays in styrene butadiene rubber in the presence of a compatibilizer

    Highlights: ► Effect of carboxylated SBR on the dispersion of organoclay in SBR matrix. ► Prepare different organoclay/CB filled SBR based nanocomposites by melt blending. ► Organoclay filled rubber compounds show improved physical and mechanical properties. - Abstract: Dual filler (organoclay and carbon black) loaded emulsion polymerized styrene butadiene rubber (E-SBR) based nanocomposites were synthesized by melt blending. Three different organically modified clays (viz. Cloisite 15A, Cloisite 20A and Cloisite 30B) were used for the present study. To disperse different organoclays selectively in the rubber matrix, oil extended carboxylated styrene butadiene rubber (XSBR) was used as a compatibilizer between organoclay and the nonpolar SBR. Wide angle X-ray diffraction analysis (WAXD) and high resolution transmission electron microscopic (HR-TEM) analysis of the nanocomposites revealed that the organoclays were intercalated and delaminated in the elastomer matrix in the presence of carbon black (CB). Different organoclay loaded SBR compounds show improvement in the overall properties such as curing features, mechanical, thermal, abrasion resistance and dynamic mechanical properties compared to the neat SBR. Among the three different hybrid nanocomposites, Cloisite 30B filled SBR compound in the presence of CB show superior properties

  13. Electrical Conductivity in the Nonconjugated Polymer Styrene-Butadiene-Rubber (SBR)

    Titus, Jitto; Khatavkar, Sanchit; Thakur, Mrinal

    2003-03-01

    Electrical conductivity as a function of doping with iodine has been measured in a nonconjugated polymer, styrene-butadiene-rubber (SBR) which is a copolymer of styrene and butadiene, used extensively in automobile tires. The conductivity reaches a value of about 0.01 S/cm upon doping with iodine. The color of the rubber film changes from colorless to black upon doping. FTIR studies of the polymer show that the intensity of the =CH bending mode decreases with doping - indicating that the dopant interacts with the double bond and leads to a charge-transfer from the double bond to the dopant. The absorption spectrum after doping at a low level has two peaks - one at 4.13 eV and the other at 3.18 eV. The first peak is due to the cation radical formed upon doping and the second one is due to the charge-transfer complex formed with the dopant. The polystyrene segments of the copolymer seem to have less interaction with the dopant since polystyrene is glassy. The radical cation peak of another nonconjugated conductive polymer, polyalloocimene having a higher number-fraction of double bonds in the repeat, is slightly red-shifted compared to that of SBR.

  14. Quantum dynamics study of singlet-triplet transitions in s-trans-1,3-butadiene

    Nikoobakht, Behnam; Köppel, Horst

    2016-05-01

    The intersystem crossing dynamics of s-trans-1,3-butadiene in its lowest singlet and triplet states is studied theoretically, employing a fully quantal approach for the first time. The electronic states 21Ag, 11Bu, 13Bu and 13Ag, which interact vibronically and via the spin-orbit coupling are treated in the calculation, thus covering the lowest spin-forbidden electronic transitions. Up to five nuclear degrees of freedom, including out-of-plane dihedral angles are included in our investigation. The calculation of potential energy surfaces relies on the CASPT2 method, and the evaluation of spin-orbit coupling matrix elements using the full two-electron Breit-Pauli Hamiltonian is performed by utilizing the MRCI wavefunction. The latter dependence on the nuclear coordinates is included for the first time. An electronic population transfer on the sub-picosecond time scale due to intersystem crossing is obtained, a mechanism that can contribute to the singlet-triplet transitions in the electron energy loss spectrum of s-trans-1, 3-butadiene. It is found that the dependence of the spin-orbit coupling on the out-of-plane coordinates plays a dominant role in these singlet-triplet transitions. The amount of population transfer to the 13Ag and 13Bu states is roughly of the same order of magnitude.

  15. Performance Analysis of Styrene Butadiene Rubber-Latex on Cement Concrete Mixes.

    Er. Kapil Soni

    2014-03-01

    Full Text Available To improve the performance of concrete, polymers are mixed with concrete. It has been observed that polymer-modified concrete (PMC is more durable than conventional concrete due to superior strength and high durability. In this research, effect of Styrene-Butadiene Rubber (SBR latex on compressive strength and flexural strength of concrete has been studied and also the optimum polymer (SBR-Latex content for concrete is calculated. This research was carried out to establish the effects of polymer addition on compressive and flexural strength using concrete with mix design of constant water-cement ratio at local ambient temperature. The mixes were prepared with Styrene-Butadiene Rubber (SBR latex -cement ratio of 0 %, 5%, 10%, 15% and 20%. Slump test was conducted on fresh concrete while compressive strength and flexural strength were determined at different age. A locally available Perma-Latex is used as SBR Latex. It has been observed that SBR latex has negative effect at early age while at 28 days, the addition of SBR latex in concrete results in enhancement of compressive strength and Flexural Strength. Based on the results of this study, latex modified concrete made using Perma-Latex may be recommended to be used with various types of concrete structures. However, for the mixes rich in cement, the dosage of SBR latex needs to be adjusted to maintain required workability of concrete.

  16. Ethanol-to-Butadiene Conversion over SiO2-MgO Catalysts: Synthesis-Structure-Performance Relationships

    Angelici, C.

    2015-01-01

    The work presented in this PhD Thesis provides new insights into the underlying reasons that make SiO2-MgO materials excellent catalysts for the ethanol-to-butadiene Lebedev process. In particular, the preparation technique of choice affects the structural properties of the resulting SiO2-MgO materi

  17. NMR study of the epoxidation of liquid hydrolyzed poly-butadiene and meta-chloro-per-benzoic acid

    This work presents a study concerning the selectivity of the different configurations of the double bond present in liquid hydrolyzed poly-butadiene towards the epoxidation reaction with meta-chloro-per-benzoic acid through hydrogen-1, carbon-13 NMR aiming the production of new materials, varying the epoxidation level

  18. Turbidimetric behavior of Styrene Butadiene Rubber (SBR) solutions in toluene and dichloromethane after heating at open air

    This paper deals with the turbidimetric behavior of Styrene Butadiene Rubber SBR solutions, a synthetic rubber, in two solvents (toluene and dichloromethane), after heating at open air till 1800C for optimal polymer cracking conditions. Concentration, solvent and temperature effects have been studied using methanol like precipitant.

  19. DYNAMIC MECHANICAL PROPERTIES OF STYRENE-BUTADIENE COMPOSITES REINFORCED BY DEFATTED SOY FLOUR AND CARBON BLACK CO-FILLER

    Carboxylated styrene-butadiene (SB) composites reinforced by a mixture of defatted soy flour (DSF) and carbon black (CB) were investigated in terms of their dynamic mechanical properties. DSF is an abundant renewable commodity and has a lower cost than CB. DSF contains soy protein, soy carbohydrat...

  20. Formation of 1,2; 3,4-diepoxybutane specific hemoglobin adducts in 1,3-butadiene exposed workers

    Boysen, G.; Georgieva, N. I.; Bordeerat, N. K.; Šrám, Radim; Vacek, P.; Albertini, R. J.; Swenberg, J. A.

    2012-01-01

    Roč. 125, č. 1 (2012), s. 30-40. ISSN 1096-6080 Institutional research plan: CEZ:AV0Z50390703 Keywords : 1,3-butadiene exposure * carcinogenicity * occupational exposure Subject RIV: DN - Health Impact of the Environment Quality Impact factor: 4.328, year: 2012

  1. Emissions of benzene, toluene, xylenes and 1,3-butadiene from a representative portion of the Australian car fleet

    Duffy, B. L.; Nelson, P. F.; Ye, Y.; Weeks, I. A.; Galbally, I. E.

    The exhaust emissions of the air toxics benzene, toluene, total xylenes and 1,3-butadiene have been measured in the cold transient (CT), cold stabilised (CS) and hot transient (HT) phases of the Australian Design Rule (ADR) 37/00 Drive cycle for 19 pre-1986 non-catalyst-equipped vehicles fuelled with leaded petrol, and 56 post-1985 catalyst-equipped vehicles fuelled with unleaded petrol. Per vehicle exhaust emissions, averaged over the 3 phases of the ADR 37/00 test, of 1,3-butadiene, benzene, toluene, and total xylenes for the older vehicles were about 19, 139, 240 and 164 mg km -1 respectively. The corresponding emissions for the better 46 of the 56 post-1985 vehicles tested were 1.7, 28.1, 36.4, and 27.0 mg km- 1 respectively. The remaining 10 high polluting post-1985 vehicles had emission rates comparable to those vehicles not equipped with catalytic converters, suggesting that about 20% of post-1985 vehicles have malfunctioning or poorly operating catalysts. For the non-catalyst-equipped, pre-1986 vehicles, CS and HT emissions were about 60% of the CT emissions. For the better 46 post-1985 vehicles, average emissions during the CS and HT phases were about 20-25%, 12-16%, 11-14%, and 7-13% of the CT emissions for benzene, toluene, the xylenes, and 1,3-butadiene, respectively. The emissions from a small number (9) of non-catalyst-equipped, pre-1986 vehicles were determined using unleaded and leaded petrol. The emissions of all four target compounds were found to be significantly lower when unleaded petrol was substituted for leaded petrol. The greatest percentage emission reductions were observed for the CT phase, ranging from 25% for 1,3-butadiene to 35% for toluene. Emissions averaged over the 3 phases were reduced by 10% for 1,3-butadiene and by 16-18% for the aromatic compounds. Per vehicle total (heat build and hot soak) evaporative emissions of 1,3-butadiene, benzene, toluene and xylenes from pre-1985 vehicles during the Sealed Housing Evaporative

  2. Non-methane exhaust composition in the sydney harbour tunnel: A focus on benzene and 1,3-butadiene

    Duffy, Bronwyn L.; Nelson, Peter F.

    The concentrations of individual hydrocarbon species in the Sydney Harbour Tunnel were measured and used to estimate the average composition of emissions from moving motor vehicles in the Sydney urban area. The mean composition of non-methane hydrocarbons in the tunnel air on a weight basis was relatively constant. The mean concentrations for benzene and 1,3-butadiene were 45 and 13 ppbv, respectively, which in turn represented ˜ 5.2% w/w and ˜ 1.0% w/w of the total non-methane C 2C 10 hydrocarbons in the tunnel air. The unit risk factor and the maximum incremental reactivity factor for 1 1,3-butadiene are approximately 30 times higher and 25 times higher, respectively, than the corresponding values for benzene. The concentration (μg m -3) of benzene, however, is only about 5 times that of 1,3-butadiene. On this basis, the relative contribution to the risk associated with exposure to fresh motor vehicle emissions in Sydney would be about 6 times higher for 1,3-butadiene than for benzene. Similarly, the contribution made by 1,3-butadiene to the total hydrocarbon reactivity of the tunnel air will be about 5 times that of benzene. Samples of three different grades of petrol (leaded, unleaded and premium unleaded) from three different brands of fuel were also analysed on two separate occasions. Compositions of leaded and standard unleaded petrol averaged across the three different brands are quite similar. The average aromatic content (% w/w) of the 3 different commercial brands were ˜ 35 and 30% for leaded and unleaded petrol, respectively. However, premium unleaded petrol has a much higher aromatic content of ˜ 47% w/w. Comparison of the petrol and tunnel compositions demonstrated that benzene is enriched relative to other aromatics in exhaust compared to its proportion in the petrol.

  3. STUDY ON THE GASEOUS PRODUCTS OF HIGH TEMPERATURE PYROLYSIS OF ACRYLONITRILE POLYMERS BY ON-LINE FTIR METHOD

    ZHAO Genxiang; CHEN Bangjie

    1987-01-01

    The gaseous products of high temperature pyrolysis (300℃ to 960℃) of acrylonitrile polymers were measured continuously under nitrogen atnosphere by on-line Fourier Transform Infrared Spectroscopic method (FTIR). From the variations of characteristic peaks it was found that the nitrogen of macromolecules evolved were mainly in the form of hydrogen cyanide and ammonia. During the pyrolysis amorphous carbonaceous element was formed, and crosslinked to form network structure. Three kinds of samples were used for comparison. The experimental results show that the gaseous products of volatile small molecules were HCN, NH3, CH4, C2H6 and cyanide. CO and CO2 were also formed when copolymers of PAN were thermally pyrolyzed.

  4. The use of poly(vinylpyridine-co-acrylonitrile) in polymer electrolytes for quasi-solid dye-sensitized solar cells

    Li, Minyu [Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080 (China); Graduate School of Chinese Academy of Sciences, Beijing 100039 (China); Feng, Shujing; Fang, Shibi; Xiao, Xurui; Li, Xueping; Zhou, Xiaowen; Lin, Yuan [Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080 (China)

    2007-04-01

    Poly(vinylpyridine-co-acrylonitrile) (P(VP-co-AN)) was used to form polymer electrolytes for dye-sensitized solar cells (DSSCs). The effects of P(VP-co-AN) on the photovoltaic performances of DSSCs have been investigated with nonaqueous electrolytes containing alkali-iodide and iodine. It was found that the effect of P(VP-co-AN) on V{sub oc} closely related to its amount in the electrolyte. Lower amount of P(VP-co-AN) was benefit for the construction of a solar cell containing P(VP-co-AN) with higher energy conversion efficiency. Chemically crosslinking solidification with backbone polymer P(VP-co-AN) amount of 3% fabricated quasi-solid DSSCs with 10% increased conversion efficiencies with relative to that of the initial liquid DSSCs. (author)

  5. The use of poly(vinylpyridine-co-acrylonitrile) in polymer electrolytes for quasi-solid dye-sensitized solar cells

    Poly(vinylpyridine-co-acrylonitrile) (P(VP-co-AN)) was used to form polymer electrolytes for dye-sensitized solar cells (DSSCs). The effects of P(VP-co-AN) on the photovoltaic performances of DSSCs have been investigated with nonaqueous electrolytes containing alkali-iodide and iodine. It was found that the effect of P(VP-co-AN) on V oc closely related to its amount in the electrolyte. Lower amount of P(VP-co-AN) was benefit for the construction of a solar cell containing P(VP-co-AN) with higher energy conversion efficiency. Chemically crosslinking solidification with backbone polymer P(VP-co-AN) amount of 3% fabricated quasi-solid DSSCs with 10% increased conversion efficiencies with relative to that of the initial liquid DSSCs

  6. Pressure induced graft-co-polymerization of acrylonitrile onto Saccharum cilliare fibre and evaluation of some properties of grafted fibre

    A S Singha; Anjali Shama; Vijay Kumar Thakur

    2008-02-01

    In the present work, graft co-polymerization of acrylonitrile (AN) onto Saccharum cilliare fibre has been carried out in the presence of potassium persulphate and ferrous ammonium sulphate (FAS–KPS) as redox initiator. The reactions were carried out under pressure in an autoclave. Various reaction parameters such as pressure, time, pH, concentrations of initiator and monomer were optimized to get maximum graft yield (35.59%). Grafted and ungrafted Saccharum cilliare fibres were then subjected to evaluation of some of their properties like swelling behaviour in different solvents, moisture absorbance under different humidity levels, water uptake and resistance towards chemicals such as hydrochloric acid and sodium hydroxide. The characterization of the graft copolymers were carried out by FTIR spectrophotometer, X-ray diffraction (XRD) and scanning electron microscopic (SEM) studies.

  7. Theoretical and experimental investigations of the 2-(4-chlorophenyl)-3-{[5-(2-cyano-2-phenylethenyl)]furan-2-yl}acrylonitrile molecule as a potential acceptor in organic solar cells.

    Kazici, Mehmet; Bozar, Sinem; Yuksel, Sureyya Aydin; Ongul, Fatih; Gokce, Halil; Gunes, Serap; Goreci, Cigdem Yorur

    2016-06-10

    A novel soluble asymmetric acrylonitrile derivative, 2-(4-Chlorophenyl)-3-{[5-(2-cyano-2-phenylethenyl)]furan-2-yl}acrylonitrile (CPCPFA, 3) was synthesized in three steps by Knoevenagel condensation. The structure of the CPCPFA was characterized using UV-vis, FTIR, (1)H NMR, (13)C NMR, and LC-MS. CPCPFA was evaluated as an electron acceptor in bulk heterojunction organic solar cells. Its optical and electronic properties as well as photovoltaic performance were investigated. PMID:27145976

  8. Theoretical and experimental investigations of the 2-(4-chlorophenyl)-3-{[5-(2-cyano-2-phenylethenyl)]furan-2-yl}acrylonitrile molecule as a potential acceptor in organic solar cells

    Kazici, Mehmet; Bozar, Sinem; Aydin Yuksel, Sureyya; Ongul, Fatih; Gokce, Halil; Gunes, Serap; Yorur Goreci, Cigdem

    2016-06-01

    A novel soluble asymmetric acrylonitrile derivative, 2-(4-Chlorophenyl)-3-{[5-(2-cyano-2-phenylethenyl)]furan-2-yl}acrylonitrile (CPCPFA, 3) was synthesized in three steps by Knoevenagel condensation. The structure of the CPCPFA was characterized using UV–vis, FTIR, 1H NMR, 13C NMR, and LC-MS. CPCPFA was evaluated as an electron acceptor in bulk heterojunction organic solar cells. Its optical and electronic properties as well as photovoltaic performance were investigated.

  9. Fluorescence efficiency and visible re-emission spectrum of tetraphenyl butadiene films at extreme ultraviolet wavelengths

    Gehman, V. M.; Seibert, S. R.; Rielage, K.; Hime, A.; Sun, Y.; Mei, D.-M.; Maassen, J.; Moore, D.

    2011-10-01

    A large number of current and future experiments in neutrino and dark matter detection use the scintillation light from noble elements as a mechanism for measuring energy deposition. The scintillation light from these elements is produced in the extreme ultraviolet (EUV) range, from 60 to 200 nm. Currently, the most practical technique for observing light at these wavelengths is to surround the scintillation volume with a thin film of tetraphenyl butadiene (TPB) to act as a fluor. The TPB film absorbs EUV photons and re-emits visible photons, detectable with a variety of commercial photosensors. Here we present a measurement of the re-emission spectrum of TPB films when illuminated with 128, 160, 175, and 250 nm light. We also measure the fluorescence efficiency as a function of incident wavelength from 120 to 250 nm.

  10. Conversion of far ultraviolet to visible radiation: absolute measurements of the conversion efficiency of tetraphenyl butadiene

    Vest, Robert E.; Coplan, Michael A.; Clark, Charles W.

    Far ultraviolet (FUV) scintillation of noble gases is used in dark matter and neutrino research and in neutron detection. Upon collisional excitation, noble gas atoms recombine into excimer molecules that decay by FUV emission. Direct detection of FUV is difficult. Another approach is to convert it to visible light using a wavelength-shifting medium. One such medium, tetraphenyl butadiene (TPB) can be vapor-deposited on substrates. Thus the quality of thin TPB films can be tightly controlled. We have measured the absolute efficiency of FUV-to-visible conversion by 1 μm-thick TPB films vs. FUV wavelengths between 130 and 300 nm, with 1 nm resolution. The energy efficiency of FUV to visible conversion varies between 1% and 5%. We make comparisons with other recent results. Work performed at the NIST SURF III Synchrotron Ultraviolet Radiation Facility,.

  11. Tetraphenyl-butadiene films: VUV-Vis optical characterization from room to liquid argon temperature

    Francini, R.; Montereali, R. M.; Nichelatti, E.; Vincenti, M. A.; Canci, N.; Segreto, E.; Cavanna, F.; Di Pompeo, F.; Carbonara, F.; Fiorillo, G.; Perfetto, F.

    2013-09-01

    A thin film of Tetraphenyl-butadiene (TPB) deposited onto the surface delimiting the active volume of the detector and/or onto the photosensor's optical window is the most common solution to down convert argon VUV scintillation light in current and planned liquid argon based experiments for dark matter searches and neutrino physics. Characterization of the main features of TPB coatings on different, commonly used substrates is reported, as a result of measurements at the specialized optical metrology labs of ENEA and University of Tor Vergata. Measured features include TPB emission spectra with lineshape and relative intensity variation recorded as a function of the film thickness and for the first time down to LAr temperature, as well as optical reflectance and transmittance spectra of the TPB coated substrates in the wavelength range of the TPB emission.

  12. Wavelength Shifting Efficiency of Tetraphenyl Butadiene (TPB) at Extreme Ultraviolet Wavelengths

    Benson, Christopher; Orebi Gann, Gabriel; Gehman, Victor

    2015-10-01

    Tetraphenyl Butadiene (TPB) is a commonly used wavelength shifter (WLS) in neutrino and dark matter liquid noble gas scintillator detectors. Thin films of wavelength shifters are used to shift ultraviolet scintillation light into the visible spectrum for event reconstruction. The wavelength shifting efficiency of TPB is a function of the incident ultraviolet photon wavelength and is an important parameter for detector design, simulation and reconstruction. The wavelength shifting efficiency and emission spectrum has been previously measured down to 120 nm [Gehman et al., 2011]. To build liquid noble gas scintillator detectors with lighter elements (Ne, He) that use TPB as a WLS medium, the wavelength shifting efficiency must be known closer to 80 nm. This talk will present the current status and preliminary results from a set of measurements that will improve the precision of the efficiency of 120 nm, and extend the data to wavelengths as low as 45 nm.

  13. Synthesis and characterization of miktoarm star copolymer of styrene and butadiene using multifunctional macromolecular initiator

    Hai Yan Zhang; Xing Ying Zhang

    2009-01-01

    A new kind of multifunctional macromolecular initiator with Sn-C bonds and polydiene arms was synthesized by living anionic polymerization.At first,polydiene-stannum chloride(PD-SnCl3)was prepared by the reaction of n-butyl-Li(n-BuLi),stannic chloride(SnCl4)and diene.Then PD-SnCl3 was used to react with the dilithium initiator to prepare the multifunctional organic macromolecular initiators.The result suggested that the initiators had a remarkable yield by GPC,nearly 90%.By using these multifunctional macromolecular initiators,styrene and butadiene were effectively polymerized via anionic polymerization,which gave birth to novel miktoarm star copolymers.The relative molecular weight and polydispersity index,microstructure contents,copolymerization components,glass transition temperature(Tg)and morphology of the miktoarm star copolymers were investigated by GPC-UV,1H NMR,DSC and TEM,respectively.

  14. Microstructural analysis of carbon nanotubes produced from pyrolysis/combustion of styrene-butadiene rubber

    Alves, Joner O.; Zhuo, Chuanwei; Levendis, Yannis A. [Northeastern Univ., Boston, MA (United States). Coll. of Engineering. Dept. of Mechanical and Industrial Engineering; Tenorio, Jorge A.S. [University of Sao Paulo (USP), SP (Brazil). Polytechnic School. Dept. of Metallurgical and Materials Engineering

    2010-07-01

    Styrene-Butadiene-Rubber (SBR) is a synthetic rubber copolymer used to fabricate several products. This study aims to demonstrate the use of SBR as feedstock for carbon nanotubes (CNTs) growth, and therefore to establish a novel process for destination for wastes produced from SBR. Pellets of this rubber were controlled burned at temperature of 1000 deg C, and a catalyst system was used to synthesize the nanomaterials. CNTs are materials with a wide range of potential applications due to their extraordinary mechanical, thermal and electrical properties. Produced materials were characterized by SEM and TEM, and the hydrocarbons emissions were measured using GC. Results showed that materials with diameters of 30-100 nm and lengths of about 30 {mu}m were formed. That materials presented similar structures of multi-walled CNTs. Therefore, the use of SBR to produce carbon nanotubes showed quite satisfactory and an interesting field for future investments. (author)

  15. Correlation of mass fractal dimension and cluster size of silica in styrene butadiene rubber composites.

    Schneider, Gerald Johannes; Vollnhals, V; Brandt, K; Roth, S V; Göritz, D

    2010-09-01

    The morphology of the precipitated silica VN3 filled in styrene butadiene rubber was studied as a function of the volume fraction Φ by means of small-angle X-ray scattering experiments. The wide q-range of 0.008 nm(-1)silica. The diameter of the primary particles and their surface roughness are independent from the silica concentration. The size of the clusters and the corresponding aggregation number depend on Φ. This observation could be ascribed to external mechanical forces because of the mixing process and to growing cluster-cluster interactions with increasing filler fraction. In contrast the mass fractal dimension does not depend on Φ, and by that means experimentally proving that there is not necessarily a correlation between the mass fractal dimension and the cluster size. PMID:20831333

  16. Fluorescence Efficiency and Visible Re-emission Spectrum of Tetraphenyl Butadiene Films at Extreme Ultraviolet Wavelengths

    Gehman, V M; Rielage, K; Hime, A; Sun, Y; Mei, D -M; Maassen, J; Moore, D

    2011-01-01

    A large number of current and future experiments in neutrino and dark matter detection use the scintillation light from noble elements as a mechanism for measuring energy deposition. The scintillation light from these elements is produced in the extreme ultraviolet (EUV) range, from 60 - 200 nm. Currently, the most practical technique for observing light at these wavelengths is to surround the scintillation volume with a thin film of Tetraphenyl Butadiene (TPB) to act as a fluor. The TPB film absorbs EUV photons and reemits visible photons, detectable with a variety of commercial photosensors. Here we present a measurement of the re-emission spectrum of TPB films when illuminated with 128, 160, 175, and 250 nm light. We also measure the fluorescence efficiency as a function of incident wavelength from 120 to 250 nm.

  17. Evaluation of tri-steps modified styrene-butadiene-styrene block copolymer membrane for wound dressing

    Tri-steps modified styrene-butadiene-styrene block copolymer (SBS) membrane was prepared with epoxidation, ring opening reaction with maleated ionomer and layer-by-layer assembled polyelectrolyte technique. The tri-steps modified SBS membrane was characterized by infrared spectroscopy and X-ray photoelectron spectroscope (XPS). The structures of the modified SBS membranes were identified with methylene blue and azocarmine G. The content of amino group on the surface of the modified membrane was calculated from uptake of an acid dye. The values of the contact angle, water absorption, water vapor transmission rate and the adsorption of fibronectin on the membranes were determined. To evaluate the biocompatibility of the tri-steps modified SBS membrane, the cytotoxicity, antibacterial and growth profile of the cell culture of 3T3 fibroblasts on the membrane were evaluated. The bactericidal activity was found on the modified SBS. From the cell culture of 3T3 fibroblasts on the membrane, it revealed that the cells not only remained viable but also proliferated on the surface of the tri-steps modified SBS membranes. As the membranes are sterile semipermeable with bactericidal activity and transparent allowing wound checks, they can be considered for shallow wound with low exudates. - Highlights: ► Styrene-butadiene-styrene block copolymer (SBS) was modified with tri-steps. ► The tri-steps are epoxidation, ring opening reaction and layer-by-layer assembly. ► Modified SBS membrane for wound dressing is evaluated. ► Membranes are sterile semipermeable with bactericidal activity and transparent. ► Membranes can be considered for shallow wound with low exudates.

  18. Dielectric study of Poly(styrene- co -butadiene) Composites with Carbon Black, Silica, and Nanoclay

    Vo, Loan T.

    2011-08-09

    Dielectric spectroscopy is used to measure polymer relaxation in styrene-butadiene rubber (SBR) composites. In addition to the bulk polymer relaxation, the SBR nanocomposites also exhibit a slower relaxation attributed to polymer relaxation at the polymer-nanoparticle interface. The glass transition temperature associated with the slower relaxation is used as a way to quantify the interaction strength between the polymer and the surface. Comparisons were made among composites containing nanoclay, silica, and carbon black. The interfacial relaxation glass transition temperature of SBR-clay nanocomposites is more than 80 °C higher than the SBR bulk glass transition temperature. An interfacial mode was also observed for SBR-silica nanocomposites, but the interfacial glass transition temperature of SBR-silica nanocomposite is somewhat lower than that of clay nanocomposites. An interfacial mode is also seen in the carbon black filled system, but the signal is too weak to analyze quantitatively. The interfacial polymer relaxation in SBR-clay nanocomposites is stronger compared to both SBR-carbon black and SBR-silica composites indicating a stronger interfacial interaction in the nanocomposites containing clay. These results are consistent with dynamic shear rheology and dynamic mechanical analysis measurements showing a more pronounced reinforcement for the clay nanocomposites. Comparisons were also made among clay nanocomposites using different SBRs of varying styrene concentration and architecture. The interfacial glass transition temperature of SBR-clay nanocomposites increases as the amount of styrene in SBR increases indicating that styrene interacts more strongly than butadiene with clay. © 2011 American Chemical Society.

  19. Evaluation of tri-steps modified styrene-butadiene-styrene block copolymer membrane for wound dressing

    Yang, Jen Ming, E-mail: jmyang@mail.cgu.edu.tw; Huang, Huei Tsz

    2012-08-01

    Tri-steps modified styrene-butadiene-styrene block copolymer (SBS) membrane was prepared with epoxidation, ring opening reaction with maleated ionomer and layer-by-layer assembled polyelectrolyte technique. The tri-steps modified SBS membrane was characterized by infrared spectroscopy and X-ray photoelectron spectroscope (XPS). The structures of the modified SBS membranes were identified with methylene blue and azocarmine G. The content of amino group on the surface of the modified membrane was calculated from uptake of an acid dye. The values of the contact angle, water absorption, water vapor transmission rate and the adsorption of fibronectin on the membranes were determined. To evaluate the biocompatibility of the tri-steps modified SBS membrane, the cytotoxicity, antibacterial and growth profile of the cell culture of 3T3 fibroblasts on the membrane were evaluated. The bactericidal activity was found on the modified SBS. From the cell culture of 3T3 fibroblasts on the membrane, it revealed that the cells not only remained viable but also proliferated on the surface of the tri-steps modified SBS membranes. As the membranes are sterile semipermeable with bactericidal activity and transparent allowing wound checks, they can be considered for shallow wound with low exudates. - Highlights: Black-Right-Pointing-Pointer Styrene-butadiene-styrene block copolymer (SBS) was modified with tri-steps. Black-Right-Pointing-Pointer The tri-steps are epoxidation, ring opening reaction and layer-by-layer assembly. Black-Right-Pointing-Pointer Modified SBS membrane for wound dressing is evaluated. Black-Right-Pointing-Pointer Membranes are sterile semipermeable with bactericidal activity and transparent. Black-Right-Pointing-Pointer Membranes can be considered for shallow wound with low exudates.

  20. INVESTIGATION INTO THE REGIOCHEMISTRY OF SOME PYRAZOLES DERIVED FROM 1, 3-DIPOLAR CYCLOADDITION OF ACRYLONITRILE WITH SOME NITRILIMINES: THEORETICAL AND EXPERIMENTAL STUDIES

    FARID MOEINPOUR; MEHDI BAKAVOLI; ABOLGHASEM DAVOODNIA; ALI MORSALI

    2011-01-01

    1,3-dipolar cycloaddition between acrylonitrile and two N-(4-substituted)phenyl-C-(4-chlorophenyl)nitrilimines which were generated in situ afforded the new pyrazoles. The regiochemistry and reactivity of these reactions has been investigated on the basis of density functional theory (DFT) -based reactivity indexes and activation energy calculations. The theoretical 13C NMR chemical shifts of the cycloadducts which were obtained by GIAO method were comparable with the observed values.

  1. The Structure of the Free Volume in Poly(styrene-co-acrylonitrile) from Positron Lifetime and Pressure Volume Temperature (PVT) Experiments

    Dlubek, Gunter; Bondarenko, Vladimir; Al-Qaradawi, Ilham Y.; Kilburn, Duncan; Krause-Rehberg, Reinhard

    2004-01-01

    Summary: The structure of the free volume and its temperature dependence between 25 and 190 °C of copolymers of styrene with acrylonitrile, SAN (0 to 50 mol-% AN), is studied by pressure volume temperature (PVT) experiments and positron annihilation lifetime spectroscopy (PALS). In this second part of the work, PALS data are reported from which the temperature dependence of the mean size and size distribution of local free volumes (subnanometer size holes) is analysed. The mean hole volume, v...

  2. 丙烯腈生殖毒理学研究概况%An Overview of the Study of Acrylonitrile on Reproductive Toxiocology

    吴鑫; 金泰; 钟先玖

    2000-01-01

    @@ 丙烯腈(acrylonitrile,ACN)为有机合成工业中广泛应用的一种重要单体物质,可合成腈纶纤维,丁腈橡胶,ABS工程塑料及某些树脂.1994年全世界的ACN生产量超过30亿磅,1995年已达到100亿磅的生产能力[1].

  3. Quantitative characterization of the sequential mers distribution in styrene-butadiene copolymers by {sup 13} C; Caracterizacao quantitativa da distribuicao sequencial dos meros em copolimeros de estireno e butadieno por RMN de {sup 13} C

    Canevarolo, Sebastiao [Sao Carlos Univ., SP (Brazil). Dept. de Engenharia de Materiais

    1996-06-01

    Various types and grades of styrene-butadiene co-polymers were analysed by {sup 13} C-NMR: random SBR, blocked SSBR (a styrene block is introduced in the random SBR chain) and SBS triblock copolymers. It was determined the styrene content (%), the styrene-butadiene mers distribution in terms of the S-B and B-S-B sequences content (characteristics of the random portions of the chain) and also the isomers content in the butadiene phase. (author)

  4. Selective hydrogenation of 1,3-butadiene on platinum-copper alloys at the single-atom limit.

    Lucci, Felicia R; Liu, Jilei; Marcinkowski, Matthew D; Yang, Ming; Allard, Lawrence F; Flytzani-Stephanopoulos, Maria; Sykes, E Charles H

    2015-01-01

    Platinum is ubiquitous in the production sectors of chemicals and fuels; however, its scarcity in nature and high price will limit future proliferation of platinum-catalysed reactions. One promising approach to conserve platinum involves understanding the smallest number of platinum atoms needed to catalyse a reaction, then designing catalysts with the minimal platinum ensembles. Here we design and test a new generation of platinum-copper nanoparticle catalysts for the selective hydrogenation of 1,3-butadiene,, an industrially important reaction. Isolated platinum atom geometries enable hydrogen activation and spillover but are incapable of C-C bond scission that leads to loss of selectivity and catalyst deactivation. γ-Alumina-supported single-atom alloy nanoparticle catalysts with <1 platinum atom per 100 copper atoms are found to exhibit high activity and selectivity for butadiene hydrogenation to butenes under mild conditions, demonstrating transferability from the model study to the catalytic reaction under practical conditions. PMID:26449766

  5. Selective hydrogenation of 1,3-butadiene on platinum-copper alloys at the single-atom limit

    Lucci, Felicia R.; Liu, Jilei; Marcinkowski, Matthew D.; Yang, Ming; Allard, Lawrence F.; Flytzani-Stephanopoulos, Maria; Sykes, E. Charles H.

    2015-10-01

    Platinum is ubiquitous in the production sectors of chemicals and fuels; however, its scarcity in nature and high price will limit future proliferation of platinum-catalysed reactions. One promising approach to conserve platinum involves understanding the smallest number of platinum atoms needed to catalyse a reaction, then designing catalysts with the minimal platinum ensembles. Here we design and test a new generation of platinum-copper nanoparticle catalysts for the selective hydrogenation of 1,3-butadiene,, an industrially important reaction. Isolated platinum atom geometries enable hydrogen activation and spillover but are incapable of C-C bond scission that leads to loss of selectivity and catalyst deactivation. γ-Alumina-supported single-atom alloy nanoparticle catalysts with <1 platinum atom per 100 copper atoms are found to exhibit high activity and selectivity for butadiene hydrogenation to butenes under mild conditions, demonstrating transferability from the model study to the catalytic reaction under practical conditions.

  6. Dominant lethal study in CD-1 mice following inhalation exposure to 1,3-butadiene: Final technical report

    Hackett, P.L.; Mast, T.J.; Brown, M.G.; Clark, M.L.; Evanoff, J.J.; Rowe, S.E.; McClanahan, B.J.; Buschbom, R.L.; Decker, J.R.; Rommereim, R.L.; Westerberg, R.B.

    1988-04-01

    The effects of whole-body inhalation exposures to 1,3-butadiene on the reproductive system was evaluated. The results of dominant lethality in CD-1 male mice that were exposed to 1,3-butadiene are described. Subsequent to exposure, males were mated with two unexposed females. Mating was continued for 8 weeks with replacement of two females each week. Gravid uteri were removed, and the total number, position and status of implantations were determined. The mice were weighed prior to exposure and at 0, 1, 2, 3, 4, 5, 6, 7, and 8 weeks after exposure and at sacrifice. The animals were observed for mortality, morbidity and signs of toxicity throughout the study. 19 refs., 5 figs., 9 tabs.

  7. Experimental study of the structure of rich premixed 1,3-butadiene/CH4/O2/Ar flame

    Gueniche, Hadj-Ali; Fournet, René; Battin-Leclerc, Frédérique

    2006-01-01

    The structure of a laminar rich premixed 1,3-C4H6/CH4/O2/Ar flame have been investigated. 1,3-Butadiene, methane, oxygen and argon mole fractions are 0.033; 0.2073; 0.3315, and 0.4280, respectively, for an equivalent ratio of 1.80. The flame has been stabilized on a burner at a pressure of 6.7 kPa (50 Torr). The concentration profiles of stable species were measured by gas chromatography after sampling with a quartz probe. Quantified species included carbon monoxide and dioxide, methane, oxygen, hydrogen, ethane, ethylene, acetylene, propyne, allene, propene, cyclopropane, 1,3-butadiene, butenes, 1-butyne, vinylacetylene, diacetylene, C5 compounds, benzene, and toluene. The temperature was measured thanks to a thermocouple in PtRh (6%)-PtRh (30%) settled inside the enclosure and ranged from 900 K close to the burner up to 2100 K.

  8. Atmospheric oxidation of isoprene and 1,3-butadiene: influence of aerosol acidity and relative humidity on secondary organic aerosol

    M. Lewandowski

    2014-11-01

    Full Text Available The effects of acidic seed aerosols on the formation of secondary organic aerosol (SOA have been examined in a number of previous studies, several of which have observed strong linear correlations between the aerosol acidity (measured as nmol H+ per m3 air sample volume and the percent change of secondary organic carbon (SOC. The measurements have used several precursor compounds representative of different classes of biogenic hydrocarbons including isoprene, monoterpenes, and sesquiterpenes. To date, isoprene has displayed the most pronounced increase in SOC, although few measurements have been conducted with anthropogenic hydrocarbons. In the present study, we examine several aspects of the effect of aerosol acidity on the secondary organic carbon formation from the photooxidation of 1,3-butadiene, as well as extending the previous analysis of isoprene. The photooxidation products measured in the absence and presence of acidic sulfate aerosols were generated either through photochemical oxidation of SO2 or by nebulizing mixtures of ammonium sulfate and sulfuric acid into a 14.5 m3 smog chamber system. The results showed that, like isoprene and β-caryophyllene, 1,3-butadiene SOC yields linearly correlate with increasing acidic sulfate aerosol. The observed acid sensitivity of 0.11% SOC increase per nmol m−3 increase in H+ was approximately a factor of three less than that measured for isoprene. The results also showed that the aerosol yield decreased with increasing humidity for both isoprene and 1,3-butadiene, although to different degrees. Increasing the absolute humidity from 2 to 12 g m−3 reduced the 1,3-butadiene yield by 45% and the isoprene yield by 85%.

  9. Pd/TOMPP-catalyzed telomerization of 1,3-butadiene: from biomass-based substrates to new mechanistic insights

    Hausoul, P.J.C.; Bruijnincx, P.C.A.; Weckhuysen, B.M.; Klein Gebbink, R.J.M.

    2012-01-01

    Studies aimed at synthesizing surfactants from biomass-based feedstocks using Pd-catalyzed telomerization of 1,3-butadiene resulted in the development of a highly active catalyst system. A ligand screening was performed, and Pd/tris(2-methoxyphenyl)phosphine (TOMPP) was identified as the most promising catalyst. A solvent- and base-free protocol was developed, which allows efficient and selective conversion of a wide variety of polyol substrates (e.g., glycerol, diols, carbohydrates, and suga...

  10. Novel Polyvinyl Alcohol/Styrene Butadiene Rubber Latex/Carboxymethyl Cellulose Nanocomposites Reinforced with Modified Halloysite Nanotubes

    Junhua Zhang; Yanjun Tang; Dingding Zhou

    2013-01-01

    Novel polyvinyl alcohol (PVA)/styrene butadiene rubber (SBR) latex/carboxymethyl cellulose (CMC)/halloysite nanotubes (HNTs) nanocomposites were successfully prepared through physical blending. The as-obtained PVA/SBR/CMC/HNTs nanocomposites were coated on the surface of old corrugated container (OCC)-based paper in an effort to improve the mechanical properties of paper. To improve the dispersion of HNTs and enhance the compatibility between HNTs and polymer matrix, HNTs were modified with t...

  11. Analysis of recycled poly (styrene-co-butadiene) sulfonation: a new approach in solid catalysts for biodiesel production

    Aguilar-Garnica, Efrén; Paredes-Casillas, Mario; Herrera-Larrasilla, Tito E; Rodríguez-Palomera, Felicia; Ramírez-Arreola, Daniel E

    2013-01-01

    The disposal of solid waste is a serious problem worldwide that is made worse in developing countries due to inadequate planning and unsustainable solid waste management. In Mexico, only 2% of total urban solid waste is recycled. One non-recyclable material is poly (styrene-co-butadiene), which is commonly used in consumer products (like components of appliances and toys), in the automotive industry (in instrument panels) and in food services (e.g. hot and cold drinking cups and glasses). In ...

  12. Physiologically based toxicokinetic modeling of 1,3-butadiene lung metabolism in mice becomes more important at low doses.

    Evelo, C T; Oostendorp, J G; ten Berge, W F; Borm, P J

    1993-01-01

    This paper describes a physiologically based toxicokinetic model for 1,3-butadiene uptake, distribution, and metabolic clearance in mice. Model parameters for metabolic activity were estimated from the correspondence between computer simulation studies and experimental results as published in the literature. The parameterized model was validated with independent literature data. With the resulting model, the relative importance of lung metabolism as compared to metabolism in the liver increas...

  13. VAPOR-PHASE CATALYTIC CONVERSION OF ETHANOL INTO 1,3-BUTADIENE ON Cr-Ba/MCM-41 CATALYSTS

    N. La-Salvia

    2015-06-01

    Full Text Available AbstractAl-MCM-41, 16%Ba/Al-MCM-41 and 1.4%Cr-16%Ba/Al-MCM-41 were used as catalysts in the vapor-phase catalytic conversion of ethanol. Physical-chemical properties of the catalysts and the effect of barium and chromium on the Al-MCM-41 activity and 1,3-butadiene yield were studied. The catalysts were characterized by X-ray diffraction (XRD, N2 physisorption (BET method, CO2chemisorption and Fourier transform infrared spectroscopy (FT-IR. When ethanol was completely converted on Al-MCM-41 and 16%Ba/Al-MCM-41, the reaction products showed a high selectivity for ethylene (90-98%. However, on the 1.4%Cr-16%Ba/Al-MCM-41 catalyst, a greater number of reaction products were obtained such as ethylene, acetaldehyde, diethyl ether and 1,3-butadiene. The maximum 1,3-butadiene yield obtained from ethanol reaction was 25% at 723 K and W/FEtOH = 15 g h mol-1. The latter result was obtained in a single step and without addition of reaction promoters (e.g., acetaldehyde, crotonaldehyde, hydrogen in the feed stream to the reactor.

  14. High-Temperature Measurements and a Theoretical Study of the Reaction of OH with 1,3-Butadiene

    Vasu, Subith [Stanford Univ., CA (United States); Zador, J. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Davidson, David F. [Stanford Univ., CA (United States); Hanson, Ronald K. [Stanford Univ., CA (United States); Golden, David [Stanford Univ., CA (United States); Miller, James A. [Sandia National Lab. (SNL-CA), Livermore, CA (United States)

    2010-07-27

    The reaction of hydroxyl (OH) radicals with 1,3-butadiene (C4H6) was studied behind reflected shock waves over the temperature range 1011-1406 K and at pressures near 2.2 atm. OH radicals were produced by shock-heating tert-butyl hydroperoxide, (CH3)3-CO-OH, and were monitored by narrow line width ring dye laser absorption of the well-characterized R1(5) line of the OH A-X (0,0) band near 306.7 nm. OH time histories were modeled using a comprehensive 1,3-butadiene oxidation mechanism, and rate constants for the reaction of OH with 1,3-butadiene were extracted by matching modeled and measured OH concentration time histories. Detailed error analyses yielded an uncertainty estimate of ±13% at 1200 K for the rate coefficient of the target reaction. The current data extends the temperature range of the only previous high-temperature study for this reaction. The rate coefficient and the branching fractions for the H-abstraction channels of the target reaction were also calculated over the temperature range 250-2500 K using variational transition-state theory based on QCISD(T)/cc-pV∞Z//B3LYP/6-311++G(d,p) quantum chemistry. The calculations are in good agreement with the experimental results above 1200 K.

  15. A UniChem and electron momentum spectroscopy investigations into the valence electronic structure of trans 1,3 butadiene

    The experimental (e,2e) coincidence spectroscopy, known as electron momentum spectroscopy (EMS) was applied to the trans 1,3 butadiene (C4H6) molecule with detailed binding energy spectra and orbital momentum distributions (MDs) being measured. A small selection of this data is presented. The usage of UniChem computational chemistry codes for the Flinders-developed AMOLD program allows to calculate theoretical MDs for each orbital, to help elucidate the valence electronic structure of butadiene. The results of the many-body Green's function calculation is also presented, to the ADC(3) level, for the binding energies and spectroscopic factors of the respective orbitals of C4H6. A critical comparison between the experimental and theoretical MDs allows to determine the optimum wavefunction from the basis sets studied. The determination of the wavefunction then allows to make further use of the UniChem package to derive butadiene's chemically interesting molecular properties. A summary of these results and comparison of them with the previous results of other workers is presented. 23 refs., 2 tabs., 2 figs

  16. Delayed light emission of Tetraphenyl-butadiene excited by liquid argon scintillation light. Current status and future plans

    Segreto, E.; Machado, A. A.; Araujo, W.; Teixeira, V.

    2016-02-01

    Tetraphenyl-butadiene is the wavelength shifter most widely used in combination with liquid argon. The latter emits scintillation photons with a wavelength of 127 nm that need to be downshifted to be detected by photomultipliers with glass or quartz windows. Tetraphenyl-butadiene has been demonstrated to have an extremely high conversion efficiency, possibly higher than 100% for 127 nm photons, while there is no precise information about the time dependence of its emission. It is usually assumed to be exponentially decaying with a characteristic time of the order of one ns, as an extrapolation from measurements with exciting radiation in the near UV . This work shows that tetraphenyl-butadiene, when excited by 127 nm photons, re-emits photons not only with a very short decay time, but also with slower ones due to triplet states de-excitations. This fact can strongly contribute to clarifying the anomalies in liquid-argon scintillation light reported in the literature since the 1970s. Precision measurements of the properties of TPB, when excited by Vacuum Ultra Violet photons are being carried on at the Brazilian Synchrotron Light Laboratory in Campinas (State of São Paulo).

  17. Radiolytic preparation and characterization of hydrophilic poly(acrylonitrile-co-vinylsulfonate)-grafted porous poly(tetrafluoroethylene) substrates

    Park, Byeong-Hee; Sohn, Joon-Yong; Shin, Junhwa

    2016-01-01

    In this study, a hydrophilic copolymer of acrylonitrile (AN) and sodium vinylsulfonate (SVS) was grafted into a highly hydrophobic porous poly(tetrafluoroethylene) (PTFE) substrate using a gamma-ray irradiation method and the grafted substrate was used as a substrate for impregnating a hydrophilic ionomer, Nafion. The results of FT-IR and TGA analysis of the prepared substrate showed that the SVS/AN monomers were successfully grafted into the porous PTFE film. The results of degree of grafting, elemental analyzer, and contact angle analysis showed that the hydrophilicity of the prepared PTFE-g-P(AN-co-VS) substrate was increased with an increase in the amount of SVS/AN graft copolymers. Also, the results of FE-SEM and Gurley number measurement showed that the pores in the substrate were reduced as the amount of SVS/AN copolymers grafted into the substrate increased. The prepared porous PTFE-g-P(AN-co-VS) substrate at an irradiation dose of 70 kGy was found to impregnate Nafion ionomer effectively compared to the original porous PTFE substrate. These results suggest that the prepared PTFE-g-P(AN-co-VS) substrate can be effectively used for the impregnation of polymer electrolyte (Nafion) to prepare a reinforced composite membrane.

  18. Acrylonitrile-contamination induced enhancement of formic acid electro-oxidation at platinum nanoparticles modified glassy carbon electrodes

    El-Nagar, Gumaa A.; Mohammad, Ahmad M.; El-Deab, Mohamed S.; Ohsaka, Takeo; El-Anadouli, Bahgat E.

    2014-11-01

    Minute amount (∼1 ppm) of acrylonitrile (AcN), a possible contaminant, shows an unexpected enhancement for the direct electro-oxidation of formic acid (FAO) at Pt nanoparticles modified GC (nano-Pt/GC) electrodes. This is reflected by a remarkable increase of the current intensity of the direct oxidation peak (Ipd, at ca. 0.3 V) in the presence of AcN, concurrently with a significant decrease of the second (indirect) oxidation current (Ipind, at ca. 0.7 V), compared to that observed in the absence of AcN (i.e., at the unpoisoned Pt electrode). The extent of enhancement depends on the surface coverage (θ) of AcN at the surface of Pt nanoparticles. AcN is thought to favor the direct FAO by disturbing the contiguity of the Pt sites, which is necessary for CO adsorption. Furthermore, XPS measurements revealed a change in the electronic structure of Pt in presence of AcN, which has a favorable positive impact on the charge transfer during the direct FAO.

  19. Effect of Vanadium and Titanium substitution over an antimony-based mixed oxide catalysts for propane ammoxidation to acrylonitrile

    Antimony (Sb) oxide is known to be the active phase for the ammoxidation of propane to acrylonitrile (ACN). The influenced of V and/ or Ti on the physicochemical properties of Sb-based mixed oxide catalysts were studied using catalysts prepared by slurry method. The dried precursor was calcined in air at 350-600 degree Celsius for a total of 10 h. The active phases in Sb-promoted catalysts were determined using X-ray Diffraction (XRD) while the changes in microstructure of these catalysts were studied using physical adsorption of nitrogen gas. The catalytic activities of these catalysts were tested in a fixed-bed reactor with online GC at 420 degree Celsius with reaction feed (% v) of 5.8:7:17.4 for propane, ammonia and oxygen, respectively. Results show that promotional of Sb with V and/ or Ti has an effect on the chemical environment of the Sb-mixed oxide catalysts, leading to differences in catalytic activity of these catalysts. (author)

  20. The effect of trichloroethylene and acrylonitrile on RNA and ribosome synthesis and ribosome content in Saccharomyces cells.

    Lochmann, E R; Ehrlich, W; Mangir, M

    1984-04-01

    The effects of trichloroethylene (TCE) and acrylonitrile (ACN) on growth, RNA synthesis, ribosome synthesis, and ribosome content were tested in yeast cells. TCE causes a delay of the growth of a cell culture (prolongation of the lag phase), but does not cause inhibition. Cells exposed to increasing concentrations of ACN show increasing damage, so that, at a certain point of the growth curve, cell division stops altogether. Similar results were obtained when RNA synthesis was investigated: After treatment with TCE, the maximum RNA synthesis of the cell culture was retarded, but subsequently reached the same level as the untreated control cells. In the presence of ACN, however, the rate of RNA synthesis was lowered with increasing ACN concentrations. The same effect was observed upon investigation of ribosome synthesis: Whereas TCE produces only a slight effect, treatment with increasing concentrations of ACN leads to a substantial decrease in ribosome synthesis, and finally to total inhibition. Parallel to this, the content of free and membrane-bound ribosomes is diminished. Obviously, the decrease in ribosome content is caused not only by an inhibition of ribosome synthesis, but also by a degradation of existing ribosomes, as well as by induction of a ribosome-associated RNase. PMID:6714140

  1. TEMPERATURE AND pH RESPONSE, AND SWELLING BEHAVIOR OF POROUS ACRYLONITRILE-ACRYLIC ACID COPOLYMER HYDROGELS

    Jian Huang; Zhi-ming Huang; Yong-zhong Bao; Zhi-xue Weng

    2006-01-01

    Macroporous acrylonitrile-acrylic acid (AN-AA) copolymer hydrogels were synthesized by free-radical solution polymerizations, using ammonium persulfate (APS)/N,N,N',N'-tetramethylethylenediamine (TEMED) redox initiator system and alcohols porogens. The morphology, temperature and pH sensitive swelling behavior, and swelling kinetics of the resulting hydrogels were investigated. It was found that alcohol type and concentration had great influences on the pore structure and porosity of hydrogels. The pore size of hydrogel increases with the moderate increase of the length of alcohol alkyl chain. However, a further increase of alkyl length would result in the formation of cauliflower-like structure and the decrease of pore size. The porosity of hydrogels increases with the increase of porogen concentration in the polymerization medium. The hydrogels with macroporous structure swell or shrink much faster in response to the change of pH in comparison with the conventional hydrogel without macroporous structure. Furthermore, the response rate is closely related to the porosity of the hydrogels, which could be easily controlled by modulating the concentration of the porogen in the medium. The circular swelling behavior of hydrogels indicated the formation of a relaxing three-dimensional network.

  2. Preparation of Mesoporous Carbons from Acrylonitrile-methyl Methacrylate Copolymer/Silica Nanocomposites Synthesized by in-situ Emulsion Polymerization

    BAO Yongzhong; ZHAO Wenting; HUANG Zhiming

    2013-01-01

    Acrylonitrile-methyl methacrylate (AN-MMA) copolymer/silica nanocomposites were synthesized by in-situ emulsion polymerization initiated by 2,2′-azobis(2-amidinopropane) dihydrochloride absorbed onto colloidal silica particles,and the mesoporous carbon materials were prepared through carbonization of the obtained AN-MMA copolymer/silica nanocomposites,followed by HF etching.Thermogravimetric analysis of AN-MMA copolymer/silica nanocomposites showed that the carbon yield of copolymer was slightly decreased as silica particle incorporated.N2 adsorption-desorption,scan electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the structure and morphology of the mesoporous carbon materials.Both SEM and TEM results showed that disordered mesopores were formed in the obtained carbon material mainly through templating effect of silica nanoparticles.The diameter of mesopores was mainly distributed in the range from 5 nm to 15 nm.The mean pore diameter and total pore volume of the material increased as the mass fraction of silica in the nanocomposites increased from 0 to 24.93%.The significant increase of the mean pore diameter and the decrease of surface area for the carbon material prepared from the nanocomposite with 24.93% silica were caused by partial aggregation of silica nanoparticles in the polymer matrix.

  3. About the cure kinetics in natural rubber/styrene Butadiene rubber blends at 433 K

    Mansilla, M.A., E-mail: mmansilla@df.uba.ar [Laboratorio de Polimeros y Materiales Compuestos, Departamento de Fisica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellon 1, C1428EGA Buenos Aires (Argentina); Marzocca, A.J. [Laboratorio de Polimeros y Materiales Compuestos, Departamento de Fisica, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellon 1, C1428EGA Buenos Aires (Argentina)

    2012-08-15

    Vulcanized blends of elastomers are employed in several goods mainly to improve physical properties and reduce costs. One of the most used blends of this kind is that composed by natural rubber (NR) and styrene butadiene rubber (SBR). The cure kinetic of these blends depends mainly on the compound formulation and the cure temperature and time. The preparation method of the blends can influence the mechanical properties of the vulcanized compounds. In this work the cure kinetic at 433 K of NR/SBR blends vulcanized with the system sulfur/TBBS (N-t-butyl-2-benzothiazole sulfenamide) is analyzed in samples prepared by mechanical mixing and solution blending. The two methods produce elastomer domains of NR and SBR, which present different microstructure due to the cure level attained during vulcanization. The cure kinetics is studied by means of rheometer tests and the model proposed by Kamal and Sourour. The analysis of the cure rate is presented and is related to the structure obtained during the vulcanization process.

  4. FRACTAL CHARACTER OF PHASE MORPHOLOGY OF HIGH IMPACT POLYSTYRENE/POLY(cis-BUTADIENE) RUBBER BLENDS

    Yun-yan Li; Yun-ping Han; Jing Sheng

    2006-01-01

    Evolution and fractal character of the phase morphology of high impact polystyrene/poly(cis-butadiene) rubber (HIPS/PcBR) blends during melting and mixing were investigated using scanning electron microscopy (SEM). The characteristic length L was defined as the size of particles of the dispersed phase in blends. Different fractal dimensions, Df and Dm, were introduced to study the distribution width of phase dimensions in the dimensionless region and the uniformity of the spatial distribution of particles, respectively. The results showed that the average characteristic length Lm and Df increase as the volume fraction of the dispersed phase increases, when the volume fraction of the dispersed phase is lower than 50%. In other words, the size of particles increases and their distribution in the dimensionless region becomes more uniform. Meanwhile, the uniformity of the spatial distribution becomes more perfect as the volume fraction increases. At a certain composition, Lm decreases in the initial stage of the mixing and levels off in the late stage. In the initial stage, Df becomes large rapidly with the process of blending, which means that the distribution of L in the dimensionless region becomes more uniform. Meanwhile, the spatial distribution tends to be ideal rapidly in the early stage and fluctuates in a definite range in the late stage of the mixing.

  5. Radiation-induced crosslinking of poly(styrene-butadiene-styrene) block copolymers and their sulfonation

    Lee, Sun-Young; Song, Ju-Myung; Sohn, Joon-Yong; Shul, Yong-Gun; Shin, Junhwa

    2013-12-01

    Several crosslinked poly(styrene-butadiene-styrene) (c-SBS) block copolymer films were prepared using a gamma ray or electron beam with various irradiation doses and the prepared c-SBS film was then subjected to sulfonation using a chlorosulfonic acid (CSA) solution to introduce a sulfonic acid group. To estimate the degree of crosslinking, the gel fractions and FT-IR spectra of the c-SBS films were used and the results indicate that the degree of crosslinking is increased with an increase in the radiation dose. The surface morphology and mechanical property of the c-SBS films were observed using SEM and UTM instruments, respectively. The sulfonated c-SBS films were investigated by measuring the ion exchange capacity (IEC) and by observing the cross-sectional distribution patterns of sulfonic acid group using an SEM-EDX instrument. The IEC and SEM-EDX studies indicate that the sulfonated c-SBS membranes can be successfully prepared through the radiation crosslinking of the SBS film and the subsequent sulfonation with a diluted CSA solution.

  6. Bond Characteristics of Macro Polypropylene Fiber in Cementitious Composites Containing Nanosilica and Styrene Butadiene Latex Polymer

    Jae-Woong Han

    2015-01-01

    Full Text Available This study evaluated the bond properties of polypropylene (PP fiber in plain cementitious composites (PCCs and styrene butadiene latex polymer cementitious composites (LCCs at different nanosilica contents. The bond tests were evaluated according to JCI SF-8, in which the contents of nanosilica in the cement were 0, 2, 4, 6, 8, and 10 wt%, based on cement weight. The addition of nanosilica significantly affected the bond properties between macro PP fiber and cementitious composites. For PCCs, the addition of 0–2 wt% nanosilica enhanced bond strength and interface toughness, whereas the addition of 4 wt% or more reduced bond strength and interface toughness. The bond strength and interfacial toughness of LCCs also increased with the addition of up to 6% nanosilica. The analysis of the relative bond strength showed that the addition of nanosilica affects the bond properties of both PCC and LCC. This result was confirmed via microstructural analysis of the macro PP fiber surface after the bond tests, which revealed an increase in scratches due to frictional forces and fiber tearing.

  7. Synthesis of Cyclododecatriene from 1,3-Butadiene by Trimerization over Amine-Titanium Complex Catalyst

    Park, Da Min; Kim, Gye Ryung; Lee, Ju Hyun; Kim, Geon-Joong [Inha University, Incheon (Korea, Republic of); Cho, Deuk Hee [Korea Research Institute of Chemical Technology, Daejeon (Korea, Republic of)

    2013-06-15

    The new complex catalysts were synthesized by the reaction of titanium compounds (titanium chloride or titanium butoxide) and diamines in this work, and they showed very high catalytic activities for the cyclododecatriene (CDT) synthesis from 1,3-butadiene through trimerization. CDT synthetic reaction was performed in an autoclave reactor, and the effects of reaction temperature, type of catalyst, catalyst amount added into the system, the mole ratio of Al/Ti and immobilization method were investigated on the yield of product CDT. The titanium complex catalyst combined to diamine with 1:1 ratio showed high selectivity to CDT more than 90%. The ratio of TTT-CDT/TTC-CDT isomers in the product revealed as different values, depending on the type of diamine combined to titanium and Ti/diamine ratios. Those homogeneous complexes could be used as a heterogenized catalyst after anchoring on the supports, and the immobilized titanium catalyst retained the catalytic activities for several times in the recycled reactions without leaching. The carbon support containing titanium has exhibited superior activity to the silica support. Especially, when the titanium complex was anchored on the support which was fabricated by the hydrolysis of tripropylaminosilane itself, the resulting titanium catalyst showed the highest BD conversion and CDT selectivity.

  8. Performance of Styrene Butadiene Rubber as a Concrete Repair Material in tropical climate

    Radhakrishnan, R.; Prakash, V. Syam; Thampan, C. K.; Varma, Prasad

    2012-11-01

    Deterioration of Concrete due to variety of reasons like corrosion of steel, inferior quality of materials as well as workmanship and exposure to aggressive environment like thermal cycling affect the performance or damage a number of Reinforced cement concrete structures. In order to repair these structures for enhancing the service life, number of methods and materials are available. But the degree of success of any repair in concrete depends mainly on the correct choice and the method of application of repair materials. This paper discusses the details of an experimental investigation on the performance of Styrene ñ Butadiene Rubber (SBR) as a concrete repair material in tropical climatic conditions. Resistance to water penetration and tensile cracking are two important performance criteria for any repair material. Cement mortar cubes of mix proportion 1:3 with SBR added at the rate of 20% of the weight of cement, and control specimens without SBR were made. Compressive strength and sorptivity values of the cubes were determined. Shear Bond strength (by slant shear test) and splitting tensile strength of the repaired cylinder specimens of standard dimensions, in which SBR used as a bonding agent were determined. These values were compared with the values obtained for the similar specimens, in which the bonding agent applied was conventional cement slurry. The influence of thermal cycling on the properties of repaired concrete specimens were also studied. A comparison has also been made with the values required to meet the standard specifications of a repair material.

  9. Devulcanization of styrene butadiene rubber by microwave energy: Effect of the presence of ionic liquid

    S. Seghar

    2015-12-01

    Full Text Available In this study, styrene butadiene rubber (SBR was devulcanized using microwave irradiation. In particular, effect of ionic liquid (IL, pyrrolidinium hydrogen sulfate [Pyrr][HSO4], on the devulcanization performance was studied. It was observed that the evolution of the temperature reached by rubber powder exposed to microwave irradiation for different energy values was favored by the presence of ionic liquid [Pyrr][HSO4] significantly over the whole range of the microwave energy values. Beyond the threshold point of 220 Wh/kg, the soluble fraction after devulcanization sharply increased with increasing devulcanization microwave energy. For the powder mixed with [Pyrr][HSO4], the increase was more significant. Furthermore, the crosslink density was observed to decrease slowly with the microwave energy up to 220 Wh/kg, beyond which the crosslink density decreased significantly for the rubber impregnated with IL. For the rubber with IL, significant and continuous increase in Tg with microwave energy values was observed in comparison with the SBR where no change in transition temperature was observed. Mechanical shearing of rubber gums in the two-roll mill favored the devulcanization process, which indicated that the combination of mechanical loading with microwave energy and IL is an efficient procedure allowing an optimal devulcanization of rubbers.

  10. Thermal Stability and Flammability of Styrene-Butadiene Rubber-Based (SBR Ceramifiable Composites

    Rafał Anyszka

    2016-07-01

    Full Text Available Ceramifiable styrene-butadiene (SBR-based composites containing low-softening-point-temperature glassy frit promoting ceramification, precipitated silica, one of four thermally stable refractory fillers (halloysite, calcined kaolin, mica or wollastonite and a sulfur-based curing system were prepared. Kinetics of vulcanization and basic mechanical properties were analyzed and added as Supplementary Materials. Combustibility of the composites was measured by means of cone calorimetry. Their thermal properties were analyzed by means of thermogravimetry and specific heat capacity determination. Activation energy of thermal decomposition was calculated using the Flynn-Wall-Ozawa method. Finally, compression strength of the composites after ceramification was measured and their micromorphology was studied by scanning electron microscopy. The addition of a ceramification-facilitating system resulted in the lowering of combustibility and significant improvement of the thermal stability of the composites. Moreover, the compression strength of the mineral structure formed after ceramification is considerably high. The most promising refractory fillers for SBR-based ceramifiable composites are mica and halloysite.

  11. SYNTHESIS AND PHARMACOLOGICAL EFFECTS OF BUTADIENE AND CYCLOPENTADIENE ADDUCTS OF METHANDROSTENOLONE IN RATS

    FAZEL SHAMSA

    2006-06-01

    Full Text Available In this study the reactivity of methandrostenolone or [(17b-17-hydroxy-17-methylandrosta-1, 4-diene-3-one], as a dienophil in a Diels-Alder type cycloaddition reaction was investigated. The purpose of this approach was to investigate whether the 1-dehydro position of methandrostenolone 1 undergoes a cycloaddition reaction with dienes, such as 1, 3 butadiene or cyclopentadiene, and to investigate the biological behavior of the reaction adducts, i.e, compound 3 {(17b-17-hydroxy-17-methyl androsta [1a, 2a] cyclohex 3’, 4-diene-3-one} and compound 4 {(17b-17-hydroxy-17-methyl androsta [1a, 2a] cyclohex (2’,5’ methylene 3’, 4-diene-3-one}, relative to compound 1. The results indicated that thedDiels-Alder reactionddid notpproceed under the usual circumstances of high pressure and temperature, but could proceed in the presence of a Lewis acid (AlCl3. The structures of compounds 3 and 4 were confirmed by spectroscopic methods. The androgenic behavior of compounds 3 and 4 in comparison to compound 1 in the apomorphine test indicated that both compounds were almost devoid of androgenic activity, but prevented apomorphine mediated penile erection in male rats in a similar manner as cyproterone acetate.

  12. Radiation crosslinking of styrene–butadiene rubber containing waste tire rubber and polyfunctional monomers

    The objective of this study was to investigate the influence of polyfunctional monomers (PFMs) and absorbed dose on the final characteristics of styrene–butadiene rubber (SBR) mixed with waste tire rubber (WTR). A series of SBR/WTR blends were prepared by varying the ratios of WTR in the presence of PFMs, namely trimethylolpropane trimethacrylate (TMPTMA) and trimethylolpropane triacrylate (TMPTA) and crosslinked using gamma rays. The physicochemical characteristics of the prepared blends were investigated. It was observed that tensile strength, hardness and gel content of the blends increased with absorbed dose while the blends containing TMPTA showed higher tensile strength, gel content and thermal stability as compared to the blends containing TMPTMA. Higher thermal stability was observed in the blends which were crosslinked by radiation as compared to the blends crosslinked by sulfur. These blends exhibited higher rate of swelling in organic solvents, whereas negligible swelling was observed in acidic and basic environment. - Highlights: • The effect of γ radiation on SBR blended with waste tire rubber was studied. • Two polyfunctional monomers were used to increase the crosslinking. • Mechanical properties of the blends were increased with absorbed dose. • TMPTA containing blend showed higher tensile strength and thermal stability. • Comparison with sulfur crosslinking was also done

  13. Influence Of Gamma Irradiation On Mechanical And Thermal Properties Of Waste Polyethylene / Nitrile Butadiene Rubber Blend

    Gamma irradiation radical-radical interaction crosslinking of elastomers and thermoplastic is a special type of crosslinking technique that has gained importance over conventional chemical crosslinking method as process is fast, pollution free and simple. In this study, a blend polymer, based on waste polyethylene and nitrile butadiene rubber, has been irradiated with gamma rays then mechanically and thermally investigated at varying NBR content. FTIR and SEM techniques were used in addition to the swelling behaviour by toluene solvent to emphasize the blend formation. The mechanical properties like tensile strength, elongation at break and modulus at different elongations were studied and compared with those of non-irradiated ones. A relatively low radiation dose was found effective in improving the level of mechanical properties. Differential scanning calorimeter and thermogravimetric analysis were used to study the thermal characteristics of the irradiated polymer. Enhancement in thermal stability has been observed for higher NBR containing blends and via radiation-induced crosslinking up to ≅ 50 kGy

  14. Adsorption of 1,3-butadiene on Si(111)7x7 surface

    Full text: The adsorption of 1,3-butadiene (BD : C4 H10) on the Si(111)7x7 surface has been investigated using synchrotron radiation photoemission spectroscopy and scanning tunneling microscopy. BD adsorbs on the Si(111)7x7 surface at room temperature, not only adatom-rest-atom bridging but also adatom-adatom bridging type. In the valence band spectrum for the Si(111)7x7 surface, the adatom and rest-atom states were observed at the binding energies of about 0.2 and 0.8 eV, respectively. With increasing BD exposure, the adatom state is completely quenched at an initial exposure, while the rest-atom state disappears at higher exposure. This indicates two different reaction pathways of BD on the Si(111)7x7 surface. STM shows three different adsorption types on the 7x7 surface, two adatom-adatom bridging and one adatom-rest-atom bridging types. By comparing the valence band and Si 2p core level spectra with STM images, it was found that the chemical reactivity of BD molecule with the adatom-rest-atom pair is strongly higher than the adatom-adatom pair

  15. Styrene-butadiene rubber/halloysite nanotubes nanocomposites modified by methacrylic acid

    Methacrylic acid (MAA) was used to improve the performance of styrene-butadiene rubber (SBR)/halloysite nanotubes (HNTs) nanocomposites by direct blending. The detailed interaction mechanisms of MAA and the in situ formed zinc methacrylate (ZDMA) were revealed by X-ray diffraction (XRD), surface area and porosity analysis, X-ray photoelectron spectroscopy (XPS) together with crosslink density determination. The strong interfacial bonding between HNTs and rubber matrix is resulted through ZDMA and MAA intermediated linkages. ZDMA connects SBR and HNTs via grafting/complexation mechanism. MAA bonds SBR and HNTs through grafting/hydrogen bonding mechanism. Significantly improved dispersion of HNTs in virtue of the interactions between HNTs and MAA or ZDMA was achieved. Effects of MAA content on the vulcanization behavior, morphology and mechanical properties of the nanocomposites were investigated. Promising mechanical properties of MAA modified SBR/HNTs nanocomposites were obtained. The changes in vulcanization behavior, mechanical properties and morphology were correlated with the interactions between HNTs and MAA or ZDMA and the largely improved dispersion of HNTs

  16. Styrene-butadiene rubber/halloysite nanotubes nanocomposites modified by methacrylic acid

    Guo Baochun [Department of Polymer Materials and Engineering, South China University of Technology, Guangzhou 510640 (China)], E-mail: psbcguo@scut.edu.cn; Lei Yanda; Chen Feng; Liu Xiaoliang; Du Mingliang; Jia Demin [Department of Polymer Materials and Engineering, South China University of Technology, Guangzhou 510640 (China)

    2008-12-30

    Methacrylic acid (MAA) was used to improve the performance of styrene-butadiene rubber (SBR)/halloysite nanotubes (HNTs) nanocomposites by direct blending. The detailed interaction mechanisms of MAA and the in situ formed zinc methacrylate (ZDMA) were revealed by X-ray diffraction (XRD), surface area and porosity analysis, X-ray photoelectron spectroscopy (XPS) together with crosslink density determination. The strong interfacial bonding between HNTs and rubber matrix is resulted through ZDMA and MAA intermediated linkages. ZDMA connects SBR and HNTs via grafting/complexation mechanism. MAA bonds SBR and HNTs through grafting/hydrogen bonding mechanism. Significantly improved dispersion of HNTs in virtue of the interactions between HNTs and MAA or ZDMA was achieved. Effects of MAA content on the vulcanization behavior, morphology and mechanical properties of the nanocomposites were investigated. Promising mechanical properties of MAA modified SBR/HNTs nanocomposites were obtained. The changes in vulcanization behavior, mechanical properties and morphology were correlated with the interactions between HNTs and MAA or ZDMA and the largely improved dispersion of HNTs.

  17. Styrene-butadiene rubber/halloysite nanotubes nanocomposites modified by sorbic acid

    Guo, Baochun; Chen, Feng; Lei, Yanda; Liu, Xiaoliang; Wan, Jingjing; Jia, Demin

    2009-05-01

    Sorbic acid (SA) was used to improve the performance of styrene-butadiene rubber (SBR)/halloysite nanotubes (HNTs) nanocomposites by direct blending. The detailed mechanisms for the largely improved performance were studied by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), differential scanning calorimetry (DSC), porosity analysis and crosslink density determination. The strong interfacial bonding between HNTs and rubber matrix is resulted through SA intermediated linkages. SA bonds SBR and HNTs through grafting copolymerization/hydrogen bonding mechanism. Significantly improved dispersion of HNTs in virtue of the interactions between HNTs and SA was achieved. Formation of zinc disorbate (ZDS) was revealed during the vulcanization of the composites. However, in the present systems, the contribution of ZDS to the reinforcement was limited. Effects of SA content on the vulcanization behavior, morphology and mechanical properties of the nanocomposites were investigated. Promising mechanical properties of SA modified SBR/HNTs nanocomposites were obtained. The changes in vulcanization behavior, mechanical properties and morphology were correlated with the interactions between HNTs and SA and the largely improved dispersion of HNTs.

  18. Styrene-butadiene rubber/halloysite nanotubes nanocomposites modified by sorbic acid

    Guo Baochun, E-mail: psbcguo@scut.edu.cn [Department of Polymer Materials and Engineering, South China University of Technology, Guangzhou 510640 (China); Chen Feng; Lei Yanda; Liu Xiaoliang; Wan Jingjing; Jia Demin [Department of Polymer Materials and Engineering, South China University of Technology, Guangzhou 510640 (China)

    2009-05-30

    Sorbic acid (SA) was used to improve the performance of styrene-butadiene rubber (SBR)/halloysite nanotubes (HNTs) nanocomposites by direct blending. The detailed mechanisms for the largely improved performance were studied by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), differential scanning calorimetry (DSC), porosity analysis and crosslink density determination. The strong interfacial bonding between HNTs and rubber matrix is resulted through SA intermediated linkages. SA bonds SBR and HNTs through grafting copolymerization/hydrogen bonding mechanism. Significantly improved dispersion of HNTs in virtue of the interactions between HNTs and SA was achieved. Formation of zinc disorbate (ZDS) was revealed during the vulcanization of the composites. However, in the present systems, the contribution of ZDS to the reinforcement was limited. Effects of SA content on the vulcanization behavior, morphology and mechanical properties of the nanocomposites were investigated. Promising mechanical properties of SA modified SBR/HNTs nanocomposites were obtained. The changes in vulcanization behavior, mechanical properties and morphology were correlated with the interactions between HNTs and SA and the largely improved dispersion of HNTs.

  19. Styrene-butadiene rubber/halloysite nanotubes nanocomposites modified by sorbic acid

    Sorbic acid (SA) was used to improve the performance of styrene-butadiene rubber (SBR)/halloysite nanotubes (HNTs) nanocomposites by direct blending. The detailed mechanisms for the largely improved performance were studied by X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), differential scanning calorimetry (DSC), porosity analysis and crosslink density determination. The strong interfacial bonding between HNTs and rubber matrix is resulted through SA intermediated linkages. SA bonds SBR and HNTs through grafting copolymerization/hydrogen bonding mechanism. Significantly improved dispersion of HNTs in virtue of the interactions between HNTs and SA was achieved. Formation of zinc disorbate (ZDS) was revealed during the vulcanization of the composites. However, in the present systems, the contribution of ZDS to the reinforcement was limited. Effects of SA content on the vulcanization behavior, morphology and mechanical properties of the nanocomposites were investigated. Promising mechanical properties of SA modified SBR/HNTs nanocomposites were obtained. The changes in vulcanization behavior, mechanical properties and morphology were correlated with the interactions between HNTs and SA and the largely improved dispersion of HNTs.

  20. Viscoelastic properties of hydroxyl-terminated poly(butadiene based composite rocket propellants

    Brzić Saša J.

    2014-01-01

    Full Text Available In the present study, the viscoelastic response of three composite solid propellants based on hydroxyl-terminated poly(butadiene, ammonium perchlorate and aluminum has been investigated. The investigation was surveyed by dynamic mechanical analysis over a wide range of temperatures and frequencies. The mechanical properties of these materials are related to the macromolecular structure of the binder as well as to the content and nature of solid fillers. The storage modulus, loss modulus, loss factor and glass transition temperature for each propellant sample have been evaluated. The master curves of storage (log G' vs log ω and loss modulus (log G'' vs log ω were generated for each propellant. A comparison of logaT vs temperature curves for all propellants indicate conformance to Williams-Landel-Ferry equation. Choosing the glass transition as the reference temperature, WLF equation constants are determined. Fractional free volume at the glass transition temperature and thermal coefficient of free volume expansion values are in accordance with the consideration that Al is reinforcing filler.

  1. Biological monitoring to determine worker dose in a butadiene processing plant

    Bechtold, W.E.; Hayes, R.B. [National Cancer Inst., Bethesda, MD (United States)

    1995-12-01

    Butadiene (BD) is a reactive gas used extensively in the rubber industry and is also found in combustion products. Although BD is genotoxic and acts as an animal carcinogen, the evidence for carcinogenicity in humans is limited. Extrapolation from animal studies on BD carcinogenicity to risk in humans has been controversial because of uncertainties regarding relative biologic exposure and related effects in humans vs. experimental animals. To reduce this uncertainty, a study was designed to characterize exposure to BD at a polymer production facility and to relate this exposure to mutational and cytogenetic effects. Biological monitoring was used to better assess the internal dose of BD received by the workers. Measurement of 1,2-dihydroxy-4-(N-acetylcysteinyl) butane (M1) in urine served as the biomarker in this study. M1 has been shown to correlate with area monitoring in previous studies. Most studies that relate exposure to a toxic chemical with its biological effects rely on exposure concentration as the dose metric; however, exposure concentration may or may not reflect the actual internal dose of the chemical.

  2. Mechanical and Thermal Properties of Styrene Butadiene Rubber - Functionalized Carbon Nanotubes Nanocomposites

    Laoui, Tahar

    2013-01-01

    The effect of reinforcing styrene butadiene rubber (SBR) with functionalized carbon nanotubes on the mechanical and thermal properties of the nanocomposite was investigated. Multi-walled carbon nanotubes (CNTs) were functionalized with phenol functional group to enhance their dispersion in SBR matrix. Surface functionalization of the CNTs was carried out using acid treatment and FTIR technique was utilized so as to ascertain the presence of phenol functional group. This was followed with the dispersion of the functionalized CNTs into a polymer solution and a subsequent evaporation of the solvent. This study has demonstrated the inherent capability of CNTs as reinforcing filler as demonstrated by the substantial improvement in Young\\'s Modulus, tensile strength and energy of absorption of the nanocomposites. The tensile strength increased from 0.17 MPa (SBR) to 0.48 MPa while the Young\\'s Modulus increased from 0.25 MPa to 0.83 MPa when 10wt% functionalized CNTs was added. With the addition of 1wt% reinforcement-a peak value of 4.1 KJ energy absorption was obtained. The homogenous dispersion of CNT-Phenol is thought to be responsible for the considerable enhancement in the reported properties. Copyright © Taylor & Francis Group, LLC.

  3. Microstructural analysis of carbon nanomaterials produced from pyrolysis/combustion of Styrene-Butadiene-Rubber (SBR

    Joner Oliveira Alves

    2011-12-01

    Full Text Available Styrene-Butadiene-Rubber (SBR is a synthetic rubber copolymer used to fabricate several products. This study aims to demonstrate the use of SBR as feedstock for carbon nanomaterials (nanofibers and nanotubes growth, and therefore to establish a novel process for destination of waste products containing SBR. A three stage electrically heated flow reactor was used. Small pellets of rubber were pyrolyzed at a temperature of 1000 ºC. The pyrolyzates were mixed with oxygen-containing gases and were burned. The products of combustion were used to synthesize the carbon nanomaterials (CNMs at the presence of a catalyst. CNMs have a wide range of potential applications due to their extraordinary mechanical, thermal and electrical properties. Produced materials were characterized by SEM and TEM, whereas combustion products were assessed using GC. Results showed that CNMs with outer diameters of 30-100 nm and lengths of about 30 µm were formed. Therefore, it was demonstrated that waste products containing SBR can be used to generate CNMs which are value-added products of intense technological interest.

  4. Atmospheric pressure plasma polymerization of 1,3-butadiene for hydrophobic finishing of textile substrates

    Samanta, Kartick K.; Jassal, Manjeet; Agrawal, Ashwini K.

    2010-02-01

    Atmospheric pressure plasma processing of textile has both ecological and economical advantages over the wet-chemical processing. However, reaction in atmospheric pressure plasma has important challenges to be overcome before it can be successfully used for finishing applications in textile. These challenges are (i) generating stable glow plasma in presence liquid/gaseous monomer, and (ii) keeping the generated radicals active in the presence of contaminants such as oxygen and air. In this study, a stable glow plasma was generated at atmospheric pressure in the mixture of gaseous reactive monomer-1,3-butadiene and He and was made to react with cellulosic textile substrate. After 12 min of plasma treatment, the hydrophilic surface of the cellulosic substrate turned into highly hydrophobic surface. The hydrophobic finish was found to be durable to soap washing. After soap washing, a water drop of 37 μl took around 250 s to get absorbed in the treated sample compared to textile substrate. The surface characterization of the plasma modified samples under SEM and AFM revealed modification of the surface under textile substrates for producing hydrophobic surface finish.

  5. Reinforcing styrene butadiene rubber with lignin-novolac epoxy resin networks

    P. Yu

    2015-01-01

    Full Text Available In this study, lignin-novolac epoxy resin networks were fabricated in the styrene butadiene rubber (SBR matrix by combination of latex compounding and melt mixing. Firstly, SBR/lignin compounds were co-coagulated by SBR latex and lignin aqueous solution. Then the novolac epoxy resin (F51 was added in the SBR/lignin compounds by melt compounding method. F51 was directly cured by lignin via the ring-opening reaction of epoxy groups of F51 and OH groups (or COOH groups of lignin during the curing process of rubber compounds, as was particularly evident from Fourier transform infrared spectroscopy (FTIR studies and maximum torque of the curing analysis. The existence of lignin-F51 networks were also detected by scanning electron microscope (SEM and dynamic mechanical analysis (DMA. The structure of the SBR/lignin/F51 was also characterized by rubber process analyzer (RPA, thermogravimetric analysis (TGA and determination of crosslinking density. Due to rigid lignin-F51 networks achieved in SBR/lignin/F51 composites, it was found that the hardness, modulus, tear strength, crosslinking density, the temperature of 5 and 10% weight-loss were significantly enhanced with the loading of F51.

  6. Degradation of Hydrogenated Nitrile-butadiene Rubber in Aqueous Solutions of H2S or HCl

    CONG Chuan-bo; CUI Can-can; MENG Xiao-yu; LU Shao-jie; ZHOU Qiong

    2013-01-01

    The degradation of hydrogenated nitrile-butadiene rubber(HNBR) soaped in aqueous solutions of H2S and HCl was investigated.The samples unexposed and exposed to different solutions were characterized by 13C nuclear magnetic resonance(13C NMR),X-ray photoelectron and infrared spectroscopies.In contrast to those of unexposed samples and samples soaped in HCl solution,the mechanical properties of samples exposed to H2S solution significantly deteriorated,in which the new groups of C(=O)-NH2,C-S-C and C=S emerged.The mechanism of C=S and C-S-C formation was speculated,except for that of the formation of group C(=O)-NH2,which was widely discussed in acidic condition such as HC1 solution.The formation of C-S-C was due to radical reaction initiated by mercapto radical and that of C=S was due to nucleophilic reaction initiated by mercapto cations.This finding is helpful to understanding the seal failure of HNBR in working environment containing H2S.

  7. Application of Composite Powders Recycled from Graphite Tailings in Styrene-Butadiene Rubber

    Hai, Yun; Liao, Libing; Lv, Guocheng; Qin, Faxiang; Mei, Lefu; Wei, Yaozu

    2015-11-01

    With styrene-butadiene rubber (SBR) as matrix and composite powders recycled from graphite tailings as fillers, the influence of the particle size and content of the composite powders on the tensile strength and electrical conductivity of the composite powder-filled SBR were studied. The results showed that composite powder recycled from graphite tailings could reinforce SBR, whose tensile strength was significantly increased with reducing the particle size of the composite powder, but it had little effect on the conductivity of the system. With composite powders as fillers in conjunction with conductive carbon black, the tensile strength and electrical conductivity of the system were greatly improved. The maximum tensile strength of the SBR filled with composite powder and conductive carbon black increased by 47% compared to that of the single composite powder-filled SBR. When the filling content of conductive carbon black was 10 phr and that of composite powder was above 30 phr, the volume resistivity of SBR showed a sharp decline, reaching a minimum about 106 Ω cm at 40 phr. All the results indicated that composite powder recycled from graphite tailings can be applied effectively as filler in SBR. It has great economic and environmental benefits.

  8. Mechanical and Thermal Properties of Irradiated Styrene Butadiene Rubber Latex Loaded With Short Carbon Fiber

    In this study, two percentages (0.5, 1%) of short carbon fiber (SCF) were added to styrene butadiene rubber latex (SBR) to prepare SBR/ SCF composites. The SBR/ SCF films were exposed to different doses (10, 30, 50, 70 and 100 kGy) of gamma radiation. The effect of radiation doses and carbon fiber loaded on mechanical and thermal properties of SBR/ SCF composites was investigated. The tensile strength of composites increased with increasing irradiation dose, while the elongation at yield strength decreased with increasing radiation dose. It was noticed that, the mechanical properties of composites improved with the addition of carbon fiber. The addition of SCF enhanced the thermal stability, while the addition of SCF and radiation vulcanization decrease the rate of thermal decomposition of SBR composites. The effects of gamma ir - radiation as well as SCF on the activation energies of SBR/SCF samples had been investigated. The activation energy of SBR, SBR/ (0.5 % SCF) and SBR/ (1 % SCF) were 133, 114 and 98.2 kJ mole-1 respectively

  9. Photochemistry of the 1,4-Diphenyl-1,3-butadienes in Ethanol. Trapping Conical Intersections.

    Saltiel, Jack; Redwood, Christopher E

    2016-05-12

    We report photoisomerization and photoaddition quantum yields in ethanol starting from each 1,4-diphenyl-1,3-butadiene, DPB, isomer. Despite the fact that the trans,trans isomer, tt-DPB, has a significant fluorescence quantum yield and lifetime, whereas no fluorescence is observed from the cis isomers, ether formation occurs with similar efficiency from tt-DPB and ct-DPB and less efficiently from cc-DPB. Photoaddition is about 72 times slower than photoisomerization to the ct- and tt-DPB isomers starting from tt- and ct-DPB, respectively. The results are consistent with addition of alcohol to the common zwitterionic trans-phenallyl cation/benzyl anion intermediate that leads to photoisomerization through a conical intersection. Ether formation from cc-DPB tracks inefficient formation of tt-DPB indicating that the small bicycle pedal cc-DPB → tt-DPB component proceeds stepwise through the same zwitterionic trans-phenallyl cation/benzyl anion intermediate. Previous results concerning the addition of methanol to the stilbenes are similarly interpreted. In contrast to trans-stilbene, the fluorescence and photoisomerization quantum yields of tt-DPB are inconsistent with the assumption of strict complementarity between radiative and torsional relaxation channels of tt-DPB in alcohols. PMID:27081783

  10. Methods for measurement of reactive metabolites as a basis for cancer risk assessment: Application to 1,3-butadiene and isoprene

    1,3-Butadiene is a general air pollutant associated with combustion of organic matter and is also an extensively used monomer in polymer production. The cancer risk estimation of 1,3-butadiene is encumbered with large uncertainties. Extrapolation from tumour frequencies in long-term animal tests has led to a relatively high figure for the risk associated with 1,3-butadiene exposure. This is mainly based on observations of very high tumour incidences in butadiene-exposed mice, which in this respect are about 100 times more sensitive than rats. It has been hypothesized that a high cancer risk from 1,3-butadiene could be associated with its metabolism to the bifunctional 1,2:3,4-diepoxybutane (DEB) which, in comparison with monofunctional epoxides, 1,2-epoxy-3-butene (EB) and 1,2-epoxy-3,4-butanediol (EBdiol), is a highly effective mutagen, i.e. cancer initiator. Measurement of in vivo doses of DEB is therefore essential for the risk assessment of 1,3-butadiene. Reaction products with hemoglobin offer a possibility of measuring reactive metabolites in vivo. Hemoglobin adducts from EBdiol have in this study been measured with available methods, which are, however, not applicable to the bifunctional DEB, and method development was therefore needed. This work presents a procedure for measurement of a specific, ring-closed adduct, Pyr-Val, formed from the reaction of DEB with N-terminal valines in hemoglobin. It is based on LC-ESI-MS/MS analysis of the Pyr-modified N-terminal peptides enriched after trypsin digestion of globin. Mouse and rat could be compared regarding the metabolism of EB, DEB and EBdiol. From the data it was concluded that, in 1,3-butadiene exposure, about 60 times higher levels of DEB are formed in mice compared to rats. Estimates of in vivo doses in published cancer tests showed that carcinogenesis in mice is mainly due to DEB, whereas in rat, and possibly man, the monofunctional EBdiol is the predominant causative factor. Preliminarily, the cancer

  11. Characterization of hemoglobin adduct formation in mice and rats after administration of [14C]butadiene or [14C]isoprene

    Occupational exposures to 1,3-butadiene or isoprene occur through their use in the manufacture of rubber and other related polymer products. The purpose of this study was to determine if butadiene or isoprene administration would result in the formation of adducts with blood hemoglobin (Hb), and if such adducts can be used as a measure of previous exposure(s). Male B6C3F1 mice and male Sprague-Dawley rats were injected intraperitoneally with 1, 10, 100, or 1000 mumol [14C]butadiene or 0.3, 3.0, 300, 1000, or 3000 mumol [14C]isoprene per kilogram body weight. Animals were killed 24 hr later. Globin was isolated from blood samples and was analyzed for 14C by liquid scintillation spectroscopy. Hb adduct formation was linearly related to administered doses up to 100 mumol [14C]butadiene or 500 mumol [14C]isoprene per kilogram body weight for mice and rats, respectively. For [14C]butadiene, the efficiency of Hb adduct formation in mice and rats within the linear response range was 0.177 +/- 0.003 and 0.407 +/- 0.019 (pmol of 14C-adducts/mg globin)/(mumol of retained [14C]butadiene/kg body wt), respectively (mean +/- SE; n = 18). For [14C]isoprene, these values for mice and rats were 0.158 +/- 0.035 and 0.079 +/- 0.016 (pmol of 14C-adducts/mg globin)/(mumol of retained [14C]isoprene/kg body wt), respectively (mean +/- SE; n = 12). Hb adducts also accumulated linearly after repeated daily administration of 100 mumol [14C]butadiene or 500 mumol [14C]isoprene per kilogram body wt to mice and rats, respectively, for 3 days. [14C]Butadiene-derived Hb adducts in blood showed lifetimes of approximately 24 and approximately 65 days for mice and rats, respectively, which correlate with the reported lifetimes for red blood cells in these rodent species. Thus, levels of butadiene- or isoprene-derived adducts on Hb in circulating blood may be a useful measure of prior repeated exposures to these compounds

  12. Effect of water on hydrogenation of 1,3-butadiene over Au (1 1 1): A joint theoretical and experimental study

    Bu, Weida; Zhao, Liang, E-mail: Liangzhao@cup.edu.cn; Zhang, Zhicheng; Zhang, Xin; Gao, Jinsen; Xu, Chunming

    2014-01-15

    The effect of water on the hydrogenation of 1,3-butadiene over Au (1 1 1) was investigated based on density functional theory calculations and the results were compared with experimental study on the same reaction over Au/γ-Al{sub 2}O{sub 3} catalysts prepared by different methods. All possible adsorption sites and geometry structures of hydrogen, water and 1,3-butadiene on Au (1 1 1) were considered in the adsorption energy calculations to obtain the optimized adsorption modes. The hydrogenation of 1,3-butadiene was found to be only feasible with dissociated H atoms adsorbed over Au (1 1 1). Our adsorption calculations suggest that H{sub 2}O tended to block the active sites and inhibited the adsorption step, fully consistent with the rapid 1,3-butadiene conversion drop from above 40% to below 10% at low water concentration (<1200 ppm) in experiments. The transition state calculations indicate that water had little impact on the reaction step given slight change of energy barrier from 0.62 eV to 0.55 eV for the major route. This result validated the experimental finding that the conversion of 1,3-butadiene on Au/γ-Al{sub 2}O{sub 3} catalysts had only a slight decrease in a high water concentration range.

  13. Melt processing and property testing of a model system of plastics contained in waste from electrical and electronic equipment.

    Triantou, Marianna I; Tarantili, Petroula A; Andreopoulos, Andreas G

    2015-05-01

    In the present research, blending of polymers used in electrical and electronic equipment, i.e. acrylonitrile-butadiene-styrene terpolymer, polycarbonate and polypropylene, was performed in a twin-screw extruder, in order to explore the effect process parameters on the mixture properties, in an attempt to determine some characteristics of a fast and economical procedure for waste management. The addition of polycarbonate in acrylonitrile-butadiene-styrene terpolymer seemed to increase its thermal stability. Also, the addition of polypropylene in acrylonitrile-butadiene-styrene terpolymer facilitates its melt processing, whereas the addition of acrylonitrile-butadiene-styrene terpolymer in polypropylene improves its mechanical performance. Moreover, the upgrading of the above blends by incorporating 2 phr organically modified montmorillonite was investigated. The prepared nanocomposites exhibit greater tensile strength, elastic modulus and storage modulus, as well as higher melt viscosity, compared with the unreinforced blends. The incorporation of montmorillonite nanoplatelets in polycarbonate-rich acrylonitrile-butadiene-styrene terpolymer/polycarbonate blends turns the thermal degradation mechanism into a two-stage process. Alternatively to mechanical recycling, the energy recovery from the combustion of acrylonitrile-butadiene-styrene terpolymer/polycarbonate and acrylonitrile-butadiene-styrene terpolymer/polypropylene blends was recorded by measuring the gross calorific value. Comparing the investigated polymers, polypropylene presents the higher gross calorific value, followed by acrylonitrile-butadiene-styrene terpolymer and then polycarbonate. The above study allows a rough comparative evaluation of various methodologies for treating plastics from waste from electrical and electronic equipment. PMID:25750055

  14. The effect of distribution of monomer moiety on the pH response and mechanical properties of poly(acrylonitrile-co-acrylic acid) copolymers

    The pH response and mechanical properties of copolymer-based hydrogels such as poly(acrylonitrile-co-acrylic acid) are usually attributed to their chemical composition. In this study, it has been shown that the architecture of the polymer chains, i.e. the distribution of comonomers in the macromolecules, also plays a major role in controlling these properties. A series of four poly(acrylonitrile-co-acrylic acids) with fixed composition (i.e. ∼30 mol% acrylic acid moieties) were synthesized, where the block lengths of both AN (acrylonitrile) and AAc (acrylic acid) moieties in the copolymers were varied by controlling the feeding pattern of the monomers during free radical copolymerization. These copolymers were then converted into fine fibers of the same dimensions. The monomer distribution in the four copolymers was estimated using quantitative carbon 13C nuclear magnetic resonance (NMR) and related to the mechanical and pH response properties of the resultant fibers. The pH response of the fibers with similar composition increased dramatically as the block length of the AAc moiety was increased, while the mechanical properties increased as a direct function of the block length of the AN moieties. The fiber's response at pH 10 in terms of the change in length increased by ∼four times while its response rate increased by ∼50 times with the increase in block length of the AAc moiety. On the other hand, the tensile properties and retractive stress increased by ∼four times with the increase in the block length of the AN moiety

  15. Synthesis of Ethylene or Propylene/1,3-Butadiene Copolymers Possessing Pendant Vinyl Groups with Virtually No Internal Olefins

    Kenji Michiue

    2015-11-01

    Full Text Available In general, ethylene/1,3-butadiene copolymerizations provides copolymers possessing both pendant vinyls and vinylenes as olefinic moieties. We, at MCI, studied the substituent effects of C2-symmetric zirconocene complexes, rac-[Me2Si(Indenyl’2]ZrCl2 (Indenyl’ = generic substituted indenyl, after activation on the ratio of the pendant vinyls and vinylenes of the resultant copolymers. Complexes examined in this study were rac-dimethylsilylbis (1-indenylzirconium dichloride (1, rac-dimethylsilyl-bis[1-(2-methyl-4,5-benzoindenyl] zirconium dichloride (2, rac-dimethylsilyl-bis[l-(2-methyl -4-phenylindenyl]zirconium dichloride (3, rac-dimethy1si1y1- bis(2-ethyl-4-phenylindenyl zirconium dichloride (4, rac-dimethylsilyl-bis[l-(2-n-propyl -4-(1-naphthylindenyl]zirconium dichloride (5, rac-dimethylsilyl-[1-(2-ethyl-4-(5-(2,2-dimethyl-2,3-dihydro-1H-cyclopenta [a]naphthalenylindenyl][1-(2-n-propyl-4-(5-(2,2-dimethyl-2,3-dihydro-1H-cyclopenta[a] naphthalenylindenyl]zirconium dichloride (6, rac-dimethylsilyl-bis[1-(2-ethyl-4-(9-phenanthrylindenyl]zirconium dichloride (7, and rac-dimethylsilyl-bis[l-(2-n-propyl-4-(9-phenanthrylindenyl]zirconium dichloride (8. We found that the ratio of the pendant vinyls and vinylenes is strongly affected by the bulkiness of the substituent on the complexes examined. The vinyl content increased linearly in the following order, 8 > 7 > 6 > 5 > 4 > 3 > 2 > 1. Notably, complex 8/DMAO formed ethylene/1,3-butadiene copolymers possessing predominant vinyl groups, which can be crucial precursors for functionalized polyolefins. Likewise, complex 8/DMAO afforded propylene/1,3-butadiene copolymers with predominant vinyl groups.

  16. Effect of preparation method and CuO promotion in the conversion of ethanol into 1,3-butadiene over SiO₂-MgO catalysts.

    Angelici, Carlo; Velthoen, Marjolein E Z; Weckhuysen, Bert M; Bruijnincx, Pieter C A

    2014-09-01

    Silica-magnesia (Si/Mg=1:1) catalysts were studied in the one-pot conversion of ethanol to butadiene. The catalyst synthesis method was found to greatly influence morphology and performance, with materials prepared through wet-kneading performing best both in terms of ethanol conversion and butadiene yield. Detailed characterization of the catalysts synthesized through co-precipitation or wet-kneading allowed correlation of activity and selectivity with morphology, textural properties, crystallinity, and acidity/basicity. The higher yields achieved with the wet-kneaded catalysts were attributed to a morphology consisting of SiO2 spheres embedded in a thin layer of MgO. The particle size of the SiO2 catalysts also influenced performance, with catalysts with smaller SiO2 spheres showing higher activity. Temperature-programmed desorption (TPD) measurements showed that best butadiene yields were obtained with SiO2-MgO catalysts characterized by an intermediate amount of acidic and basic sites. A Hammett indicator study showed the catalysts' pK(a) value to be inversely correlated with the amount of dehydration by-products formed. Butadiene yields could be further improved by the addition of 1 wt% of CuO as promoter to give butadiene yields and selectivities as high as 40% and 53%, respectively. The copper promoter boosts the production of the acetaldehyde intermediate changing the rate-determining step of the process. TEM-energy-dispersive X-ray (EDX) analyses showed CuO to be present on both the SiO2 and MgO components. UV/Vis spectra of promoted catalysts in turn pointed at the presence of cluster-like CuO species, which are proposed to be responsible for the increased butadiene production. PMID:25045112

  17. Use of Yb-based catalyst for AGET ATRP of acrylonitrile to simultaneously control molecular mass distribution and tacticity

    Yb-based catalyst was used for the first time for atom transfer radical polymerization using activators generated by electron transfer (AGET ATRP) of acrylonitrile (AN) with 2-bromopropionitrile (BPN) as initiator, 2, 2′-bipyridine (bipy) as ligand, and tisn(II) bis(2-ethylhexanoate) (Sn(EH)2) as reducing agent in the presence of air. With respect to AGET ATRP of AN catalyzed by CuBr2, an evident increase of polymer tacticity was observed for AGET ATRP of AN. The increase of syndiotacticity became more and more pronounced than the increase of isotacticity of polyacrylonitrile (PAN) along with YbBr3 content. The block copolymer PAN-b-PMMA with molecular weight at 60,000 and polydispersity at 1.36 was successfully prepared. - Graphical abstract: Yb-based catalyst was used for the first time for AGET ATRP of AN with BPN as the initiator, bipy as the ligand, and Sn(EH)2 as the reducing agent in the presence of air. With respect to AGET ATRP with CuBr2 as catalyst, an obvious increase of polymer tacticity was observed for AGET ATRP of AN. The increase of syndiotacticity became more and more pronounced than the increase of isotacticity of polyacrylonitrile (PAN) along with YbBr3 content. The block copolymer PAN-b-PMMA with molecular weight at 60000 and polydispersity at 1.36 was successfully prepared. Highlights: ► Yb-based catalyst was used for the first time for AGET ATRP of AN. ► The reaction simultaneously controls polydispersity and tacticity of PAN. ► Well-defined block copolymer PAN-b-PMMA was successfully prepared.

  18. Use of Yb-based catalyst for AGET ATRP of acrylonitrile to simultaneously control molecular mass distribution and tacticity

    Ma Jing; Chen Hou, E-mail: lduchenhou@hotmail.com; Zhang Min; Wang Chunhua; Zhang Ying; Qu Rongjun

    2012-08-01

    Yb-based catalyst was used for the first time for atom transfer radical polymerization using activators generated by electron transfer (AGET ATRP) of acrylonitrile (AN) with 2-bromopropionitrile (BPN) as initiator, 2, 2 Prime -bipyridine (bipy) as ligand, and tisn(II) bis(2-ethylhexanoate) (Sn(EH){sub 2}) as reducing agent in the presence of air. With respect to AGET ATRP of AN catalyzed by CuBr{sub 2}, an evident increase of polymer tacticity was observed for AGET ATRP of AN. The increase of syndiotacticity became more and more pronounced than the increase of isotacticity of polyacrylonitrile (PAN) along with YbBr{sub 3} content. The block copolymer PAN-b-PMMA with molecular weight at 60,000 and polydispersity at 1.36 was successfully prepared. - Graphical abstract: Yb-based catalyst was used for the first time for AGET ATRP of AN with BPN as the initiator, bipy as the ligand, and Sn(EH){sub 2} as the reducing agent in the presence of air. With respect to AGET ATRP with CuBr{sub 2} as catalyst, an obvious increase of polymer tacticity was observed for AGET ATRP of AN. The increase of syndiotacticity became more and more pronounced than the increase of isotacticity of polyacrylonitrile (PAN) along with YbBr{sub 3} content. The block copolymer PAN-b-PMMA with molecular weight at 60000 and polydispersity at 1.36 was successfully prepared. Highlights: Black-Right-Pointing-Pointer Yb-based catalyst was used for the first time for AGET ATRP of AN. Black-Right-Pointing-Pointer The reaction simultaneously controls polydispersity and tacticity of PAN. Black-Right-Pointing-Pointer Well-defined block copolymer PAN-b-PMMA was successfully prepared.

  19. The uranium recovery from aqueous solutions using amidoxime modified cellulose derivatives. Pt. 1. Preparation, characterization and amidoxime conversion of radiation grafted ethyl cellulose-acrylonitrile copolymers

    Graft copolymers were prepared by 60Co-γ irradiation of binary mixture of ethyl cellulose (EC) and acrylonitrile (AN). Conversion %-dose graphs were obtained, and 95% copolymer yield has been reached at around 8 kGy dose. Conversion of nitrile groups to amidoxime (AO) were achieved by aqueous solutions of NH2OH.HCl-NaOH at 50 C. The amidoxime conversion was followed by using FT-IR spectrophotometer and determined as percentage. After 72 h period, nearly 100% amidoxime conversion was provided. The structures of EC-g-AN and EC-g-AO were characterized by FTIR/ATR, TGA, and SEM methods.

  20. Mechanical and tribological properties of acrylonitrile–butadiene rubber filled with graphite and carbon black

    Highlights: ► Graphite/carbon black/rubber micro- and nano-composites were prepared. ► Nanocomposites showed better mechanical properties and wear resistance. ► The effect of load and sliding speed on friction and wear is significant. ► Graphite lubricant film can reduce friction coefficient and wear rate. -- Abstract: In this work, acrylonitrile–butadiene rubber (NBR)/expanded graphite (EG)/carbon black (CB) micro- and nanocomposites were prepared by two different methods, and the resulting mechanical and tribological properties were compared with those of NBR/CB composites. Meanwhile, the effects of graphite dispersion and loading content, as well as the applied load and sliding velocity on the tribological behavior of the above composites under dry friction condition were also evaluated. The worn surfaces were analyzed by scanning electron microscopy (SEM) to disclose wear mechanism. As expected, the better the dispersion of graphite, the more remarkable enhancement on tensile and dynamic mechanical properties, and the greater reduction in the coefficient of friction (COF) and specific wear rate (Ws). It was found that a small amount of EG could effectively decrease COF and Ws of NBR/CB composites because of the formation of graphite lubricant films. The COF and Ws of NBR/CB/EG composites show a decreasing trend with a rise in applied load and sliding velocity. NBR/CB/EG nanocomposite always shows a stable wearing process with relatively low COF and Ws. It is thought that well-dispersed graphite nano-sheets were beneficial to the formation of a fine and durable lubricant film.

  1. Functional carbo-butadienes: nonaromatic conjugation effects through a 14-carbon, 24-π-electron backbone.

    Rives, Arnaud; Maraval, Valérie; Saffon-Merceron, Nathalie; Chauvin, Remi

    2014-01-01

    A systematic study of carbo-butadiene motifs not embedded in an aromatic carbo-benzene ring is described. Dibutatrienylacetylene (DBA) targets R(1) C(R)CCC(Ph)C≡CC(Ph)CCC(R)R(2) are devised, in which R is C≡CSiiPr3 and R(1) and R(2) are R, H, or 4-X-C6 H4 , with the latter including three known representatives (X: H, NMe2 , or NH2 ). The synthesis method is based on the SnCl2 -mediated reduction of pentaynediols prepared by early or late divergent strategies; the latter allows access to a OMe-NO2 push-pull diaryl-DBA. If R(1) and R(2) are H, an over-reduced dialkynylbutatriene (DAB) with two allenyl caps was isolated instead of the unsubstituted DBA. If R(1) =R(2) =R, the tetraalkynyl-DBA target was obtained, along with an over-reduced DBA product with a 12-membered 1,2-alkylidene-1H2 ,2H2 -carbo-cyclobutadiene ring. X-ray crystallography shows that all of the acyclic DBAs adopt a planar trans-transoid-trans configuration. The maximum UV/Vis absorption wavelength is found to vary consistently with the overall π-conjugation extent and, more intriguingly, with the π-donor character of the aryl X substituents, which varies consistently with the first (reversible) reduction potential and first (irreversible) oxidation peak, as determined by voltammetry. PMID:24311108

  2. Interaction of Chloroprene and Nitrile- Butadiene Rubber with Lubricating Greases and Base Oils

    2006-01-01

    The present communication addresses compatibility of two synthetic rubber types, chloroprene and nitrilebutadiene ones, with a number of base oils of petroleum origin and lubricating greases produced thereof. Four base oils,including three naphthenic products with varying degrees of refining and one paraffinic product,were compared with each other in terms of their effect on the rubbers. Degenerative changes occurring in the rubbers on contact with the oils and greases were studied using accelerated ageing tests. Alterations in rubber parameters, such as hardness, weight and glass transition temperature, caused by interaction with oil were monitored. The main physicochemical mechanisms standing behind the changes observed in the rubber properties were found to be (i) migration of plasticizer from rubber into the oil phase, (ii) absorption of oil by rubber,and (iii) oxidation of rubber. An increase in glass transition temperature (Tg) of rubber aged in a base oil or grease was considered as an indirect indication that the plasticizer had migrated out of rubber;the plasticizer accumulation in the oil phase being directly confirmed by gas chromatography. In order to suppress the plasticizer migration, oil additivation with dioctyl adipate (DOA), a common plasticizer used in rubber formulations, was attempted. However, the BOA-additivated oils, while reducing plasticizer migration, were found to cause more swelling than the original oils in the case of chloroprene rubber. As an alternative, replacement of BOA by an alkylated aryl phosphate in nitrile- butadiene rubber formulations was considered, but it did not solve the problem either.The results of this study suggest conclusively that the type of rubber, the plasticizer, and the base oil are all the crucial parameters that should be considered when matching rubber with oil in real- life applications. Interaction of rubber with base oils and with greases produced thereof is largely controlled by (i) solvency of the

  3. Pharmacokinetics of Polymersomes Composed of Poly(Butadiene-Ethylene Oxide); Healthy versus Tumor-Bearing Mice.

    Wang, G; de Kruijff, R M; Abou, D; Ramos, N; Mendes, E; Franken, L E; Wolterbeek, H T; Denkova, A G

    2016-02-01

    Vesicles composed of block copolymers (i.e., polymersomes) are one of the most versatile nano-carriers for medical purposes due to their tuneable physicochemical properties and the possibility to encapsulate simultaneously hydrophobic and hydrophilic substances, allowing, for instance, the combination of therapy and imaging. In cancer treatment, these vesicles need to remain long enough in the blood stream to be sufficiently taken up by tumors. Here, we have investigated the biodistribution and the pharmacokinetics of polymersomes, composed of poly(butadiene-b-ethylene oxide) having dimensions around 80 nm. The polymersomes have been radiolabeled with ¹¹¹In via the so-called active loading method achieving a loading efficiency of 92.9 ± 0.9% with radionuclide retention in mouse serum of more than 95% at 24 h. The optimized ¹¹¹In containing polymersomes have been intravenously administered in healthy and tumor bearing mice for pharmacokinetic determination using microSPECT (Single Photon Emission Computed Tomography). In healthy mice these polymersomes have been found to exhibit relatively long blood circulation (> 6 h), low liver uptake (6 ± 1.5%ID/g, 48 h p.i.) and elevated spleen uptake (188 ± 30%ID/g). The blood circulation in tumor bearing mice is dramatically reduced (< 1.5 h) most likely due to elevated splenic filtration, clearly indicating the importance of in vivo studies in diseased mice. Finally, the polymersomes have been injected subcutaneously in tumor bearing mice revealing retention of 77% in the mice, primarily accumulated at the site of injection, up to 48 hours after administration. PMID:27305765

  4. Mechanical performance of styrene-butadiene-rubber filled with carbon nanoparticles prepared by mechanical mixing

    Highlights: → We compare influence of carbon blacks and carbon nanotube on properties of SBR. → We model mechanical behavior of SBR nanocomposites by the micromechanical model. → Mechanical properties of carbon black/SBR is greatly dominated by bound rubber. → Mechanical properties of SBR/nanotube is governed by big aspect ratio of nanotube. - Abstract: Reinforcement of styrene-butadiene-rubber (SBR) was investigated using two different carbon blacks (CBs) with similar particle sizes, including highly structured CB and conventional CB, as well as multi-walled carbon nanotube (MWCNT) prepared by mechanical mixing. The attempts were made to examine reinforcing mechanism of these two different classes of carbon nanoparticles. Scanning electron microscopy and electrical conductivity measurement were used to investigate morphology. Tensile, cyclic tensile and stress relaxation analyses were performed. A modified Halpin-Tsai model based on the concept of an equivalent composite particle, consisting of rubber bound, occluded rubber and nanoparticle, was proposed. It was found that properties of CB filled SBR are significantly dominated by rubber shell and occluded rubber in which molecular mobility is strictly restricted. At low strains, these rubber constituents can contribute in hydrodynamic effects, leading to higher elastic modulus. However, at higher strains, they contribute in stress hardening resulting in higher elongation at break and higher tensile strength. These elastomeric regions can also influence stress relaxation behaviors of CB filled rubber. For SBR/MWCNT, the extremely great inherent mechanical properties of nanotube along with its big aspect ratio were postulated to be responsible for the reinforcement while their interfacial interaction was not so efficient.

  5. Glass Transition and Molecular Mobility in Styrene-Butadiene Rubber Modified Asphalt.

    Khabaz, Fardin; Khare, Rajesh

    2015-11-01

    Asphalt, a soft matter consisting of more than a thousand chemical species, is of vital importance for the transportation infrastructure, yet it poses significant challenges for microscopic theory and modeling approaches due to its multicomponent nature. Polymeric additives can potentially enhance the thermo-mechanical properties of asphalt, thus helping reduce the road repair costs; rational design of such systems requires knowledge of the molecular structure and dynamics of these systems. We have used molecular dynamics (MD) simulations to investigate the volumetric, structural, and dynamic properties of the neat asphalt as well as styrene-butadiene rubber (SBR) modified asphalt systems. The volume-temperature behavior of the asphalt systems exhibited a glass transition phenomenon, akin to that observed in experiments. The glass transition temperature, room temperature density, and coefficient of volume thermal expansion of the neat asphalt systems so evaluated were in agreement with experimental data when the effect of the high cooling rate used in simulations was accounted for. While the volumetric properties of SBR modified asphalt were found to be insensitive to the presence of the SBR additive, the addition of SBR led to an increase in the aggregation of asphaltene molecules. Furthermore, addition of SBR caused a reduction in the mobility of the constituent molecules of asphalt, with the reduction being more significant for the larger constituent molecules. Similar to other glass forming liquids, the reciprocal of the diffusion coefficient of the selected molecules was observed to follow the Vogel-Fulcher-Tammann (VFT) behavior as a function of temperature. These results suggest the potential for using polymeric additives for enhancing the dynamic mechanical properties of asphalt without affecting its volumetric properties. PMID:26451630

  6. VAPOR-PHASE CATALYTIC CONVERSION OF ETHANOL INTO 1,3-BUTADIENE ON Cr-Ba/MCM-41 CATALYSTS

    N. La-Salvia; J. J. Lovón-Quintana; G.P. VALENÇA

    2015-01-01

    AbstractAl-MCM-41, 16%Ba/Al-MCM-41 and 1.4%Cr-16%Ba/Al-MCM-41 were used as catalysts in the vapor-phase catalytic conversion of ethanol. Physical-chemical properties of the catalysts and the effect of barium and chromium on the Al-MCM-41 activity and 1,3-butadiene yield were studied. The catalysts were characterized by X-ray diffraction (XRD), N2 physisorption (BET method), CO2chemisorption and Fourier transform infrared spectroscopy (FT-IR). When ethanol was completely converted on Al-MCM-41...

  7. Ethanol-to-Butadiene Conversion over SiO2-MgO Catalysts: Synthesis-Structure-Performance Relationships

    Angelici, C.

    2015-01-01

    The work presented in this PhD Thesis provides new insights into the underlying reasons that make SiO2-MgO materials excellent catalysts for the ethanol-to-butadiene Lebedev process. In particular, the preparation technique of choice affects the structural properties of the resulting SiO2-MgO materials considerably and therefore the distribution, i.e. nature and amount, of acidic-basic sites. Given the complex cascade of elementary steps required, striking a precise balance in the latter is k...

  8. Diastereo- and Enantioselective Ruthenium Catalyzed Hydrohydroxyalkylation of 2-Silyl-Butadienes: Carbonyl syn-Crotylation from the Alcohol Oxidation Level

    Zbieg, Jason R.; Moran, Joseph; Krische, Michael J.

    2011-01-01

    Exposure of alcohols 2a-2j to 2-silyl-butadienes in the presence of ruthenium complexes modified by (R)-SEGPHOS or (R)-DM-SEGPHOS results in redox-triggered generation of allylruthenium-aldehyde pairs, which combine to form products of carbonyl crotylation 4a-4j in the absence of stoichiometric byproducts and with high levels of syn-diastereo- and enantioselectivity. In the presence of isopropanol under otherwise identical conditions, aldehydes 3a-3j are converted to an equivalent set of addu...

  9. Comparison between phosphine and NHC-modified Pd catalysts in the telomerization of butadiene with methanol – a kinetic study combined with model-based experimental analysis

    Hopf, Lisa; Recker, Sebastian; Niedermaier, Matthias; Kiermaier, Stephan; Strobel, Vinzent; Maschmeyer, Dietrich; Cole-Hamilton, David; Marquardt, Wolfgang; Wasserscheid, Peter; Haumann, Marco

    2015-01-01

    The authors thank the European Community within its project SYNFLOW (FP7; grant agreement n8 NMP2-LA-2010-246461) for financial support. The telomerization of butadiene with methanol was investigated in the presence of different palladium catalysts modified either with triphenylphosphine (TPP) or 1,3-dimesityl-imidazol-2-ylidene (IMes) ligand. When pure butadiene was used as substrate, a moderate selectivity for the Pd-TPP catalyst toward the desired product 1-methoxy-2,7-octadiene (1-Mode...

  10. Influence of acid-base properties on the Lebedev ethanol-to-butadiene process catalyzed by SiO2-MgO materials

    Angelici, Carlo; Velthoen, Marjolein E. Z.; Weckhuysen, Bert M.; Bruijnincx, Pieter C. A.

    2015-01-01

    The Lebedev ethanol-to-butadiene process entails a complex chain of reactions that require catalysts to possess a subtle balance in the number and strength of acidic and basic sites. SiO2-MgO materials can be excellent Lebedev catalysts if properly prepared, as catalyst performance has been found to depend significantly on the synthesis method. To assess the specific requirements for butadiene production in terms of active sites and to link their presence to the specific preparation method ap...

  11. Analysis of recycled poly (styrene-co-butadiene) sulfonation: a new approach in solid catalysts for biodiesel production.

    Aguilar-Garnica, Efrén; Paredes-Casillas, Mario; Herrera-Larrasilla, Tito E; Rodríguez-Palomera, Felicia; Ramírez-Arreola, Daniel E

    2013-01-01

    The disposal of solid waste is a serious problem worldwide that is made worse in developing countries due to inadequate planning and unsustainable solid waste management. In Mexico, only 2% of total urban solid waste is recycled. One non-recyclable material is poly (styrene-co-butadiene), which is commonly used in consumer products (like components of appliances and toys), in the automotive industry (in instrument panels) and in food services (e.g. hot and cold drinking cups and glasses). In this paper, a lab-scale strategy is proposed for recycling poly (styrene-co-butadiene) waste by sulfonation with fuming sulfuric acid. Tests of the sulfonation strategy were carried out at various reaction conditions. The results show that 75°C and 2.5 h are the operating conditions that maximize the sulfonation level expressed as number of acid sites. The modified resin is tested as a heterogeneous catalyst in the first step (known as esterification) of biodiesel production from a mixture containing tallow fat and canola oil with 59% of free fatty acids. The preliminary results show that esterification can reach 91% conversion in the presence of the sulfonated polymeric catalyst compared with 67% conversion when the reaction is performed without catalyst. PMID:24098857

  12. Evaluation of 1,3-butadiene dimerization and secondary reactions in the presence and absence of oxygen.

    Aldeeb, A A; Rogers, W J; Mannan, M S

    2004-11-11

    Thermal stability evaluation of exothermic chemical reactions is of great importance to the safer design and operation of chemical processes. Dominant reaction stoichiometries and their thermochemistry parameters are key elements in the evaluation process. Identification of significant reaction pathways under possible process conditions will lead to an understanding of the overall thermodynamic and kinetic behavior. The kinetics of 1,3-butadiene (BD) is an excellent example of conjugated dienes that undergo addition reactions. At elevated temperatures, 1,3-butadiene monomers can dimerize exothermally, and as temperature increases, secondary exothermic reactions will take place. The very high temperature and pressure rates that these reactions can attain may lead to a reaction runaway or even a thermal explosion. BD is a vapor at ambient conditions, usually stored as a pressurized liquid, and is a carcinogen, so the experimental evaluation is potentially difficult and hazardous. In this paper, the thermal stability of BD is evaluated. Dimerization and other secondary reactions are investigated by experimental thermal analysis using an automatic pressure adiabatic calorimeter (APTAC), by theoretical computational quantum chemistry methods, and empirical thermodynamic-energy correlations. A theoretical approach is conducted to predict some of the BD reaction behavior. Results are compared to other literature data obtained using different experimental methods. PMID:15518964

  13. Low-temperature 1 3-butadiene Hydrogenation over Supported Pt/3d/gamma-Al2O3 Bimetallic Catalysts

    W Lonergan; X Xing; R Zheng; S Qi; B Huang; J Chen

    2011-12-31

    Low-temperature 1,3-butadiene hydrogenation is used as a probe reaction to investigate the hydrogenation activity over several {gamma}-Al{sub 2}O{sub 3} supported Pt/3d (3d = Co, Ni, Cu) bimetallic catalysts. Batch and flow reactor studies are employed to quantify the kinetic activity and steady-state conversion, respectively, of each catalyst. Transmission electron microscopy (TEM) is utilized to characterize particle sizes and extended X-ray absorption fine structure (EXAFS) measurements are performed to verify the Pt-3d bimetallic bond formation. Pulse carbon monoxide chemisorption measurements are also performed to characterize the number of active sites. Additionally, density functional theory (DFT) calculations are included to determine the binding energies of 1,3-butadiene and atomic hydrogen on the corresponding model surfaces. The binding energies of the adsorbates are found to correlate with the hydrogenation activity, allowing for use of such correlation to potentially predict hydrogenation catalysts with enhanced activity based on the binding energies of the adsorbates of interest.

  14. Thermal stability and kinetic study of poly(ethyl methacrylate-co-acrylonitrile) nanocomposites prepared by in situ polymerization in presence of an Algerian bentonite

    Graphical abstract: - Highlights: • poly(ethyl methacrylate-co-acrylonitrile) nanocomposites were successfully prepared. • These nanocomposites were of higher Tg and improved thermal stability. • Their (Eα) of thermal decomposition were higher than those of the virgin copolymer. • Increase of (Eα), confirmed change in the degradation mechanism with clay loading. - Abstract: Poly(ethyl methacrylate-co-acrylonitrile) (PEAMN20) nanocomposites were successfully prepared via free radical in situ polymerization using a bentonite from Algeria modified by Hexadecyltrimethylammonium chloride (HDTMA). X-ray diffraction (XRD) and transmission electronic microscopy (TEM) investigations revealed that depending on the OMMT loading, intercalated or partially exfoliated nanocomposites were obtained. These nanocomposites exhibited an overall improved thermal stability and an increase in their glass transition temperature compared to the pure copolymer (PEMAN20) as evidenced by Thermogravimetric (TGA) and Differential Scanning Calorimetry (DSC) analysis. Apparent activation energies (Eα) of thermal decomposition of the elaborated nanocomposites, determined by Tang method, were higher than those of the virgin copolymer. The significant increase of (Eα), observed with PEMAN20/OMMT (1 wt%) confirmed the change in the degradation mechanism with OMMT loading and the ratio of intercalated/exfoliated structures

  15. Thermal stability and kinetic study of poly(ethyl methacrylate-co-acrylonitrile) nanocomposites prepared by in situ polymerization in presence of an Algerian bentonite

    Kadi, Souad [Université des Sciences et de la Technologie Houari Boumediene, Laboratoire des Matériaux Polymères, Faculté de Chimie, BP 32 El-Alia, Bab-Ezzouar, 16111 Algiers (Algeria); Djadoun, Saïd, E-mail: matpolylab@yahoo.fr [Université des Sciences et de la Technologie Houari Boumediene, Laboratoire des Matériaux Polymères, Faculté de Chimie, BP 32 El-Alia, Bab-Ezzouar, 16111 Algiers (Algeria); Sbirrazzuoli, Nicolas [Univ. Nice Sophia Antipolis, CNRS, LPMC, UMR 7336, 06100 Nice (France)

    2013-10-10

    Graphical abstract: - Highlights: • poly(ethyl methacrylate-co-acrylonitrile) nanocomposites were successfully prepared. • These nanocomposites were of higher T{sub g} and improved thermal stability. • Their (E{sub α}) of thermal decomposition were higher than those of the virgin copolymer. • Increase of (E{sub α}), confirmed change in the degradation mechanism with clay loading. - Abstract: Poly(ethyl methacrylate-co-acrylonitrile) (PEAMN20) nanocomposites were successfully prepared via free radical in situ polymerization using a bentonite from Algeria modified by Hexadecyltrimethylammonium chloride (HDTMA). X-ray diffraction (XRD) and transmission electronic microscopy (TEM) investigations revealed that depending on the OMMT loading, intercalated or partially exfoliated nanocomposites were obtained. These nanocomposites exhibited an overall improved thermal stability and an increase in their glass transition temperature compared to the pure copolymer (PEMAN20) as evidenced by Thermogravimetric (TGA) and Differential Scanning Calorimetry (DSC) analysis. Apparent activation energies (E{sub α}) of thermal decomposition of the elaborated nanocomposites, determined by Tang method, were higher than those of the virgin copolymer. The significant increase of (E{sub α}), observed with PEMAN20/OMMT (1 wt%) confirmed the change in the degradation mechanism with OMMT loading and the ratio of intercalated/exfoliated structures.

  16. NanoLC/ESI+ HRMS3 quantitation of DNA adducts induced by 1,3-butadiene.

    Sangaraju, Dewakar; Villalta, Peter W; Wickramaratne, Susith; Swenberg, James; Tretyakova, Natalia

    2014-07-01

    Human exposure to 1,3-butadiene (BD) present in automobile exhaust, cigarette smoke, and forest fires is of great concern because of its potent carcinogenicity. The adverse health effects of BD are mediated by its epoxide metabolites such as 3,4-epoxy-1-butene (EB), which covalently modify genomic DNA to form promutagenic nucleobase adducts. Because of their direct role in cancer, BD-DNA adducts can be used as mechanism-based biomarkers of BD exposure. In the present work, a mass spectrometry-based methodology was developed for accurate, sensitive, and precise quantification of EB-induced N-7-(1-hydroxy-3-buten-2-yl) guanine (EB-GII) DNA adducts in vivo. In our approach, EB-GII adducts are selectively released from DNA backbone by neutral thermal hydrolysis, followed by ultrafiltration, offline HPLC purification, and isotope dilution nanoLC/ESI(+)-HRMS(3) analysis on an Orbitrap Velos mass spectrometer. Following method validation, EB-GII lesions were quantified in human fibrosarcoma (HT1080) cells treated with micromolar concentrations of EB and in liver tissues of rats exposed to sub-ppm concentrations of BD (0.5-1.5 ppm). EB-GII concentrations increased linearly from 1.15 ± 0.23 to 10.11 ± 0.45 adducts per 10(8) nucleotides in HT1080 cells treated with 0.5-10 μM EB. EB-GII concentrations in DNA of laboratory rats exposed to 0.5, 1.0, and 1.5 ppm BD were 0.17 ± 0.05, 0.33 ± 0.08, and 0.50 ± 0.04 adducts per 10(8) nucleotides, respectively [corrected]. We also used the new method to determine the in vivo half-life of EB-GII adducts in rat liver DNA (2.20 ± 0.12 d) and to detect EB-GII in human blood DNA. To our knowledge, this is the first application of nanoLC/ESI(+)-HRMS(3) Orbitrap methodology to quantitative analysis of DNA adducts in vivo. PMID:24867429

  17. Reaction pathways by quantum Monte Carlo: Insight on the torsion barrier of 1,3-butadiene, and the conrotatory ring opening of cyclobutene

    Barborini, Matteo; Guidoni, Leonardo

    2012-12-01

    Quantum Monte Carlo (QMC) methods are used to investigate the intramolecular reaction pathways of 1,3-butadiene. The ground state geometries of the three conformers s-trans, s-cis, and gauche, as well as the cyclobutene structure are fully optimised at the variational Monte Carlo (VMC) level, obtaining an excellent agreement with the experimental results and other quantum chemistry high level calculations. Transition state geometries are also estimated at the VMC level for the s-trans to gauche torsion barrier of 1,3-butadiene and for the conrotatory ring opening of cyclobutene to the gauche-1,3-butadiene conformer. The energies of the conformers and the reaction barriers are calculated at both variational and diffusional Monte Carlo levels providing a precise picture of the potential energy surface of 1,3-butadiene and supporting one of the two model profiles recently obtained by Raman spectroscopy [Boopalachandran et al., J. Phys. Chem. A 115, 8920 (2011), 10.1021/jp2051596]. Considering the good scaling of QMC techniques with the system's size, our results also demonstrate how variational Monte Carlo calculations can be applied in the future to properly investigate the reaction pathways of large and correlated molecular systems.

  18. The industion of micronuclei, single.strand breaks in DNA and DNA repair in mice exposed to 1,3-butadiene by inhalation

    Štětina, R.; Vodička, Pavel; Vodičková, Ludmila; Šmerák, P.; Bárta, I.

    Prague : EEMS, 2006. s. 181-181. [Annual Meeting of the European Environmental Mutagen Society /36./. 02.07.2006-06.07.2006, Prague] R&D Projects: GA MZd NR8563 Institutional research plan: CEZ:AV0Z50390512 Keywords : 1,3-butadiene Subject RIV: EB - Genetics ; Molecular Biology

  19. Inner Stucture of Thin Films of Lamellar Poly(styrene-b-butadiene) Diblock Copolymers as revealed by Grazing-Incidence Small-Angle Scattering

    Busch, Peter; Posselt, Dorthe; Smilgies, Detlef-Matthias;

    2007-01-01

    The lamellar orientation in supported, thin films of poly(styrene-b-butadiene) (P(S-b-B)) depends on block copolymer molar mass. We have studied films from nine block copolymer samples with molar masses between 13.9 and 183 kg/mol using grazing-incidence small-angle X-ray scattering (GISAXS) and ...

  20. Acrylonitrile exposure: the effect on p53 and p21WAF1 protein levels in the blood plasma of occupationally exposed workers and in vitro in human diploid lung fibroblasts

    Rössner ml., Pavel; Binková, Blanka; Chvátalová, Irena; Šrám, Radim

    č. 517 (2002), s. 239-250. ISSN 0027-5107 R&D Projects: GA MŽP SI/340/1/97 Institutional research plan: CEZ:AV0Z5039906 Keywords : Acrylonitrile * p53 protein * p21WAF1 protein Subject RIV: DN - Health Impact of the Environment Quality Impact factor: 3.158, year: 2002

  1. Molecular epidemiological studies in 1,3-butadiene exposed Czech workers: female-male comparisons.

    Albertini, Richard J; Sram, Radim J; Vacek, Pamela M; Lynch, Jeremiah; Rossner, Pavel; Nicklas, Janice A; McDonald, Jake D; Boysen, Gunnar; Georgieva, Nadia; Swenberg, James A

    2007-03-20

    Results of a recent molecular epidemiological study of 1,3-butadiene (BD) exposed Czech workers, conducted to compare female to male responses, have confirmed and extended the findings of a previously reported males only study (HEI Research Report 116, 2003). The initial study found that urine concentrations of the metabolites 1,2-dihydroxy-4-(acetyl) butane (M1) and 1-dihydroxy-2-(N-acetylcysteinyl)-3-butene (M2) and blood concentrations of the hemoglobin adducts N-[2-hydroxy-3-butenyl] valine (HB-Val) and N-[2,3,4-trihydroxy-butyl] valine (THB-Val) constitute excellent biomarkers of exposure, both being highly correlated with BD exposure levels, and that GST genotypes modulate at least one metabolic pathway, but that irreversible genotoxic effects such as chromosome aberrations and HPRT gene mutations are neither associated with BD exposure levels nor with worker genotypes (GST [glutathione-S-transferase]-M1, GSTT1, CYP2E1 (5' promoter), CYP2E1 (intron 6), EH [epoxide hydrolase] 113, EH139, ADH [alcohol dehydrogenase]2 and ADH3). The no observed adverse effect level (NOAEL) for chromosome aberrations and HPRT mutations was 1.794 mg/m(3) (0.812 ppm)--the mean exposure level for the highest exposed worker group in this initial study. The second Czech study, reported here, initiated in 2003, included 26 female control workers, 23 female BD exposed workers, 25 male control workers and 30 male BD exposed workers (some repeats from the first study). Multiple external exposure measurements (10 full 8-h shift measures by personal monitoring per worker) over a 4-month period before biological sample collections showed that BD workplace levels were lower than in the first study. Mean 8-h TWA exposure levels were 0.008 mg/m(3) (0.0035 ppm) and 0.397 mg/m(3) (0.180 ppm) for female controls and exposed, respectively, but with individual single 8-h TWA values up to 9.793 mg/m(3) (4.45 ppm) in the exposed group. Mean male 8-h TWA exposure levels were 0.007 mg/m(3) (0.0032 ppm

  2. Pathway and Surface Mechanism Studies of 1,3-butadiene Selective Oxidation Over Vanadium-Molybdenum-Oxygen Catalysts

    William David Schroeder

    2002-05-27

    The partial oxidation of 1,3-butadiene has been investigated over VMoO catalysts synthesized by sol-gel techniques. Surface areas were 9-14 m{sup 2}/g, and compositions were within the solid solution regime, i.e. below 15.0 mol % MoO{sub 3}/(MoO{sub 3} + V{sub 2}O{sub 5}). Laser Raman Spectroscopy and XRD data indicated that solid solutions were formed, and pre- and post-reaction XPS data indicated that catalyst surfaces contained some V{sup +4} and were further reduced in 1,3-butadiene oxidation. A reaction pathway for 1,3-butadiene partial oxidation to maleic anhydride was shown to involve intermediates such as 3,4-epoxy-1-butene, crotonaldehyde, furan, and 2-butene-1,4-dial. The addition of water to the reaction stream substantially increased catalyst activity and improved selectivity to crotonaldehyde and furan at specific reaction temperatures. At higher water addition concentrations, furan selectivity increased from 12% to over 25%. The catalytic effects of water addition were related to competitive adsorption with various V{sub 2}O{sub 5}-based surface sites, including the vanadyl V=O, corner sharing V-O-V and edge sharing V-O oxygen. Higher levels of water addition were proposed to impose acidic character by dissociative adsorption. In addition, a novel combinatorial synthesis technique for VMoO was used to investigate the phase transitions of V{sub 2}O{sub 5}, solid solutions of Mo in V{sub 2}O{sub 5}, V{sub 9}Mo{sub 6}O{sub 40}, and other reduced VMoO compounds, characterized by laser Raman spectroscopy. The natural composition gradient imposed by the sputter deposition apparatus was used to create VMoO arrays containing 225 samples ranging from 7.0-42 mol% MoO{sub 3}/(V{sub 2}O{sub 5} + MoO{sub 3}), determined by EDS analysis.

  3. Carbon Nanotube-thermally Reduced Graphene Hybrid/Styrene Butadiene Rubber Nano Composites: Mechanical, Morphological and Dielectric Studies

    Jiji Abraham

    2015-07-01

    Full Text Available Styrene Butadiene Rubber composites with mixture of carbon nanotube and thermally reduced graphene were prepared and morphological, mechanical and dielectric properties of the composites were studied. Aim of this study is to understand the dispersion and reinforcement behaviour of hybrid filler in rubber matrix. Improved mechanical properties in the presence of graphene are due to the good dispersion and improved compatibility with the matrix. The formation of a mixed filler network showed a synergistic effect on the improvement of electrical as well as various mechanical properties. This method provides a simple route to enhance the dispersion of carbon nanotubes and to improve the electrical property of the polymer composites. It is concluded that introduction of thermally reduced graphene to CNT-SBR composites can improve the mechanical properties of the composites up to an optimum concentration of the graphene after that performance will be diminished due to the agglomeration of graphene.

  4. Improved ozone resistance of styrene-butadiene rubber cured by a combination of sulfur and ionizing radiation

    Fourier Transform (FTIR) studies performed in this work indicate that high ozone resistance of Styrene-Butadiene Rubber (SBR) formulations cured by a combination of sulfur and ionizing radiation is associated with unusually high vinyl concentration. On the other hand, sulfur cured SBR formulations with low vinyl concentration have poor ozone resistance. Curing with peroxides which involves chemistry similar to that of radiation curing, also leads to high vinyl concentration (relative to sulfur curing) and high ozone resistance. Increasing the absorbed dose in sulfur-radiation cured samples decreased the high vinyl content to a point where the ozone resistance declined greatly. Carbon black was shown to reduce the absorption of both the transvinylene and the vinyl unsaturation groups, but not to the same extent in all formulations. Also, the carbon black seems to play a greater role in the absorption of the unsaturation as sulfur increases. (Author)

  5. Improved ozone resistance of styrene-butadiene rubber cured by a combination of sulfur and ionizing radiation

    Fourier Transform Infrared (FTIR) studies performed in this work indicate that high ozone resistance of Styrene-Butadiene Rubber (SBR) formulations cured by a combination of sulfur and ionizing radiation is associated with unusually high vinyl concentration. On the other hand, sulfur cured SBR formulations with low vinyl concentration have poor ozone resistance. Curing with peroxides which involves chemistry similar to that of radiation curing, also leads to high vinyl concentration (relative to sulfur curing) and high ozone resistance. Increasing the absorbed dose in sulfur-radiation cured samples decreased the high vinyl content to a point where the ozone resistance declined greatly. Carbon black was shown to reduce the absorption of both the transvinylene and the vinyl unsaturation groups, but not to the same extent in all formulations. Also, the carbon black seems to play a greater role in the absorption of the unsaturation as sulfur increases. (Author)

  6. Processing of styrene butadiene rubber-carbon black nanocomposites with gradation of crosslink density: Static and dynamic mechanical characterization

    The concentrations of sulfur and accelerator were varied in the nanocomposites of carbon black (CB)-filled styrene-butadiene rubber (SBR) matrix to introduce the gradation of the crosslink density. These curatives were varied from 1 to 11 phr (per hundred rubber) along the span of 3-mm thick sheet using the construction-based layering method. The static and dynamic mechanical characterizations of these functionally graded polymeric nanocomposites (FGPNCs) were carried out. With increasing crosslink density along thickness, hardness and modulus increase while the ultimate properties like tensile strength and elongation at break droop down. The dynamic mechanical analysis of FGPNCs exhibits the increment in the storage modulus than the uniformly dispersed polymeric nanocomposites (UDPNCs) employing the same average amount of curatives. The peak position of tan δmax remains at the same temperature while the value mitigates in FGPNCs. In FGPNCs, tan δ peak intimates the broadness in the transition region

  7. Studies on gel electrolyte based on nitrile-butadiene copolymers. Final report, 1 November 1991-30 November 1992

    Sircar, A.K.; Kumar, B.; Linden, S.M.; Weissman, P.T.

    1993-06-01

    This study is concerned with the preparation of a hybrid electrolyte, suitable for solid-polymer batteries. Based on the study of ionic conductivity in the presence of LiBF4 of a number of nitrile-butadiene copolymers (NBR), hydrogenated NBR (HNBR) was selected as the host polymer. DC conductivity studies with three different lithium salts in different plasticizers showed the highest conductivity for LiBF4. Conductivity of LiBF4 in different plasticizers decreases in the order DMF > DMAC > Gamma butyrolactone > NMP > PC=gamma-valerolactone > glymes. NMP was chosen as the plasticizer for hybrid films based on its moderate conductivity, low vapor pressure, and low freezing point. Polymer electrolytes, Gel electrolytes, Ionic conductivity.

  8. Study of the reinforcement of rubber styrene-butadiene with mesoporous silices by solid-state nuclear magnetic resonance

    The knowledge about the interaction rubber/filler for the rubber reinforced with carbon black of silica is important to understand the physical properties, which determine the reinforcement. This paper presents a comparative study of the interactions between styrene butadiene rubber (SBR) and silica for a silica Ultrasil type and mesoporous silica MCM-41 type prepared by different procedures, based on solid state nuclear magnetic resonance: 1H MAS NMR; 13C MAS NMR, 13C CP/MAS, 29Si MAS and 29Si CP/MAS NMR. Mesoporous silica synthesized under certain specific conditions showed better interaction with the rubber than the ultrasil VN3 silica, commonly used as a reinforcement load. Mechanical tests for the SBR vulcanised with this silica indicate an important increase for values of elongation and tearing resistance, but an increase in the vulcanization time in it is compared with the SBR vulcanise with Ultrasil

  9. OSHA's approach to risk assessment for setting a revised occupational exposure standard for 1,3-butadiene.

    Grossman, E A; Martonik, J

    1990-06-01

    In its 1980 benzene decision [Industrial Union Department, ALF-CIO v. American Petroleum Institute, 448 U.S. 607 (1980)], the Supreme Court ruled that "before he can promulgate any permanent health or safety standard, the Secretary [of Labor] is required to make a threshold finding that a place of employment is unsafe--in the sense that significant risks are present and can be lessened by a change in practices" (448 U.S. at 642). The Occupational Safety and Health Administration (OSHA) has interpreted this to mean that whenever possible, it must quantify the risk associated with occupational exposure to a toxic substance at the current permissible exposure limit (PEL). If OSHA determines that there is significant risk to workers' health at its current standard, then it must quantify the risk associated with a variety of alternative standards to determine at what level, if any, occupational exposure to a substance no longer poses a significant risk. For rulemaking on occupational exposure to 1,3-butadiene, there are two studies that are suitable for quantitative risk assessment. One is a mouse inhalation bioassay conducted by the National Toxicology Program (NTP), and the other is a rat inhalation bioassay conducted by Hazelton Laboratories Europe. Of the four risk assessments that have been submitted to OSHA, all four have used the mouse and/or rat data with a variety of models to quantify the risk associated with occupational exposure to 1,3-butadiene. In addition, OSHA has performed its own risk assessment using the female mouse and female rat data and the one-hit and multistage models.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:2401254

  10. Effect of kaolin–metal oxides core–shell pigments on the properties of styrene–butadiene rubber composites

    Highlights: ► SBR was loaded with MeO/K pigments. ► CaO/K mixes showed the best properties. ► CaO⋅MgO/K possessed the least. -- Abstract: This study investigated the effects of core–shell kaolin–metal oxide pigments on the rheological, physico-mechanical and dielectric properties of styrene–butadiene rubber composites. In this way, newly prepared core–shell pigments based on kaolin as the core representing 90% of the whole pigment was covered with different metal oxides (CaO, MgO and CaO⋅MgO) comprising the shell which represents only 10% of the prepared pigments were incorporated with different concentrations in styrene–butadiene (SBR) rubber composites. Studying the different properties of pigmented and unpigmented SBR composites were done. Scanning electron microscopy (SEM) was used to feature out the surface morphology. Addition of the new pigments increased the tensile strength and strain energy, while elastic modulus was decreased. This study revealed that there is a significant effect of the new prepared pigments on SBR properties and the optimum pigment loading was 40 phr for CaO/kaolin, while it was 2.5 phr for MgO/kaolin. The dielectric results also showed that, the values of ε′ (relative permittivity) and ε′′ (dielectric loss) increased with increasing core shell content. Moreover, the samples containing MgO/kaolin and MgO⋅CaO/kaolin showed promising dielectric properties with low relative permittivity and electrical insulating properties. The different measurements showed good agreement in their results.

  11. Acrylonitrile grafted to PVDF

    Yang, Jin; Eitouni, Hany Basam

    2015-03-31

    PVDF-g-PAN has been synthesized by grafting polyacrylonitrile onto polyvinylidene fluoride using an ATRP/AGET method. The novel polymer is ionically conducive and has much more flexibility than PVDF alone, making it especially useful either as a binder in battery cell electrodes or as a polymer electrolyte in a battery cell.

  12. Infrared thermochromic behaviour of a composite Sm0.65Ca0.35MnO3-poly(styrene-co-acrylonitrile) film

    Ammar, M. R.; Napierala, C.; Laffez, P.

    2009-05-01

    Samarium calcium perovskite manganite Sm0.65Ca0.35MnO3 was dispersed homogeneously in a solution of poly(styrene-co-acrylonitrile). A thin film was deposited on (100) oriented silicon substrate by spin-coating and the optical thermochromic behaviour in the infrared range was studied. In the wavelength range 8-14 µm, the optical transmittance of the thermochromic composite coating exhibited a large variation between 173 and 343 K due to a semiconductor-metal first-order transition at Tc = 250 K. The thermochromic behaviour of the composite coatings was optimized. The contrast in the transmittance first increased with pigment content, then reached a maximum value.

  13. Infrared thermochromic behaviour of a composite Sm0.65Ca0.35MnO3–poly(styrene-co-acrylonitrile) film

    Samarium calcium perovskite manganite Sm0.65Ca0.35MnO3 was dispersed homogeneously in a solution of poly(styrene-co-acrylonitrile). A thin film was deposited on (100) oriented silicon substrate by spin-coating and the optical thermochromic behaviour in the infrared range was studied. In the wavelength range 8–14 µm, the optical transmittance of the thermochromic composite coating exhibited a large variation between 173 and 343 K due to a semiconductor–metal first-order transition at Tc = 250 K. The thermochromic behaviour of the composite coatings was optimized. The contrast in the transmittance first increased with pigment content, then reached a maximum value

  14. One-step Preparation and Antibacterial Property of Poly(N-iso- propyl-acrylamide) Grafted Poly(acrylonitrile/styrene) Micro- spheres Immobilized with Silver Nanoparticles

    FENG,Jiao; FAN,Liheng; CHU,Hong; XIONG,Wanbin; JIANG,Jinqiang; CHEN,Mingqing

    2009-01-01

    Monodispersed silver nanoparticles were immobilized onto the surface of poly(N-isopropylacrylamide) grafted poly(acrylonitrile/styrene) (PNIPAAm-g-PAN/PSt) microspheres by a one-step method using AgNO3 as a silver source. This process was performed via the coordination interaction between Ag ions and amide groups on PNIPAAm-g-PAN/PSt microsphere surfaces with the reduction of the corresponding ions by ethanol taking place simultaneously. Fourier transform infrared (FTIR) spectroscopy and ultraviolet (UV)-visible spectra illustrated that the silver nanoparticles were successfully immobilized onto the PNIPAAm-g-PAN/PSt microspheres. The size and morphology of silvered microspheres were characterized by transmission electron microscopy (TEM). The weight percent of silver nanoparticles immobilized onto the microspheres was 12% based on the determination of thermogravimetric analysis (TGA). The antibacterial tests demonstrated that the as-prepared silvered microspheres showed activity against Gram-negative bacteria.

  15. Modification on liquid retention property of cassava starch by radiation grafting with acrylonitrile. I. Effect of γ-irradiation on grafting parameters

    Kiatkamjornwong, S.; Chvajarernpun, J.; Nakason, C.

    1993-07-01

    Radiation modification on liquid retention properties of native cassava starch, gelatinized at 85°C, by graft copolymerization with acrylonitrile was carried out by mutual irradiation to gamma-rays. A thin aluminum foil was used to cover the inner wall of the reaction vessel, so that the homopolymer concentration was reduced to be less than 1.0% with a distilled water retention value of 665 g/g of the dry weight of the saponified grafted product. Confirmation of graft copolymerization and saponification reactions was made by the infrared spectrophotometric technique. The combined effect of radiation parameters in terms of an irradiation time and a dose rate to the total dose on the extent of the grafting reaction expressed in terms of grafting parameters which directly influenced liquid retention values was evaluated in conjunction with statistical analysis.

  16. Thermosensitive Poly(N-isopropylacrylamide-co-acrylonitrile) Hydrogels with Rapid Response%非离子型凝胶球在水中的溶胀行为

    黄健; 黄志明; 包永忠; 翁志学

    2006-01-01

    Acrylonitrile (AN) was copolymerized with N-isopropylacrylamide (NIPA) to synthesize thermosensitive bydrogels, and the on-off switch behavior of poly(NIPA-co-AN) hydrogels with different fraction of hydrophobic component (AN) was investigated. It is found that the lower critical solution temperature (LCST), the swelling ratio at certain temperature and the reswelling rate of poly(NIPA-co-AN) hydrogels decreased as AN unit fraction in copolymers increased. In order to improve the responsive rate of poly(NIPA-co-AN) hydrogels, they were further treated by surface crosslinking using N, N'-methylene bisacrylamide (BIS) as a crosslinking agent. The swelling and deswelling behaviors of these copolymers were compared with those of the untreated hydrogels. The results indicated that the responsive rate of poly(NIPA-co-AN) hydrogel was improved by surface crosslinking. The resulting hydrogels bearing cyano groups with fast response have potential applications in the field of drug-controlled release and immobilization of biomolecules.

  17. Single-Atom Pd₁/Graphene Catalyst Achieved by Atomic Layer Deposition: Remarkable Performance in Selective Hydrogenation of 1,3-Butadiene.

    Yan, Huan; Cheng, Hao; Yi, Hong; Lin, Yue; Yao, Tao; Wang, Chunlei; Li, Junjie; Wei, Shiqiang; Lu, Junling

    2015-08-26

    We reported that atomically dispersed Pd on graphene can be fabricated using the atomic layer deposition technique. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure spectroscopy both confirmed that isolated Pd single atoms dominantly existed on the graphene support. In selective hydrogenation of 1,3-butadiene, the single-atom Pd1/graphene catalyst showed about 100% butenes selectivity at 95% conversion at a mild reaction condition of about 50 °C, which is likely due to the changes of 1,3-butadiene adsorption mode and enhanced steric effect on the isolated Pd atoms. More importantly, excellent durability against deactivation via either aggregation of metal atoms or carbonaceous deposits during a total 100 h of reaction time on stream was achieved. Therefore, the single-atom catalysts may open up more opportunities to optimize the activity, selectivity, and durability in selective hydrogenation reactions. PMID:26268551

  18. Kinetic study of photo-grafting and photo-cross-linking of a cis-poly butadiene onto cellulose from asymmetric membranes

    Photochemical grafting onto cellulose and successive photo cross-linking of 2,00-12,00 mg.cm-2 of a cys-poly butadiene, containing 80% cis groups, were investigated kinetically at 30 0 C in the presence of 1,2-diphenyl-2,2-dimethoxy ethanone as a photo initiator to polymer varied between 0,070 and 1,115. Irradiations were carried out poly chromatically, in air or under a stream of nitrogen, with incident radiation of flux I of 2,1.10-8 einstein.s-1.cm-2. In light of this information, the mechanism of photo-grafting and photo-cross linking of cis-poly-butadiene on cellulose surface is discussed. (author)

  19. VUV-Vis optical characterization of Tetraphenyl-butadiene films on glass and specular reflector substrates from room to liquid Argon temperature

    Francini, R.; Montereali, R. M.; Nichelatti, E.; Vincenti, M. A.; Canci, N.; Segreto, E.; F. Cavanna; Di Pompeo, F.; Carbonara, F.; Fiorillo, G.; Perfetto, F.

    2013-01-01

    The use of efficient wavelength-shifters from the vacuum-ultraviolet to the photosensor's range of sensitivity is a key feature in detectors for Dark Matter search and neutrino physics based on liquid argon scintillation detection. Thin film of Tetraphenyl-butadiene (TPB) deposited onto the surface delimiting the active volume of the detector and/or onto the photosensor optical window is the most common solution in current and planned experiments. Detector design and response can be evaluated...

  20. Synthesis of oxa-bridged derivatives from Diels–Alder bis-adducts of butadiene and 1,2,3,4-tetrahalo-5,5-dimethoxycyclopentadiene

    Faiz Ahmed Khan

    2010-06-01

    Full Text Available Bis-adducts of 1,2,3,4-tetrahalo-5,5-dimethoxycyclopentadiene and 1,3-butadiene, generated in situ from 3-sulfolene, have been synthesized in excellent yield. Ruthenium catalyzed oxidation of the bis-adducts followed by a one-pot transformation of the resulting α-diketone furnished oxa-bridged compounds. Unambiguous stereochemical assignments of both diastereomeric series are reported.

  1. The effect of acrylonitrile exposure on the expression of p53 and p21WAF1 proteins in the blood plasma of occupationally exposed workers and in human diploid lung fibroblasts

    Rössner ml., Pavel; Binková, Blanka; Chvátalová, Irena; Šrám, Radim

    San Francisco: American Association for Cancer Research, 2002. s. 1. [Anual Meeting of AACR /93./. 06.04.2002-10.04.2002, San Francisco] R&D Projects: GA MŠk OK 390; GA ČR GP310/01/P030 Grant ostatní: IC(EC) 15-CT97-0302 Keywords : acrylonitrile * p53 protein * occupational exposure Subject RIV: EB - Genetics ; Molecular Biology

  2. The effect of acrylonitrile exposure on the expression of p53 and p21WAF1 proteins in the blood plasma of occupationally exposed workers and in human diploid lung fibroblasts

    Rössner ml., Pavel; Binková, Blanka; Chvátalová, Irena; Šrám, Radim

    Amsterdam : IOS Press, 2003 - (Cebulska-Wasilewska, A.; Au, W.; Šrám, R.), s. 262 - (NATO Sci. Series I.. 351) R&D Projects: GA MŠk OK 390; GA ČR GP310/01/P030 Grant ostatní: EC(XE) IC 15-CT97-0302 Institutional research plan: CEZ:AV0Z5039906 Keywords : acrylonitrile * occupational exposure * p53 protein Subject RIV: EB - Genetics ; Molecular Biology

  3. Vibrational quasi-degenerate perturbation theory with optimized coordinates: Applications to ethylene and trans-1,3-butadiene

    A perturbative extension to optimized coordinate vibrational self-consistent field (oc-VSCF) is proposed based on the quasi-degenerate perturbation theory (QDPT). A scheme to construct the degenerate space (P space) is developed, which incorporates degenerate configurations and alleviates the divergence of perturbative expansion due to localized coordinates in oc-VSCF (e.g., local O–H stretching modes of water). An efficient configuration selection scheme is also implemented, which screens out the Hamiltonian matrix element between the P space configuration (p) and the complementary Q space configuration (q) based on a difference in their quantum numbers (λpq = ∑s|ps − qs|). It is demonstrated that the second-order vibrational QDPT based on optimized coordinates (oc-VQDPT2) smoothly converges with respect to the order of the mode coupling, and outperforms the conventional one based on normal coordinates. Furthermore, an improved, fast algorithm is developed for optimizing the coordinates. First, the minimization of the VSCF energy is conducted in a restricted parameter space, in which only a portion of pairs of coordinates is selectively transformed. A rational index is devised for this purpose, which identifies the important coordinate pairs to mix from others that may remain unchanged based on the magnitude of harmonic coupling induced by the transformation. Second, a cubic force field (CFF) is employed in place of a quartic force field, which bypasses intensive procedures that arise due to the presence of the fourth-order force constants. It is found that oc-VSCF based on CFF together with the pair selection scheme yields the coordinates similar in character to the conventional ones such that the final vibrational energy is affected very little while gaining an order of magnitude acceleration. The proposed method is applied to ethylene and trans-1,3-butadiene. An accurate, multi-resolution potential, which combines the MP2 and coupled-cluster with singles

  4. Ruthenium-Catalyzed Asymmetric Hydrohydroxyalkylation of Butadiene: The Role of the Formyl Hydrogen Bond in Stereochemical Control

    Grayson, Matthew N.; Krische, Michael J.; Houk, K. N.

    2016-01-01

    The catalyst generated in situ from RuH2(CO)(PPh3)3, (S)-SEGPHOS, and a chiral phosphoric acid promotes asymmetric hydrohydroxyalkylation of butadiene and affords enantioenriched α-methyl homoallylic alcohols. The observed diastereo- and enantioselectivities are determined by both the chiral phosphine and chiral phosphate ligands. Density functional theory calculations (M06/SDD-6-311G(d,p)-IEFPCM(acetone)//B3LYP/SDD-6-31G(d)) predict that the product distribution is controlled by the kinetics of carbon-carbon bond formation, and this process occurs via a closed-chair Zimmerman-Traxler-type transition structure (TS). Chiral phosphate-dependent stereoselectivity arising from this TS is enabled through a hydrogen bond between the phosphoryl oxygen and the aldehyde formyl proton present in TADDOL-derived catalysts. This interaction is absent in the corresponding BINOL-derived systems and the opposite sense of attack on the aldehyde occurs. Additional factors influencing stereochemical control are determined. PMID:26107070

  5. Mortality of a cohort of workers in the styrene-butadiene polymer manufacturing industry (1943-1982)

    Matanoski, G.M.; Santos-Burgoa, C.; Schwartz, L. (Johns Hopkins School of Hygiene and Public Health, Baltimore, MD (USA))

    1990-06-01

    A cohort of 12,110 male workers employed 1 or more years in eight styrene-butadiene polymer (SBR) manufacturing plants in the United States and Canada has been followed for mortality over a 40-year period, 1943 to 1982. The all-cause mortality of these workers was low (standardized mortality ratio (SMR) = 0.81) compared to that of the general population. However, some specific sites of cancers had SMRs that exceeded 1.00. These sites were then examined by major work divisions. The sites of interest included leukemia and non-Hodgkin's lymphoma in whites. The SMRs for cancers of the digestive tract were higher than expected, especially esophageal cancer in whites and stomach cancer in blacks. The SMR for arteriosclerotic heart disease in black workers was significantly higher than would be expected based on general population rates. Employees were assigned to a work area based on job longest held. The SMRs for specific diseases differed by work area. Production workers showed increased SMRs for hematologic neoplasms and maintenance workers, for digestive cancers. A significant excess SMR for arteriosclerotic heart disease occurred only in black maintenance workers, although excess mortality from this disease occurred in blacks regardless of where they worked the longest. A significant excess SMR for rheumatic heart disease was associated with work in the combined, all-other work areas. For many causes of death, there were significant deficits in the SMRs.

  6. Trans-1,4 selective polymerization of 1,3-butadiene with symmetry pincer chromium complexes activated by MMAO

    Gong, Dirong

    2014-09-01

    Tridentate chromium complexes (Cr1-Cr7) incorporated with symmetrical pincer ligand bis(arylimino)pyridine and bis(pyrzaolyl)pyridine have been synthesized and characterized by elemental analyis, FT-IR as well as ESI-MS. X-ray diffraction reveals solids-state structures of Cr2, Cr4 and Cr6 all adopt pseudo-octahedral coordination environment with respect to metal center. All complexes have been tested in stereoregulated polymerization of butadiene under various polymerization conditions. The trans-1,4 and cis-1,4 enchainment of resultant polymer are found to be dependent on the structure of ligand and amount of activator used. Under the optimized condition, free ortho-substitutes Cr catalysts Cr1, Cr3, Cr4 and Cr6 are capable of initiating high trans-1,4 selectivity (trans-1,4: 89.2%-92.0%) with good polymer yields (71.5%-78.0%), while counterparts with ortho-positioned alkyl groups Cr2, Cr5 and Cr7 display mixed selectivities with moderate polymer yields. The sterical effect of ligand and amount of MMAO on the catalytic performance, in particular, the stereoselectivity and polymer yield, has been also elucidated by conjugated diene polymerization mechanism. © 2014 Elsevier B.V. All rights reserved.

  7. Characterization on the phase separation behavior of styrene-butadiene rubber/polyisoprene/organoclay ternary blends under oscillatory shear

    Liu, Xianggui; Dong, Xia; Liu, Wei; Xing, Qian; Zou, Fasheng; Han, Charles C.; Wang, Dujin; Liang, Aimin; Li, Chuanqing; Xie, Ximing

    2015-09-01

    The present work investigated the influence of organoclay (organo-montmorillonite, OMMT) on the phase separation behavior and morphology evolution of solution polymerized styrene-butadiene rubber (SSBR)/low vinyl content polyisoprene (LPI) blends with rheological methodology. It was found that the incorporation of OMMT not only reduced the droplet size of the dispersion phase, slowed down the phase separation kinetics, also enlarged the processing miscibility window of the blends. The determination on the wetting parameters indicated that due to the oscillatory shear effect, the OMMT sheets might localize at the interface between the two phases and act as compatibilizer or rigid barrier to prevent domain coarsening, resulting in slow phase separation kinetics, small droplet size, and stable morphology. The analysis of rheological data by the Palierne model provided further confirmation that the addition of OMMT can decrease the interfacial tension and restrict the relaxation of melt droplets. Therefore, a vivid "sea-fish-net" model was proposed to describe the effect of OMMT on the phase separation behavior of SSBR/LPI blends, in which the OMMT sheets acted as the barrier (net) to slow down the domain coarsening/coalescence in phase separation process of SSBR/LPI blends.

  8. Fluorescence Efficiency and Stability of Radio-Pure Tetraphenyl-butadiene Based Coatings for VUV Light Detection in Cryogenic Environments

    Baudis, Laura; Dressler, Rugard; Piastra, Francesco; Usoltsev, Ilya; Walter, Manuel

    2015-01-01

    The detection of VUV scintillation light, e.g. in (liquid) argon detectors, commonly includes a reflector with a fluorescent coating, converting UV photons to visible light. The light yield of these detectors depends directly on the conversion efficiency. Several coating/reflector combinations were produced using VM2000, a specular reflecting multi layer polymer, and Tetratex, a diffuse reflecting PTFE fabric, as reflector foils. The efficiency of these coatings was optimised and has been measured in a dedicated liquid argon setup built at the University of Zurich. It employs a small, 1.3 kg LAr cell viewed by a 3-inch, low radioactivity PMT of type R11065-10 from Hamamatsu. The cryogenic stability of these coatings was additionally studied. The optimum reflector/coating combination was found to be Tetratex dip coated with Tetraphenyl-butadiene with a thickness of 0.9 mg/cm$^2$ resulting in a 3.6 times higher light yield compared to uncoated VM2000. Its performance was stable in long term measurements, ran up...

  9. Stepwise swelling of a thin film of lamellae-forming poly(styrene-b- butadiene) in cyclohexane vapor

    Di, Zhenyu

    2012-06-26

    We investigated the swelling of a thin film of lamellae-forming poly(styrene-b-butadiene) in cyclohexane vapor. The vapor pressure and thus the degree of swelling of the film are increased in a stepwise manner using a custom-built sample cell. The resulting structural changes during and after each step were followed in situ using time-resolved grazing-incidence small-angle X-ray scattering (GISAXS). During the first step, the lamellar thickness increases strongly, before it decreases again. At the same time, the full width at half-maximum (FWHM) of the diffuse Bragg reflection along the film normal has a sharp maximum. These observations point to the formation of new lamellae. During the subsequent swelling steps, the lamellar thickness overshoots only weakly. The behavior thus resembles qualitatively our previous results on a similar thin film during swelling in saturated vapor of cyclohexane; however, it deviates from earlier theoretical predictions. We propose a theory that is quantitatively correct for the description of the dependence of the lamellar thickness on the polymer volume fraction in the late stage of the swelling steps. © 2012 American Chemical Society.

  10. Plane-interface-induced lignin-based nanosheets and its reinforcing effect on styrene-butadiene rubber

    C. Jiang

    2014-09-01

    Full Text Available Lignin was viewed as a spherical microgel in aqueous alkali. While spread out in a monolayer or adsorbed on a surface, lignin was made up of flexible, disk-like molecules with approximately the same thickness of 2 nm. According to this principle, we employed the lamina of montmorillonite (MMT as a plane template to anchor cationic lignin (CL on its two sides, resulting in the formation of CL-MMT hybrid materials (CLM. The isotherm adsorption behavior and structure characteristics of CLM were studied. The results showed that CLM was individually dispersed nanosheets with a thickness of about 5 nm when the mass ratio of CL to MMT is more than 2:1 and prepared at acidic or neutral pH. Compared to the cocoagulation of lignin and styrene-butadiene rubber (SBR, CLM obviously accelerated the coagulation rate, due to the reduction of surface activity of CL restricted by MMT. The nanoscale dispersion of CLM in SBR matrix significantly improved the tensile strength of CLM/SBR nanocomposites to 14.1 MPa by adding only 10 phr CLM and cardanol glycidyl ether (CGE as compatibilizer. Dynamic mechanical analysis (DMA showed that the glass transition temperature of SBR/CLM nanocomposites decreased with increasing CLM loading. Correspondingly, a special interfacial structure was proposed.

  11. Endocrine disruptive effects of chemicals eluted from nitrile-butadiene rubber gloves using reporter gene assay systems.

    Satoh, Kanako; Nonaka, Ryouichi; Ohyama, Ken-ichi; Nagai, Fumiko; Ogata, Akio; Iida, Mitsuru

    2008-03-01

    Disposable gloves made of nitrile-butadiene rubber (NBR) are used for contact with foodstuffs rather than polyvinyl chloride gloves containing di(2-ethylhexyl)phthalate (DEHP), because endocrine-disruptive effects are suspected for phthalate diesters including DEHP. However, 4,4'-butylidenebis(6-t-butyl-m-cresol) (BBBC), 2,4-di-t-butylphenol, and 2,2,4-trimetyl-1,3-pentanediol diisobutyrate can be eluted from NBR gloves, and possibly also detected in food. In this study, we examined the endocrine-disrupting effects of these chemicals via androgen receptor (AR) and estrogen receptor (ER)-mediated pathways using stably transfected reporter gene cell lines expressing AR (AR-EcoScreen system) and ER (MVLN cells), respectively. We also examined the binding activities of these chemicals to AR and ER. The IC50 value of BBBC for antagonistic androgen was in the range of 10(-6)M. The strength of inhibition was about 5 times that of a known androgen antagonist, 1,1'-(2,2-dichloroethylidene)bis[4-chlorobenzene] (p,p'-DDE), and similar to that of bisphenol A. The IC50 value of BBBC for antagonistic estrogen was in the range of 10(-6)M. These results suggest that BBBC and its structural homologue, 4,4'-thiobis(6-t-butyl-m-cresol) are androgen and estrogen antagonists. It is therefore necessary to study these chemicals in vivo, and clarify their effect on the endocrine system. PMID:18310895

  12. Wavelength-shifting materials for the use in RICH detectors - p-terphenyl and tetraphenyl-butadiene revisited

    Koczon, P; Joram, C; Solevi, P; D¨urr, M; H¨ohne, C

    2010-01-01

    P-terphenyl (PT) and tetraphenyl-butadiene (TPB) in form of thin films have been investigated as possible wavelength shifting material for application in Ring Imaging Cherenkov (RICH) detectors. Films of dierent thickness were evaporated onto borosilicate windows of photomultiplier tubes (PMT) and the quantum eciency of the modified PMTs was determined as a function of wavelength. Gain factors for the number of measured photoelectrons in dependence on the cuto wavelength (energy) for application in Cherenkov counters were established. Using PT, a strong increase in quantum eciency between 200 nm and 300 nm was observed leading to gain factors as high as 1.71 ± 0.11 for a cutoff energy of 6.2 eV. Due to strong absorption in the wavelength range between 300 nm and 400 nm, TPB shows inferior results. No significant thickness dependence was observed for films thicker than 600 nm. Film morphology and wavelength dependent fluorescence was measured to back the results. Simulations encourage the use on flat panel mu...

  13. Transport properties of carboxylated nitrile butadiene rubber (XNBR)-nanoclay composites; a promising material for protective gloves in occupational exposures.

    Mirzaei Aliabadi, Mostafa; Naderi, Ghasem; Shahtaheri, Seyed Jamaleddin; Forushani, Abbas Rahimi; Mohammadfam, Iraj; Jahangiri, Mehdi

    2014-01-01

    This study was conducted in response to one of the research needs of National Institute for Occupational Safety and Health (NIOSH), i.e. the application of nanomaterials and nanotechnology in the field of occupational safety and health. In order to fill this important knowledge gap, the equilibrium solubility and diffusion of carbon tetrachloride and ethyl acetate through carboxylated nitrile butadiene rubber (XNBR)-clay nanocomposite, as a promising new material for chemical protective gloves (or barrier against the transport of organic solvent contaminant), were examined by swelling procedure. Near Fickian diffusion was observed for XNBR based nanocomposites containing different amounts of nanoclay. Decontamination potential is a key factor in development of a new material for reusable chemical protective gloves applications, specifically for routine or highly toxic exposures. A thermal decontamination regime for nanocomposite was developed for the first time. Then, successive cycles of exposure/decontamination for nanocomposite were performed to the maximum 10 cycles for the first time. This result confirms that the two selected solvents cannot deteriorate the rubber-nanoclay interaction and, therefore, such gloves can be reusable after decontamination. PMID:24581248

  14. Wear resistance and friction reduction in acrylo nitrile butadiene rubber through hybrid combination of graphite flakes and nano tungsten disulphide

    Agrawal, Neha; Pandey, Akanksha; Parihar, A. S.; Mishra, A. K.; Gandhi, M. N.; Bhattacharyya, A. R.; Mukhopadhyay, K.; Prasad, N. E.

    2016-05-01

    Friction and wear have considerable role in the life span of two interacting parts. Incorporation of nanofillers in polymers/elastomers matrix causes commendable changes in its tribologicalproperties. The main purpose of this work is to reduce the coefficient of friction and wear rate of Acrylo Nitrile Butadiene rubber (NBR). To achieve such objective traditionally well knownlubricants graphite(G), tungsten disulphide (WS2) and there hybrid combination was incorporated in NBR matrix. Effect of applied load (force) and concentration of fillers on tribological properties of NBR had been studied. The filler incorporation enhanced the hardnessby 8%, showed resistance to hydraulic oil and aging effect also got improved significantly. A particular optimized concentration of NBR with hybrid combination of 2% WS2 and 4% Graphite showed minimum coefficient of friction as well as wear rate. A hypothesis could be attributed that similar lamellar structure of WS2 and Graphite along with formation of a stable nanoscale disulfide tribofilmcould result in lowering of friction. These substantially improved properties of nanoreinforced rubber materials would definitely pave promising path for plethora of potential technological applications.

  15. Surface modification of halloysite nanotubes by vulcanization accelerator and properties of styrene-butadiene rubber nanocomposites with modified halloysite nanotubes

    Zhong, Bangchao; Jia, Zhixin; Hu, Dechao; Luo, Yuanfang; Guo, Baochun; Jia, Demin

    2016-03-01

    Vulcanization accelerant N-cyclohexyl-2-benzothiazole sulfenamide (CZ) was used as a surface modifier and chemically grafted on the surface of halloysite nanotubes (HNTs) to obtain CZ-functionalized HNTs (HNTs-s-CZ). It was found that HNTs-s-CZ could be homogeneously dispersed into styrene-butadiene rubber (SBR). The grafted CZ molecules, exactly located at the filler-rubber interface, reduced the activation energy of vulcanization of SBR/HNTs-s-CZ compounds. Besides, the density of chain segments introduced by the interfacial phase of SBR/HNTs-s-CZ nanocomposites was higher than the other nanocomposites with silane-modified HNTs (m-HNTs) or pristine HNTs, manifesting an indication of enhanced filler-rubber interfacial interaction in SBR/HNTs-s-CZ nanocomposites. Consequently, SBR/HNTs-s-CZ nanocomposites showed excellent mechanical properties. The tensile strength could be enhanced by as much as 38.6% and 102.5% compared to those of SBR/m-HNTs and SBR/HNTs nanocomposites, respectively, though containing equivalent accelerant component. The value of this work lies in the fact that apparent properties improvement of elastomer composites has been achieved by the incorporation of vulcanization accelerant-functionalized HNTs, which may be fruitful for the rational design of filler surface treatment and offer new scientific and technological opportunities for the preparation of high performance elastomer composites.

  16. THE DISSOCIATIVE RECOMBINATION OF PROTONATED ACRYLONITRILE, CH2CHCNH+, WITH IMPLICATIONS FOR THE NITRILE CHEMISTRY IN DARK MOLECULAR CLOUDS AND THE UPPER ATMOSPHERE OF TITAN

    Measurements on the dissociative recombination (DR) of protonated acrylonitrile, CH2CHCNH+, have been performed at the heavy ion storage ring CRYRING located in the Manne Siegbahn Laboratory in Stockholm, Sweden. It has been found that at ∼2 meV relative kinetic energy about 50% of the DR events involve only ruptures of X-H bonds (where X = C or N) while the rest leads to the production of a pair of fragments each containing two heavy atoms (alongside H and/or H2). The absolute DR cross section has been investigated for relative kinetic energies ranging from ∼1 meV to 1 eV. The thermal rate coefficient has been determined to follow the expression k(T) = 1.78 x 10-6 (T/300) -0.80 cm3 s-1 for electron temperatures ranging from ∼10 to 1000 K. Gas-phase models of the nitrile chemistry in the dark molecular cloud TMC-1 have been run and results are compared with observations. Also, implications of the present results for the nitrile chemistry of Titan's upper atmosphere are discussed.

  17. Simultaneous determination of acrylonitrile, carbon disulfide, methyl ethyl ketone, and isobutanol leachates by purge and trap- gas chromatography-mass spectrometry

    According to the Mexican General Law of the Ecological Equilibrium and Environmental Protection, issued by the National Institute of Ecology, some chemicals such as acrylonitrile, methyl ethyl ketone, carbon disulfide, and isobutanol must be monitored in industrial residues because of their toxicity. This report describes an analytical method for the simultaneous determination of these four analytes in leachates. A purge and trap concentrator coupled to a computerized gas-chromatograph-mass selective detector was used to achieve the analysis. Quantitation measurements were based on the internal standardization method, using the area ratios of the molecular ions of the analytes and the internal standard obtained by deconvolution of the data. The scope of this method as well as the validation data is reported. The method is reliable in spite of the fact that, in some cases, the analytes or the standard coeluted with other compounds of the samples. Because the data acquisition is carried out in the scan mode it is possible to detect and identify other substances in the samples. (Author)

  18. Gel electrolyte derived from poly(ethylene glycol) blending poly(acrylonitrile) applicable to roll-to-roll assembly of electric double layer capacitors

    Huang, Cheng-Wei; Wu, Ching-An; Hou, Sheng-Shu; Kuo, Ping-Lin [Department of Chemical Engineering and Research Center for Energy Technology and Strategy, National Cheng Kung University, Tainan 70101 (China); Hsieh, Chien-Te [Department of Chemical Engineering and Materials Science, Yuan Ze Fuel Cell Center, Yuan Ze University, Taoyuan 32023 (China); Teng, Hsisheng [Department of Chemical Engineering and Research Center for Energy Technology and Strategy, National Cheng Kung University, Tainan 70101 (China); Center for Micro/Nano Science and Technology, National Cheng Kung University, Tainan 70101 (China)

    2012-11-21

    The synthesis of a gelled polymer electrolyte (GPE) using poly(ethylene glycol) blending poly(acrylonitrile) (i.e., PAN-b-PEG-b-PAN) as a host, dimethyl formamide (DMF) as a plasticizer and LiClO{sub 4} as an electrolytic salt for electric double layer capacitors (EDLCs) is reported. The PAN-b-PEG-b-PAN copolymer in the GPE has a linear configuration for high ionic conductivity and excellent compatibility with carbon electrodes. When assembling the GPE in a carbon-based symmetric EDLC, the copolymer network facilitates ion motion by reducing the equivalent series resistance and Warburg resistance of the capacitor. This symmetric cell has a capacitance value of 101 F g{sup -1} at 0.125 A g{sup -1} and can deliver an energy level of 11.5 Wh kg{sup -1} at a high power of 10 000 W kg{sup -1} over a voltage window of 2.1 V. This cell shows superior stability, with little decay of specific capacitance after 30 000 galvanostatic charge-discharge cycles. The distinctive merit of the GPE film is its adjustable mechanical integrity, which makes the roll-to-roll assembly of GPE-based EDLCs readily scalable to industrial levels. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  19. Microwave absorption properties of lightweight absorber based on Fe50Ni50-coated poly(acrylonitrile) microspheres and reduced graphene oxide composites

    Zhang, Bin; Wang, Jun; Wang, Junpeng; Huo, Siqi; Zhang, Bin; Tang, Yushan

    2016-09-01

    In this paper, we proposed a facile method to obtain the lightweight composites consisting of surface modified Fe50Ni50-coated poly(acrylonitrile) microspheres (PANS@SMF), reduced graphene oxide (RGO) and epoxy resin. The as-prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), vibrating sample magnetometry (VSM) and vector network analyzer (VNA). Impedance matching condition and electromagnetic wave attenuation characteristic were used for the reflection loss (RL) performance of the composites. Compared with pure PANS@SMF and RGO composites, the -10 dB absorption bandwidth and the minimum RL of the hybrid composites were enhanced. The bandwidth less than -10 dB was almost 4.5 GHz in the range of 10 GHz to 14.5 GHz, with a matching thickness of 2.5 mm. The density of the hybrid composites was in the range of 0.25-0.34 g/cm3. Therefore, the hybrid composite can be considered as a potential lightweight microwave absorber.

  20. Production of activated carbon from acrylonitrile and methyl acrylate copolymers. Akurironitoriru/akuriru san mechiru kyojugotai wo mochiita kagaku shoriho ni yoru tansokei kyuchakuzai no seizoho

    Noda, Y.; Yamada, K.; Ishibashi, K. (Government Industrial Development Lab. Hokkaido, Sapporo (Japan)); Kumamoto, S.; Takahashi, Y. (Environmental Research Inst. of Sanyu Plant Co. Ltd., Kanagawa (Japan)); Kobashi, T.; Takagi, J. (Japan Exlan Co. Ltd., Okayama (Japan))

    1993-06-20

    Carbonization of carbonaceous adsorbents, in which acrylonitrile (AN) and methyl acrylate copolymers(PANA) are used as raw materials, in order to discover high functionability, manufacture condition of the activated coal by chemical activation method using phosphate and zinc chloride as an activation promoters, and the performance of each formed products, are reported. The maximum value of methylene blue absorption quantity(MB) and the inner surface area(S) was shown by both the samples within the activation temperature range of 600[degree]C to 900[degree]C. The values of MB and S has increased linearly with the increase of activation temperature for both PANACHZ and PANACHP which are obtained by adding ZnCl2 and H3PO4 respectively in thermal condensation product(PANACH). Adsorbability of PANACHZ and PANACHP increased with the increase of activation temperature. The amounts of adsorption by activation products and organic gases of PANACHZ and PANACHP were pursued. As a result, it was revealed that the amounts of adsorption for both chars increased with the increase of activation temperature. Furthermore, adsorption quantity of butyl mercaptan gas was more than twice of comparative activated carbon on the market, and highly efficient adsorbent was obtained. 19 refs., 11 figs., 2 tabs.

  1. 端羧基丁腈橡胶改性环氧树脂的结构与性能%Structual and Properties of Carboxyl-Terminated Poly(Butadiene-co-Acrylonitrile) Modified Diglycidyl Ether of Bisphenol-A Epoxy Resin

    刘敬成; 张胜文; 周琼; 刘仁; 刘晓亚; 王春林

    2010-01-01

    用液体端羧基丁腈橡胶(CTBN)对固体环氧树脂(EP)进行改性,合成了CTBN-EP预聚物,研究了CTBN-EP/HTP-305体系的微观形貌、力学性能和热性能.研究结果表明,随着CTBN含量的增大,冲击强度及断裂伸长率显著提高,说明通过CTBN化学预聚改性的EP韧性提高,而体系的拉伸强度和热性能略有下降.动态热机械分析(DMA)测试体系的动态力学性能结果表明,体系出现了两相结构(Tg对应温度分别是-60℃和80℃~100℃).扫描电镜(SEM)分析表明,固化过程中析出了橡胶相并均匀分散在环氧树脂基体中,形成了剪切空洞变形结构.

  2. 端羧基丁腈橡胶改性环氧树脂的结构与性能%Structure and Properties of Carboxyl-Terminated Poly(Butadiene-co-Acrylonitrile) Modified Diglycidyl Ether of Bisphenol-A Epoxy Resin

    石敏先; 黄志雄; 郦亚铭; 杨国瑞

    2008-01-01

    用液体端羧基丁腈橡胶(CTBN)对环氧树脂(EP)进行改性,合成了CTBN/EP预聚物,FT-IR分析表明,在反应中EP的环氧基开环后与CTBN的羧基反应生成了酯键.研究了CTBN/EP/聚醚胺(PEA)体系的力学性能,结果表明,随着CTBN含量的增大,其弯曲强度、拉伸强度降低,冲击强度、断裂伸长率增大,说明CTBN通过化学预聚改性的EP具有良好的韧性.SEM分析表明,固化过程中析出了橡胶相并均匀分散在环氧树脂基体中.

  3. Structure Sensitivity in Pt Nanoparticle Catalysts for Hydrogenation of 1,3-Butadiene: In Situ Study of Reaction Intermediates Using SFG Vibrational Spectroscopy

    Michalak, William D.

    2013-01-31

    The product selectivity during 1,3-butadiene hydrogenation on monodisperse, colloidally synthesized, Pt nanoparticles was studied under reaction conditions with kinetic measurements and in situ sum frequency generation (SFG) vibrational spectroscopy. SFG was performed with the capping ligands intact in order to maintain nanoparticle size by reduced sintering. Four products are formed at 75 C: 1-butene, cis-2-butene, trans-2-butene, and n-butane. Ensembles of Pt nanoparticles with average diameters of 0.9 and 1.8 nm exhibit a ∼30% and ∼20% increase in the full hydrogenation products, respectively, as compared to Pt nanoparticles with average diameters of 4.6 and 6.7 nm. Methyl and methylene vibrational stretches of reaction intermediates observed under working conditions using SFG were used to correlate the stable reaction intermediates with the product distribution. Kinetic and SFG results correlate with previous DFT predictions for two parallel reaction pathways of 1,3-butadiene hydrogenation. Hydrogenation of 1,3-butadiene can initiate with H-addition at internal or terminal carbons leading to the formation of 1-buten-4-yl radical (metallocycle) and 2-buten-1-yl radical intermediates, respectively. Small (0.9 and 1.8 nm) nanoparticles exhibited vibrational resonances originating from both intermediates, while the large (4.6 and 6.7 nm) particles exhibited vibrational resonances originating predominately from the 2-buten-1-yl radical. This suggests each reaction pathway competes for partial and full hydrogenation and the nanoparticle size affects the kinetic preference for the two pathways. The reaction pathway through the metallocycle intermediate on the small nanoparticles is likely due to the presence of low-coordinated sites. © 2012 American Chemical Society.

  4. The enhanced catalytic performance of cobalt catalysts towards butadiene polymerization by introducing a labile donor in a salen ligand.

    Gong, Dirong; Wang, Baolin; Jia, Xiaoyu; Zhang, Xuequan

    2014-03-14

    A family of cobalt complexes supported by a tridentate Schiff base ligand with a labile donor (O, S, N) as a pendant arm (Co1-Co12, formulated as CoL2) were synthesized by the treatment of the corresponding ligands with cobalt acetate tetrahydrate. The resultant complexes were well characterized by elemental analysis, FT-IR, magnetic moment as well as EI-MS. The solid-state structures of Co7 and Co12 were determined by X-ray diffraction and both established a distorted octahedron geometry around the cobalt center. The butadiene polymerization capabilities of the 12 complexes were evaluated and compared in representative cases. Diethylaluminum chloride (AlEt2Cl) was found to be the compatible activator resulting in highly active catalysts for producing polybutadiene of 93.8-98.2% cis-1,4 enchainment with negligible 1,2-structure and trans-1,4 units. It appears that a certain degree of lability of the donor is beneficial for high catalytic activity, generally following the order of O > S > N, and the high cis-1,4 selectivity. Moreover, the remarkable thermal stability of these systems has been achieved: the catalytic systems have the ability of conducting a high level of active and selective polymerization, reaching an upper limit of polymerization temperature of about 70 °C. The enhanced catalytic performances were further rationalized by the established diene polymerization mechanism, which could shed light on developing highly selective and reactive industrially applicable catalysts with an enhanced thermal stability. PMID:24468706

  5. Synthesis of mixed-ligand cobalt complexes and their applications in high cis-1,4-selective butadiene polymerization

    Liu, Wen

    2015-08-03

    Incomplete oxidation of (N-di-tert-butylphosphino)-6-(2-methyl-2’H-benzoimidazole)-2-aminepyridine dichlorocobalt (PN3CoCl2) in DMF results in a unique co-crystal I formed with three parts including DMF, unit A and unit B complex with Co1 and Co2, respectively, (PN3 ligand in unit A: (N-di-tert-butylphosphino)-6-(2’-methyl-2’H-benzoimidazole)-2-aminepyridine, and O=PN3 ligand in unit B: (N-di-tert-butylphosphinoxide)-6-(2’-methyl-2’H-benzoimidazole)-2-aminepyridine) with 1:1:1 molar ratio. Co1 and Co2 complexes both display a five-coordinated distorted-square-pyramidal geometry around the metal center. The Co1 center is coordinated with PN3 ligand via two N atoms from pyridine, benzoimidazole moiety as well as one P atom, and the Co2 center is coordinated with the oxidized ligandO=PN3 via two N atoms from pyridine, benzoimidazole moiety as well as one O atom from DMF molecule, while the oxidized phosphine moiety (O=P) being excluded from the coordination sphere. Activated with AlEt2Cl, the co-crystallized complexes I are able to actively convert butadiene to polybutadiene, affording cis-1,4 polybutadiene with cis-1,4 unit up to 95.5-97.8% and number average molecular weight of cal. 105g/mol. The high cis-1,4 selectivity and monomodal GPC curve of resultant polymer imply that the identical active species generated from two distinctive cobalt centers.

  6. Isolation and identification of some unknown substances in disposable nitrile-butadiene rubber gloves used for food handling.

    Mutsuga, M; Wakui, C; Kawamura, Y; Maitani, T

    2002-11-01

    In Japan, disposable gloves made from nitrile-butadiene rubber (NBR) are frequently used in contact with foods. In a previous paper, we investigated substances migrating from various gloves made of polyvinyl chloride, polyethylene, natural rubber and NBR. Zinc di-n-butyldithiocarbamate (ZDBC), diethyldithiocarbamate (ZDEC) used as vulcanization accelerators, di(2-ethylhexyl)phthalate (DEHP) used as a plasticizer and many unknown compounds that migrated from NBR gloves into n-heptane were detected by GC/MS. In this paper, six unknown compounds were obtained from one kind of NBR glove by n-hexane extraction and each was isolated by silica gel chromatography. From the results of NMR and mass spectral analysis of the six unknown compounds, their structures are proposed as 1,4-dione-2,5-bis(1,1-dimethylpropyl)cyclohexadiene (1), 2-(1,1-dimethylethyl)-4-(1,1,3,3-tetra methylbutyl)phenol (2), 2,6-bis(1,1-dimethylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol (3), 2,4-bis(1,1,3,3-tetramethylbutyl)phenol (4), 2-(1,1-dimethylethyl)4,6-bis(1,1,3,3-tetramethylbutyl)phenol (5) and 2,4,6-tris(1,1,3,3-tetramethylbutyl)phenol (6). Compound 1 was observed in five of the seven kinds of NBR gloves, and compounds 2-4 and 6, which are not listed in Chemical Abstract (CA), were present in four kinds of gloves. PMID:12456282

  7. Effect of montmorillonite on carboxylated styrene butadiene rubber/hindered phenol damping material with improved extraction resistance

    Highlights: • MMT and XSBR display synergic effect on protecting HP1098 from being extracted. • A new hindered phenol HP1098 was used to prepare damping material. • Effects of three preparation methods on the material properties were studied. - Abstract: Three methods of blending, including direct blending, melt blending and latex blending, were introduced to disperse sodium based montmorillonite (Na-MMT) and N,N′-hexane-1,6-diylbis{3-(5-di-tert-butyl-4-hydroxyphenyl-propionamide)} (HP1098) into the carboxylated styrene butadiene (XSBR) matrix. Small angle X-ray Diffraction testing indicated that melting Na-MMT with HP1098 enlarged the d-spacing of Na-MMT, which was further enlarged by mechanical blending with XSBR, and this led to homogeneous dispersion of Na-MMT and HP1098, which was indicated by Transmission Electronic Microscopy; latex blending was found most advantageous in dispersing HP1098 which was essential for improved damping performance. Dynamic Mechanical Analysis was utilized to characterize damping properties, and enhanced static mechanical properties were presumably originated from molecule chains being intercalated into the enlarged galleries of Na-MMT by mechanical blending. Formation of hydrogen bonds was observed by Fourier Transformation Infrared Spectrum and was supposed to be responsible for exceptional damping performance at elevated temperature. Extraction measurement of XSBR/Na-MMT/HP1098 composite indicated that XSBR and Na-MMT showed synergic effect in protecting HP1098 molecules from being extracted, which is a promising method in preparing rubber/hindered phenol damping materials with improved extraction resistance, whereby increasing the performance stability and lifespan of the composite materials. Additional advantage of this type of materials is better processability and shortened vulcanization process

  8. Effect of magnetic and thermal properties of iron oxide nanoparticles (IONs) in nitrile butadiene rubber (NBR) latex

    Ong, Hun Tiar; Julkapli, Nurhidayatullaili Muhd; Hamid, Sharifah Bee Abd; Boondamnoen, O.; Tai, Mun Foong

    2015-12-01

    Nitrile butadiene rubber (NBR) gloves are one of the most important personal protective equipments but they are possible to tear off and contaminate food or pharmaceutical and healthcare products during manufacturing and packaging process. High tendency of torn glove remaining in food or products due to white or light flesh-coloured glove is not easy to be detected by naked eyes. In this paper, iron oxide nanoparticles (IONs) selected as additive for NBR to improve its detectability by mean of magnetic properties. IONs synthesized via precipitation method and compounded with NBR latex before casting on petri dish. The properties of IONs were investigated by X-ray Diffractometry (XRD), Transmission Electron Microscope (TEM), Raman Spectroscopy and Vibrating Sample Magnetometer (VSM). Meanwhile NBR/IONs composites were studied by Thermogravimetry Analysis (TGA), Differential Scanning Calorimetry (DSC) and Vibrating Sample Magnetometer (VSM). It observed that, synthesized IONs shows of 25.28 nm crystallite with 25.86 nm semipherical (changed as) shape. Meanwhile, Magnetite and maghemite phase are found in range of 670 cm-1 and 700 cm-1 respectively, which it contributes magnetization saturation of 73.96 emu/g at 10,000 G by VSM. Thermal stability and magnetic properties were increased with incorporating IONs into NBR latex up to 20 phr. NBR/IONs 5 phr has the optimum thermal stability, lowest glass transition temperature (-14.83 °C) and acceptable range of magnetization saturation (3.83 emu/g at 10,000 G) to form NBR gloves with magnetic detectability.

  9. Effect of magnetic and thermal properties of iron oxide nanoparticles (IONs) in nitrile butadiene rubber (NBR) latex

    Nitrile butadiene rubber (NBR) gloves are one of the most important personal protective equipments but they are possible to tear off and contaminate food or pharmaceutical and healthcare products during manufacturing and packaging process. High tendency of torn glove remaining in food or products due to white or light flesh-coloured glove is not easy to be detected by naked eyes. In this paper, iron oxide nanoparticles (IONs) selected as additive for NBR to improve its detectability by mean of magnetic properties. IONs synthesized via precipitation method and compounded with NBR latex before casting on petri dish. The properties of IONs were investigated by X-ray Diffractometry (XRD), Transmission Electron Microscope (TEM), Raman Spectroscopy and Vibrating Sample Magnetometer (VSM). Meanwhile NBR/IONs composites were studied by Thermogravimetry Analysis (TGA), Differential Scanning Calorimetry (DSC) and Vibrating Sample Magnetometer (VSM). It observed that, synthesized IONs shows of 25.28 nm crystallite with 25.86 nm semipherical (changed as) shape. Meanwhile, Magnetite and maghemite phase are found in range of 670 cm−1 and 700 cm−1 respectively, which it contributes magnetization saturation of 73.96 emu/g at 10,000 G by VSM. Thermal stability and magnetic properties were increased with incorporating IONs into NBR latex up to 20 phr. NBR/IONs 5 phr has the optimum thermal stability, lowest glass transition temperature (−14.83 °C) and acceptable range of magnetization saturation (3.83 emu/g at 10,000 G) to form NBR gloves with magnetic detectability. - Highlights: • We synthesized IONs with high magnetization saturation (Ms). • High Ms of IONs were incorporated into NBR latex in order to induce magnetic properties in the NBR composite. • Introduction of IONs into NBR latex would improve thermal properties. • The produced NBR/IONs 5 phr composite exceeded the minimum magnetic moment sensor of the detector. • They have high potential for the

  10. Actinide-to-carbon bonds in Cp2An(alkyl)2, -(butadiene), -(metallacyclopentadiene), and -(cyclobutadiene) complexes

    The electronic structure of actinide bis(cyclopentadienyl)dialkyl, -butadiene, -metallacyclopentadiene, and -cyclobutadiene complexes is examined. Some Cp*2Th(alkyl)2 complexes display an interesting structural deformation in which a Th-C-C(alkyl) angle (α) opens up considerably. A molecular orbital analysis of Cp2Th(C2H5)2 traces the deformation to the characteristic shape of the d/sub σ/ fragment orbital of Cp2Th(C2H5)+. The potential energy curve for the ethyl pivoting was found to be very soft, with a shallow minimum at α ∼ 1600. Nonrigidity of the ethyl orientation indicates that not only an α hydrogen but also a β hydrogen can come close to Th without a loss of Th-C bond strength; the discussion should provide a theoretical basis for understanding important aspects of C-H activation chemistry involving actinide centers. The Cp2An(s-cis-C4H6) complex was calculated to be 0.74 eV (Th) or 0.42 eV (U) more stable than its s-trans-C4H6 isomer, in contrast to the analogous Cp2Zr(C4H6) complex where the stability of the two geometrical isomers was well-balanced. The σ2,π character of the s-cis-C4H6 coordination to An is somewhat less pronounced than that in the Zr congener, in harmony with the X-ray structures, while highly negative charges are accumulated on the s-cis-C4H6 terminal carbons

  11. Probing α-relaxation with nuclear magnetic resonance echo decay and relaxation: a study on nitrile butadiene rubber.

    Sturniolo, Simone; Pieruccini, Marco; Corti, Maurizio; Rigamonti, Attilio

    2013-01-01

    One dimensional (1)H NMR measurements have been performed to probe slow molecular motions in nitrile butadiene rubber (NBR) around its calorimetric glass transition temperature Tg. The purpose is to show how software aided data analysis can extract meaningful dynamical data from these measurements. Spin-lattice relaxation time, free induction decay (FID) and magic sandwich echo (MSE) measurements have been carried out at different values of the static field, as a function of temperature. It has been evidenced how the efficiency of the MSE signal in reconstructing the original FID exhibits a sudden minimum at a given temperature, with a slight dependence from the measuring frequency. Computer simulations performed with the software SPINEVOLUTION have shown that the minimum in the efficiency reconstruction of the MSE signal corresponds to the average motional frequency taking a value around the inter-proton coupling. The FID signals have been fitted with a truncated form of a newly derived exact correlation function for the transverse magnetization of a dipolar interacting spin pair, which allows one to avoid the restriction of the stationary and Gaussian approximations. A direct estimate of the conformational dynamics on approaching the Tg is obtained, and the results are in agreement with the analysis performed via the MSE reconstruction efficiency. The occurrence of a wide distribution of correlation frequencies for the chains motion, with a Vogel-Fulcher type temperature dependence, is addressed. A route for a fruitful study of the dynamics accompanying the glass transition by a variety of NMR measurements is thus proposed. PMID:23379979

  12. The role of neutral and radical anionic organozinc complexes in the alkylation reactions of 1,4-diaza-1,3-butadienes with diorganozinc compounds

    van Koten, G; Rijnberg, E.; Boersma, J.; Jastrzebski, J.T.B.H.; Lakin, M.T.; Spek, A.L.

    1997-01-01

    We have earlier postulated the intermediacy of organozinc radical species in the regioselective alkylation reactions of 1,4-di-tert-butyl-1,4-diaza-1,3-butadiene (t-BuNCHCHN-t-Bu) with diorganozinc compounds (ZnR2). To verify these postulates, we have prepared and studied the neutral organozinc radical complex MeO(CH2)3Zn(t-BuNCHCHN-t-Bu) (A) and two diorganozinc radical-anionic complexes, K[R2Zn(t-BuNCHCHN-t-Bu)] (R = Me (8a), Et (8b)). A was prepared in situ by the reaction of t-BuNCHCHN-t-...

  13. Enhancement of Compatibility between Ultrahigh-Molecular-Weight Polyethylene Particles and Butadiene.Nitrile Rubber Matrix with Nanoscale Ceramic Particles and Characterization of Evolving Layer

    Shadrinov, Nikolay V.; Sokolova, Marina D.; Cho, Jinho [Institute of Oil and Gas Issues, Yakutsk (Russian Federation); Okhlopkova, A. A. [North-Eastern Federal Univ., Yakutsk (Russian Federation); Lee, Jungkeun; Jeong, Daeyong [Myongji Univ., Seoul (Korea, Republic of)

    2013-12-15

    This article examines the modification of surface properties of ultrahigh-molecular-weight polyethylene (UHMWPE) with nanoscale ceramic particles to fabricate an improved composite with butadiene.nitrile rubber (BNR). Adhesion force data showed that ceramic zeolite particles on the surface of UHMWPE modulated the surface state of the polymer and increased its compatibility with BNR. Atomic force microscopy phase images showed that UHMWPE made up the microphase around the zeolite particles and formed the evolving layer with a complex interface. The complex interface resulted in improvements in the mechanical properties of the composite, especially its low-temperature resistance coefficients, thereby improving its performance in low-temperature applications.

  14. The use of styrene-butadiene rubber waste as a potential filler in nitrile rubber: order of addition and size of waste particles

    D. A. Baeta; J. A. Zattera; M. G. Oliveira; Oliveira, P J

    2009-01-01

    Styrene-butadiene rubber (SBR) has large applications in the shoe industry, especially as expanded sheets used to produce insoles and inner soles. According to TG analysis, the rubber content in SBR residues (SBR-r) was found to be around 26-wt%. Based on that data, a cost-effective technique for the reuse of SBR-r in Nitrile rubber (NBR) was developed. Later, the effect of SBR-r on the cure behavior, mechanical performance, swelling, and crosslink density of reused rubber was investigated, w...

  15. DFT studies for the substituent effect on the diels-alder reaction of 1,4-diaza-1,3-butadienes

    DFT calculations have been performed on several substituted 1,4-diaza-1,3-butadienes (1,4-DABs) with electron donating and withdrawing groups at the terminal two nitrogens to investigate the reactivity of Diels-Alder reaction with acrolein. The calculated FMO (Frontier Molecular orbital) energies for the optimized 1,4-disubstituted-1,4DABs have been used to explain both normal and inverse electron demand Diels-Alder reactions. It is shown that the electron donating and withdrawing substituents lead to the normal(HOMO diene controlled) and inverse electron demand (LUMO diene controlled) Diels-Alder reactions, respectively

  16. STUDY ON THE SEQUENCE STRUCTURE OF BUTADIENE-STYRENE RUBBER BY 13C-NMR METHOD Ⅲ. QUANTITATIVE CHARACTERIZATION OF SEQUENCE STRUCTURE

    CHEN Xiaonong; HU Liping; YAN Baozhen; JIAO Shuke

    1990-01-01

    The quantitative description of the sequence structure of emulsion-processed SBR and solution-processed SBR (by lithium catalyst)was carried out based on their spectral data of 13C-NMR.The calculating formulae which could be used to obtain diad concentration from the peak intensities of carbon spectra, average block length, average number of block, and the microstructure composition of the molecular chain were derived. The quantitative result showed that on the molecular chain styrene unit had the tendency to attach to trans-1,4 butadiene unit. The calculated result of the microstructure was in good agreement with that obtained through IR measurement.

  17. 二甲基甲酰胺法萃取精馏生产1,3-丁二烯的模拟计算%Simulation of 1,3-Butadiene Production Process by Dimethylfomamide Extractive Distillation

    杨小健; 殷绚; 欧阳平凯

    2009-01-01

    Nowadays, extractive distillation is the main technique to produce 1,3-butadiene. This study simulated the 1,3-butadiene production process with DMF extractive distillation by Aspen Plus. The solvent ratio is the most important parameter to the extractive distillation process. The article has given out the proper solvent ratios, reflux ratios, distillate ratios, and bottom product ratios of the columns. It also discusses the thermal loads of several columns. The results of simulation are consequently compared with the plant data, which shows good accordance with each other.

  18. Toughening of carbon fibre reinforced polymer composites with rubber nanoparticles for advanced industrial applications

    N. G. Ozdemir; Zhang, T.; I. Aspin; Scarpa, F.; Hadavinia, H.; Song, Y.

    2016-01-01

    This study investigates the effects of nano carboxylic acrylonitrile butadiene rubber (CNBR-NP) and nano acrylonitrile butadiene rubber (NBR-NP) on the interlaminar shear strength and fracture toughness of carbon fibre reinforced polymer composites (CFRP) with dicyandiamide-cured epoxy matrix. The results show that nano-size dispersion of rubber significantly improved the Mode I delamination fracture toughness (GIC) of the CFRP by 250% and its Mode II delamination fracture toughness (GIIC) by...

  19. Zinc oxide nanorod assisted rapid single-step process for the conversion of electrospun poly(acrylonitrile) nanofibers to carbon nanofibers with a high graphitic content

    Nain, Ratyakshi; Singh, Dhirendra; Jassal, Manjeet; Agrawal, Ashwini K.

    2016-02-01

    The effect of incorporation of rigid zinc oxide (ZnO) nanostructures on carbonization behavior of electrospun special acrylic fiber grade poly(acrylonitrile) (PAN-SAF) nanofibers was investigated. ZnO nanorods with high aspect ratios were incorporated into a PAN-N,N-dimethylformamide system and the composite nanofibers reinforced with aligned ZnO rods up to 50 wt% were successfully electrospun, and subsequently, carbonized. The morphology and the structural analysis of the resultant carbon nanofibers revealed that the rigid ZnO nanorods, present inside the nanofibers, possibly acted as scaffolds (temporary support structures) for immobilization of polymer chains and assisted in uniform heat distribution. This facilitated rapid and efficient conversion of the polymer structure to the ladder, and subsequently, the graphitized structure. At the end of the process, the ZnO nanorods were found to completely separate from the carbonized fibers yielding pure carbon nanofibers with a high graphitic content and surface area. The approach could be used to eliminate the slow, energy intensive stabilization step and achieve fast conversion of randomly laid carbon nanofiber webs in a single step to carbon nanofibers without the application of external tension or internal templates usually employed to achieve a high graphitic content in such systems.The effect of incorporation of rigid zinc oxide (ZnO) nanostructures on carbonization behavior of electrospun special acrylic fiber grade poly(acrylonitrile) (PAN-SAF) nanofibers was investigated. ZnO nanorods with high aspect ratios were incorporated into a PAN-N,N-dimethylformamide system and the composite nanofibers reinforced with aligned ZnO rods up to 50 wt% were successfully electrospun, and subsequently, carbonized. The morphology and the structural analysis of the resultant carbon nanofibers revealed that the rigid ZnO nanorods, present inside the nanofibers, possibly acted as scaffolds (temporary support structures) for

  20. Technical scheme for integration of DCC unit and acrylonitrile unit%DCC装置和丙烯腈装置一体化技术方案

    刘福安; 朱校春; 王飞

    2013-01-01

    The technical scheme for integration of DCC unit and acrylonitrile unit is presented.The internal mutual feedstock supply,the comprehensive utilization of steam and sour gas treatment technologies of the integrated unit are analyzed.The analysis of internal feedstock supply has found that the volume of intermediate storage tanks for propylene can be reduced,and the temperature of propylene from gas stripper to acrylonitrile unit is raised by 5℃.As the result,the unit energy consumption is lowered.The study of comprehensive steam utilization has concluded that a 4.0 MPa steam boiler can be saved and the steam utilization can be improved.The analysis of DCC sour gas treatment technology has concluded that the application of this technology can save a LO-CAT sulfur recovery unit for DCC unit.All these analysis demonstrate that the application of this integration technology offers good economic benefits.1.39 × 108 RMB ¥ of capital investment can be saved from no installation of a 4.0 MPa steam boiler and a LO-CAT sulfur recovery unit.The conversion of sour gas into on-spec sulfuric acid and increasing of propylene feed supply temperature can add an economic benefit of 3.67 × 106 RMB ¥ a year.%提出DCC装置和丙烯腈装置一体化技术方案,对该技术方案的物料直供、蒸汽综合利用以及酸性气处理技术进行了具体的分析.通过物料互供分析,可以适当减少丙烯的中间储存罐容,提高丙烯从气分装置进丙烯腈装置的温度约5℃,降低装置运行能耗;通过蒸汽综合利用分析,可省去一台4.0 MPa的中压蒸汽锅炉,同时还能提高蒸汽的利用效率;通过对DCC装置酸性气处理技术的分析,发现该技术方案可省去一套与DCC装置配套的LO-CAT硫黄装置.分析表明该组合技术方案有很好的经济效益,省去的一台4.0 MPa中压蒸汽锅炉和一套LO-CAT硫黄装置可为企业节约工程投资1.39×108 RMB¥;酸性气转化为合格硫酸产品和提高丙烯

  1. Differential metabolism of acrylonitrile to cyanide is responsible for the greater sensitivity of male vs female mice: role of CYP2E1 and epoxide hydrolases

    Acrylonitrile (AN) is a potent toxicant and a known rodent carcinogen. AN epoxidation to cyanoethylene oxide (CEO) via CYP2E1 and its subsequent metabolism via epoxide hydrolases (EH) to yield cyanide is thought to be responsible for the acute toxicity and mortality of AN. Recent reports showed that male mice are more sensitive than females to the acute toxicity/mortality of AN. The present work was undertaken to assess the metabolic and enzymatic basis for the greater sensitivity of male vs female mice to AN toxicity. Male and female wild-type and CYP2E1-null mice received AN at 0, 2.5, 10, 20, or 40 mg/kg by gavage. Cyanide concentrations were measured at 1 or 3 h after dosing. Current data demonstrated that cyanide levels in blood and tissues of AN-treated wild-type mice of both sexes were significantly greater than in vehicle-treated controls and increased in a dose-dependent manner. In contrast, cyanide levels in AN-treated CYP2E1-null mice were not statistically different from those measured in vehicle-treated controls. Furthermore, higher levels of cyanide were detected in male wild-type mice vs females in association with greater sensitivity of males to the acute toxicity/mortality of this chemical. Using Western blot analysis, negligible difference in CYP2E1 expression with higher levels of soluble and microsomal EH (sEH and mEH) was detected in the liver of male vs female mice. In kidneys, male mice exhibited higher expression of both renal CYP2E1 and sEH than did female mice. In conclusion, higher blood and tissue cyanide levels are responsible for the greater sensitivity of male vs female mice to AN. Further, higher expression of CYP2E1 and EH in male mice may contribute to greater formation of CEO and its subsequent metabolism to yield cyanide, respectively

  2. Copper-catalyzed retro-aldol reaction of β-hydroxy ketones or nitriles with aldehydes: chemo- and stereoselective access to (E)-enones and (E)-acrylonitriles.

    Zhang, Song-Lin; Deng, Zhu-Qin

    2016-07-26

    A copper-catalyzed transfer aldol type reaction of β-hydroxy ketones or nitriles with aldehydes is reported, which enables chemo- and stereoselective access to (E)-α,β-unsaturated ketones and (E)-acrylonitriles. A key step of the in situ copper(i)-promoted retro-aldol reaction of β-hydroxy ketones or nitriles is proposed to generate a reactive Cu(i) enolate or cyanomethyl intermediate, which undergoes ensuing aldol condensation with aldehydes to deliver the products. This reaction uses 1.2 mol% Cu(IPr)Cl (IPr denotes 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) as the catalyst in the presence of 6.0 mol% NaOtBu cocatalyst at room temperature or 70 °C. A range of aryl and heteroaryl aldehydes as well as acrylaldehydes are compatible with many useful functional groups being tolerated. Under the mild and weakly basic conditions, competitive Cannizzaro-type reaction of benzaldehydes and side reactions of base-sensitive functional groups can be effectively suppressed, which show synthetic advantages of this reaction compared to classic aldol reactions. The synthetic potential of this reaction is further demonstrated by the one-step synthesis of biologically active quinolines and 1,8-naphthyridine in excellent yields (up to 91%). Finally, a full catalytic cycle for this reaction has been constructed using DFT computational studies in the context of a retro-aldol/aldol two-stage mechanism. A rather flat reaction energy profile is found indicating that both stages are kinetically facile, which is consistent with the mild reaction conditions. PMID:27397647

  3. 丙烯腈吸收过程模拟优化%Simulation and Optimization of the Absorption Process to a Acrylonitrile Plant

    杨家军; 霍凤华; 崔吉成

    2015-01-01

    Throughout its history,chemical process simulation software has been widely used in chemical process design,operational evaluation and optimization.As well known by chemical technicans,the PROII software was used for the simulation of the absorption process of acrylonitrile production plant in the study.Firstly,the operating parameters of the absorption process were analyzed to determine the optimization variables.After that, the absorption tower was simulated with PROII software.By comparing the simulation results of different conditions,the process parameters related to the sbsorption process were analyzed,such as the comsuption of absorption water and side withdrawing,and the operating pressure. The optimum values in the corresponding conditions were obtained.%化工过程模拟软件发展至今已被广泛地应用于化工过程的设计计算、操作评估和优化中。该文应用化工技术人员熟知的PROII软件对丙烯腈的吸收过程进行模拟研究。首先对年产20万吨的丙烯腈生产过程吸收塔单元中的操作参数进行分析,确定要优化的参数。然后应用PROII软件对丙烯腈吸收塔进行模拟,通过改变操作参数后模拟结果的比较对操作参数中的吸收水用量、侧线采出量和吸收塔的操作压力进行了模拟分析,并得到相应条件下的最佳值。

  4. 丙烯腈吸收过程模拟优化%Simulation and Optimization of the Absorption Process to a Acrylonitrile Plant

    杨家军; 霍凤华; 崔吉成

    2015-01-01

    Throughout its history,chemical process simulation software has been widely used in chemical process design,operational evaluation and optimization.As well known by chemical technicans,the PROII software was used for the simulation of the absorption process of acrylonitrile production plant in the study.Firstly,the operating parameters of the absorption process were analyzed to determine the optimization variables.After that, the absorption tower was simulated with PROII software.By comparing the simulation results of different conditions,the process parameters related to the sbsorption process were analyzed,such as the comsuption of absorption water and side withdrawing,and the operating pressure. The optimum values in the corresponding conditions were obtained.%化工过程模拟软件发展至今已被广泛地应用于化工过程的设计计算、操作评估和优化中.该文应用化工技术人员熟知的PROII软件对丙烯腈的吸收过程进行模拟研究.首先对年产20万吨的丙烯腈生产过程吸收塔单元中的操作参数进行分析,确定要优化的参数.然后应用PROII软件对丙烯腈吸收塔进行模拟,通过改变操作参数后模拟结果的比较对操作参数中的吸收水用量、侧线采出量和吸收塔的操作压力进行了模拟分析,并得到相应条件下的最佳值.

  5. Preparation, characterization and evaluation of proton-conducting hybrid membranes based on sulfonated hydrogenated styrene-butadiene and polysiloxanes for fuel cell applications

    Monroy-Barreto, M.; Aguilar, J.C.; Rodriguez de San Miguel, E.; de Gyves, J. [Departamento de Quimica Analitica, Facultad de Quimica, UNAM, Ciudad Universitaria, 04360 Mexico, D.F. (Mexico); Acosta, J.L.; del Rio, C.; Ojeda, M.C. [Instituto de Ciencia y Tecnologia de Polimeros (CSIC), c/Juan de la Cierva 3, 28006 Madrid (Spain); Munoz, M. [Departament de Quimica Analitica, Facultat de Ciencies, U.A.B., Bellaterra 08193 Barcelona (Spain)

    2010-12-15

    This paper describes the preparation of proton-conducting hybrid membranes (HMs) obtained by a solvent casting procedure using a solution containing sulfonated hydrogenated styrene-butadiene (HSBS-S) and an inorganic-organic mixture (polysiloxanes) previously prepared by a sol-gel route. HSBS-S copolymers with different sulfonation degrees were obtained and characterized by means of elemental analysis (EA), chemical titration and electrochemical impedance spectroscopy (EIS). HSBS-S with the best properties in terms of proton conductivity and solubility for the casting procedure was selected to prepare the HMs. The solvent casting procedure permitted the two phases to be homogeneously distributed while maintaining a relatively high proton conductivity in the membrane. HMs with different blend ratios were characterized using structural (Fourier transform infrared-attenuated total reflectance (FTIR-ATR), dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC)), electrical (EIS), physicochemical (water uptake, ion-exchange capacity) and thermal (TGA-MS) methods. Finally, the optimized HSBS-S membrane and HMs were tested in hydrogen single fuel cells to obtain the polarization and power curves at different cell temperatures and gas pressures. Results indicate that HMs show a considerable improvement in performance compared to the optimized HSBS-S membrane denoting the benefit of incorporating the inorganic-organic network in the hydrogenated styrene-butadiene matrix. A Nafion membrane was used as reference material throughout this work. (author)

  6. Synthesis and characterization of butadiene-1,3 and octene-1 copolymer prepared by a Ziegler-Natta catalyst based on neodymium

    Gustavo M. Silva

    2011-01-01

    Full Text Available The aim of this work is to evaluate the influence of octene-1 incorporation in the polybutadiene chain on the polymerization reaction and polymer characteristics. Thus, copolymerization of butadiene-1,3 with octene-1 using a Ziegler-Natta ternary catalyst based on neodymium was performed. The weight ratios of butadiene-1,3/α-olefin 100/0, 99/1, 97/3, 95/5, 90/10, 80/20 and 70/30 were evaluated. The copolymers were characterized by size exclusion chromatography (SEC, infrared spectroscopy (FTIR and thermogravimetric analysis (TG. The results showed that the degradation temperature (Tmax was not affected by the addition of alpha-olefin, while the thermal behavior has undergone significant changes. The polymer microstructure was not influenced by the increasing of octene-1 content. However, a tendency to molecular mass increase was observed with the increasing of octene-1 content. It was also observed a trend in reduction of the polymerization conversion as the octene-1 content increased.

  7. The Diels-Alder Cycloaddition Reaction of Substituted Hemifullerenes with 1,3-Butadiene: Effect of Electron-Donating and Electron-Withdrawing Substituents

    Martha Mojica

    2016-02-01

    Full Text Available The Diels-Alder (DA reaction provides an attractive route to increase the number of six member rings in substituted Polycyclic Aromatic Hydrocarbons (PAHs. The density functional theory (DFT B3LYP method has been used in this work to inquire if the substitution of H over the edge of triindenetriphenylene (pristine hemifullerene 1 and pentacyclopentacorannulene (pristine hemifullerene 2, could improve the DA cycloaddition reaction with 1,3-butadiene. The substituents tested include electron-donating (NH2, OMe, OH, Me, i-Pr and electron-withdrawing groups (F, COOH, CF3, CHO, CN, NO2. The electronic, kinetic and thermodynamic parameters of the DA reactions of the substituted hemifullerenes with 1,3-butadiene have been analyzed. The most promising results were obtained for the NO2 substituent; the activation energy barriers for reactions using this substituent were lower than the barriers for the pristine hemifullerenes. This leads us to expect that the cycloadditions to a starting fullerene fragment will be possible.

  8. Low-Temperature 1,3-Butadiene Hydrogenation over Supported Pt/3d/gamma-Al2O3 Bimetallic Catalysts

    Lonergan, William W; Xing, X; Zheng, Renyang; Qi, Suitao; Huang, B; Chen, Jingguang

    2011-02-02

    Low-temperature 1,3-butadiene hydrogenation is used as a probe reaction to investigate the hydrogenation activity over several γ-Al{sub 2}O{sub 3} supported Pt/3d (3d = Co, Ni, Cu) bimetallic catalysts. Batch and flow reactor studies are employed to quantify the kinetic activity and steady-state conversion, respectively, of each catalyst. Transmission electron microscopy (TEM) is utilized to characterize particle sizes and extended X-ray absorption fine structure (EXAFS) measurements are performed to verify the Pt–3d bimetallic bond formation. Pulse carbon monoxide chemisorption measurements are also performed to characterize the number of active sites. Additionally, density functional theory (DFT) calculations are included to determine the binding energies of 1,3-butadiene and atomic hydrogen on the corresponding model surfaces. The binding energies of the adsorbates are found to correlate with the hydrogenation activity, allowing for use of such correlation to potentially predict hydrogenation catalysts with enhanced activity based on the binding energies of the adsorbates of interest.

  9. Methoxy Silane in Styrene-butadiene Synthetic Resin%甲氧基硅烷在丁苯合成树脂的研究

    王平; 舒畅; 蓝晓; 钟凤清

    2012-01-01

    The star styrene-butadiene copolymerization were synthesized by using styrene and butadiene as monomers, n-BuLi as initiator, Methyl-trimethoxy-silane as coupling agent and cyclohexane as solvent by anionic polymerization. The effect of quantity of coupling agent, feed stock times, polymerization temperature and polymerization time on the coupling efficiency(CE%) and average branching number(BN) were investigated.%以苯乙烯、丁二烯为单体,N—BuLi为引发剂,环己烷为溶剂,甲基三甲氧基硅烷为偶联剂,通过负离子聚合和偶联反应,制备含有多种嵌段水平的星形r苯透明抗冲树脂。并初步探讨了偶联剂加入量、加料次数、温度、时间和基峰分子量与偶联效率、支化度(臂数)的关系。

  10. Selective hydrogenation of 1,3-butadiene from crude C{sub 4} cracker stream with a solid catalyst with ionic liquid layer (SCILL). DSC and solubility study

    Mangartz, T.; Korth, W.; Kern, C.; Jess, A. [Bayreuth Univ. (Germany). Dept. of Chemical Engineering

    2013-11-01

    In petroleum as well as in fine chemical industry, selective catalytic hydrogenation is an important reaction. The selective hydrogenation of 1,3-butadiene (BD) to butene (trans-,1- and cis-butene) from the crude C4 steam cracker fraction represents one example, but under today's technical conditions undesired butane forms inevitably in relevant amounts. To increase the butene yield, the concept of Solid Catalyst with Ionic Liquid Layer (SCILL) was employed. The SCILL catalyst, in contrast to the uncoated catalyst, yielded a remarkably high selectivity to butenes (S{sub butenes} > 99 %) even at high residence times or at high hydrogen partial pressure. Nearly no butane (S{sub butane} {approx} 0 %) was analytically detected. We expected that due to different solubility, the poorer soluble compounds discharged from the ionic liquid and, thus, caused the shift in selectivity to a great extent. Temperature dependent solubility measurements in the used ionic liquid ([DMIM][DMP]) revealed that the order of increasing solubility is 1,3-butadiene > butenes > butane which matches the assumption. However, since differences in solubility cannot explain this SCILL effect satisfyingly, ionic liquids are expected to affect the surface of the catalyst (side-specific ligand-type effect). Investigations using spectroscopic methods (e.g. FTIR) confirmed this suggestion. (orig.)

  11. 1,3-Butadiene, styrene and lymphohematopoietic cancer among male synthetic rubber industry workers--Preliminary exposure-response analyses.

    Sathiakumar, Nalini; Brill, Ilene; Leader, Mark; Delzell, Elizabeth

    2015-11-01

    We updated the mortality experience of North American synthetic rubber industry workers to include follow-up from 1944 through 2009, adding 11 years of mortality data to previous investigations. The present analysis used Cox regression to examine the exposure-response relationship between 1,3-butadiene (BD) and styrene (STY) parts per million (ppm)-years and leukemia (N = 114 deaths), non-Hodgkin lymphoma (NHL) (N = 89) and multiple myeloma (MM) (N = 48). A pattern of largely monotonically increasing rate ratios across deciles of BD ppm-years and a positive, statistically significant exposure-response trend were observed for BD ppm-years and leukemia. Using continuous, untransformed BD ppm-years the regression coefficient (β) adjusted only for age was 2.6 × 10(-4) (p race and plant was 2.9 × 10(-4) (p separate effects of these two agents could not be estimated. For NHL, a pattern of approximately monotonically increasing rate ratios across deciles of exposure was seen for STY but not for BD; the test of trend was statistically significant in one of five models that used different STY exposure metrics and adjusted for age and other covariates. BD ppm-years and STY ppm-years were not associated with MM. The present analyses indicated a positive exposure-response relationship between BD cumulative exposure and leukemia. This result along with other research and biological information support an interpretation that BD causes leukemia in humans. STY exposure also was positively associated with leukemia, but its independent effect could not be delineated because of its strong correlation with BD, and there is no external support for a STY-leukemia association. STY, but not BD, was associated positively with NHL. The interpretation of this result is uncertain because the exposure-response data were statistically imprecise and because consistent support for causality from other studies is lacking. The current study provides no support for an association

  12. Effect of magnetic and thermal properties of iron oxide nanoparticles (IONs) in nitrile butadiene rubber (NBR) latex

    Ong, Hun Tiar; Julkapli, Nurhidayatullaili Muhd; Hamid, Sharifah Bee Abd, E-mail: sharifahbee@um.edu.my; Boondamnoen, O.; Tai, Mun Foong

    2015-12-01

    Nitrile butadiene rubber (NBR) gloves are one of the most important personal protective equipments but they are possible to tear off and contaminate food or pharmaceutical and healthcare products during manufacturing and packaging process. High tendency of torn glove remaining in food or products due to white or light flesh-coloured glove is not easy to be detected by naked eyes. In this paper, iron oxide nanoparticles (IONs) selected as additive for NBR to improve its detectability by mean of magnetic properties. IONs synthesized via precipitation method and compounded with NBR latex before casting on petri dish. The properties of IONs were investigated by X-ray Diffractometry (XRD), Transmission Electron Microscope (TEM), Raman Spectroscopy and Vibrating Sample Magnetometer (VSM). Meanwhile NBR/IONs composites were studied by Thermogravimetry Analysis (TGA), Differential Scanning Calorimetry (DSC) and Vibrating Sample Magnetometer (VSM). It observed that, synthesized IONs shows of 25.28 nm crystallite with 25.86 nm semipherical (changed as) shape. Meanwhile, Magnetite and maghemite phase are found in range of 670 cm{sup −1} and 700 cm{sup −1} respectively, which it contributes magnetization saturation of 73.96 emu/g at 10,000 G by VSM. Thermal stability and magnetic properties were increased with incorporating IONs into NBR latex up to 20 phr. NBR/IONs 5 phr has the optimum thermal stability, lowest glass transition temperature (−14.83 °C) and acceptable range of magnetization saturation (3.83 emu/g at 10,000 G) to form NBR gloves with magnetic detectability. - Highlights: • We synthesized IONs with high magnetization saturation (M{sub s}). • High M{sub s} of IONs were incorporated into NBR latex in order to induce magnetic properties in the NBR composite. • Introduction of IONs into NBR latex would improve thermal properties. • The produced NBR/IONs 5 phr composite exceeded the minimum magnetic moment sensor of the detector. • They have high

  13. The Influence of Preparation Variables on the Performance of Pd/Al2O3 Catalyst in the Hydrogenation of 1,3-butadiene: Building a Basis for Reproducible Catalyst Synthesis

    Čukić, T.; Kraehnert, R.; Holeňa, Martin; Herein, D.; Linke, D.; Dingerdissen, U.

    2007-01-01

    Roč. 323, - (2007), s. 25-37. ISSN 0926-860X Source of funding: V - iné verejné zdroje Keywords : Pd/Al2O3 * butadiene hydrogenation * preparation variables * experimental design * high-throughput experimentation * regression tree * reproducibility of chemical recipes Subject RIV: IN - Informatics, Computer Science Impact factor: 3.166, year: 2007

  14. Cytotoxicity, genotoxicity, and mutagenicity of 1-chloro-2-hydroxy-3-butene and 1-chloro-3-buten-2-one, two alternative metabolites of 1,3-butadiene

    The cytotoxicity, genotoxicity, and mutagenicity of 1-chloro-2-hydroxy-3-butene (CHB), a known in vitro metabolite of the human carcinogen 1,3-butadiene, have not previously been investigated. Because CHB can be bioactivated by alcohol dehydrogenases to yield 1-chloro-3-buten-2-one (CBO), a bifunctional alkylating agent that caused globin-chain cross-links in erythrocytes, in the present study we investigated the cytotoxic and genotoxic potential of CHB and CBO in human normal hepatocyte L02 cells using the MTT assay, the relative cloning efficiency assay and the comet assay. We also investigated the mutagenic potential of these compounds with the Ames test using Salmonella strains TA1535 and TA1537. The results provide clear evidence for CHB and CBO being both cytotoxic and genotoxic with CBO being approximately 100-fold more potent than CHB. Interestingly, CHB generated both single-strand breaks and alkali-labile sites on DNA, whereas CBO produced only alkali-labile sites. CHB did not directly result in DNA breaks, whereas CBO was capable of directly generating breaks on DNA. Interestingly, both compounds did not induce DNA cross-links as examined by the comet assay. The Ames test results showed that CHB induced point mutation but not frameshift mutation, whereas the toxic effects of CBO made it difficult to reliably assess the mutagenic potential of CBO in the two strains. Collectively, the results suggest that CHB and CBO may play a role in the mutagenicity and carcinogenicity of 1,3-butadiene. - Highlights: • 1-Chloro-2-hydroxy-3-butene (CHB) is cytotoxic and genotoxic in human liver cells. • The CHB metabolite, 1-chloro-3-buten-2-one (CBO) is ∼ 100-fold more toxic than CHB. • CHB and CBO cause DNA alkali-labile sites, but only CBO directly causes DNA breaks. • CHB is mutagenic in the Ames test, but CBO is too toxic in the assay. • The results suggest a role for CHB in 1,3-butadiene genotoxicity and mutagenicity

  15. Cytotoxicity, genotoxicity, and mutagenicity of 1-chloro-2-hydroxy-3-butene and 1-chloro-3-buten-2-one, two alternative metabolites of 1,3-butadiene

    Liu, Xin-Jie; Zeng, Fang-Mao; An, Jing; Yu, Ying-Xin [Institute of Environmental Pollution and Health, School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444 (China); Zhang, Xin-Yu, E-mail: xyzhang999@shu.edu.cn [Institute of Environmental Pollution and Health, School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444 (China); Elfarra, Adnan A., E-mail: elfarra@svm.vetmed.wisc.edu [Department of Comparative Biosciences, University of Wisconsin-Madison, Madison, WI 53706 (United States); Molecular and Environmental Toxicology Center, University of Wisconsin-Madison, Madison, WI 53706 (United States)

    2013-08-15

    The cytotoxicity, genotoxicity, and mutagenicity of 1-chloro-2-hydroxy-3-butene (CHB), a known in vitro metabolite of the human carcinogen 1,3-butadiene, have not previously been investigated. Because CHB can be bioactivated by alcohol dehydrogenases to yield 1-chloro-3-buten-2-one (CBO), a bifunctional alkylating agent that caused globin-chain cross-links in erythrocytes, in the present study we investigated the cytotoxic and genotoxic potential of CHB and CBO in human normal hepatocyte L02 cells using the MTT assay, the relative cloning efficiency assay and the comet assay. We also investigated the mutagenic potential of these compounds with the Ames test using Salmonella strains TA1535 and TA1537. The results provide clear evidence for CHB and CBO being both cytotoxic and genotoxic with CBO being approximately 100-fold more potent than CHB. Interestingly, CHB generated both single-strand breaks and alkali-labile sites on DNA, whereas CBO produced only alkali-labile sites. CHB did not directly result in DNA breaks, whereas CBO was capable of directly generating breaks on DNA. Interestingly, both compounds did not induce DNA cross-links as examined by the comet assay. The Ames test results showed that CHB induced point mutation but not frameshift mutation, whereas the toxic effects of CBO made it difficult to reliably assess the mutagenic potential of CBO in the two strains. Collectively, the results suggest that CHB and CBO may play a role in the mutagenicity and carcinogenicity of 1,3-butadiene. - Highlights: • 1-Chloro-2-hydroxy-3-butene (CHB) is cytotoxic and genotoxic in human liver cells. • The CHB metabolite, 1-chloro-3-buten-2-one (CBO) is ∼ 100-fold more toxic than CHB. • CHB and CBO cause DNA alkali-labile sites, but only CBO directly causes DNA breaks. • CHB is mutagenic in the Ames test, but CBO is too toxic in the assay. • The results suggest a role for CHB in 1,3-butadiene genotoxicity and mutagenicity.

  16. Between Ni(mnt)2 and Ni(tfd)2 dithiolene complexes: the unsymmetrical 2-(trifluoromethyl)acrylonitrile-1,2-dithiolate and its nickel complexes.

    Jeannin, Olivier; Delaunay, Jacques; Barrière, Frédéric; Fourmigué, Marc

    2005-12-26

    A novel 1,2-dithiolate ligand, that is, the 2-(trifluoromethyl)acrylonitrile-1,2-dithiolate, abbreviated here as tfadt, is prepared from the corresponding cyclic dithiocarbonate. This ligand, substituted with both a CN and a CF(3) group, is compared with the well-known maleonitrile- and bis(trifluoromethyl)ethane-1,2-dithiolates. The preparation, electrochemical properties, and X-ray crystal structures of the square-planar nickel complexes, in both their dianionic diamagnetic [Ni(tfadt)(2)](2)(-) and their monoanionic paramagnetic [Ni(tfadt)(2)](*)(-) forms, are reported, as n-Bu(4)N(+), PPh(4)(+), and (18-crown-6)Na(+) salts, respectively. In the [(18-crown-6)Na](2)[Ni(tfadt)(2)] salt, each CN moiety of the [Ni(tfadt)(2)](2)(-) dianion is coordinated to a (18-crown-6)Na(+) cation through a CN...Na interaction [N...Na = 2.481(3) A], affording an "axle with wheels" model where two MeOH molecules act as axle caps. On the other hand, in [(18-crown-6)Na][Ni(tfadt)(2)], each (18-crown-6)Na(+) cation is coordinated on both sides by the CN groups of two monoanionic [Ni(tfadt)(2)](*)(-) complexes with N...Na(+) distances at 2.434(5) and 2.485(4) A, giving rise to heterobimetallic chains with alternating (18-crown-6)Na(+) and [Ni(tfadt)(2)](*)(-) ions. These two examples demonstrate the attractive ability of the CN moieties in the [Ni(tfadt)(2)](2)(-)(,)(*)(-) complexes to coordinate metallic cationic centers. The paramagnetic salts of the anionic [Ni(tfadt)(2)](*)(-) complex follow Curie-type law in the 2-300 K temperature range, indicating the absence of intermolecular magnetic interactions in the solid state. The complexes are found in their trans form in all crystal structures, while density functional theory calculations establish that both forms have essentially the same energy. A cis-trans interconversion process is observed by variable-temperature NMR on the dianionic [Ni(tfadt)(2)](2)(-) complex with a coalescence temperature T(c) of 260 K and a free energy of

  17. Study of ageing effects in polymer-in-salt electrolytes based on poly(acrylonitrile-co-butyl acrylate) and lithium salts

    Highlights: • Properties of freshly cast and aged poly(AN-co-BuA) – LiTFSI electrolytes are studied. • For fresh electrolytes, conductivity increases and Tg decreases with increasing salt content. • Ageing of polymer-in-salt electrolytes results in a drop of conductivity and a rise of Tg. • Ageing effects can be explained by changes of properties of amorphous salt domains. • Precipitation of salt is observed in electrolytes containing over 84 wt.% of LiTFSI. • Electrolytes with mixture of LiI and LiTFSI are more stable than those with LiTFSI only. -- Abstract: Polymer electrolytes composed of an acrylonitrile and butyl acrylate copolymer poly(AN-co-BuA) with addition of LiN(CF3SO2)2 (LiTFSI) or LiI and LiTFSI salt mixture are studied by impedance spectroscopy, DSC, Raman spectroscopy, X-ray diffraction, SEM and TEM. Impedance study shows that the ionic conductivity of the electrolytes containing LiTFSI is strongly dependent on the salt content and transition from “salt-in-polymer” to “polymer-in-salt” regime is observed at high salt content. Gradual changes of physical properties of the studied polymer electrolytes are observed in the course of their prolonged storage under argon atmosphere. These include the increase of glass transition temperature and decrease of ionic conductivity. In order to study the effects of this ageing process, measurements on samples of electrolyte films were repeated after several months. Precipitation of salt, which occurred at the nanometer length scale is observed with the aid of electron microscopy in electrolytes containing more than 84 wt.% of salt. Crystalline salt is not observed in electrolytes with lower amount of salt – however, the results indicate the structural changes of salt aggregates, which strongly influence transport of ions through the electrolyte. For preparation of electrolytes with mixed LiTFSI and LiI salts, a mixture of salts (16 wt.% LiI, 84 wt.% LiTFSI) is used, which exhibits the

  18. Comparative metabolism of methacrylonitrile and acrylonitrile to cyanide using cytochrome P4502E1 and microsomal epoxide hydrolase-null mice

    Methacrylonitrile (MAN) and acrylonitrile (AN) are metabolized via glutathione (GSH) conjugation or epoxide formation. We have recently shown that CYP2E1 is essential for AN epoxidation and subsequent cyanide liberation. Current studies were designed to compare the enzymatic basis of MAN vs. AN metabolism to cyanide using wild-type (WT), CYP2E1-, and mEH-null mice. Mice received a single gavage dose of 0.047, 0.095, 0.19, or 0.38 mmol/kg of MAN or AN, and blood cyanide was measured at 1 or 3 h later. Blood cyanide levels in WT mice treated with AN or MAN were dose and time dependent. At equimolar doses, significantly higher levels of cyanide were detected in the blood of MAN- vs. AN-treated mice. Further, while significant reduction in blood cyanide levels occurred in MAN-treated CYP2E1-null vs. WT mice, AN metabolism to cyanide was largely abolished in CYP2E1-null mice. Pretreatment of mice with 1-aminobenzotriazole (ABT, CYP inhibitor) demonstrated that CYPs other than CYP2E1 also contribute to MAN metabolism to cyanide. Blood cyanide levels in mEH-null mice treated with aliphatic nitriles are generally lower than levels in similarly treated WT mice. Western blot analysis showed that expression of sEH was greater in male vs. female mice. The role of various epoxide hydrolases (EHs) in the production of cyanide from aliphatic nitriles is apparently structure and dose dependent. Regardless of genotype, significantly higher levels of cyanide were measured in the blood of male vs. female mice treated with MAN or AN. In conclusion, these data showed that (1) at equimolar doses, higher blood cyanide levels were detected in mice treated with MAN vs. AN; (2) while CYP2E1 is the only enzyme responsible for AN metabolism to cyanide, other CYPs also contribute to MAN metabolism; and (3) significantly higher levels of cyanide were measured in the blood of male vs. female treated with either nitrile. Higher blood cyanide levels in male vs. female mice and in MAN- vs. AN

  19. Regioselective ethyl transfer reactions between diethylzinc and 1,4-dialkyl-1,4-diaza-1,3-butadienes: Synthesis of EtZn[R(Et)NCH=CHNR],

    van Koten, G; Gosselink, J.W.; Jastrzebski, J.T.B.H.; Vrieze, K.

    1982-01-01

    The l/l reaction of diethylzinc with 1,4dialkyl-1,4-diaza-1,3-butadienes (R-DAB = R-N=C(R’)-C(R’)=N-R) below -50°C results in formation of the l/l complex Et*Zn(R-DAB) (R = alkyl), containing o,a-N,N’ chelate bonded R-DAB. Above -50°C these complexes are unstable and undergo selective transfer of an ethyl group from Zn to the adjacent N atom, thus producing the novel species Et%[R(Et)NCR’=CR’NR] in quantitative yield. The proposed monomeric structure consists of a three-coordinate zinc atom b...

  20. Copolymerization of 1-hexene and 1-dodecene with 1,3-butadiene by a versatate/diisobutylaluminum hydride/t-butyl chloride catalyst system

    Gustavo Monteiro da Silva

    2014-01-01

    Full Text Available The aim of this study was to incorporate an alpha-olefin (1-hexene or 1-dodecene in a high cis polybutadiene chain, using a neodymium versatate/diisobutylaluminum hydride/t-butyl chloride catalyst system. The influence of alpha-olefin on polymerization reaction and polymer characteristics, using different weight ratios of butadiene/α-olefin, was evaluated. The copolymers were characterized by SEC, FTIR, NMR, TGA and viscosimetric analysis. The thermal stability of the polymer tended to increase with incorporation of alpha-olefins, while its microstructure was not affected. The weight average molecular mass (Mw tended to increase and the polymerization conversion tended to decrease with increasing alpha-olefins content. The copolymers showed a lower intrinsic viscosity than for the homopolymer. The results indicated that the alpha-olefins were incorporated in the polybutadiene chain.

  1. Comparative study of the monomer grafting: ethylene, acetylene, 1,3-butadiene and estyrene in the matrix of recycled polytetrafluoroethylene (PTFE)

    In this study it is used the recycled polytetrafluoroethylene (PTFE), that with the gamma radiation under inert atmosphere or in presence of air, it is obtained free radicals and a posterior the monomer grafting (ethylene, acetylene, styrene or 1.3 butadiene), obtaining the copolymer polytetrafluoroethylene-g-monomer. It is studied the obtention of the polymer by two methods: by direct way, via grafting, where the polymer is irradiated in presence of monomer, and via grafting when the polymer is irradiated in absence of monomer and under inert or air. The characterization of the copolymer was performed by the techniques of infrared region absorption spectroscopy with Fourier transformation (FTIR), thermogravimetric (TGA) and derivative thermogravimetry (DTG), and percentage of mass grafting (DOG)

  2. Variation of long periodicity in blends of styrene butadiene, styrene copolymer/polyaniline using small angle X-ray scattering data

    B G Soares; Fernando G Souza Jr; A Manjunath; H Somashekarappa; R Somashekar; Siddaramaiah

    2007-09-01

    Small angle X-ray scattering data have been recorded for the blends of styrene butadiene, styrene copolymer/polyaniline using the beamline of the LNLS (Laboratorio Nacional de Luz sincroton-Campinas, Brazil). Employing one-dimensional Hosemann's paracrystalline model, we have simulated the meridional reflections of these blends in order to compute the long periodicity and hence to find the variation with concentrations of the blends. Within the region of available experimental data we observe that there is a linear relationship between long periodicity and concentration of blends. These parameters are compared with physical measurements like tensile strength to find the structure–property relation in these blends.

  3. Temperature dependence of alpha-induced scintillation in the 1,1,4,4-tetraphenyl-1,3-butadiene wavelength shifter

    Veloce, L M; Di Stefano, P C F; Noble, A J; Boulay, M G; Nadeau, P; Pollmann, T; Clark, M; Piquemal, M; Schreiner, K

    2015-01-01

    Liquid noble gas based particle detectors often use the organic wavelength shifter 1,1,4,4-tetraphenyl-1,3-butadiene (TPB) which shifts UV scintillation light to the visible regime, facilitating its detection, but which also can scintillate on its own. Dark matter searches based on this type of detector commonly rely on pulse-shape discrimination (PSD) for background mitigation. Alpha-induced scintillation therefore represents a possible background source in dark matter searches. The timing characteristics of this scintillation determine whether this background can be mitigated through PSD. We have therefore characterized the pulse shape and light yield of alpha induced TPB scintillation at temperatures ranging from 300 K down to 4 K, with special attention given to liquid noble temperatures. We find that the pulse shapes and light yield depend strongly on temperature. In addition, the significant contribution of long time constants above ~50 K provides an avenue for discrimination between alpha decay events ...

  4. VUV-VIS optical characterization of Tetraphenyl-butadiene films on glass and specular reflector substrates from room to liquid Argon temperature

    Francini, R; Nichelatti, E; Vincenti, M A; Canci, N; Segreto, E; Cavanna, F; Di Pompeo, F; Carbonara, F; Fiorillo, G; Perfetto, F

    2013-01-01

    The use of efficient wavelength-shifters from the vacuum-ultraviolet to the photosensor's range of sensitivity is a key feature in detectors for Dark Matter search and neutrino physics based on liquid argon scintillation detection. Thin film of Tetraphenyl-butadiene (TPB) deposited onto the surface delimiting the active volume of the detector and/or onto the photosensor optical window is the most common solution in current and planned experiments. Detector design and response can be evaluated and correctly simulated only when the properties of the optical system in use (TPB film + substrate) are fully understood. Characterization of the optical system requires specific, sometimes sophisticated optical methodologies. In this paper the main features of TPB coatings on different, commonly used substrates is reported, as a result of two independent campaigns of measurements at the specialized optical metrology labs of ENEA and University of Tor Vergata. Measured features include TPB emission spectra with lineshap...

  5. High throughput HPLC-ESI(-)-MS/MS methodology for mercapturic acid metabolites of 1,3-butadiene: Biomarkers of exposure and bioactivation.

    Kotapati, Srikanth; Esades, Amanda; Matter, Brock; Le, Chap; Tretyakova, Natalia

    2015-11-01

    1,3-Butadiene (BD) is an important industrial and environmental carcinogen present in cigarette smoke, automobile exhaust, and urban air. The major urinary metabolites of BD in humans are 2-(N-acetyl-L-cystein-S-yl)-1-hydroxybut-3-ene/1-(N-acetyl-L-cystein-S-yl)-2-hydroxybut-3-ene (MHBMA), 4-(N-acetyl-L-cystein-S-yl)-1,2-dihydroxybutane (DHBMA), and 4-(N-acetyl-L-cystein-S-yl)-1,2,3-trihydroxybutyl mercapturic acid (THBMA), which are formed from the electrophilic metabolites of BD, 3,4-epoxy-1-butene (EB), hydroxymethyl vinyl ketone (HMVK), and 3,4-epoxy-1,2-diol (EBD), respectively. In the present work, a sensitive high-throughput HPLC-ESI(-)-MS/MS method was developed for simultaneous quantification of MHBMA and DHBMA in small volumes of human urine (200 μl). The method employs a 96 well Oasis HLB SPE enrichment step, followed by isotope dilution HPLC-ESI(-)-MS/MS analysis on a triple quadrupole mass spectrometer. The validated method was used to quantify MHBMA and DHBMA in urine of workers from a BD monomer and styrene-butadiene rubber production facility (40 controls and 32 occupationally exposed to BD). Urinary THBMA concentrations were also determined in the same samples. The concentrations of all three BD-mercapturic acids and the metabolic ratio (MHBMA/(MHBMA+DHBMA+THBMA)) were significantly higher in the occupationally exposed group as compared to controls and correlated with BD exposure, with each other, and with BD-hemoglobin biomarkers. This improved high throughput methodology for MHBMA and DHBMA will be useful for future epidemiological studies in smokers and occupationally exposed workers. PMID:25727266

  6. Principais aspectos da polimerização do 1,3-butadieno Principles aspects of butadiene 1,3 polymerization

    Denise S. S. Nunes

    2005-11-01

    Full Text Available Atualmente, há uma grande demanda pelo polibutadieno com alto teor de unidades 1,4-cis, devido às suas excelentes propriedades físicas, tais como alta resistência à abrasão, baixo desenvolvimento de calor, baixa resistência ao rolamento, maior resistência à tensão, alta resistência à fadiga, baixa histerese e alta resistência à fratura. Tais características fazem com que esse elastômero seja cada vez mais utilizado na indústria pneumática. Assim, este trabalho apresenta uma breve revisão sobre a polimerização do 1,3-butadieno com diferentes sistemas catalíticos, sendo os sistemas à base de lantanídeos o principal foco desta revisão, pois esses sistemas são os mais estereoespecíficos para a polimerização 1,4-cis do butadieno.Nowadays, there is a great demand for polybutadiene with high contents of cis groups owing to its excellent physical properties, such as high abrasion resistance and low heat build up. These characteristics make this elastomer one of the most used in pneumatic industry. Thus, this paper presents a brief review about the 1,3-butadiene polymerization by different catalysts systems, with the systems based on lanthanides being the main focus, as they are the most stereospecific for cis-1,4 polymerization of butadiene.

  7. Study on Teratogenicity of Acrylonitrile in Rats by Subcutaneous Injection%皮下注射丙烯腈对大鼠致畸作用研究

    崔金山; 杨衍凯; 付守林; 张玉敏; 段志文; 李海山; 王瀛; 张岸舸

    2001-01-01

    目的评价丙烯腈对雌性大鼠有无致畸作用。方法于雌性大鼠妊娠第7~16天皮下注射丙烯腈(AN)15,25,35 mg·kg-1,常规方法检测AN的胚胎毒性和致畸作用。结果 25 mg·kg-1组死胎率、吸收胎率升高,胎鼠平均体重、体长、尾长减小,与阴性对照组比较差异有显著性(P<0.05);35 mg·kg-1组除窝平均活胎数减少,差异有显著性( P<0.05),其余各指标与阴性对照组比较差异有非常显著性(P <0.01);25,35 mg·kg-1组畸胎率、母体畸胎率、活胎畸形率升高,与对照组相比差异有显著性和/或非常显著性(P<0.05或P <0.01),且有明确的剂量效应或剂量反应关系。本实验皮下注射AN染毒的致畸最低剂量为 15 mg·kg-1,致畸指数为6.3,以骨骼畸形为主,外观畸形主要为无尾、短尾等。结论丙烯腈皮下注射染毒有明显的胚胎毒性,致畸剂量小于经口染毒阈剂量,是一种弱致畸物。%Objective The teratogenicity of acrylonitrile(AN)on fe male rats was evaluated.Methods 15,25 and 35 mg/kg AN were administ ered by subcutaneous injection to rats on the time 7~16 d of gestation.Embryoto x icity and teratogenicity of AN were examined by a traditional teratogenic method .Results At the dosage of 25 mg/kg,AN could induce higher incidence of fetal resorption and death,and decrease the average fetal body weight and le ngth with significant difference(P<0.05)when compared with neg ative controls.At the dosage of 35 mg/kg,AN could decrease average vital fet us p er litter with significant difference(P<0.05),and induce chang es of other indexes with highly significant difference(P<0.0 1).At the dosage of 25 and 35 mg/kg,AN could induce higher teras rate,maternal t eras rate and malformation rate of vital fetus with significant and/or highly s ignificant difference(P<0.05 or P<0.01),resp ectively.There existed a dose-effect or dose-response relationship between abo ve

  8. 无机盐对丙烯腈与N-乙烯基吡咯烷酮共聚物溶液黏度的影响%EFFECT OF INORGANIC SALTS ON VISCOSITY OF ACRYLONITRILE/N-VINYLPYRROLIDONE COPOLYMER SOLUTIONS

    陈厚; 王成国; 蔡华甦

    2003-01-01

    Effect of inorganic salts on viscosities of dimethyl sulphoxide(DMSO)solutions of acrylonitrile(AN)/N-vinylpyrrolidone(N-VP) copolymer was discussed. Viscosity was determined by revolving viscosimeter. It was shown that solution viscosity decreased quickly with addition of KCl and NaCl and the effect of NaCl was more prominent than KCl. As the concentration of KCl and NaCl beyond 0.025mol*L-1, the viscosity tended to increase. The viscosity increased considerably with addition of FeCl3 and CuCl2. The change of solution viscosity became less obvious with addition of ZnCl2.With increasing temperature, the viscosity of copolymer solution containing NaCl decreased most quickly and the copolymer solution containing FeCl3 decreased most slowly.

  9. GC Determination of Acetaldehyde, Acrolein and Acrylonitrile in Water with Purge and Trap Technique%吹扫捕集-气相色谱法测定水中乙醛、丙烯醛、丙烯腈

    陆文娟; 王晋宇; 陈玲瑚; 赵辰

    2011-01-01

    Purge and trap technique was applied in the GC determination of acetaldehyde, acrolein and acrylonitrile in water. The analytes were purged, trapped and thermodesorbed using the Trap Vocarb 3000, and determined by CR2 with flame ionization detector (FID). Linear relationships between values of peak area and mass concentration of acetaldehyde, acrolein and acrylonitrile obtained were same in the range of 0. 020--0.20 mg·L^-1 , with detection limits (3S/N) of 0. 005, 0. 010, 0. 001mg·L^-1 respectively. Tests for recovery and precision were made by standard addition method, values of recovery found were in the range of 90. 0%-110.0% and values of RSD's (n=7) were less than 50%.%提出了吹扫捕集-气相色谱法测定水中乙醛、丙烯醛和丙烯腈的分析方法。样品用Trap Vocarb 3000捕集阱吹扫、捕集及热解析后,用气相色谱法氢火焰离子化检测器分析。3种化合物的质量浓度在0.020~0.20mg·L^-1的相同范围内与其峰面积呈线性关系,方法的检出限(3S/N)分别为0.005,0.010,0.001mg·L^-。标准加入回收率在90.0%~110.0%之间,相对标准偏差(n=7)均小于5%。

  10. Pengaruh suhu vulkanisasi terhadap sifat mekanis vulkanisat karet alam dan karet akrilonitril-butadiena

    Norma Arisanti Kinasih

    2015-12-01

    Full Text Available Natural and acrylonitrile-butadiene rubbers possess different vulcanization characteristics. Selection of the vulcanization system and temperature affects the mechanical properties of vulcanized natural rubber (NR and acrylonitrile-butadiene rubber (NBR. In the present work, the effect of vulcanization temperature (150, 160, 170 and 180oC on the mechanical properties of NR and NBR vulcanizates was studied. The effect of different vulcanization system (semi efficient, efficient and sulfur donor was studied in NR blends, while the effect of different acrylonitrile content (26, 28 and 33 wt % was studied in NBR blends. The NBR curing characteristics and mechanical properties data showed that vulcanization at low temperature (150oC was suitable for low acrylonitrile-NBR, whereas that at high temperature (170oC was suitable for high acrylonitrile-NBR. In addition, the semi efficient system at low temperature vulcanization (150oC was suitable for natural rubber.

  11. Thermal [4 + 2] Cycloadditions of 3-Acetyl-, 3-Carbamoyl-, and 3-Ethoxycarbonyl-Coumarins with 2,3-Dimethyl-1,3-butadiene under Solventless Conditions: A Structural Study

    Itzia I. Padilla-Martínez

    2010-03-01

    Full Text Available The thermal [4+2] cycloadditions of 3-acetyl-, 3-carbamoyl, and 3-ethoxycarbonylcoumarins with 2,3-dimethyl-1,3-butadiene under solvent free conditions are reported, as well as the epoxidation reactions of some adducts. Discussion is focused on the structural features of the Diels-Alder adducts and their epoxides, based upon NMR, X-ray, and mass spectral data, and supported by ab initio theoretical calculations.

  12. 丁二烯橡胶门尼粘度比对与统计分析%The Comparison and Statistical Analysis of Butadiene Rubber Mooney Viscosity

    李淑萍; 黄世英; 汤妍雯; 曹帅英

    2015-01-01

    CNAS-RL02:2012《能力验证规则》中规定,申请认可和已获认可的实验室,根据检验领域和项目,选择1次/1年或1次/2年的周期参加相关项目的能力验证或测量审核,没有能力验证计划的项目可选择与权威机构进行比对,也可以选择参加权威机构组织的实验室间比对,证明其检验项目在该领域的检验能力。为此,国家合成橡胶质量监督检验中心策划组织46家合成橡胶行业所属的实验室,开展了丁二烯橡胶门尼粘度的比对工作。丁二烯橡胶门尼粘度实验室间的比对,比对结果统计与分析采用稳健统计技术,Z值绝对值平均值均小于0.87,满意结果在95%以上,有2个离群结果,占样本总数的4.4%,各实验室的测试水平较以往有大幅度提升。%《The ability to verify the rules》 of CNAS-RL02:2012 specifies:The laboratory ask for recognition and accredited laboratory,according to the test area and project,could select once a year or 2 years to participate in the ability verification or measurement audit of relevant projects,the labs without proof test projects can prove their test capacity through comparison with authority laboratories organized by authority. Therefore,national quality supervi-sion and inspection center of synthetic rubber planned and organized 46 laboratories in synthetic rubber industry, carried out the butadiene rubber Mooney viscosity comparison work. Comparison of butadiene rubber Mooney vis-cosity between the laboratories,each participating laboratory used Mooney viscometer calibrated with standard mate-rial,the average of Z absolute values was below 0. 87,satisfactory results exceeded 95%,two results deviated from the group,accounting for 4. 4% of the total number of samples,the laboratory test level has been increased greatly than in the past.

  13. Infrared absorption of trans-1-chloromethylallyl and trans-1-methylallyl radicals produced in photochemical reactions of trans-1,3-butadiene and C Script-Small-L {sub 2} in solid para-hydrogen

    Bahou, Mohammed; Wu, Jen-Yu; Tanaka, Keiichi [Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, 1001 Ta-Hsueh Rd., Hsinchu 30010, Taiwan (China); Lee, Yuan-Pern [Department of Applied Chemistry and Institute of Molecular Science, National Chiao Tung University, 1001 Ta-Hsueh Rd., Hsinchu 30010, Taiwan (China); Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan (China)

    2012-08-28

    The reactions of chlorine and hydrogen atoms with trans-1,3-butadiene in solid para-hydrogen (p-H{sub 2}) were investigated with infrared (IR) absorption spectra. When a p-H{sub 2} matrix containing C Script-Small-L {sub 2} and trans-1,3-butadiene was irradiated with ultraviolet light at 365 nm, intense lines at 650.3, 809.0, 962.2, 1240.6 cm{sup -1}, and several weaker ones due to the trans-1-chloromethylallyl radical, Bullet (CH{sub 2}CHCH)CH{sub 2}C Script-Small-L , appeared. Observed wavenumbers and relative intensities agree with the anharmonic vibrational wavenumbers and IR intensities predicted with the B3PW91/6-311++g(2d, 2p) method. That the C Script-Small-L atom adds primarily to the terminal carbon atom of trans-1,3-butadiene is in agreement with the path of minimum energy predicted theoretically, but in contrast to the reaction of C Script-Small-L + propene in solid p-H{sub 2}[J. Amicangelo and Y.-P. Lee, J. Phys. Chem. Lett. 1, 2956 (2010)] in which the addition of C Script-Small-L to the central C atom is favored, likely through steric effects in a p-H{sub 2} matrix. A second set of lines, intense at 781.6, 957.9, 1433.6, 2968.8, 3023.5, 3107.3 cm{sup -1}, were observed when the UV-irradiated C Script-Small-L {sub 2}/trans-1,3-butadiene/p-H{sub 2} matrix was further irradiated with IR light from a SiC source. These lines are assigned to the trans-1-methylallyl radical, Bullet (CH{sub 2}CHCH)CH{sub 3}, produced from reaction of 1,3-butadiene with a H atom resulted from the reaction of C Script-Small-L atoms with solid p-H{sub 2} exposed to IR radiation.

  14. Dissociative double-photoionization of butadiene in the 25-45 eV energy range using 3-D multi-coincidence ion momentum imaging spectrometry

    Dissociative double-photoionization of butadiene in the 25-45 eV energy range has been studied with tunable synchrotron radiation using full three-dimensional ion momentum imaging. Using ab initio calculations, the electronic states of the molecular dication below 33 eV are identified. The results of the measurement and calculation show that double ionization from π orbitals selectively triggers twisting about the terminal or central C–C bonds. We show that this conformational rearrangement depends upon the dication electronic state, which effectively acts as a gateway for the dissociation reaction pathway. For photon energies above 33 eV, three-body dissociation channels where neutral H-atom evaporation precedes C–C charge-separation in the dication species appear in the correlation map. The fragment angular distributions support a model where the dication species is initially aligned with the molecular backbone parallel to the polarization vector of the light, indicating a high probability for double-ionization to the “gateway states” for molecules with this orientation

  15. Novel adducts from the reaction of 1-chloro-3-buten-2-one with 2'-deoxyguanosine. Structural characterization and potential as tools to investigate 1,3-butadiene carcinogenicity.

    Zheng, Jin; Li, Yan; Yu, Ying-Xin; An, Jing; Zhang, Xin-Yu; Elfarra, Adnan A

    2015-01-25

    1-Chloro-3-buten-2-one (CBO) is a potential reactive metabolite of 1,3-butadiene (BD), a carcinogenic air pollutant. To develop tools that may help investigate the role of CBO in BD carcinogenicity and to develop biomarkers that can be used to assess BD exposure, the reaction of CBO with 2'-deoxyguanosine (dG) under in vitro physiological conditions (pH 7.4, 37°C) was investigated and the products (designated as CG-1, CG-2, CG-3, CG-4, CG-5, and CG-6 based on their retention times on HPLC) were characterized by MS and NMR spectroscopy. The structures of CG-1, CG-2, CG-3, and CG-4 were 1,N2-(3-hydroxy-3-hydroxymethylpropan-1,3-diyl)-2'-deoxyguanosine, N7-(4-chloro-3-oxobutyl)-2'-deoxyguanosine, N7,8-(3-hydroxy-3-chloromethylpropan-1,3-diyl)guanine and N2-(4-chloro-3-oxobutyl)-2'-deoxyguanosine, respectively. CG-5 and CG-6, a pair of diastereomers, were characterized as 1,N2-(3-hydroxy-3-chloromethylpropan-1,3-diyl)-2'-deoxyguanosine. CG-1 was stable under in vitro physiological conditions, whereas CG-2, CG-3, CG-4, and CG-5/6 were unstable and exhibited the half-lives at mechanism of BD carcinogenicity and could also be used to develop biomarkers for BD exposure. PMID:25500269

  16. Enhancement of light yield and stability of radio-pure tetraphenyl-butadiene based coatings for VUV light detection in cryogenic environments

    Baudis, L.; Benato, G.; Dressler, R.; Piastra, F.; Usoltsev, I.; Walter, M.

    2015-09-01

    The detection of VUV scintillation light in (liquid) argon (LAr) detectors commonly includes a reflector with a fluorescent coating, converting UV photons to visible light. The light yield of these detectors depends directly on the conversion efficiency. Several coating/reflector combinations were produced using VM2000, a specular reflecting multi-layer polymer, and Tetratex®, a diffuse reflecting PTFE fabric, as reflector foils. The light yield of these coatings was optimised and has been measured in a dedicated liquid argon setup built at the University of Zurich. It employs a small, 1.3 kg LAr cell viewed by a 3-inch, low radioactivity PMT of type R11065-10 from Hamamatsu. The cryogenic stability of these coatings was additionally studied. The optimum reflector/coating combination was found to be Tetratex® dip-coated with Tetraphenyl-butadiene with a thickness of 0.9 mg/cm2, resulting in a 3.6 times higher light yield compared to uncoated VM2000. Its performance was stable in long-term measurements, performed up to 100 days in liquid argon. This coated reflector was also investigated concerning radioactive impurities and found to be suitable for current and upcoming low-background experiments. Therefore it is used for the liquid argon veto in Phase II of the GERDA neutrinoless double beta decay experiment.

  17. The effect of multifunctional monomers/oligomers Additives on electron beam radiation crosslinking of poly (styrene-block-isoprene/butadiene-block-styrene) (SIBS)

    Wu, Jinping; Soucek, Mark D.

    2016-02-01

    The effect of multifunctional monomers or oligomers (MFM/O) additives on electron beam (E-beam) radiation induced crosslinking of poly (styrene-block-isoprene/butadiene-block-styrene) (SIBS) was studied. Ten types of MFM/O were investigated, including trimethylolpropane trimethacrylate (TMPTMA), trimethylolpropane triacrylate (TMPTA), triallyl cyanurate (TAC), polybutadiene diacrylate (PB-diacrylate), ethylene glycol dimethylacrylate (EGDMA), butylene glycol dimethacrylate (BGDMA), 1,2-polybutadiene. The effects of MFM/O concentration and E-beam radiation dose on properties of SIBS were studied including tensile strength, elongation-at-break, modulus, gel content, equilibrium swelling and crosslink density. TMPTA significantly improved the tensile modulus and crosslink density of SIBS. SIBS with TMPTMA and TMTPMA with inhibitor showed a 50% increase in tensile strength. The solubility of MFM/O in SIBS was also investigated by a selective swelling method. The MFM/O were found to be soluble in both phases of SIBS. The viscosity of SIBS with methacrylate type MFM/O was stable at 200 °C.

  18. Adhesion properties of styrene-butadiene rubber (SBR/Standard Malaysian Rubber (SMR L-based adhesives in the presence of phenol formaldehyde resin

    2007-10-01

    Full Text Available The adhesion properties, i. e. viscosity, tack and peel strength of styrene-butadiene rubber (SBR/Standard Malaysian Rubber (SMR L-based pressure-sensitive adhesive was studied using phenol formaldehyde resin as the tackifying resin. Toluene was used as the solvent throughout the experiment. SBR composition in SBR/SMR L blend used was 0, 20, 40, 60, 80, 100%. Three different resin loadings, i. e. 40, 80 and 120 parts per hundred parts of rubber (phr were used in the adhesive formulation. The viscosity of adhesive was determined by a HAAKE Rotary Viscometer whereas loop tack and peel strength of paper/polyethylene terephthalate (PET film were measured using a Lloyd Adhesion Tester operating at 30 cm/min. Results indicate that the viscosity of adhesive decreases with increasing % SBR whereas loop tack passes through a maximum value at 20% SBR for all resin loadings. Except for the control sample (without resin, the peel strength shows a maximum value at 60% SBR for the three modes of peel tests. For a fixed % SBR, adhesive sample containing 40 phr phenol formaldehyde resin always exhibits the highest loop tack and peel strength, an observation which is associated to the optimum wettability of adhesive on the substrate.

  19. Utilizing carbon dioxide as a reaction medium to mitigate production of polycyclic aromatic hydrocarbons from the thermal decomposition of styrene butadiene rubber.

    Kwon, Eilhann E; Yi, Haakrho; Castaldi, Marco J

    2012-10-01

    The CO(2) cofeed impact on the pyrolysis of styrene butadiene rubber (SBR) was investigated using thermogravimetric analysis (TGA) coupled to online gas chromatography/mass spectroscopy (GC/MS). The direct comparison of the chemical species evolved from the thermal degradation of SBR in N(2) and CO(2) led to a preliminary mechanistic understanding of the formation and relationship of light hydrocarbons (C(1-4)), aromatic derivatives, and polycyclic aromatic hydrocarbons (PAHs), clarifying the role of CO(2) in the thermal degradation of SBR. The identification and quantification of over 50 major and minor chemical species from hydrogen and benzo[ghi]perylene were carried out experimentally in the temperature regime between 300 and 500 °C in N(2) and CO(2). The significant amounts of benzene derivatives from the direct bond dissociation of the backbone of SBR, induced by thermal degradation, provided favorable conditions for PAHs by the gas-phase addition reaction at a relatively low temperature compared to that with conventional fuels such as coal and petroleum-derived fuels. However, the formation of PAHs in a CO(2) atmosphere was decreased considerably (i.e., ∼50%) by the enhanced thermal cracking behavior, and the ultimate fates of these species were determined by different pathways in CO(2) and N(2) atmospheres. Consequently, this work has provided a new approach to mitigate PAHs by utilizing CO(2) as a reaction medium in thermochemical processes. PMID:22950720

  20. The use of styrene-butadiene rubber waste as a potential filler in nitrile rubber: order of addition and size of waste particles

    D. A. Baeta

    2009-03-01

    Full Text Available Styrene-butadiene rubber (SBR has large applications in the shoe industry, especially as expanded sheets used to produce insoles and inner soles. According to TG analysis, the rubber content in SBR residues (SBR-r was found to be around 26-wt%. Based on that data, a cost-effective technique for the reuse of SBR-r in Nitrile rubber (NBR was developed. Later, the effect of SBR-r on the cure behavior, mechanical performance, swelling, and crosslink density of reused rubber was investigated, with more emphasis placed on the effect of both particle size and loading of waste filler. Cure characteristics such as optimum cure time and scorch time were then reduced by the increasing amount of SBR-r filler. Owing to the reinforced nature of the largest particle size SBR-r, the best results for the mechanical properties of NBR were those in which SBR-r was added at the end of the cure process. The study has thus shown that SBR residue (SBR-r can be used as an economical alternative filler in NBR.

  1. Theoretical Investigation on The Reaction Mechanism of 2-methyl-1, 3-cis-butadiene with benzaldehyde Catalyzed by Rh(Ⅰ)

    The reaction mechanism of 2-methyl-1, 3-cis-butadiene with benzaldehyde catalyzed by Rh(Ⅰ) has been calculated by DFT, The LanL2DZ basis set has been adopted for Rh. For the other atoms, the 6-31+G* basis set has been used. In this paper, all the intermediates and transition states have been fully optimized to obtain their molecular geometries and electronic structures. Ground or transition state properties have been established by full-frequency calculations. The energies given below have been corrected for zero point vibrational energy (ZPVE). To further insight into the nature of bonding interaction, AIM analysis has been performed by using AIM2000. The analyses of the charge distribution and charge-transfer processes have been carried out with the NBO theory. Feasible reaction pathways were investigated, which are IA : Re→IMA1→TSA1→IMA2→IMA3→TSA2→IMA4→IMA5→TSA3→IMA6→PA and IB: Re→IMB1→TSB1→IMB2→IMB3→TSB2→IMB4→IMB5T→SB3→IMB6→PB. Computation results indicate that reaction pathway IB is the main pathway, the activation energy of which is smaller, which is in good agreement with experimental results. (authors)

  2. Synthesis and Molecular Structures of Two [1,4-bis(3-pyridyl-2,3-diazo-1,3-butadiene]-dichloro-Zn(II Coordination Polymers

    Hsin-Ta Wang

    2006-08-01

    Full Text Available Two novel coordination polymers with 3D metal-organic frameworks (MOFs have been synthesized by reacting 1,4-bis(3-pyridyl-2,3-diazo-1,3-butadiene (L with zinc dichloride. Both compounds have the same repeating unit consisting of a distorted tetrahedral Zn(II center coordinated by two chlorides and two pyridyl nitrogen atoms of two bridging bismonodentate L ligands, however, different structural conformations have been found, one forming a helical chain and the other producing a square-wave chain. The intermolecular C−H···Cl hydrogen bonds in 1 and 2 play important roles in the formation of three-dimensional coordination polymers. Compound 1 crystallized in an orthorhombic space group Pna21 with a = 7.9652(3, b = 21.4716(7, c = 8.2491(3Å, V = 1410.81(9 Å 3 and Z = 4. Compound 2 crystallized in a monoclinic space group P21/n with a = 9.1752(3, b = 14.5976(4, c = 10.3666(3 Å , β = 98.231(2°, V = 1374.16(7 Å 3 and Z = 4.

  3. Iminopyridine-Based Cobalt(II and Nickel(II Complexes: Synthesis, Characterization, and Their Catalytic Behaviors for 1,3-Butadiene Polymerization

    Quanquan Dai

    2016-01-01

    Full Text Available A series of iminopyridine ligated Co(II (1a–7a and Ni(II (1b–7b complexes were synthesized. The structures of complexes 3a, 4a, 5a, 7a, 5b, and 6b were determined by X-ray crystallographic analyses. Complex 3a formed a chloro-bridged dimer, whereas 4a, 5a, and 7a, having a substituent (4a, 5a: CH3; 7a: Br at the 6-position of pyridine, producing the solid structures with a single ligand coordinated to the central metal. The nickel atom in complex 5b features distorted trigonal-bipyramidal geometry with one THF molecule ligating to the metal center. All the complexes activated by ethylaluminum sesquichloride (EASC were evaluated in 1,3-butadiene polymerization. The catalytic activity and selectivity were significantly influenced by the ligand structure and central metal. Comparing with the nickel complexes, the cobalt complexes exhibited higher catalytic activity and cis-1,4-selectivity. For both the cobalt and nickel complexes, the aldimine-based complexes showed higher catalyst activity than their ketimine counterparts.

  4. Temperature dependence of alpha-induced scintillation in the 1,1,4,4-tetraphenyl-1,3-butadiene wavelength shifter

    Veloce, L. M.; Kuźniak, M.; Di Stefano, P. C. F.; Noble, A. J.; Boulay, M. G.; Nadeau, P.; Pollmann, T.; Clark, M.; Piquemal, M.; Schreiner, K.

    2016-06-01

    Liquid noble based particle detectors often use the organic wavelength shifter 1,1,4,4-tetraphenyl-1,3-butadiene (TPB) which shifts UV scintillation light to the visible regime, facilitating its detection, but which also can scintillate on its own. Dark matter searches based on this type of detector commonly rely on pulse-shape discrimination (PSD) for background mitigation. Alpha-induced scintillation therefore represents a possible background source in dark matter searches. The timing characteristics of this scintillation determine whether this background can be mitigated through PSD. We have therefore characterized the pulse shape and light yield of alpha induced TPB scintillation at temperatures ranging from 300 K down to 4 K, with special attention given to liquid noble gas temperatures. We find that the pulse shapes and light yield depend strongly on temperature. In addition, the significant contribution of long time constants above ~50 K provides an avenue for discrimination between alpha decay events in TPB and nuclear-recoil events in noble liquid detectors.

  5. VUV-Vis optical characterization of Tetraphenyl-butadiene films on glass and specular reflector substrates from room to liquid Argon temperature

    Francini, R.; Montereali, R. M.; Nichelatti, E.; Vincenti, M. A.; Canci, N.; Segreto, E.; Cavanna, F.; Di Pompeo, F.; Carbonara, F.; Fiorillo, G.; Perfetto, F.

    2013-09-01

    The use of efficient wavelength-shifters from the vacuum-ultraviolet to the photo-sensor's range of sensitivity is a key feature in detectors for Dark Matter search and neutrino physics based on liquid argon scintillation detection. Thin film of Tetraphenyl-butadiene (TPB) deposited onto the surface delimiting the active volume of the detector and/or onto the photosensor optical window is the most common solution in current and planned experiments. Detector design and response can be evaluated and correctly simulated only when the properties of the optical system in use (TPB film + substrate) are fully understood. Characterization of the optical system requires specific, sometimes sophisticated optical methodologies. In this paper the main features of TPB coatings on different, commonly used substrates is reported, as a result of two independent campaigns of measurements at the specialized optical metrology labs of ENEA and University of Tor Vergata. Measured features include TPB emission spectra with lineshape and relative intensity variation recorded as a function of the film thickness and for the first time down to LAr temperature, as well as optical reflectance and transmittance spectra of the TPB coated substrates in the wavelength range of the TPB emission.

  6. Radiation-induced graft polymerization of maleic acid and maleic anhydride onto ultra-fine powdered styrene-butadiene rubber (UFSBR)

    The functionalization of ultra-fine powdered styrene-butadiene rubber (UFSBR) was carried out using gamma radiation-induced graft polymerization of maleic acid (MA) and maleic anhydride (MAH), respectively. It was found that the graft yield of MA onto UFSBR increased rapidly up to the peak and then decreased with increasing MA content. Moreover, the peak shifted to the direction of lower MA content with increasing absorbed dose. Similarly, there was the peak of graft yield with increasing MAH content for grafting of MAH onto UFSBR, whereas the peak of graft yield was achieved at 10 wt% MAH content at different absorbed doses. On the other hand, increasing absorbed dose and decreasing monomer contents are useful to improve the graft efficiency of MA and MAH. At high dose and low monomer content, the graft yield of MAH onto UFSBR is higher than that of MA. FTIR spectra confirmed that both MA and MAH can be grafted successfully onto the UFSBR under gamma irradiation, respectively. Comparing with maleation of rubber by melt grafting, the graft yield of MAH on UFSBR is higher, which can be attributed to the network structure and nanometer size of UFSBR as well as high energy provided by radiation

  7. Dissociative double-photoionization of butadiene in the 25-45 eV energy range using 3-D multi-coincidence ion momentum imaging spectrometry.

    Oghbaie, Shabnam; Gisselbrecht, Mathieu; Laksman, Joakim; Månsson, Erik P; Sankari, Anna; Sorensen, Stacey L

    2015-09-21

    Dissociative double-photoionization of butadiene in the 25-45 eV energy range has been studied with tunable synchrotron radiation using full three-dimensional ion momentum imaging. Using ab initio calculations, the electronic states of the molecular dication below 33 eV are identified. The results of the measurement and calculation show that double ionization from π orbitals selectively triggers twisting about the terminal or central C-C bonds. We show that this conformational rearrangement depends upon the dication electronic state, which effectively acts as a gateway for the dissociation reaction pathway. For photon energies above 33 eV, three-body dissociation channels where neutral H-atom evaporation precedes C-C charge-separation in the dication species appear in the correlation map. The fragment angular distributions support a model where the dication species is initially aligned with the molecular backbone parallel to the polarization vector of the light, indicating a high probability for double-ionization to the "gateway states" for molecules with this orientation. PMID:26395707

  8. Use of rice husks as potential filler in styrene butadiene rubber/linear low density polyethylene blends in the presence of maleic anhydride

    In the present study, rice husks filled styrene butadiene rubber (SBR)/linear low density polyethylene (LLDPE) 50/50 blends with a compatibilizer, maleic anhydride (MAH) were prepared using a brabender plasti-corder. Virgin SBR/LLDPE blend was also prepared. The physico-mechanical as well as dielectric properties were investigated. Increasing MAH concentrations in SBR/LLDPE blends resulted in an increase in the tensile strength, elongation at break and hardness. After a certain concentration (2.5 phr), a reduction in these properties was found. On the other hand an increase in the dielectric properties as well as in the mass swell in both toluene and oil with MAH was noticed. After certain concentration of rice husk filler (25 phr) an abrupt increase in permittivity ε' and dielectric loss ε'' was obtained. These results are supported by the mechanical properties measurements. The scanning electron microscopy (SEM) indicates that the presence of MAH increases the interfacial interaction between SBR/LLDPE blends on one hand and also rice husk filler and the blend on the other hand.

  9. Water soluble styrene butadiene rubber and sodium carboxyl methyl cellulose binder for ZnFe2O4 anode electrodes in lithium ion batteries

    Zhang, Rongyu; Yang, Xu; Zhang, Dong; Qiu, Hailong; Fu, Qiang; Na, Hui; Guo, Zhendong; Du, Fei; Chen, Gang; Wei, Yingjin

    2015-07-01

    ZnFe2O4 nano particles as an anode material for lithium ion batteries are prepared by the glycine-nitrate combustion method. The mixture of styrene butadiene rubber and sodium carboxyl methyl cellulose (SBR/CMC) with the weight ratio of 1:1 is used as the binder for ZnFe2O4 electrode. Compared with the conventional polyvinylidene-fluoride (PVDF) binder, the SBR/CMC binder is much cheaper and environment benign. More significantly, this water soluble binder significantly improves the rate capability and cycle stability of ZnFe2O4. A discharge capacity of 873.8 mAh g-1 is obtained after 100 cycles at the 0.1C rate, with a very little capacity fading rate of 0.06% per cycle. Studies show that the SBR/CMC binder enhances the adhesion of the electrode film to the current collector, and constructs an effective three-dimensional network for electrons transport. In addition, the SBR/CMC binder helps to form a uniform SEI film thus prohibiting the formation of lithium dendrite. Electrochemical impedance spectroscopy shows that the SBR/CMC binder lowers the ohmic resistance of the electrode, depresses the formation of SEI film and facilitates the charge transfer reactions at the electrode/electrolyte interface. These advantages highlight the potential applications of SBR/CMC binder in lithium ion batteries.

  10. 丙烯腈-苯乙烯磺酸共聚物/层状双金属氢氧化物纳米复合质子传导聚合物电解质的制备与表征%Synthesis and characterization of proton-conducting polymer electrolytes based on acrylonitrile-styrene sulfonic acid copolymer/layered double hydroxides nanocomposites

    王盎然; 包永忠; 翁志学; 黄志明

    2008-01-01

    Acrylonitrile-sodium styrene sulfonate copolymer/layered double hydroxides nanocomposites were prepared by in situ aqueous precipitation copolymerization of acrylonitrile (AN) and sodium styrene sulfonate (SSS) in the presence of 4-vinylbenzene sulfonate intercalated layered double hydroxides (MgAl-VBS LDHs) and transferred to acrylonitrile-styrene sulfonic acid (AN-SSA) copolymer/LDHs nanocomposites as a proton-conducting polymer electrolyte. MgAl-VBS LDHs were prepared by a coprecipitation method, and the structure and composition of MgAl-VBS LDHs were determined by X-ray diffraction (XRD), infrared spectroscopy, and elemental analysis. X-ray diffraction result of AN-SSS copolymer/LDHs nanocomposites indicated that the LDHs layers were well dispersed in the AN-SSS copolymer matrix. All the AN-SSS copolymer/LDHs nanocomposites showed significant enhancement of the decomposition temperatures compared with the pristine AN-SSS copolymer, as identified by the thermogravimetric analysis. The methanol crossover was decreased and the proton conductivity was highly enhanced for the AN-SSA copolymer/LDHs nanocomposite electrolyte systems In the case of the nanocomposite electrolyte containing 2% (by mass) LDHs, the proton conductivity of 2.60×10-3 S·m-1 was achieved for the polymer electrolyte.

  11. 氢化度与丙烯腈含量对HNBR硫化胶性能的影响%Effect of Acrylonitrile Content and Hydrogenation on Properties of Hydrogenated Nitrile Rubber(HNBR) Vulcanizates

    张成龙; 李再峰; 白延光; 王宁; 李岩峰; 熊召举

    2013-01-01

    研究了氢化度和丙烯腈含量对氢化丁腈橡胶(HNBR)硫化特性、力学性能、热老化性能以及热性能的影响.利用核磁共振(NMR)考察了不同型号HNBR橡胶的交联性能;并采用凝胶色谱法(GPC)对生胶的分子量和分子量分布进行了测定,给出了橡胶门尼黏度与其分子量和分子量分布之间的关系.结果表明,随着氢化度与丙烯腈含量的增加,Tg升高;硫化胶的交联密度随着不饱和度和丙烯腈含量的增加而增加;氢化度升高,硫化胶的拉伸强度变化不大,扭断伸长率和撕裂强度降低,100%定伸增加;丙烯腈含量升高,硫化胶的拉伸强度、撕裂强度和100%定伸提高,扯断伸长率变化不大.%In this paper, effects of crylonitrile content and hydrogenation on vulcanization characteristics, physical performances, thermal aging performance and thermal properties of hydrogenated nitrile rubber (HNBR) were investigated. Crosslinking density of vulcanizates was tested by the nuclear magnetic resonance (NMR), and crosslinking properties of different types of HNBR rubber were investigated further. Relative molecular weight and molecular weight distribution of raw material were tested by GPC. The relationship between molecular weight distribution and mooney viscosity of rubber was given. The glass-transition temperature is enhanced with an increase in the acrylonitrile content and hydrogenation, and the crosslinking density raises with the increase of the acrylonitrile and double bond content. High unsaturated HNBR shows low break elongation, tear strength, higher stress at 100% , and tensile strength is improved little. With the incensement in crylonitrile content, tensile strength and tear strength are improved, stress at 100% is increased, however, break elongation has little change.

  12. Mechanical Characterization of Hybrid Vesicles Based on Linear Poly(Dimethylsiloxane-b-Ethylene Oxide and Poly(Butadiene-b-Ethylene Oxide Block Copolymers

    Jeffery Gaspard

    2016-03-01

    Full Text Available Poly(dimethylsiloxane-ethylene oxide (PDMS-PEO and poly(butadiene-b-ethylene oxide (PBd-PEO are two block copolymers which separately form vesicles with disparate membrane permeabilities and fluidities. Thus, hybrid vesicles formed from both PDMS-PEO and PBd-PEO may ultimately allow for systematic, application-specific tuning of vesicle membrane fluidity and permeability. However, given the relatively low strength previously noted for comb-type PDMS-PEO vesicles, the mechanical robustness of the resulting hybrid vesicles must first be confirmed. Toward this end, we have characterized the mechanical behavior of vesicles formed from mixtures of linear PDMS-PEO and linear PBd-PEO using micropipette aspiration. Tension versus strain plots of pure PDMS12-PEO46 vesicles revealed a non-linear response in the high tension regime, in contrast to the approximately linear response of pure PBd33-PEO20 vesicles. Remarkably, the area expansion modulus, critical tension, and cohesive energy density of PDMS12-PEO46 vesicles were each significantly greater than for PBd33-PEO20 vesicles, although critical strain was not significantly different between these vesicle types. PDMS12-PEO46/PBd33-PEO20 hybrid vesicles generally displayed graded responses in between that of the pure component vesicles. Thus, the PDMS12-PEO46/PBd33-PEO20 hybrid vesicles retained or exceeded the strength and toughness characteristic of pure PBd-PEO vesicles, indicating that future assessment of the membrane permeability and fluidity of these hybrid vesicles may be warranted.

  13. Mechanical Characterization of Hybrid Vesicles Based on Linear Poly(Dimethylsiloxane-b-Ethylene Oxide) and Poly(Butadiene-b-Ethylene Oxide) Block Copolymers.

    Gaspard, Jeffery; Casey, Liam M; Rozin, Matt; Munoz-Pinto, Dany J; Silas, James A; Hahn, Mariah S

    2016-01-01

    Poly(dimethylsiloxane-ethylene oxide) (PDMS-PEO) and poly(butadiene-b-ethylene oxide) (PBd-PEO) are two block copolymers which separately form vesicles with disparate membrane permeabilities and fluidities. Thus, hybrid vesicles formed from both PDMS-PEO and PBd-PEO may ultimately allow for systematic, application-specific tuning of vesicle membrane fluidity and permeability. However, given the relatively low strength previously noted for comb-type PDMS-PEO vesicles, the mechanical robustness of the resulting hybrid vesicles must first be confirmed. Toward this end, we have characterized the mechanical behavior of vesicles formed from mixtures of linear PDMS-PEO and linear PBd-PEO using micropipette aspiration. Tension versus strain plots of pure PDMS12-PEO46 vesicles revealed a non-linear response in the high tension regime, in contrast to the approximately linear response of pure PBd33-PEO20 vesicles. Remarkably, the area expansion modulus, critical tension, and cohesive energy density of PDMS12-PEO46 vesicles were each significantly greater than for PBd33-PEO20 vesicles, although critical strain was not significantly different between these vesicle types. PDMS12-PEO46/PBd33-PEO20 hybrid vesicles generally displayed graded responses in between that of the pure component vesicles. Thus, the PDMS12-PEO46/PBd33-PEO20 hybrid vesicles retained or exceeded the strength and toughness characteristic of pure PBd-PEO vesicles, indicating that future assessment of the membrane permeability and fluidity of these hybrid vesicles may be warranted. PMID:26999148

  14. From Sugars to Wheels: The Conversion of Ethanol to 1,3-Butadiene over Metal-Promoted Magnesia-Silicate Catalysts.

    Shylesh, Sankaranarayanapillai; Gokhale, Amit A; Scown, Corinne D; Kim, Daeyoup; Ho, Christopher R; Bell, Alexis T

    2016-06-22

    1,3-Butadiene (1,3-BD) is a high-value chemical intermediate used mainly as a monomer for the production of synthetic rubbers. The ability to source 1,3-BD from biomass is of considerable current interest because it offers the potential to reduce the life-cycle greenhouse gas (GHG) impact associated with 1,3-BD production from petroleum-derived naphtha. Herein, we report the development and investigation of a new catalyst and process for the one-step conversion of ethanol to 1,3-BD. The catalyst is prepared by the incipient impregnation of magnesium oxide onto a silica support followed by the deposition of Au nanoparticles by deposition-precipitation. The resulting Au/MgO-SiO2 catalyst exhibits a high activity and selectivity to 1,3-BD and low selectivities to diethyl ether, ethylene, and butenes. Detailed characterization of the catalyst shows that the desirable activity and selectivity of Au/MgO-SiO2 are a consequence of a critical balance between the acidic-basic sites associated with a magnesium silicate hydrate phase and the redox properties of the Au nanoparticles. A process for the conversion of ethanol to 1,3-BD, which uses our catalyst, is proposed and analyzed to determine the life-cycle GHG impact of the production of this product from biomass-derived ethanol. We show that 1,3-BD produced by our process can reduce GHG emissions by as much as 155 % relative to the conventional petroleum-based production of 1,3-BD. PMID:27198471

  15. Association between Genetic Polymorphisms of DNA Repair Genes and Chromosomal Damage for 1,3-Butadiene-Exposed Workers in a Matched Study in China

    Menglong Xiang

    2015-01-01

    Full Text Available The aim of the study was to examine the association between polymorphisms of DNA repair genes and chromosomal damage of 1,3-butadiene- (BD- exposed workers. The study was conducted in 45 pairs of occupationally exposed workers in a BD product workshop and matched control workers in an administrative office and a circulatory water workshop in China. Newly developed biomarkers (micronuclei, MNi; nucleoplasmic bridges, NPBs; nuclear buds, NBUDs in the cytokinesis-blocked micronucleus (CBMN cytome assay were adopted to detect chromosomal damage. PCR and PCR-restriction fragment length polymorphism (RFLP are adopted to analyze polymorphisms of DNA repair genes, such as X-ray repair cross-complementing Group 1 (XRCC1, O6-methylguanine-DNA methyltransferase (MGMT, poly (adenosine diphosphate-ribose polymerases (ADPRT, and apurinic/apyrimidinic endonucleases (APE1. The BD-exposed workers exhibited increased frequencies of MNi and NPBs when compared to subjects in the control group. The results also show that the BD-exposed workers carrying XRCC1 diplotypes TCGA-CCGG (4.25±2.06‰ (FR=2.10, 95% CI: 1.03–4.28 and TCGG-TCGA (5.80±3.56‰ (FR=2.75, 95% CI: 0.76–2.65 had statistically higher NBUD frequencies than those who carried diplotype TCGG-TCGG (1.89±1.27‰. Our study suggests that polymorphisms of XRCC1 gene may influence chromosomal damage in BD-exposed workers.

  16. Effect of expanded graphite and modified graphite flakes on the physical and thermo-mechanical properties of styrene butadiene rubber/polybutadiene rubber (SBR/BR) blends

    Highlights: • Modified graphite flakes/carbon black filled SBR and SBR/BR blend were synthesized. • Mechanical and thermomechanical properties of the composites were widely studied. • Composites with improved antiskid property and low rolling resistance were obtained. - Abstract: The aim of the present research work is to develop expanded graphite (EG) and isocyanate modified graphite nanoplatelets (i-MG) filled SBR/BR blends, which can substitute natural rubber (NR) in some application areas. The present study investigated the effect of i-MG on the physical, mechanical and thermo-mechanical properties of polybutadiene rubber (BR), styrene butadiene rubber (SBR) and SBR/BR blends in the presence of carbon black (CB). Graphite sheets were modified to enhance its dispersion in the rubber matrices, which resulting in an improvement in the overall physical and mechanical properties of the rubber vulcanizates. Compounds based on 50:50 of BR and SBR with ∼3 wt% nanofillers with CB were fabricated by melt mixing. The morphology of the filled rubber blends was investigated by wide angle X-ray diffraction (WAXD) and high resolution transmission electron microscopic (HR-TEM) analyses. The intercalated and delaminated structures of the nanofiller loaded rubber blends were observed. Scanning electron microscopic (SEM) analysis of the cryo-fractured surfaces of the rubber compounds showed more rough and tortuous pathway of the fractured surfaces compared to the fractured surfaces of the only CB loaded rubber composites. Filled rubber compounds exhibit increase in the ΔS (torque difference) value, reduced scorch and cure time compared to their respective controls. Dynamic mechanical thermal analysis (DMTA) of the filled rubber compounds shows an increase in the storage modulus compared to the controls. Isocyanate modified graphite nanoplatelets (i-MG) containing rubber compounds in the presence of CB showed an increase in the mechanical, dynamic mechanical, hardness

  17. Anharmonic Vibrational Analysis of the Infrared and Raman Gas-Phase Spectra of s-trans- and s-gauche-1,3-Butadiene.

    Krasnoshchekov, Sergey V; Craig, Norman C; Boopalachandran, Praveenkumar; Laane, Jaan; Stepanov, Nikolay F

    2015-10-29

    A quantum-mechanical (hybrid MP2/cc-pVTZ and CCSD(T)/cc-pVTZ) full quartic potential energy surface (PES) in rectilinear normal coordinates and the second-order operator canonical Van Vleck perturbation theory (CVPT2) are employed to predict the anharmonic vibrational spectra of s-trans- and s-gauche-butadiene (BDE). These predictions are used to interpret their infrared and Raman scattering spectra. New high-temperature Raman spectra in the gas phase are presented in support of assignments for the gauche conformer. The CVPT2 solution is based on a PES and electro-optical properties (EOP; dipole moment and polarizability) expanded in Taylor series. Higher terms than those routinely available from Gaussian09 software were calculated by numerical differentiation of quadratic force fields and EOP using the MP2/cc-pVTZ model. The integer coefficients of the polyad quantum numbers were derived for both conformers of BDE. Replacement of harmonic frequencies by their counterparts from the CCSD(T)/cc-pVTZ model significantly improved the agreement with experimental data for s-trans-BDE (root-mean-square deviation ≈ 5.5 cm(-1)). The accuracy in predicting the rather well-studied spectrum of fundamentals of s-trans-BDE assures good predictions of the spectrum of s-gauche-BDE. A nearly complete assignment of fundamentals was obtained for the gauche conformer. Many nonfundamental transitions of the BDE conformers were interpreted as well. The predictions of multiple Fermi resonances in the complex CH-stretching region correlate well with experiment. It is shown that solving a vibrational anharmonic problem through a numerical-analytic implementation of CVPT2 is a straightforward and computationally advantageous approach for medium-size molecules in comparison with the standard second-order vibrational perturbation theory (VPT2) based on analytic expressions. PMID:26437183

  18. Polymerization of 1,3-butadiene catalyzed by pincer cobalt(II) complexes derived from 2-(1-arylimino)-6-(pyrazol-1-yl)pyridine ligands

    Gong, Dirong

    2013-08-01

    A new class of air stable and structurally well-defined cobalt complexes with unsymmetrical pincer type ligands ([2-(ArNCMe)-6-(Py)C5H 3N]CoCl2) (Ar = C6H5, Py = pyrazol-1-yl, 5a; Ar = 2,4,6-Me3C6H2, Py = pyrazol-1-yl, 5b; Ar = 2,6-iPr2C6H3, Py = pyrazol-1-yl, 5c; Ar = C6H5, Py = 3,5-Me 2pyrazol-1-yl, 5d; Ar = 2,4,6-Me3C6H 2, Py = 3,5-Me2pyrazol-1-yl, 5e; Ar = 2,6- iPr2C6H3, Py = 3,5-Me 2pyrazol-1-yl, 5f; Ar = 2,6-iPr2C 6H3, Py = 3,5-iPr2pyrazol-1-yl, 5g and [2-(OCMe)-6-(3,5-diphenylpyrazol-1-yl)C5H3N]CoCl 2 5h) were prepared and the molecular structures of 5a, 5c and 5f were determined by single crystal X-ray crystallography. Upon activation by methylaluminoxane (MAO) in toluene at room temperature, all complexes initiate polymerization of 1,3-butadiene (polymer yields: 65-99%), affording polybutadiene with excellent cis-1,4 regularity (97.5-98.7%). The polymer yields and properties in terms of molecular weight and distribution are well controlled by the substituents on iminoaryl rings and pyrazole rings. Selectivity switch from cis-1,4 to syndio-1,2 was also achievable by adding phosphine as microstructure regulator. © 2013 Elsevier B.V. All rights reserved.

  19. Mechanical Characterization of Hybrid Vesicles Based on Linear Poly(Dimethylsiloxane-b-Ethylene Oxide) and Poly(Butadiene-b-Ethylene Oxide) Block Copolymers

    Gaspard, Jeffery; Casey, Liam M.; Rozin, Matt; Munoz-Pinto, Dany J.; Silas, James A.; Hahn, Mariah S.

    2016-01-01

    Poly(dimethylsiloxane-ethylene oxide) (PDMS-PEO) and poly(butadiene-b-ethylene oxide) (PBd-PEO) are two block copolymers which separately form vesicles with disparate membrane permeabilities and fluidities. Thus, hybrid vesicles formed from both PDMS-PEO and PBd-PEO may ultimately allow for systematic, application-specific tuning of vesicle membrane fluidity and permeability. However, given the relatively low strength previously noted for comb-type PDMS-PEO vesicles, the mechanical robustness of the resulting hybrid vesicles must first be confirmed. Toward this end, we have characterized the mechanical behavior of vesicles formed from mixtures of linear PDMS-PEO and linear PBd-PEO using micropipette aspiration. Tension versus strain plots of pure PDMS12-PEO46 vesicles revealed a non-linear response in the high tension regime, in contrast to the approximately linear response of pure PBd33-PEO20 vesicles. Remarkably, the area expansion modulus, critical tension, and cohesive energy density of PDMS12-PEO46 vesicles were each significantly greater than for PBd33-PEO20 vesicles, although critical strain was not significantly different between these vesicle types. PDMS12-PEO46/PBd33-PEO20 hybrid vesicles generally displayed graded responses in between that of the pure component vesicles. Thus, the PDMS12-PEO46/PBd33-PEO20 hybrid vesicles retained or exceeded the strength and toughness characteristic of pure PBd-PEO vesicles, indicating that future assessment of the membrane permeability and fluidity of these hybrid vesicles may be warranted. PMID:26999148

  20. Butadiene-isoprene copolymerization with diglycoldimethyl ether as modifier%以二乙醇二甲醚(2 G)为调节剂的丁二烯-异戊二烯共聚合

    任艳; 王玉荣; 张春庆; 刘海峰; 郑仰才; 任春晓

    2006-01-01

    @@ Polymerizations of conjugated diolefins are interesting topics in rubber and thermoplastic elastomer industries. Especially the copolymerization of butadiene(Bd) and isoprene (Ip) takes an important place in tire. Many investigations on rare earth catalysts system for the copolymerization have been reported, but rarely reported on that of using alkyllithium as initiator. In the research, it is reported a study on the copolymerization of Bd and Ip at 50 ℃ in the presence of diglycoldimethyl ether(2 G)and n-BuLi as initiator, cyclohexane as solvent.

  1. 稀土催化剂上丁二烯气相聚合的宏观动力学研究%Studies on Macro-kinetics of Gas Phase Polymerization of Butadiene with Rare-earth Catalyst

    方东宇; 孙建中; 周其云; 冯博

    2002-01-01

    The study of the kinetics of gas phase polymerization of butadiene with heterogeneous catalyst based on neodymium (Nd) was carried out. The effects of reaction temperature, reaction pressure, dispersing medium,and types of catalyst on kinetics of polymerization were investigated. A kinetic model with two kinds of active sites was proposed. The results show that the effects of the reaction temperature and the types of dispersing medium and catalyst on the kinetic performance of polymerization are significant, and that the combined model of first and second order decay of active site of catalyst can be used to describe the phenomena.

  2. Evaluation of the detoxication efficiencies for acrylonitrile wastewater treated by a combined anaerobic oxic-aerobic biological fluidized tank (A/O-ABFT) process: Acute toxicity and zebrafish embryo toxicity.

    Na, Chunhong; Zhang, Ying; Deng, Minjie; Quan, Xie; Chen, Shuo; Zhang, Yaobin

    2016-07-01

    Acrylonitrile (ACN) wastewater generated during ACN production has been reported to be toxic to many aquatic organisms. However, few studies have evaluated toxicity removal of ACN wastewater during and after the treatment process. In this study, the detoxication ability of an ACN wastewater treatment plant (WWTP) was evaluated using Daphnia magna, Danio rerio and zebrafish embryo. This ACN WWTP has a combined anaerobic oxic-aerobic biological fluidized tank (A/O-ABFT) process upgraded from the traditional anaerobic oxic (A/O) process. Moreover, the potential toxicants of the ACN wastewaters were identified by gas chromatography-mass spectrometry (GC-MS). The raw ACN wastewater showed high acute and embryo toxicity. 3-Cyanopyridine, succinonitrile and a series of nitriles were detected as the toxic contributors of ACN wastewater. The A/O process was effective for the acute and embryo toxicity removal, as well as the organic toxicants. However, the A/O effluent still showed acute and embryo toxicity which was attributed by the undegraded and the newly generated toxicants during the A/O process. The residual acute and embryo toxicity as well as the organic toxicants in the A/O effluent were further reduced after going through the downstream ABFT process system. The final effluent displayed no significant acute and embryo toxicity, and less organic toxicants were detected in the final effluent. The upgrade of this ACN WWTP results in the improved removal efficiencies for acute and embryo toxicity, as well as the organic toxicants. PMID:27037768

  3. Morphology, mechanical, cross-linking, thermal, and tribological properties of nitrile and hydrogenated nitrile rubber/multi-walled carbon nanotubes composites prepared by melt compounding: The effect of acrylonitrile content and hydrogenation

    The purpose of this work was to prepare nanocomposites by mixing multi-walled carbon nanotubes (MWCNT) with nitrile and hydrogenated nitrile elastomers (NBR and HNBR). Utilization of transmission electronic microscopy (TEM), scanning electron microscopy (SEM), and small- and wide-angle X-ray scattering techniques (SAXS and WAXS) for advanced morphology observation of conducting filler-reinforced nitrile and hydrogenated nitrile rubber composites is reported. Principal results were increases in hardness (maximally 97 Shore, type A), elastic modulus (maximally 981 MPa), tensile strength (maximally 27.7 MPa), elongation at break (maximally 216%), cross-link density (maximally 7.94 x 1028 m-3), density (maximally 1.16 g cm-3), and tear strength (11.2 kN m-1), which were clearly visible at particular acrylonitrile contents both for unhydrogenated and hydrogenated polymers due to enhanced distribution of carbon nanotubes (CNT) and their aggregated particles in the applied rubber matrix. Conclusion was that multi-walled carbon nanotubes improved the performance of nitrile and hydrogenated nitrile rubber nanocomposites prepared by melt compounding.

  4. The effect of graphene oxide on the polymerization of acrylonitrile and its rheological properties%氧化石墨烯对丙烯腈聚合及溶液流变性能的影响

    巩娜娟; 吕永根; 杨常玲; 陆叶涛

    2013-01-01

    Graphene oxide modified polyacrylonitrile (GO/PAN) was prepared by in situ polymerization. The effects of the GO on the polymeration of acrylonitrile and the rheological properties of PAN solution were studied. The results showed that GO slightly hindered the polymerization, and the molecular weight and conversion rate of GO/PAN solution decreased with the increasing content of GO. GO facilitated the fluidity of PAN solution. All the storage modulus, loss modulus and viscosity of the GO/PAN solution decreased with the increasing content of GO, and the GO/PAN solution is prone to be viscous with increasing content of GO.%采用原位聚合法制备了氧化石墨烯/聚丙烯腈(GO/PAN)共聚物,研究了GO对丙烯腈聚合及PAN纺丝溶液流变性能的影响.结果表明,GO对聚合反应有一定的抑制作用,GO/PAN的相对分子质量和转化率均随着GO质量分数的增加而减小;GO的加入增加了PAN的流动性,GO/PAN溶液的储能模量、损耗模量和粘度均随着GO质量分数的增加而减小,并且随着GO质量分数的增加更倾向于粘性.

  5. Method Development and Validation for Determining 1,3-Butadiene in Human Blood by Gas Chromatography-Mass Spectrometry and Head-Space Gas Chromatography%Method Development and Validation for Determining1,3-Butadiene in Human Blood by Gas Chromatography-Mass Spectrometry and Head-Space Gas Chromatography

    ZHANG Su-jing; SHEN Bao-hua; ZHUO Xian-yi

    2013-01-01

    To develop a simple,validated method for identifying and quantifying 1,3-butadiene (BD) in human blood by gas chromatography-mass spectrometry (GC-MS) and head-space gas chromatography (HS-GC).BD was identified by GC-MS and HS-GC,and quantified by HS-GC.The method showed that BD had a good linearity from 50 to 500 μg/mL (r>0.99).The limits of detection and quantification were 10 μg/mL and 50 μg/mL,respectively.Both the intra-day precision and inter-day precision were <6.08%,and the accuracy was 96.98%-103.81%.The method was applied to an actual case,and the concentration of BD in the case was 242 μg/mL in human blood.This simple method is found to be useful for the routine forensic analysis of acute exposure to BD.

  6. 丁腈橡胶应力加速老化行为的研究%Study of Stress Accelerated Aging Behavior of Sulfured Nitrile-butadiene Rubber

    熊英; 付宝强; 郭少云; 芦忠

    2012-01-01

    The storage life of nitrile-butadiene rubber (NBR) was calculated according to Arrhenius equation by using high temperature accelerated aging method and the criterion of elongation. The aging behavior of NBR under different stress was studied and the aging mechanism was discussed. The results showed that stress has important impact on aging behavior of NBR; when there is no stress, NBR's storage life is over 19 years according to Arrhenius equation; its storage life reduces 50% under bending stress; its storage life is less than 2 years under tensile-bending stress. This is because stress will induce the orientation and deformation of NBR molecular chain, and change and restrain its bond lengths and bond angles, which also reduce the breaking activation energy of the molecular chain, accelerate the aging process, and shorten the storage life or the service life of NBR.%以丁腈橡胶为例,采用高温加速老化法,以拉伸断裂伸长率作为贮存寿命指标,通过Arrhenius方程对丁腈橡胶贮存寿命的推算,研究了不同应力作用下丁腈橡胶的老化行为,并初步探讨了应力作用下丁腈橡胶的老化机理.结果表明,应力作用对丁腈橡胶的老化行为有较大影响,当丁腈橡胶不承受任何应力作用时,采用Arrhenius方程推算其在常温下的贮存寿命超过19a;受弯曲应力作用时,其贮存寿命降低了50%;在拉伸应力和弯曲应力同时作用时,其贮存寿命小于2a.原因是在应力作用下丁腈橡胶的分子链发生取向变形,键长和键角发生改变并受到约束,分子链的断裂活化能降低、老化进程加快,寿命缩短.

  7. Model for calculation of benzene and 1,3-butadiene concentrations in ambient air from geographic information, including biofuel burning and traffic; Modell foer beraekning av bensen- och 1,3-butadienhalter i omgivningsluft utifraan geografisk information om bland annat biobraensleeldning och trafik

    Modig, Lars; Hagenbjoerk-Gustafsson, Annika; Jonsson, Lennart; Olsson, David; Forsberg, Bertil [Umeaa Univ., Faculty of Medicine, Dept. of Public Health and Clinical Medicine, Occupational and Environmental Medicine, Umeaa (Sweden); Stroemgren, Magnus [Umeaa Univ., Faculty of Social Sciences, Dept. of Geography and Economic History, Umeaa (Sweden)

    2012-07-01

    The aim of the project was to apply a type of statistical calculation model, 'Land Use Regression (LUR)', to predict the concentrations of air pollutants benzene and 1,3-butadiene in a number of urban areas with a high proportion of small-scale biofuel burning in and around Umeaa.

  8. 淀粉丙烯腈接枝共聚物皂化制备吸水剂%The Preparation Technology of Water-Absorbent by the Saponification of the Graft Copolymer of Starch and Acrylonitrile

    顾正彪; 吴嘉根

    2001-01-01

    通过对淀粉丙烯腈接枝共聚物(SPAN)皂化制备吸水剂HSPAN的研究表明:HSPAN为水不溶性凝胶,但具有很强的吸水能力.以氢氧化钾皂化,酸作沉淀剂,经洗涤、分散和干燥制备HSPAN的工艺路线较为理想.皂化工艺条件在用碱量为SPAN中接枝链部分摩尔数的1.1倍、皂化温度95°C以上、皂化时间大于3h,且HSPAN的平板干燥温度在70°C时最好.当SPAN接枝百分率在70%左右时,制得的HSPAN吸水率最高.%Studies on the Preparation Technology of Water-absorbent (HSPAN)by the Saponification of the graft Copolymer of Starch and Acrylonitrile (SPAN) showed that, HSPAN was a kind of gel which was insoluble in water but could absorb a great amount of water. The best technology for the preparation of HSPAN was that,after SPAN was saponified by potassium hydroxide, precipited by sulfuric acid, washed and dispersed in water again, HSPAN was obtained by drying it on a plate. Moreover, the best conditions were that,the quantity of potassium hydroxide used in saponification was 1.1 as much as the mole of polyacrylonitrile in SPAN, saponifying temperature over 95°C, reaction time more than 3 h and drying temperature at 70°C. In addition, the highest water-absorbing capacity could be obtained from the SPAN in which grafted ratio was 70% or so.

  9. 腈纶皂化制备电流变液悬浮粒子的研究%Studies on Saponification of Acrylonitrile Terpolymer for Suspending Particles of Electrorheological Fluids

    吴孟强; 陈艾

    2001-01-01

    In order to prepare suspending particles for electrorheological fluids, hetergeneous hydrolysis of acrylonitrile terpolymer is conducted in presence of saponifying agent(sodium hydroxide) in this paper. The effects of the saponification conditions such as the amount of added sodium hydroxide, time duration and temperature on the degree of saponification are studied in detail. Meanwhile, the conversion of nitrile groups is discussed with the result that the saponification of nitrile groups of the terpolymer initially yields amide groups, then slows down to carboxylic groups. The research sets a way for the preparation of dispersing particles of water-free electrorheological fluids tentatively used for controlling light transmittance.%为了制备无水电流变液用悬浮粒子,研究了腈纶在碱性条件下的多相水解。详细考察了皂化试剂氢氧化钾的用量,皂化时间和温度等皂化条件对皂化程度的影响; 讨论了氰基转化过程。研究结果表明,在皂化初期,腈纶分子链上的氰基转化为酰胺基,然后缓慢转化为羧基。给出了一条制备无水电流变液用悬浮粒子的方法,并初步考察了该类电流变液的控光特性。

  10. In vivo doses of butadiene epoxides as estimated from in vitro enzyme kinetics by using cob(I)alamin and measured hemoglobin adducts: An inter-species extrapolation approach

    Motwani, Hitesh V., E-mail: hitesh.motwani@mmk.su.se; Törnqvist, Margareta

    2014-12-15

    1,3-Butadiene (BD) is a rodent and human carcinogen. In the cancer tests, mice have been much more susceptible than rats with regard to BD-induced carcinogenicity. The species-differences are dependent on metabolic formation/disappearance of the genotoxic BD epoxy-metabolites that lead to variations in the respective in vivo doses, i.e. “area under the concentration-time curve” (AUC). Differences in AUC of the most gentoxic BD epoxy-metabolite, diepoxybutane (DEB), are considered important with regard to cancer susceptibility. The present work describes: the application of cob(I)alamin for accurate measurements of in vitro enzyme kinetic parameters associated with BD epoxy-metabolites in human, mouse and rat; the use of published data on hemoglobin (Hb) adduct levels of BD epoxides from BD exposure studies on the three species to calculate the corresponding AUCs in blood; and a parallelogram approach for extrapolation of AUC of DEB based on the in vitro metabolism studies and adduct data from in vivo measurements. The predicted value of AUC of DEB for humans from the parallelogram approach was 0.078 nM · h for 1 ppm · h of BD exposure compared to 0.023 nM · h/ppm · h as calculated from Hb adduct levels observed in occupational exposure. The corresponding values in nM · h/ppm · h were for mice 41 vs. 38 and for rats 1.26 vs. 1.37 from the parallelogram approach vs. experimental exposures, respectively, showing a good agreement. This quantitative inter-species extrapolation approach will be further explored for the clarification of metabolic rates/pharmacokinetics and the AUC of other genotoxic electrophilic compounds/metabolites, and has a potential to reduce and refine animal experiments. - Highlights: • In vitro metabolism to in vivo dose extrapolation of butadiene metabolites was proposed. • A parallelogram approach was introduced to estimate dose (AUC) in humans and rodents. • AUC of diepoxybutane predicted in humans was 0.078 nM h/ppm h

  11. In vivo doses of butadiene epoxides as estimated from in vitro enzyme kinetics by using cob(I)alamin and measured hemoglobin adducts: An inter-species extrapolation approach

    1,3-Butadiene (BD) is a rodent and human carcinogen. In the cancer tests, mice have been much more susceptible than rats with regard to BD-induced carcinogenicity. The species-differences are dependent on metabolic formation/disappearance of the genotoxic BD epoxy-metabolites that lead to variations in the respective in vivo doses, i.e. “area under the concentration-time curve” (AUC). Differences in AUC of the most gentoxic BD epoxy-metabolite, diepoxybutane (DEB), are considered important with regard to cancer susceptibility. The present work describes: the application of cob(I)alamin for accurate measurements of in vitro enzyme kinetic parameters associated with BD epoxy-metabolites in human, mouse and rat; the use of published data on hemoglobin (Hb) adduct levels of BD epoxides from BD exposure studies on the three species to calculate the corresponding AUCs in blood; and a parallelogram approach for extrapolation of AUC of DEB based on the in vitro metabolism studies and adduct data from in vivo measurements. The predicted value of AUC of DEB for humans from the parallelogram approach was 0.078 nM · h for 1 ppm · h of BD exposure compared to 0.023 nM · h/ppm · h as calculated from Hb adduct levels observed in occupational exposure. The corresponding values in nM · h/ppm · h were for mice 41 vs. 38 and for rats 1.26 vs. 1.37 from the parallelogram approach vs. experimental exposures, respectively, showing a good agreement. This quantitative inter-species extrapolation approach will be further explored for the clarification of metabolic rates/pharmacokinetics and the AUC of other genotoxic electrophilic compounds/metabolites, and has a potential to reduce and refine animal experiments. - Highlights: • In vitro metabolism to in vivo dose extrapolation of butadiene metabolites was proposed. • A parallelogram approach was introduced to estimate dose (AUC) in humans and rodents. • AUC of diepoxybutane predicted in humans was 0.078 nM h/ppm h

  12. Atmospheric oxidation of 1,3-butadiene: characterization of gas and aerosol reaction products and implications for PM2.5

    Jaoui, M.; Lewandowski, M.; Docherty, K.; Offenberg, J. H.; Kleindienst, T. E.

    2014-12-01

    Secondary organic aerosol (SOA) was generated by irradiating 1,3-butadiene (13BD) in the presence of H2O2 or NOx. Experiments were conducted in a smog chamber operated in either flow or batch mode. A filter/denuder sampling system was used for simultaneously collecting gas- and particle-phase products. The chemical composition of the gas phase and SOA was analyzed using derivative-based methods (BSTFA, BSTFA + PFBHA, or DNPH) followed by gas chromatography-mass spectrometry (GC-MS) or high-performance liquid chromatography (HPLC) analysis of the derivative compounds. The analysis showed the occurrence of more than 60 oxygenated organic compounds in the gas and particle phases, of which 31 organic monomers were tentatively identified. The major identified products include glyceric acid, d-threitol, erythritol, d-threonic acid, meso-threonic acid, erythrose, malic acid, tartaric acid, and carbonyls including glycolaldehyde, glyoxal, acrolein, malonaldehyde, glyceraldehyde, and peroxyacryloyl nitrate (APAN). Some of these were detected in ambient PM2.5 samples, and could potentially serve as organic markers of 13BD. Furthermore, a series of oligoesters were detected and found to be produced through chemical reactions occurring in the aerosol phase between compounds bearing alcoholic groups and compounds bearing acidic groups. SOA was analyzed for organic mass to organic carbon (OM /OC) ratio, effective enthalpy of vaporization (Δ Hvapeff), and aerosol yield. The average OM /OC ratio and SOA density were 2.7 ± 0.09 and 1.2 ± 0.05, respectively. The average Δ Hvapeff was -26.08 ± 1.46 kJ mol-1, a value lower than that of isoprene SOA. The average laboratory SOA yield measured in this study at aerosol mass concentrations between 22.5 and 140.2 μg m-3 was 0.025 ± 0.011, a value consistent with the literature (0.021-0.178). While the focus of this study has been examination of the particle-phase measurements, the gas-phase photooxidation products have also been

  13. The Feasibility for the Project of Introducing 25 kt/a Butadiene - Based Chloroprene Rubber (CR) Plant%引进25 kt/a丁二烯法氯丁橡胶(CR)项目可行性探讨

    张泗文

    2001-01-01

    The project of introducing 25 kt/a butadiene - based CR plant is to the advantage of any chloro - alkali enterprise at or near a petrochemical complex. But the introduction of the technology for CR is a key for the project, then the success of the project is entirely dependent on whether marketable and high - tech grades for CR to be produced.%上25 kt/a CR新项目对石化厂或靠近石化厂的氯碱企业有利;但技术引进难度高,引进后能否生产出适销对路且技术含量高的CR品种,决定项目的前途。

  14. Henry's constants and infinite dilution activity coefficients of propane, propene, butane, isobutane, 1-butene, isobutene, trans-2-butene, and 1,3-butadiene in isobutanol and tert-butanol

    The Henry's constants and the infinite dilution activity coefficients of propane, propene, butane, isobutane, 1-butene, isobutene, trans-2-butene and 1,3-butadiene in isobutanol at T = (250 to 330) K and tert-butanol at T (300 to 330) K are measured by a gas stripping method. The rigorous formula for evaluating the Henry's constants from the gas stripping measurements is used for data reduction of these highly volatile mixtures. The accuracy of the measurements is about 2% for Henry's constants and 3% for the estimated infinite dilution activity coefficients. In the evaluations for the infinite dilution activity coefficients, the nonideality of the solute such as the fugacity coefficient and the Pointing correction is not negligible, especially at higher temperatures, and the estimation uncertainty in the infinite dilution activity coefficients includes 1% for nonideality

  15. Henry's law constants and infinite dilution activity coefficients of propane, propene, butane, isobutane, 1-butene, isobutene, trans-2-butene, and 1,3-butadiene in 1-pentanol, 2-pentanol, and 3-pentanol

    Henry's law constants and infinite dilution activity coefficients of propane, propene, butane, isobutane, 1-butene, isobutene, trans-2-butene, and 1,3-butadiene in 1-pentanol, 2-pentanol in the temperature range of (250 to 330) K and 3-pentanol in the temperature range of (260 to 330) K were measured by a gas stripping method. A rigorous formula for evaluating the Henry's law constants from the gas stripping measurements was used for the data reduction of these highly volatile mixtures. The uncertainty is about 2% for the Henry's law constants and 3% for the estimated infinite dilution activity coefficients. In the evaluation of the infinite dilution activity coefficients, the nonideality of the solute such as the fugacity coefficient and Pointing correction factor cannot be neglected, especially at higher temperatures. The estimated uncertainty of the infinite dilution activity coefficients includes 1% for nonideality

  16. Caraterização composicional do AES - um copolímero de enxertia de poli(estireno-co-acrilonitrila em poli(etileno-co-propileno-co-dieno Compositional characterization of AES a graft copolymer based on poly(styrene-co-acrylonitrile and poly(etyhlene-co-propylene-co-diene

    Renato Turchet

    2006-06-01

    Full Text Available O objetivo deste trabalho é a caracterização do AES, um copolímero de enxertia de poli(estireno-co-acrilonitrila, SAN, em poli(etileno-co-propileno-co-dieno, EPDM. Para tanto, o AES foi submetido à extração seletiva de seus componentes: o SAN livre, o EDPM livre, e o copolímero de enxertia EPDM-g-SAN. O AES e suas frações foram caracterizados por espectroscopia de infravermelho, análise elementar, calorimetria diferencial de varredura e ressonância magnética nuclear, RMN¹H e RMN13C. O AES analisado apresenta a seguinte composição em massa: 65% de EPDM-g-SAN, 13% de EPDM livre e 22% de SAN livre. O EPDM apresenta 69,8% em massa de etileno, 26,5% em massa de propileno e 4,6% em massa do dieno, 2-etilideno-5-norboneno, ENB. O SAN apresenta razão em massa acrilonitrila/estireno de 28/72 e distribuição randômica de comonômeros de estireno e acrilonitrila. Estes resultados são concordantes com a composição do AES fornecida pelo fabricante, indicando que a metodologia proposta é adequada.This work aims the characterization of AES, a graft copolymer based on poly(styrene-co-acrylonitrile, SAN, and poly(etyhlene-co-propylene-co-diene, EPDM. AES was submitted to selective extraction of its components: free SAN, EPDM chains and the graft copolymer EPDM-g-SAN. AES and its fractions were characterized by infrared spectroscopy, elemental analysis, differential scanning calorimetry, 13C and ¹H nuclear magnetic resonance. The AES has 65 wt % of EPDM-g-SAN, 13 wt % of free EPDM and 22 wt % of free SAN. EPDM has 69.8 wt % of ethylene, 26.5 wt % of propylene and 4.6 wt % of diene, 2-ethylidene-5-norbonene ENB. SAN presents acrylonitrile/styrene mass ratio of 28/72 and a random distribution of acrylonitrile and styrene comonomers. These results are in agreement with the composition reported by the AES supplier, indicating that the proposed methodology is adequate.

  17. Media surface properties and the development of nitrifying biofilms in mixed cultures for wastewater treatment.

    Stephenson, Tom; Reid, E.; Avery, L. M.; Jefferson, Bruce

    2013-01-01

    Plastic was tested to select biofilm support media that would enhance nitrification in the presence of heterotrophs. Eight different types (acrylonitrile butadiene styrene, nylon, polycarbonate, polyethylene, polypropylene, polytetraflouroethylene (PTFE), polyvinyl chloride and tufnol) were immersed in an aerobic fed-batch reactor receiving domestic settled wastewater. Nitrification rates did not correlate with biomass concentrations, nor surface roughness of the plastics as measured by atomi...

  18. 40 CFR 180.960 - Polymers; exemptions from the requirement of a tolerance.

    2010-07-01

    ... specified for defining a low-risk polymer in 40 CFR 723.250, as an inert ingredient in a pesticide chemical... Acrylonitrile-butadiene copolymer conforming to 21 CFR 180.22, minimum average molecular weight (in amu), 1,000... Federal Register citations affecting § 180.960, see the List of CFR Sections Affected, which appears...

  19. Occupational exposure to acrylonitrile - fish analysis

    Beskid, Olena; Šrám, Radim

    Budapest : EEMS, 2000, s. P71. [Annual Meeting of EEMS /30./. Budapest (HU), 22.08.2000-26.08.2000] R&D Projects: GA MŽP SI/340/2/00 Grant ostatní: EU(XE) (PHARE II, AC/HEA/18) Institutional research plan: CEZ:AV0Z5039906 Subject RIV: DN - Health Impact of the Environment Quality

  20. Enzymatic surface modification of acrylonitrile fibers

    Battistel, Ezio; Morra, Marco; Marinetti, Massimo

    2001-06-01

    The surface of polyacrylonitrile polymer (containing 10% acetate groups) as fibers and finely ground powder have been modified by enzymatic treatment. The enzyme used was a nitrile hydratase, member of the class of nitrile converting enzymes, present in the microorganisms Brevibacterium imperiale and Corynebacterium nitrilophilus. The pendant nitrile groups were selectively converted into the corresponding amides as assessed by XPS analysis. As indicated by the increase of the O/C atomic ratio, the fiber surface showed a significant increase in hydrophilicity. The newly formed amide groups were then able to react with the acid dyes typically used to stain natural fibers, conferring the coloring properties to the otherwise inert polymer surface.

  1. Study on Sulfomethylation of Cellulose Copolymer Copolymerized with Acrylonitrile and Acrylamide%纤维素-丙烯腈-丙烯酰胺共聚物磺甲基化改性研究

    黄统琳; 刘明华; 刘剑锋; 詹怀宇

    2011-01-01

    The nitrile spherical cellulose adsorbent (SCAN) was prepared by sulfomethylating the prepared copolymer of grafting acrylonitrile and acrylamide onto the spherical cellulose beads, doing so is in order to provide reference data for getting higher application value of cellulose. The spherical cellulose beads were prepared by NMMO (N-methylmorpholine-N-oxide) process and sequential cooling technique. The sulfomethylation process was optimized through the orthogonal experiments and single-factor experiments. The results indicate that the adsorbent prepared has a specific surface area of 207.9 m2g-1, and sulfonation degree of 56.32% can be obtained under following optimal operating conditions: the solution pH=12, the mass ratio of HCHO, NaHSO3 and copolymer is 4:6:10, the reaction temperature is 50℃ and the reaction time is 5 h. In addition, the effect of sulfonation degree on the adsorption capacity of SCAN was also studied by using berberine hydrochloride as adsorbate. The results indicate that the increase of sulfonation degree is beneficial to the adsorption capacity, the maximum adsorption capacity of SCAN could reach 16.64 mg-g-1.%研制和开发新型改性纤维素类吸附剂,将是吸附剂研究的一个焦点.研究在球形纤维素珠体接枝丙烯腈和丙烯酰胺的基础上对其进行磺甲基化改性,制备出一种含腈基球形纤维素吸附剂(SCAN),以期为纤维素高值化利用提供参考数据.球形纤维素珠体由NMMO法和程序降温法制备.并通过正交试验和单因素实验进行工艺优化.实验结果表明,SCAN具有较大比表面积—207.9 m2·g-1,且在溶液pH=12,m(HCHO)∶m(NaHSO3)∶m(copolymer)=4∶6∶10,反应温度50℃下反应5h时的磺化度最高,为56.32%,以盐酸小檗碱为吸附质,研究磺化度对吸附剂吸附效果的影响,结果表明,在实验研究的磺化度范围内,磺化度越高,吸附效果越好,最大吸附量达16.64 mg·g-1.

  2. 硅烷偶联剂改性纳米二氧化钛并接枝丙烯腈的机理%Mechanism of nano-TiO2 modified silane coupling agent and grafting acrylonitrile

    王雅珍; 陈国力; 岳成娥; 赵宇; 何子健

    2015-01-01

    主要研究了硅烷偶联剂(KH-560)改性纳米二氧化钛(TiO2)制备TiO2(KH-560)以及TiO2(KH-560)与丙烯腈(AN)接枝聚合生成TiO2(KH-560)-g-AN的反应机理。通过傅里叶变换红外(FT-IR)分析确定了TiO2(KH-560)和TiO2(KH-560)-g-AN的官能团结构。通过X射线光电子能谱(XPS)分析,由TiO2(KH-560)中的氧元素和碳元素结合能的微小变化,引起 C1s、O1s 化学环境的变化,来确定 TiO2(KH-560)的结构;由 TiO2(KH-560)-g-AN的氧元素、碳元素和氮元素的结合能微小变化引起 C1s、O1s、N1s 化学环境的变化,从而确定了TiO2(KH-560)-g-AN的结构。结合FTIR和XPS两者的分析,最终确定TiO2(KH-560)-g-AN的反应机理。%The reaction mechanism of nano-titanium dioxide (TiO2) modified with the silane coupling agent (KH-560) grafted with acrylonitrile(AN) to produce TiO2(KH-560)-g-AN was studied. Functional group structures of TiO2 (KH-560) and TiO2(KH-560)-g-AN were determined by Fourier transform infrared (FT-IR) analysis. The results of X-ray photoelectron spectroscopy (XPS) analysis show that chemical environment of C1s,O1s in TiO2(KH-560) are caused by slight variations of oxygen and carbon element binding energy in TiO2(KH-560). So the structure of TiO2(KH-560) is determined. Chemical environment of C1s,O1s,and N1s in TiO2(KH-560)-g-AN are caused by slight variations of oxygen,carbon,and nitrogen element binding energy in TiO2(KH-560)-g-AN. So the structure of TiO2(KH-560)-g-AN is determined. The graft polymerization mechanism of TiO2(KH-560) and AN is determined ultimately by the analysis of both FT-IR and XPS.

  3. 丙烯腈与N-乙烯基吡咯烷酮在H2O/DMSO混合试剂中共聚反应动力学研究%Kinetics of Copolymerization of Acrylonitrile with N-Vinylpyrrolidone in H2O/Dimethyl Sulphoxide Mixture

    陈厚; 王成国; 梁英; 蔡华甦

    2003-01-01

    Kinetics of copolymerization of acrylonitrile(AN) with N-vinylpyrrolidone(NVP) initiated by azodiisobutyronitrile(AIBN) was investigated in H2O/dimethyl sulphoxide(DMSO) mixture between 50℃ and 70℃ under N2 atmosphere. The rate of copolymerization and particle size were measured respectively. The kinetic equation 0.651±0.123 1.59±0.35 1.17±0.14of copolymerization system is obtained as Rp ∝ cAIBN cAN cNVP at 60℃. The overall activation energy for copolymerization system was computed as 87.3 kJ.mol-1. Effect of additives of hydroquinone and dioxane on copolymerization was discussed. The polymerization is retarded by hydroquinone and accelerated by dioxane, which confirms the free radical copolymerization of AN with NVP.

  4. Synthesis and catalytic property of 1,3-butadiene of calixarene neodynium complex%杯芳烃钕配合物的合成及其催化丁二烯聚合

    倪旭峰; 张一烽; 沈之荃; 陶骏

    2001-01-01

    Three kinds of calixarene neodynium complexes(C[4]NdCl,C[6]NdCl,C[8]Nd2Cl2) were synthesized. Polymerization of 1,3-butadiene with binary catalytic systems composed of calixarene neodynium/triisobutyl-aluminum and ternary catalytic system composed of calixarene neodynium, triisobutyl-aluminum, and a Lewis acid (Al2Et3Cl3 or Al(i-Bu)2Cl or PhCH2Cl) as the third component was studied. The binary catalysts were found to be active even in the absence of halogen source, the sequence of catalytic activity of calixarene neodynium complexes is C[8]Nd2Cl2>C[6]NdCl>C[4]NdCl. While the ternary system has higher activity especially using Al2Et3Cl3.as the third component, and the polymer obtained has higher cis-1,4 content. The effect of chloride sort and catalyst preparation mode, Cl/Nd ratio, and the reaction temperature on polymerization and polymer microstructure of ternary system use C[8]Nd2Cl2 was investigated. It was found that when Al2Et3Cl3 as the third component and Cl/Nd=1, the catalytic system has highest activity to polymerization of 1,3-butadiene. The cis-1,4 content of polybutadiene is decreased with the increase of reaction temperature. High cis-polybutadiene(96%) formed when polymerization was carried out at 5 ℃.%首次应用新型配体——杯芳烃.钕配合物与三异丁基铝构成催化体系催化丁二烯聚合。研究发现杯[6,8]芳烃钕/Al(i-Bu)3/汽油体系中,当Al/Nd=40~100,50℃时具有中等催化聚合活性,所制得聚丁二烯的粘均分子量为10~20万,顺-1,4结构含量为89%左右。添加适量Al2Et3Cl3,或Al(i-Bu)2Cl能提高催化活性。但不能提高顺-1,4结构含量。降低聚合反应温度,5℃聚合所得产物的顺-1,4结构含量可达96%。

  5. 共聚物-深剂体系的气液平衡:新UNIFAC基团热力学模型与实验研究%Vapor-Liquid Equilibrium of Copolymer+solvent Systems:Experimental Data and Thermodynamic Modeling with New UNIFAC groups

    Rogério A.G. Sé; Martín Aznar

    2008-01-01

    Vapor-liquid equilibrium (VLE)data for copolymer solutions are necessary for several chemical processes.However,VLE data for copolymer solutions in the published report are rare.In this study.experimental VLE data for binary systems copolymer+solvent were obtained using a gravimetric-sorption apparatus.The studied systems were hexane+poly(21%acrylonitrile-co-butadiene),hexanc+poly(33%acrylonitrile-co-butadiene),hexane+poly(51%acrylonitrile-co-butadiene),hexanc+poly(23%styrene-co-butadiene),hexane+poly(45%styrene-co-butadiene),and benzene+poly(44%styrene-co-methyl methacrylate)in the range 50-70℃.The experimental data were correlated with the UNIFAC and Elbro-FV group contribution models for the activity coefficient.Two sets of functional groups had been used to represent the monomers in copolymers:literature groups and new proposed groups.The mean deviations between experimental and calculated mass fractions about 2.4%with ElbroFV and 13.3%witll Zhong were observed when the groups proposed in this study were USed.and of 3.5%for E1bro-FV and 13.2%for Zhong when literature groups were used.

  6. Sum Frequency Generation Vibrational Spectroscopy of 1,3-Butadiene Hydrogenation on 4 nm Pt@SiO 2 , Pd@SiO 2 , and Rh@SiO 2 Core–Shell Catalysts

    Krier, James M.

    2015-01-14

    © 2014 American Chemical Society. 1,3-Butadiene (1,3-BD) hydrogenation was performed on 4 nm Pt, Pd, and Rh nanoparticles (NPs) encapsulated in SiO2 shells at 20, 60, and 100 °C. The core-shells were grown around polyvinylpyrrolidone (PVP) coated NPs (Stöber encapsulation) prepared by colloidal synthesis. Sum frequency generation (SFG) vibrational spectroscopy was performed to correlate surface intermediates observed in situ with reaction selectivity. It is shown that calcination is effective in removing PVP, and the SFG signal can be generated from the metal surface. Using SFG, it is possible to compare the surface vibrational spectrum of Pt@SiO2 (1,3-BD is hydrogenated through multiple paths and produces butane, 1-butene, and cis/trans-2-butene) to Pd@SiO2 (1,3-BD favors one path and produces 1-butene and cis/trans-2-butene). In contrast to Pt@SiO2 and Pd@SiO2, SFG and kinetic experiments of Rh@SiO2 show a permanent accumulation of organic material.

  7. Effect of adding of the styrene-butadiene-styrene (SBS) copolymer in chemical and rheological properties of the brazilian asphalt; Efeito da adicao de SBS nas propriedades quimicas e reologicas de asfalto oriundo de petroleo brasileiro

    Lucena, M.C.C.; Soares, S.A. [Ceara Univ., Fortaleza, CE (Brazil). Dept. de Quimica Organica e Inorganica]. E-mail: mccl@dqoi.ufc.br; sas@ufc.br; Soares, J.B. [Ceara Univ., Fortaleza, CE (Brazil). Dept. de Engenharia de Transportes]. E-mail: jsoares@det.ufc.br

    2003-07-01

    Chemical and rheological characterization of the asphalt cement (AC) from the Fazenda Alegre petroleum, and the effect of adding 4.5% of the styrene-butadiene-styrene (SBS) copolymer were investigated. Structural characteristics were analyzed by infrared spectroscopy (FTIR) and nuclear magnetic resonance (NMR). A structure similar to the Arabian and Venezuelan petroleum was observed. The simulated aging led to structural modification noticed by the increment in the carbonyl and sulphoxide groups. Thermogravimetry (TGA) showed that SBS did not affect the AC thermal decomposition at both inert and oxidative atmosphere. However, the differential scanning calorimetry (DSC) showed a decrease in the glass transition temperature of the material when SBS was added. The effect of SBS on the absolute viscosity revealed that SBS is not an inert additive and causes an increase in viscosity, in a nonlinear fashion. The commonly found Newtonian behavior of asphalt binders under high temperatures was also found on the SBS modified binder. Dynamic mechanical tests have shown that SBS increases the binder performance grade. (author)

  8. Effect of acrylonitrile on the expression of Bcl-2 and Bax in spermatogenic cell of mice%丙烯腈对小鼠生精细胞Bcl-2、Bax蛋白表达的影响

    裴凌云; 马国燕; 金娜; 陈亚; 冯玉娟; 党瑜慧; 薛红丽; 李芝兰

    2012-01-01

    Objective To explore the effect of acrylonitrile exposure on the expression of Bcl-2 and Bax in mice spermatogenic cells. Methods Based on body weight, 250 SPF Kunming adult male mice were randomly divided into five groups; negative control group (normal saline 0. 01ml/g), three AN exposure groups (intraperitoneal injection of 1.25, 2. 50 or 5. 00 mg/kg of AN daily for 5 days, respectively) and positive control group (intraperitoneal injection of cyclophosphamide 40mg/kg) . Mice were killed in the 7th, 14th, 21st, 28th and 35th day after the first exposure by cervical dislocation. Immunohistochemical method ( SABC ) was used to detect the expression of Bcl-2 and Bax protein in spermatogenic cells. Results The average optical density values of Bcl-2 at five time points of the AN 2. 50 mg/kg group and the 21th day point of the AN 1. 25 mg/kg group were significantly lower than the negative control group ( P < 0. 05 ) . Except the 21st day point of the AN 1. 25 mg/kg group, the mean optical density values of Bax in all time points of AN exposure groups were significantly higher than the negative control group (P < 0. 05 ). The decreased expression of Bcl-2 protein was most distinct in AN 2. 50mg/kg group and the positive control group at all time points. The expression of Bax protein was significantly increased in all groups at the 14th day point. Conclusion The expression of Bel-2 protein could be weakened in spermatogenic cells induced by AN, especially in the AN 2. 50 mg/kg8roup; while the expression of Bax was enhanced, and the amplitude of change in the 14th day point was more obvious.%目的 探讨丙烯腈(AN)暴露对小鼠睾丸生精细胞Bcl-2、Bax蛋白表达水平的影响.方法 将250只成年健康SPF级昆明种雄性小鼠,按体重随机分为阴性对照组、3个AN染毒组和阳性对照组,阴性对照组用生理盐水,各染毒组分别以1.25、2.50、5.00mg/kg AN腹腔注射(注射剂量为0.01 ml/g BW),每天1次,连续5天,阳性

  9. Synthesis of star-shaped solution-polymerized styrene-butadiene rubber using 1,1-diphenylhexyllithium%1,1-二苯基己基锂合成星形溶聚丁苯橡胶

    陈波; 穆春雨; 白玉; 徐利民; 赵素合; 张兴英

    2011-01-01

    1,1 -diphenylhexyllithium ( DPHL) was prepared by the addition reaction of n-butyllithium ( n-BuLi) and 1,1 -diphenylethlene ( DPE) , with cyclohexane as solvent, and the factors affecting the yield, stability and initial activity of the product were studied. Linear-shaped solution-polymerized styrene-butadiene rubber (SSBR) was synthesized by ionic polymerization with DPHL as initiator, cyclohexane as solvent, and tetrahydrofuran (THF) as polar regulator. Star-shaped SSBR was subsequently prepared by a coupling reaction, using SnCl4 as the coupling agent. The coupling efficiency was measured. The effects of varying the structure of the chain ends, reaction time, and amount of SnCl4 on the coupling efficiency and the properties of the resulting SSBR were investigated. The results showed that the yield and purity of the DPHL were maximimized when n(DPE)/n(n-BuLi) was 1, the concentration decreased to below 90% of the original value if it was kept over 30 days at 2 t , and the diphenylalkyl group introduced by the initiator was present at the chain end of the polymers. The coupling efficiency was the highest when using the following reaction conditions; a molecular weight of 7. 0 × 104, reaction time of 60 min, and n( Cl- )/n(Li+ ) of 1. 12; it could be increased further by converting the chain ends to butadiene. Compared with that obtained using n-BuLi as an initiator, the star-shaped SSBR initiated by DPHL possessed higher tensile strength, tear strength and elongation at break, lower compression temperature rise, higher tan5 at 0 ℃ and lower tanδ at 60 ℃ .%以环己烷为溶剂,1,1-二苯基乙烯(DPE)与正丁基锂(n-BuLi)反应得到1,1-二苯基己基锂(DPHL),对其产率、稳定性和引发活性进行了研究.然后以DPHL为引发剂,四氢呋喃为结构调节剂,采用负离子聚合方法合成了线形溶聚丁苯橡胶(SSBR);最后以SnC14偶联制备星形SSBR.用凝胶渗透色谱仪、核磁共振对产物进行了表征,考查了端基结

  10. Scientific Opinion on the safety assessment of the substances (butadiene, ethyl acrylate, methyl methacrylate, styrene copolymer either not crosslinked or crosslinked with divinylbenzene or 1,3-butanediol dimethacrylate, in nanoform, for use in food contact materials

    EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids (CEF

    2014-04-01

    Full Text Available This scientific opinion of the EFSA Panel on Food Contact Materials, Enzymes, Flavourings and Processing Aids deals with the safety assessment of the additives (butadiene, ethyl acrylate, methyl methacrylate, styrene copolymer either not crosslinked or crosslinked with divinylbenzene or 1,3-butanediol dimethacrylate, in nanoform, (FCM substance Nos 998, 859 and 1043, intended to be used up to 10 % w/w as an impact modifier in rigid (unplasticized polyvinylchloride (PVC. The final material is intended to be used for contact with all food types, at room temperature or lower, for long time storage. The monomers constituting the copolymer are listed in Regulation (EU 10/2011. The migration from PVC of the low molecular weight fraction of the additive below 1000 Da was estimated to be about 0.009 mg/kg food. Considering that these low molecular weight oligomers are made from authorised monomers, which by reaction are expected to lack the reactive functional groups, they do not give rise to safety concern. The migration of the additive in nanoparticle form from the PVC was estimated, using conservative migration modelling, to be about 1 x 10-6 mg/kg food and so consumer exposure would be very low, if any. The CEF Panel concluded that there is no safety concern for the consumer if the substances are used as additives individually or in combination at up to a total of 10 % w/w in rigid PVC used in contact with all food types at ambient temperature or below including long-term storage.

  11. A comparison between the effects of gamma radiation and sulfur cure system on the microstructure and crosslink network of (styrene butadiene rubber/ethylene propylene diene monomer) blends in presence of nanoclay

    Rubber blends based on (styrene–butadiene rubber (SBR)/ethylene–propylene-diene monomer (EPDM)) with and without organoclay (OC) were prepared through a melt mixing process. The concentration ratio of the rubber phases (EPDM/SBR; 50/50 wt%) and the amount of the OC were kept constant. The samples were then vulcanized by means of gamma radiation using a Co-60 gamma source as well as sulfur cure system. The effect of absorbed dose on the formation of the crosslinks was confirmed by the Fourier transform infrared spectroscopy (FTIR). The effects of absorbed dose, sulfur cure system and OC on the gel content, and crosslink density were evaluated by the chemical tests. Applying the Charlesby–Pinner equation to estimate the radiation chemical yield, revealed that the use of OC in the blend caused 20% reduction in the degradation/crosslinking ratio. Employing the swelling test data, some thermodynamic parameters were determined. Using field emission scanning electron microscopy (FE-SEM) to investigate microstructure of the samples revealed a more homogeneous structure and also an increase in compatibility of the blend components in the sample cured by the irradiation in comparison to that cured by the sulfur curing system. - Highlights: • SBR/EPDM and SBR/EPDM/OC samples were prepared and irradiated by gamma radiation. • Increasing the absorbed dose and using OC enhanced gel content and crosslink density. • The increase in the absorbed dose resulted in an increase in ΔS and decrease in ΔG. • The use of OC in the blend caused 20% reduction in the degradation/crosslinking ratio. • In compare to sulfur cure sample the irradiated one showed more homogeneous structure

  12. Desempenho físico-químico e mecânico de concreto de cimento Portland com borracha de estireno-butadieno reciclada de pneus Physicochemical and mechanical performance of portland cement concrete with recycled styrene-butadiene tyre-rubber waste

    Camila Freitas

    2009-01-01

    Full Text Available Physicochemical and mechanical techniques were carried out to characterize three concrete tyre-rubber waste dosages such as 5, 10 and 15%, w/w. The elastomeric material was identified as styrene-butadiene rubber (SBR. It was observed that the growing SBR content in the mixture decreased the concrete performance. The best results were presented by 5% w/w tyre-rubber waste concrete sample. This composition was tested at Mourão hydroelectric powerplant spillway as repairing material.

  13. Simultaneous determination of acrylonitrile, carbon disulfide, methyl ethyl ketone, and isobutanol leachates by purge and trap- gas chromatography-mass spectrometry; Determinacion simultanea de acrilonitrilo, disulfuro de carbono, metiletilcetona e isobutanol en lixiviados por purga y trampa -cromatografia de gas-espectrometria de masas

    Garcia M, J.A. [Gerencia de Laboratorio Central del Instituto Mexicano del Petroleo. Eje Central Lazaro Cardenas 152. 07730 Mexico D.F. (Mexico)

    1998-12-01

    According to the Mexican General Law of the Ecological Equilibrium and Environmental Protection, issued by the National Institute of Ecology, some chemicals such as acrylonitrile, methyl ethyl ketone, carbon disulfide, and isobutanol must be monitored in industrial residues because of their toxicity. This report describes an analytical method for the simultaneous determination of these four analytes in leachates. A purge and trap concentrator coupled to a computerized gas-chromatograph-mass selective detector was used to achieve the analysis. Quantitation measurements were based on the internal standardization method, using the area ratios of the molecular ions of the analytes and the internal standard obtained by deconvolution of the data. The scope of this method as well as the validation data is reported. The method is reliable in spite of the fact that, in some cases, the analytes or the standard coeluted with other compounds of the samples. Because the data acquisition is carried out in the scan mode it is possible to detect and identify other substances in the samples. (Author)

  14. Effects of milk and coenzyme Q10 on the interference of acrylonitrile on vascular endothelial functions%牛奶和辅酶Q10对丙烯腈致血管内皮功能紊乱的影响

    郭进; 王卫群; 龚辉

    2011-01-01

    目的 探讨牛奶或辅酶Q10预处理对丙烯腈致大鼠血管内皮功能紊乱的影响.方法 将80只大鼠分为4组:对照组、单纯丙烯腈组、牛奶组、辅酶Q10组.采用灌胃染毒法,对照组仅予玉米油(丙烯腈的溶剂,1 ml/100 g),其他3组予丙烯腈25 mg/kg染毒.牛奶组和辅酶Q10组在染毒前30 min分别给予牛奶、辅酶Q10预处理.染毒12周后检测血清及主动脉组织中诱导型一氧化氮合酶(iNOS)和内皮型一氧化氮合酶(eNOS)的活力.结果 单纯丙烯腈组、牛奶组、辅酶Q10组血清iNOS水平[(42.9±2.5)U/ml、(26.5±4.4)U/ml、(26.7±3.3)U/ml]比对照组[(21.9±1.6)U/ml,P<0.05]升高.主动脉组织中iNOS在单纯丙烯腈组、牛奶组、辅酶Q10组[(0.812±0.008)、(0.773±0.019)、(0.622±0.013)U/mg蛋白]比对照组[(0.540±0.028)U/mg蛋白,P<0.05]高;而辅酶Q10组的主动脉eNOS活力[(0.471±0.011)U/mg蛋白]高于对照组、单纯丙烯腈组和牛奶组[(0.371±0.029)、(0.380±0.016)、(0.425±0.020)U/mg蛋白,P<0.05].结论 牛奶和辅酶Ql0可以缓解丙烯腈致血管内皮功能紊乱作用.%Objective To explore the influences of milk or coenzyme Q10 pretreatment to acrylonitrile on vascular endothelial functions in rats.Methods A total of 80 rats were randomly divided into 4 groups:control group(Con),acrylonitrile exposure group(ACN),milk pretreatment group (M + ACN)and coenzyme Q10 pretreatment group(Q10 + ACN).The experiment was conducted by the method of gavage exposure in rats.Control group was exposed to corn oil;acrylonitrile was administered to other three groups at the doses of 25 mg/kg.The M + ACN and Q10 + ACN groups were pretreated by milk or coenzyme Q10 at 30 minutes before acrylonitrile exposureAfter a 12-week exposure,the activities of inducible nitric oxide synthase(iNOS)and endothelial nitric oxide synthase(eNOS)were measured in serum and aortal tissues.Results As compared with Con group[(21.9 ± 1.6)U/ml],the activity of blood serum i

  15. Investigation of the interfacial bonding in composite propellants. 1,3,5-Trisubstituted isocyanurates as universal bonding agents

    GORDANA S. USCUMLIC

    2006-05-01

    Full Text Available A series of 1,3,5-trisubstituted isocyanurates (substituents: CH2CH2OH, CH2CH=CH2 and CH2CH2COOH was synthesized according to a modified literature procedure. Experimental investigations included modification of the synthetic procedure in terms of the starting materials, solvents, temperature, isolation techniques, as well as purification and identification of the products. All the synthesized isocyanurates were identified by their melting point and FTIR, 1H NMR and UV spectroscopic data. Fourier transform infrared spectrophotometry was also used to study the interaction between ammonium perchlorate, hydroxyl terminated poly(butadiene, carboxyl terminated poly(butadiene, poly(butadiene-co-acrylonitrile, poly(propylene ether, cyclotrimethylenetrinitramine and the compounds synthesized in this work, which can serve as bonding agents. The results show that tris(2-hydroxyethylisocyanurate is a universal bonding agent for the ammonium perchlorate/carboxyl terminated poly(butadiene/cyclotrimethylenetrinitramine composite propellant system.

  16. Tunable regioselectivity in 1,3-butadiene polymerization by using 2,6-bis(dimethyl-2-oxazolin-2-yl)pyridine incorporated transition metal (Cr, Fe and Co) catalysts

    Gong, Dirong

    2015-05-21

    Tridentate complexes Cr(III)Cl3L, [L = 2,6-bis(dimethyl-2-oxazolin-2-yl) pyridine], Fe(III)Cl3L, Fe(II)Cl2L and Co(II)Cl2L have been prepared and fully characterized. The solid structures of Cr(III)Cl3L, Fe(III)Cl3L and Co(II)Cl2L have been revealed by single crystal X-ray diffraction, and the Cr(III)Cl3L and Fe(III)Cl3L complexes both exhibit a distorted octahedral geometry, while the Co(II)Cl2L complex has a trigonal bipyramidal conformation. Four complexes have been examined in regioselective polymerization of butadiene in combination with MAO in toluene at room temperature. The trans-1,4, cis-1,4 enchainment of resultant polybutadiene are controlled by the metal center. Activated by MAO, complex Cr(III)Cl3L produces high level of trans-1,4 selectivity (trans-1,4 up to 93.3%) with moderate polymer yield, complexes Fe(III)Cl3L and Fe(II)Cl2L both show equal cis-1,4 and trans-1,4 with minor 1,2 selectivity (<10%), and Co(II)Cl2L catalyst displays predominated cis-1,4 selectivity, which can be shifted to 1,2 selectivity by adding PPh3 as an additive. Thus, tuning of the cis-1,4, trans-1,4 and 1,2 selectivity in full range via central metal and additive chosen by these 2,6-bis(dimethyl-2-oxazolin-2-yl) pyridine supported catalysts has been achieved. © 2015 Elsevier B.V. All rights reserved.

  17. Physical properties of blended and vulcanizednitrile-butadiene rubber/chloroprene rubber%共混硫化丁腈橡胶-氯丁橡胶的物理性能

    蒋利辉

    2014-01-01

    将丁腈橡胶(NBR)和氯丁橡胶(CR)按不同质量分数共混并硫化,研究了硫化橡胶在自然环境、热空气老化、热油老化等条件下的物理性能,并测定了硫化橡胶与镀铜钢丝的粘合性能.结果表明,随着 CR 质量分数的增大,混炼胶的焦烧时间逐渐缩短.经热空气老化后,NBR 的硬度增加幅度比 CR 的硬度增加幅度大,拉断强度降低幅度则比 CR 的小得多.此外,NBR 的耐油性能优于 CR.就物理性能以及与镀铜钢丝的粘合性能而言,单一 NBR 和单一 CR 优于共混 NBR/CR.%Nitrile-butadiene rubber (NBR)and chloroprene rubber (CR)were blended at differ-ent mass fractions and vulcanized,followed by aging at various conditions.The physical prop-erties of the vulcanized rubbers aged at ambient condition as well as in hot air and hot oil were determined,and their adhesion to Cu-coated steel wires was measured as well.Results indicate that,with the increase of the mass fraction of CR,the scorch time of the gross rubber tends to decline gradually.After being aged in hot air,the hardness of vulcanized NBR tends to rise more noticeably than that of vulcanized CR,while the tensile strength of the vulcanized NBR reduces at a much less extent than that of the vulcanized CR.Moreover,vulcanized NBR exhib-its better resistance against oil than vulcanized CR,while mono NBR and mono CR are advan-tageous over blended NBR/CR in terms of the physical properties and adhesion to Cu-coated steel wire.

  18. 丁二烯橡胶(BR)9000门尼黏度标准物质的研制%Preparation of mooney viscosity of butadiene rubber(BR) 9000

    刘俊保; 翟月勤; 赵家琳; 汤妍雯; 笪敏峰; 李淑萍; 曹帅英

    2012-01-01

    对经过筛选、通过均匀性、稳定性检验后符合标准物质定值的丁二烯橡胶样品,采用多家实验室联合定值.并对各家实验室定值的结果按照标准物质定值数据处理程序,进行了异常数据判断、数据正态分布检验、等精度检验、不确定度评估.丁二烯橡胶门尼黏度标准物质定值各实验室的数据在a =0.05的显著水平时,数据无可疑值、处于正态分布、等精度,定值标准物质的标称值为ML(1+4) 100℃(45.6±0.5).该标准物质的研制成功,普遍用于校准门尼黏度计,将会在合成橡胶行业得到广泛的应用,同时为合成橡胶行业生产控制、产品检验、产品贸易、质量仲裁提供技术支撑.%The value of butadiene rubber was defined according with standard material value after preparated, passed by uniformity and stability measure by laboratories. The dispose of proceed of standard material value was used to judge of unusual numbers, inspect of distributed numbers, testy of equal precision, appraised of uncertainty. When remarkable level a =0. 05 of standard material of mooney viscosity after tested by laboratory, the number was certainty, normal distribution and equal precision, the value of standard was (45.6 ±0.5)ML( 1+4) 100 %. Successful preparation of standard material should be supported to control of produce, trade of goods and arbitration of quality.

  19. Properties of a new thermoplastic elastomer-sulfonated styrene-butadiene rubber ionomers and their blends%热塑性橡胶——磺化丁苯橡胶离聚体的性能及其共混

    敖枝平; 谢洪泉

    2001-01-01

    丁苯橡胶(SBR)作为高不饱和度的橡胶被成功地用硫酸乙酸酐作为磺化剂在石油醚及丁酮混合溶剂配成的浓溶液中磺化,并用乙酸盐中和成离聚体。研究了离聚体及其他聚合物的共混物的熔融流动性及力学性能。结果表明,SBR离聚体能很容易在硬脂酸锌存在下熔融加工,其行为象热塑性橡胶,硬脂酸锌能降低布拉本特(Brabender)混和机的扭矩所表示的熔融粘度,并增加流动活化能和离聚体的拉伸强度。离聚体的磺酸基含量能增加熔融粘度及拉伸强度。用于中和的阳离子的种类明显地影响离聚体的性能。离聚体与聚丙烯或SBS的共混物在拉伸强度上表现出协同效应,而它与聚苯乙烯或顺-1,4聚丁二烯则呈现抵消效应。%Styrene-butadiene rubber(SBR)synthesized from emulsion polymerization was sulfonated successfully by sulfuric acid and acetic anhydride in a mixed solvent of petroleum ether and methy ethyl ketone at high concentration and neutralized with metallic acetate to form ionomer.Melt flow and mechanical properties of the ionomers and of their blends with polypropylene,SBS,polystyrene or cis-1,4 polybutadiene were studied.

  20. Effect of bound acrylonitrile content on structure and properties of carbon black reinforced hindered phenol/nitrile rubber composites%丁腈橡胶/受阻酚AO-80/炭黑复合材料中结合丙烯腈量对其结构与性能的影响

    宋洪松; 李静; 曹亚君; 赵秀英; 王松

    2011-01-01

    在结合丙烯腈量不同的丁腈橡胶(NBR)中加入受阻酚AO-80和炭黑,制备了NBR/AO-80/炭黑(NBR/AO-80/CB)复合材料,用差示扫描量热仪、动态力学分析仪及物理机械性能测试等手段对复合材料的热性能、动态力学性能及物理机械性能进行了研究.结果表明,与纯NBR硫化胶相比,NBR/AO-80/CB复合材料的玻璃化转变温度大幅度升高,且随着NBR基质中结合丙烯腈量的增大而向高温方向移动;NBR/AO-80/CB复合材料具有较好的阻尼性能,其损耗峰的峰值高于1.22,有效阻尼温域(损耗因子不小于0.3)大于38 ℃,在不同的参考温度下均具有较宽的有效阻尼频率范围;同时,NBR/AO-80/CB复合材料具有较好的物理机械性能和耐热老化性能,尤其是N 220 S/AO-80/CB复合材料的综合性能最好.%Crosslinked nitrile rubber ( NBR )/hindered phenol (AO-80)/carbon black composites were prepared by mixing AO-80 and carbon black into NBR with different bound acrylonitrile contents. The thermal properties, dynamic mechanical properties and mechanical properties of the composites were characterized by differential scanning calorimetry, dynamic mechanical analysis and tensile tester. The results showed that compared with pure NBR, the glass transition temperature of NBR/AO-80/carbon black composites increased greatly, and shifted to high temperature direction with increasing the bound acrylonitrile content of NBR. NBR/AO-80/carbon black composites showed excellent damping properties: loss factor ( tan δ) was more than 1.22, and the effective damping temperature range( tan δ equal to or more than 0. 3 ) was more than 38 ℃ ,the frequency range with high tan δ was wide at different reference temperatures. NBR/AO-80/carbon black composites had good mechanical properties and thermal aging resistance.Especially, N 220 S/AO-80/carbon black composites were the best in all-round properties.