Sample records for styrene divinylbenzene copolymer

  1. N-containing carbons from styrene-divinylbenzene copolymer by urea treatment

    Energy Technology Data Exchange (ETDEWEB)

    Zhuravsky, Sergey V.; Kartel, Mykola T.; Tarasenko, Yuriy O. [Chuiko Institute of Surface Chemistry, National Academy of Sciences of Ukraine, 17 General Naumov Street, Kiev, 03164 (Ukraine); Villar-Rodil, Silvia [Instituto Nacional del Carbon, INCAR-CSIC, Apartado 73, 33080 Oviedo (Spain); Dobos, Gabor [Department of Atomic Physics, Budapest University of Technology and Economics, H-1521 Budapest (Hungary); Toth, Ajna [Department of Physical Chemistry and Materials Science, Budapest University of Technology and Economics, H-1521 Budapest, PO Box 92 (Hungary); Tascon, Juan M.D. [Instituto Nacional del Carbon, INCAR-CSIC, Apartado 73, 33080 Oviedo (Spain); Laszlo, Krisztina, E-mail: [Department of Physical Chemistry and Materials Science, Budapest University of Technology and Economics, H-1521 Budapest, PO Box 92 (Hungary)


    N-containing synthetic carbons with narrow porosity were prepared from a chlorinated styrene and divinylbenzene copolymer by a multistep method with a yield of 34 wt%. Surface chemical treatment and thermal carbonization of the starting copolymer was monitored by urea impregnation. Steam activation, oxidation and an additional heat treatment gave the final product. The synthesis route was designed in a cost-effective way. The porosity and the concentration of the introduced nitrogen atoms were determined at each step. The final product has a surface area of 1135 m{sup 2}/g. More than 70% of the pore volume comes from micropores with an average width of 0.7 nm. The 2.3 at.% surface nitrogen atoms are distributed among five detectable species, of which about 44% is quaternary nitrogen.

  2. 21 CFR 177.2710 - Styrene-divinylbenzene resins, cross-linked. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Styrene-divinylbenzene resins, cross-linked. 177.2710 Section 177.2710 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN... resins, cross-linked. Styrene-divinylbenzene cross-linked copolymer resins may be safely used as articles...

  3. 21 CFR 173.70 - Chloromethylated aminated styrene-divinylbenzene resin. (United States)


    ... resin. 173.70 Section 173.70 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN... Chloromethylated aminated styrene-divinylbenzene resin. Chloromethylated aminated styrene-divinylbenzene copolymer... resin dispersion. (c) The additive is used as a decolorizing and clarification agent for treatment of...

  4. 40 CFR 721.10151 - Modified styrene, divinylbenzene polymer (generic). (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Modified styrene, divinylbenzene polymer (generic). 721.10151 Section 721.10151 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY... Specific Chemical Substances § 721.10151 Modified styrene, divinylbenzene polymer (generic). (a) Chemical...

  5. Síntese do butirato de n-butila empregando lipase microbiana imobilizada em copolímero de estireno-divinilbenzeno Synthesis of butyl butyrate by microbial lipase immobilized onto styrene-divinylbenzene copolymer

    Directory of Open Access Journals (Sweden)

    Pedro Carlos de Oliveira


    Full Text Available This work investigates the reaction parameters of an immobilized lipase in the esterification reaction of n-butanol and butyric acid. Microbial lipase from Candida rugosa was immobilized onto styrene-divinylbenzene copolymer (STY-DVB and subsequently introduced in an organic medium containing substrates in appropriate concentrations. Heptane was selected as solvent on the basis of its compatibility with the resin and the enzyme. The influence of molar ratio of acid to alcohol, amount of immobilized lipase and temperature on the butyl butyrate formation was determined. The results were compared with those achieved with free lipase and Lipozyme (commercially immobilized lipase under the same operational conditions.

  6. Síntese e caracterização de copolímeros de estireno e divinilbenzeno clorometilados Synthesis and characterization of chloromethylated styrene-divinylbenzene copolymers

    Directory of Open Access Journals (Sweden)

    Viviane G. Teixeira


    Full Text Available A reação de clorometilação de copolímeros de estireno e divinilbenzeno (S-DVB em presença de HCl, formaldeído e cloreto de zinco foi estudada em meios aquoso e orgânico. O copolímero S-DVB foi, primeiramente, sintetizado por polimerização em suspensão e caracterizado quanto às suas propriedades porosas. Em meio aquoso, o copolímero foi clorometilado borbulhando-se HCl na mistura de solução aquosa de formaldeído a 37% (formalina 37% e solução aquosa de cloreto de zinco (catalisador. Em meio orgânico (1,2-dicloroetano, foram usados HCl (borbulhado na solução reacional, paraformaldeído e cloreto de zinco sólido. A presença de grupos clorometila foi identificada por espectroscopia na região do infravermelho e o teor desses grupos foi determinado por titulação potenciométrica dos íons cloreto, liberados após a reação de quaternização com piridina. A reação em meio aquoso originou copolímeros com baixos graus de clorometilação, mesmo sob condições drásticas (uso do catalisador sólido e ácido clorídrico concentrado como meio reacional. Em meio orgânico, devido à maior estabilidade do eletrófilo, foram originados copolímeros com teores mais altos de grupos clorometila. Foi estudada a influência dos parâmetros reacionais sobre o grau de clorometilação dos copolímeros em meio orgânico. A temperatura e a razão copolímero/catalisador foram parâmetros determinantes do grau de clorometilação obtido.Cloromethylation of styrene-divinylbenzene copolymer (S-DVB in presence of hydrogen chloride, formaldehyde and zinc chloride was studied in aqueous and organic media. S-DVB was first synthesized by suspension polymerization and its porosity was characterized. In aqueous medium, S-DVB was chloromethylated by using a mixture of hydrogen chloride, aqueous formaldehyde solution (formalin 37% and aqueous zinc chloride solution as catalyst. In organic medium (1,2-dichloroethane, a mixture of hydrogen chloride

  7. Synthesis of crosslinked poly (styrene-co-divinylbenzene-co ...

    Indian Academy of Sciences (India)

    divinylbenzene--sulfopropyl methacrylate) copolymer colloidal particles using emulsion polymerization. The effects of concentration of the emulsifier and the initiator on the particle size and the charge density of the colloidal particles are studied.

  8. Ion-exclusion chromatographic behavior of aliphatic carboxylic acids and benzenecarboxylic acids on a sulfonated styrene--divinylbenzene co-polymer resin column with sulfuric acid containing various alcohols as eluent. (United States)

    Ohta, Kazutoku; Towata, Atsuya; Ohashi, Masayoshi


    The addition of C1-C7 alcohols (methanol, ethanol, propanol, butanol, heptanol, hexanol and heptanol) to dilute sulfuric acid as eluent in ion-exclusion chromatography using a highly sulfonated styrene-divinylbenzene co-polymer resin (TSKgel SCX) in the H+ form as the stationary phase was carried out for the simultaneous separations of both (a) C1-C7 aliphatic carboxylic acids (formic, acetic, propionic, isobutyric, butyric, isovaleric, valeric, 2-methylvaleric, isocaproic, caproic, 2,2-dimethyl-n-valeric, 2-methylhexanoic, 5-methylhexanoic and heptanoic acids) and (b) benzenecarboxylic acids (pyromellitic, hemimellitic, trimellitic, o-phthalic, m-phthalic, p-phthalic, benzoic and salicylic acids and phenol). Heptanol was the most effective modifier in ion-exclusion chromatography for the improvement of peak shapes and a reduction in retention volumes for higher aliphatic carboxylic acids and benzenecarboxylic acids. Excellent simultaneous separation and relatively highly sensitive conductimetric detection for these C1-C7 aliphatic carboxylic acids were achieved on the TSKgel SCX column (150 x 6 mm I.D.) in 30 min using 0.5 mM sulfuric acid containing 0.025% heptanol as eluent. Excellent simultaneous separation and highly sensitive UV detection at 200 nm for these benzenecarboxylic acids were also achieved on the TSKgel SCX column in 30 min using 5 mM sulfuric acid containing 0.075% heptanol as eluent.

  9. A study of the initiator concentration’s effect on styrene-divinylbenzene polymerization with iron particles

    Directory of Open Access Journals (Sweden)

    Bárbara M. da Conceição


    Full Text Available This paper describes the preparation of magnetic copolymer obtained from suspension polymerization of styrene (Sty and divinylbenzene (DVB in the presence of iron particles treated and not treated with oleic acid. The magnetic copolymers were characterized according to their morphology, particle size distribution and magnetic properties. The results show that incorporation of iron particles significantly changed the particles’ morphology. All samples presented higher saturation magnetization than the values reported in the literature and the particle size distribution was more monodisperse when the polymerization was conducted with 5%wt of benzoyl peroxide (BPO.

  10. Poly(styrene-co-divinylbenzene-co-2-ethylhexyl)acrilate membranes with interconnected macroporous structure


    Sevšek, Urška; Stropnik, Črtomir; Krajnc, Peter; Pulko, Irena; Seifried, Silvo


    A combination of doctor blading and emulsion templating was used to prepare macroporous poly(styrene-co-divinylbenzene-co-2-ethylhexylacrylate) and poly(styrene-co-divinylbenzene) membranes with an interconnected porous structure. Water in oil high internal phase emulsions including monomers in the oil phase were cast onto a glass plate and polymerised at elevated temperature. After purification porous polyHIPE membranes were obtained. The volume ratio of aqueous phase (75 % or 85 %) and the ...

  11. 78 FR 6213 - Styrene-2-Ethylhexyl Acrylate Copolymer; Tolerance Exemption (United States)


    ... AGENCY 40 CFR Part 180 Styrene-2-Ethylhexyl Acrylate Copolymer; Tolerance Exemption AGENCY: Environmental...; also known as styrene-2-ethylhexyl acrylate copolymer when used as an inert ingredient in a pesticide...-risk polymers are described in 40 CFR 723.250(d). Styrene-2-ethylhexyl acrylate copolymer conforms to...

  12. Poly(styrene-divinylbenzene) beads surface functionalized with di-block polymer grafting and multi-modal ligand attachment: performance of reversibly immobilized lipase in ester synthesis. (United States)

    Bayramoglu, Gulay; Karagoz, Bunyamin; Altintas, Begum; Arica, M Yakup; Bicak, Niyazi


    Fibrous poly(styrene-b-glycidylmethacrylate) brushes were grafted on poly(styrene-divinylbenzene) (P(S-DVB)) beads using surface-initiated atom transfer radical polymerization. Tetraethyldiethylenetriamine (TEDETA) ligand was incorporated on P(GMA) block. The ligand attached beads were used for reversible immobilization of lipase. The influences of pH, ionic strength, and initial lipase concentration on the immobilization capacities of the beads have been investigated. Lipase adsorption capacity of the beads was about 78.1 mg/g beads at pH 6.0. The Km value for immobilized lipase was about 2.1-fold higher than that of free enzyme. The thermal, and storage stability of the immobilized lipase also was increased compared to the native lipase. It was observed that the same support enzyme could be repeatedly used for immobilization of lipase after regeneration without significant loss in adsorption capacity or enzyme activity. A lipase from Mucor miehei immobilized on styrene-divinylbenzene copolymer was used to catalyze the direct esterification of butyl alcohol and butyric acid.

  13. Evaluation of Styrene-Divinylbenzene Beads as a Support to Immobilize Lipases

    Directory of Open Access Journals (Sweden)

    Cristina Garcia-Galan


    Full Text Available A commercial and very hydrophobic styrene-divinylbenzene matrix, MCI GEL® CHP20P, has been compared to octyl-Sepharose® beads as support to immobilize three different enzymes: lipases from Thermomyces lanuginosus (TLL and from Rhizomucor miehie (RML and Lecitase® Ultra, a commercial artificial phospholipase. The immobilization mechanism on both supports was similar: interfacial activation of the enzymes versus the hydrophobic surface of the supports. Immobilization rate and loading capacity is much higher using MCI GEL® CHP20P compared to octyl-Sepharose® (87.2 mg protein/g of support using TLL, 310 mg/g using RML and 180 mg/g using Lecitase® Ultra. The thermal stability of all new preparations is much lower than that of the standard octyl-Sepharose® immobilized preparations, while the opposite occurs when the inactivations were performed in the presence of organic co-solvents. Regarding the hydrolytic activities, the results were strongly dependent on the substrate and pH of measurement. Octyl-Sepharose® immobilized enzymes were more active versus p-NPB than the enzymes immobilized on MCI GEL® CHP20P, while RML became 700-fold less active versus methyl phenylacetate. Thus, the immobilization of a lipase on this matrix needs to be empirically evaluated, since it may present very positive effects in some cases while in other cases it may have very negative ones.

  14. Reversed preparation of low-density poly(divinylbenzene/styrene) foam columns coated with gold films

    Energy Technology Data Exchange (ETDEWEB)

    Dai, Yinhai; Wang, Ni; Li, Yaling; Yao, Mengqi; Gan, Haibo; Hu, Wencheng, E-mail:


    Highlights: • A reversed fabrication of low density foam columns coated with gold films was proposed. • The uniformity in thickness and purity of gold film are easy to be controlled. • A compact layer is prepared through an electrophoretic deposition method. • A low density (12 mg/cc) foam column coated with gold film is obtained. - Abstract: This work aims to fabricate low-density, porous, non-conductive, structural poly(divinylbenzene/styrene) foam columns by high-internal-phase emulsion templating. We prepare these non-conductive foam columns coated with a thin gold layer by electrochemical deposition and the reversed preparation technique. As expected, the density of the foam obtained through this novel method was about 12 mg cm{sup −3}, and the thickness of the gold coating was about 3 μm. We performed field emission scanning electron microscopy to morphologically and microstructurally characterize the products and X-ray diffraction and energy dispersive spectroscopy to determine the composition of the gold coating.

  15. Nickel ion removal using nanoporous poly(styrene-co divinyl benzene) copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Bagherian, Abbas; Ghorbani, Mohsen; Mirzababaei, Seyed Nima [Babol University of Technology, Babol (Iran, Islamic Republic of)


    To achieve a suitable porous structure and high mechanical strength that is extremely valuable properties in adsorbent polymeric particles, poly(styrene-co-divinylbenzene) with high amounts of cross-linker and diverse proportions of diluent agent (porogen) were synthesized according to the methodology of the suspension polymerization technique. The structural characteristics of the particles and their adsorption properties for adsorption of Nickel ions were studied. Effect of solvent type and monomeric fraction on particles morphology and porosity was discussed. The solvents including n-heptane (HEP) and acetonitrile and monomer fraction was 50% and 30% of divinylbenzene (DVB). From the results obtained, we decided to apply an adsorbent with high mechanical strength and a porous structure appropriate for absorbing the Ni(II). The copolymer was characterized by Fourier transform infrared (FT-IR) analysis. We used scanning electron microscopy (SEM) and transmission electron microscopy (TEM) tests to study the morphology and particle size of the nanoparticles. According to the results, the copolymers synthesized with n-heptane have more porosity. Also an increase in the percentage of DVB caused finer pores. After synthesis of copolymer the applicability of these polymer beads to separation and concentration of Ni(II) is discussed. In separation of Ni(II) from aqueous solution, the effects of pH, temperature and time are discussed and thermodynamic and kinetic calculations are done and its isotherm are fitted with various equations.

  16. In-situ polymerized PLOT columns III: divinylbenzene copolymers and dimethacrylate homopolymers (United States)

    Shen, T. C.; Fong, M. M.


    Studies of divinylbenzene copolymers and dimethacrylate homopolymers indicate that the polymer pore size controls the separation of water and ammonia on porous-layer-open-tubular (PLOT) columns. To a lesser degree, the polarity of the polymers also affects the separation of a water-ammonia gas mixture. Our results demonstrate that the pore size can be regulated by controlling the cross-linking density or the chain length between the cross-linking functional groups. An optimum pore size will provide the best separation of water and ammonia.

  17. 78 FR 20032 - Styrene-Ethylene-Propylene Block Copolymer; Tolerance Exemption (United States)


    ... AGENCY 40 CFR Part 180 Styrene-Ethylene-Propylene Block Copolymer; Tolerance Exemption AGENCY... from the requirement of a tolerance for residues of styrene-ethylene-propylene block copolymer (CAS Reg... permissible level for residues of styrene-ethylene-propylene block copolymer on food or feed commodities...

  18. 21 CFR 177.1040 - Acrylonitrile/styrene copoly-mer. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Acrylonitrile/styrene copoly-mer. 177.1040 Section... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1040 Acrylonitrile/styrene copoly-mer. Acrylonitrile/styrene copolymers identified in this section may be safely used as a component...

  19. Morphology and Phase Transitions in Styrene-Butadiene-Styrene Triblock Copolymer Grafted with Isobutyl Substituted Polyhedral Oligomeric Silsesquioxanes (Postprint)

    National Research Council Canada - National Science Library

    Drazowski, Daniel B; Lee, Andre; Haddad, Timothy S


    Two symmetric triblock polystyrene-butadiene-polystyrene (SBS) copolymers with different styrene content were grafted with varying amounts of isobutyl-substituted polyhedral oligomeric silsesquioxane (POSS) molecules...

  20. Adsorption of uranium from aqueous solution by PAMAM dendron functionalized styrene divinylbenzene

    Energy Technology Data Exchange (ETDEWEB)

    Ilaiyaraja, P., E-mail: [Radiological Safety Division, Radiological Safety and Environmental Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamilnadu (India); Singha Deb, Ashish Kumar; Sivasubramanian, K. [Radiological Safety Division, Radiological Safety and Environmental Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamilnadu (India); Ponraju, D. [Safety Engineering Division, Reactor Design Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamilnadu (India); Venkatraman, B. [Radiological Safety Division, Radiological Safety and Environmental Group, Indira Gandhi Centre for Atomic Research, Kalpakkam 603102, Tamilnadu (India)


    Highlights: ► A new chelating resin PAMAMG{sub 3} -SDB has been synthesized for uranium adsorption. ► The maximum adsorption capacity was determined to be 130.25 mg g{sup −1} at pH 5.5. ► Adsorption capacity increases linearly with increasing dendron generation. ► The adsorbed uranium shall be easily desorbed by simply adjusting the pH < 3. ► Quantitative adsorption of uranium was observed even at high ionic strength. -- Abstract: A new polymeric chelating resin was prepared by growing third generation poly(amido)amine (PAMAMG{sub 3}) dendron on the surface of styrene divinylbenzene (SDB) and characterized by FTIR, TGA and SEM. The ideal branching of dendron in the chelating resin was determined from potentiometric titration. Adsorption of uranium (VI) from aqueous solution using PAMAMG{sub 3}-SDB chelating resin was studied in a series of batch experiments. Effect of contact time, pH, ionic strength, adsorbent dose, initial U(VI) concentration, dendron generation and temperature on adsorption of U(VI) were investigated. Kinetic experiments showed that U(VI) adsorption on PAMAMG{sub 3}-SDB followed pseudo-second-order kinetics model appropriately and equilibrium data agreed well with the Langmuir isotherm model. Thermodynamic parameters (ΔH°, ΔS°, ΔG°) were evaluated from temperature dependent adsorption data and the uranium adsorption on PAMAMG{sub 3}-SDB was found to be endothermic and spontaneous in nature. The sticking probability value (5.303 × 10{sup −9}), kinetic and isotherm data reveal the chemisorption of uranium on PAMAMG{sub 3}-SDB and adsorption capacity of the chelating resin was estimated to be 130.25 mg g{sup −1} at 298 K. About 99% of adsorbed U(VI) can be desorbed from PAMAMG{sub 3}-SDB by a simple acid treatment suggesting that the chelating resin is reusable.

  1. Controlled Functionalization of Olefin/styrene Copolymers through Free Radical Processes

    NARCIS (Netherlands)

    Passaglia, Elisa; Aglietto, Mauro; Ciardelli, Francesco; Picchioni, Francesco


    The functionalization of styrene-b-(ethylene-co-1-butene)-b-styrene triblock copolymer (SEBS) and styrene-co-butadiene (SBR) random copolymer by free radical processes is presented. SEBS was functionalized in the melt with diethyl maleate (DEM) and dicumyl peroxide (DCP) as initiator. The

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

    Directory of Open Access Journals (Sweden)

    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.

  3. Nanostructured synthetic carbons obtained by pyrolysis of spherical acrylonitrile/divinylbenzene copolymers. (United States)

    Malik, Danish J; Trochimczuk, Andrzej W; Ronka, Sylwia


    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.

  4. Poly(styrene-co-divinylbenzene-co-2-ethylhexyl)acrilate membranes with interconnected macroporous structure: Poli(stiren-ko-divinilbenzen-ko-2-etilheksil)akrilatne membrane s povezano porozno strukturo:


    Krajnc, Peter; Pulko, Irena; Seifried, Silvo; Sevšek, Urška; Stropnik, Črtomir


    A combination of doctor blading and emulsion templating was used to prepare macroporous poly(styrene-co-divinylbenzene-co-2-ethylhexylacrylate) and poly(styrene-co-divinylbenzene) membranes with an interconnected porous structure. Water in oil high internal phase emulsions including monomers in the oil phase were cast onto a glass plate and polymerised at elevated temperature. After purification porous polyHIPE membranes were obtained. The volume ratio of aqueous phase (75 % or 85 %) and the ...

  5. Morphology-properties relationship on nanocomposite films based on poly(styrene-block-diene-block-styrene copolymers and silver nanoparticles

    Directory of Open Access Journals (Sweden)


    Full Text Available A comparative study on the self-assembled nanostructured morphology and the rheological and mechanical properties of four different triblock copolymers, based on poly(styrene-block-diene-block-styrene and poly(styrene-block-diene-block-styrene matrices, and of their respective nanocomposites with 1 wt% silver nanoparticles, is reported in this work. In order to obtain well-dispersed nanoparticles in the block copolymer matrix, dodecanethiol was used as surfactant, showing good affinity with both nanoparticles and the polystyrene phase of the matrices as predicted by the solubility parameters calculated based on Hoftyzer and Van Krevelen theory. The block copolymer with the highest PS content shows the highest tensile modulus and tensile strength, but also the smallest elongation at break. When silver nanoparticles treated with surfactant were added to the block copolymer matrices, each system studied shows higher mechanical properties due to the good dispersion and the good interface of Ag nanoparticles in the matrices. Furthermore, it has been shown that semiempirical models such as Guth and Gold equation and Halpin-Tsai model can be used to predict the tensile modulus of the analyzed nanocomposites.


    Directory of Open Access Journals (Sweden)

    A. V. Firsova


    Full Text Available The article discusses the use of organomagnesium initiators in the synthesis of styrene-butadiene random copolymer (SBR obtained solution polymerization and their influence on the properties of rubber. Selected organic magnesium dialkyl initiator is combined with a modifier, which is a mixed alkoxide of an alkali and alkaline earth metals, which allows to control the micr ostructure of the diene polymer and its molecular weight characteristics. Alcohol derivatives selected high-boiling alcohols tetra (hydroxypropyl ethylenediamine (lapromol 294 and tetrahydrofurfuryl alcohol (TGFS. Selection of high-boiling alcohols due to the fact that the destruction of alkoxide with aqueous polymer degassing they do not fall into the return solvent and almost fall into the exact water. The metal components of alkoxides are lithium, sodium, potassium, magnesium and calcium. The resulting solutions are stable when stored modifier t hroughout the year even at -40 °C. The scheme of obtaining the new catalyst systems based organomagnesium and alcoxide of alkali and alkaline earth metals, which yields as functionalized SBR with a statistical and a distribution block of butadiene and styrene was developed. The process of copolymerization with styrene to butadiene organomagnesium initiators as using an organolithium compound (n-butyllithium was carried out, and without it. Found that the addition of n-butyllithium in the reaction mixture leads to a sharp increase in the rate of reaction. The results of studies of the effect of composition of the initiator system on the structure of diene polymers. It was revealed that a mixed initiator system affords a high conversion of monomers (to 90 % in 1 hour 1,2-polybutadiene content increased to 60 %. The process of polymerization of only a mixture of organomagnesium initiators and alcoxide of alkali and alkaline earth metals are not actively proceeds, conversion of the monomers reaches to 90 % in 4 hours, the microstructure

  7. Principais métodos de caracterização da porosidade de resinas à base de divinilbenzeno The most important methods for the characterization of porosity of styrene-divinylbenzene based resins

    Directory of Open Access Journals (Sweden)

    Viviane Gomes Teixeira


    Full Text Available This paper reviews the most important methods used to characterize the porosity of styrene-divinylbenzene resins. Methods such as adsorption of nitrogen for determination of surface area and mercury intrusion porosimetry for characterization of pore size distribution are related.

  8. -Styrene)

    KAUST Repository

    Sutisna, Burhannudin


    Membranes are prepared by self-assembly and casting of 5 and 13 wt% poly(styrene-b-butadiene-b-styrene) (PS-b-PB-b-PS) copolymers solutions in different solvents, followed by immersion in water or ethanol. By controlling the solution-casting gap, porous films of 50 and 1 µm thickness are obtained. A gradient of increasing pore size is generated as the distance from the surface increased. An ordered porous surface layer with continuous nanochannels can be observed. Its formation is investigated, by using time-resolved grazing incident small angle X-ray scattering, electron microscopy, and rheology, suggesting a strong effect of the air-solution interface on the morphology formation. The thin PS-b-PB-b-PS ordered films are modified, by promoting the photolytic addition of thioglycolic acid to the polybutadiene groups, adding chemical functionality and specific transport characteristics on the preformed nanochannels, without sacrificing the membrane morphology. Photomodification increases fivefold the water permeance to around 2 L m(-2) h(-1) bar(-1) , compared to that of the unmodified one. A rejection of 74% is measured for methyl orange in water. The membranes fabrication with tailored nanochannels and chemical functionalities can be demonstrated using relatively lower cost block copolymers. Casting on porous polyacrylonitrile supports makes the membranes even more scalable and competitive in large scale.

  9. Surfactant effects on morphology-properties relationships of silver-poly(styrene-b-isoprene-b-styrene) block copolymer nanocomposites. (United States)

    Peponi, Laura; Tercjak, Agnieszka; Torre, Luigi; Kenny, Josè M; Mondragon, Iñaki


    Good dispersion of silver nanoparticles in poly(styrene-b-isoprene-b-styrene) block copolymer matrix has been achieved by adding dodecanethiol as surfactant to lower the high surface energy of metal nanoparticles. First, the influence of surfactant in the cylindrical nanostructure of neat block copolymer matrix has been analyzed. Taking into account the high solubility between dodecanethiol and the PS block of the SIS block copolymer, when silver nanoparticles and surfactant have been added to the block copolymer matrix its morphology changes from cylindrical to lamellar nanostructure. For the nanocomposite without surfactant, the block copolymer matrix loses its capability to self-assemble in lamellar nanostructure and in this case, agglomeration of silver nanoparticles occurs. Rheological, mechanical and morphological analysis were carried out in order to study the optimal content of surfactant necessary to obtain well-dispersed nanoparticles without worsen the final properties of the nanocomposite. The best silver/dodecanethiol w/w ratio appears to be 1, as confirmed by UV-Vis analysis. Moreover, semi-empirical models, such as Guth and Gold, and Halpin-Tsai, have been used in order to both predict and verify experimental tensile modulus of the obtained nanocomposites. The Guth and Gold equation, applicable to elastomers filled with spherical nanoparticles, provides a result closer to the experimental values than Halpin-Tsai model.

  10. Simultaneous determination of the styrene unit content and assessment of molecular weight of triblock copolymers in adhesives by a size exclusion chromatography method. (United States)

    Wang, Mingfang; Wang, Yuerong; Luo, Pei; Zhang, Hongyang; Zhang, Min; Hu, Ping


    The content of styrene units in nonhydrogenated and hydrogenated styrene-butadiene-styrene and styrene-isoprene-styrene triblock copolymers significantly influences product performance. A size exclusion chromatography method was developed to determine the average styrene content of triblock copolymers blended with tackifier in adhesives. A complete separation of the triblock copolymer from the other additives was realized with size exclusion chromatography. The peak area ratio of the UV and refraction index signals of the copolymers at the same effective elution volume was correlated to the average styrene unit content using nuclear magnetic resonance spectroscopy with commercial copolymers as standards. The obtained calibration curves showed good linearity for both the hydrogenated and nonhydrogenated styrene-butadiene-styrene and styrene-isoprene-styrene triblock copolymers (r = 0.974 for styrene contents of 19.3-46.3% for nonhydrogenated ones and r = 0.970 for the styrene contents of 23-58.2% for hydrogenated ones). For copolymer blends, the developed method provided more accurate average styrene unit contents than nuclear magnetic resonance spectroscopy provided. These results were validated using two known copolymer blends consisting of either styrene-isoprene-styrene or hydrogenated styrene-butadiene-styrene and a hydrocarbon tackifying resin as well as an unknown adhesive with styrene-butadiene-styrene and an aromatic tackifying resin. The methodology can be readily applied to styrene-containing polymers in blends such as poly(acrylonitrile-butadiene styrene). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Characterization by SEM, TEM and Quantum-Chemical Simulations of the Spherical Carbon with Nitrogen (SCN Active Carbon Produced by Thermal Decomposition of Poly(vinylpyridine-divinylbenzene Copolymer

    Directory of Open Access Journals (Sweden)

    Vladyslav V. Lisnyak


    Full Text Available Amorphous Spherical Carbon with Nitrogen (SCN active carbon has been prepared by carbonization of poly(vinylpyridine-divinylbenzene (PVPDVB copolymer. The PVPDVB dehydrogenation copolymer has been quantum chemically (QC simulated using cluster and periodic models. Scanning electron microscopy (SEM, transmission electron microscopy (TEM and energy dispersive X-ray (EDX studies of the resulting product have conformed the QC computation results. Great structural similarity is found both at the nano- and micro-levels between the N-doped SCN carbon and its pure carbonic SKS analog.

  12. Influence of morphology on electrical breakdown characteristics of ethylen-styrene copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Ikeda, Masaaki; Matsuo, Katsuya; Oki, Yoshimichi; Hozumi, Naohiro; Harashige, Masahiro


    For developing the insulating material of ethylene-styrene copolymer to be applicable to 500 Kv electric cable, a study was conducted on the relation between higher order molecular structure and breakdown characteristics of insulator. The experiment was composed of measurement of intensity of electric field at breakdown, of its dependency on the wave shape of voltage, of melting behavior of crystal by differential scanning calorimeter, of degree of crystallinity by x-ray diffraction, and of the observation by transmission type electronic microscope. As the result of experiment, dependency of crystallinity on styrene content, linear correlation of total absorbed heat with ethylene content, and of hardness and styrene content, were shown as graphs. Relation between the intensity of breakdown electric field and styrene content was approximated by two broken straight lines. As the consideration, it was obtained that the breakdown occurred at the weak point of polyethylene structure, that the intensity of breakdown electric field was increased proportionally with styrene content, and that, for achieving higher breakdown voltage by increasing the energy absorbing capacity of benzene ring, randomly copolymerized copolymer with uniform dispersion of styrene molecule was better than graft polymer of the same components. (13 figs, 8 refs)

  13. Hemocompatibility of styrenic block copolymers for use in prosthetic heart valves. (United States)

    Brubert, Jacob; Krajewski, Stefanie; Wendel, Hans Peter; Nair, Sukumaran; Stasiak, Joanna; Moggridge, Geoff D


    Certain styrenic thermoplastic block copolymer elastomers can be processed to exhibit anisotropic mechanical properties which may be desirable for imitating biological tissues. The ex-vivo hemocompatibility of four triblock (hard-soft-hard) copolymers with polystyrene hard blocks and polyethylene, polypropylene, polyisoprene, polybutadiene or polyisobutylene soft blocks are tested using the modified Chandler loop method using fresh human blood and direct contact cell proliferation of fibroblasts upon the materials. The hemocompatibility and durability performance of a heparin coating is also evaluated. Measures of platelet and coagulation cascade activation indicate that the test materials are superior to polyester but inferior to expanded polytetrafluoroethylene and bovine pericardium reference materials. Against inflammatory measures the test materials are superior to polyester and bovine pericardium. The addition of a heparin coating results in reduced protein adsorption and ex-vivo hemocompatibility performance superior to all reference materials, in all measures. The tested styrenic thermoplastic block copolymers demonstrate adequate performance for blood contacting applications.

  14. UV-induced polymerization of size-controlled platinum/poly[styrene-divinylbenzene-tri(propylene glycol diacrylate] hydrophobic catalyst beads in microfluidics

    Directory of Open Access Journals (Sweden)

    Jun Wei


    Full Text Available The catalytic exchange of hydrogen isotopes between hydrogen and water has been known to be a very useful process for the separation of tritium from tritiated water. For the process, a highly active hydrophobic catalyst is needed. This study provides an effective fabrication method of size-controlled platinum/poly[styrene-divinylbenzene-tri(propylene glycol diacrylate] [Pt/poly(SDB-TPGDA] hydrophobic catalyst beads with a narrow size distribution. Platinum nanoparticles were prepared by γ-ray-induced reduction in the aqueous phase first, and then uniformly dispersed in SDB-TPGDA comonomer after the hydrophobization of platinum nanoparticles with alkylamine stabilizers. The porous Pt/poly(SDB-TPGDA hydrophobic catalyst beads were synthesized by the UV-initiated polymerization of the mixture droplets prepared in a capillary-based microfluidic system. The size of as-prepared catalyst beads can be controlled in the range of 200–1,000 μm by adjusting the flow rate of dispersed and continuous phases, as well as the viscosity of the continuous phase. Sorbitan monooleate and cyclohexanol were used as coporogens to control the porosities of the catalyst beads.

  15. UV-induced polymerization of size-controlled platinum/poly[styrene-divinylbenzene-tri(propylene glycol) diacrylate] hydrophobic catalyst beads in microfluidics

    Energy Technology Data Exchange (ETDEWEB)

    Wi, Jun; Li, Xiang; Song, Tong; Song, Zi Fan; Chang, Zhen Qi [School of Nuclear Science and Technology, University of Science and Technology of China, Hefei (China); Meng, Da Qiao [Si Chuan Institute of Materials and Technology, Jiang You (China)


    The catalytic exchange of hydrogen isotopes between hydrogen and water has been known to be a very useful process for the separation of tritium from tritiated water. For the process, a highly active hydrophobic catalyst is needed. This study provides an effective fabrication method of size-controlled platinum/poly[styrene-divinylbenzene-tri(propylene glycol) diacrylate] [Pt/poly(SDB-TPGDA)] hydrophobic catalyst beads with a narrow size distribution. Platinum nanoparticles were prepared by γ-ray-induced reduction in the aqueous phase first, and then uniformly dispersed in SDB-TPGDA comonomer after the hydrophobization of platinum nanoparticles with alkylamine stabilizers. The porous Pt/poly(SDB-TPGDA) hydrophobic catalyst beads were synthesized by the UV-initiated polymerization of the mixture droplets prepared in a capillary-based microfluidic system. The size of as-prepared catalyst beads can be controlled in the range of 200-1,000 μm by adjusting the flow rate of dispersed and continuous phases, as well as the viscosity of the continuous phase. Sorbitan monooleate and cyclohexanol were used as coporogens to control the porosities of the catalyst beads.

  16. The electrospinning of the copolymer of styrene and butyl acrylate for its application as oil absorbent. (United States)

    Xu, Naiku; Cao, Jipeng; Lu, Yuyao


    Electrospun polystyrene materials have been employed as oil absorbents, but they have visible drawbacks such as poor strength at low temperature and unreliable integrity because of brittleness and insufficient cohesive force among fibers. Butyl acrylate can polymerize into flexible chains, and its polymer can be used as elastomer and adhesive material. Thereby it is possible to obtain the material that has better performance in comparison with electrospun polystyrene material through the electrospinning of the copolymer of styrene and butyl acrylate. In this work, a polymer was synthesized through suspension polymerization by using styrene and butyl acrylate as comonomers. The synthesis of the copolymer of styrene and butyl acrylate was verified through dissolution and hydrolysis experimental data; as well through nuclear magnetic resonance spectrometry. The viscous flow activation energy of the solution consisting of copolymer and N, N-dimethylformamide was determined via viscosity method and then adopted to establish the entanglement characteristics of butyl acrylate's chain segments. Finally, in order to electrospin the copolymer solution into fibrous membrane, the effects of monomer feed ratio and spinning parameters were investigated. The prepared fibrous membrane was found to have a potential use as oil absorbent.

  17. Sulfonation and characterization of styrene-indene copolymers for the development of proton conducting polymer membranes

    Directory of Open Access Journals (Sweden)

    Cristiane M. Becker


    Full Text Available The aim of this work is to obtain polymer precursors based on styrene copolymers with distinct degrees of sulfonation, as an alternative material for fuel cell membranes. Acetyl sulfate was used to carry out the sulfonation and the performance of the polyelectrolyte was evaluated based on the content of acid polar groups incorporated into the macromolecular chain. Polymeric films were produced by blending the sulfonated styrene-indene copolymer with poly(vinylidene fluoride. The degree of sulfonation of the polymer was strongly affected by the sulfonation reaction parameters, with a direct impact on the ionic exchange capacity and the ionic conductivity of the sulfonated polymers and the membranes obtained from them. The films produced with the blends showed more suitable mechanical properties, although the conductivity of the membranes was still lower than that of commercially available membranes used in fuel cells.

  18. Production of Natural Rubber Grafted Styrene Copolymer Latex as Water Base Coatings

    Directory of Open Access Journals (Sweden)

    M Utama


    Full Text Available Twelve kinds formulation of natural rubber grafted copolymer styrene (NR-g-S prepared by gamma radiation co-polymerization technique has been carried out. The characteristic of NR-g-S and its water base coating such as molecular structure, particle size, and the properties of latex and its film were evaluated. The results showed that the NR-g-S latex as a water base coating has low viscosity, height strength, good grease resistance, good flexibility, good aging and corrosion resistance on concrete cement and metal. The average particle size is between 270-300 nm, and the bonding between poly-isoprene of NRL and styrene molecules were grafted copolymer

  19. Thermodynamics of coil-hyperbranched poly(styrene-b-acrylated epoxidized soybean oil) block copolymers (United States)

    Lin, Fang-Yi; Hohmann, Austin; Hernández, Nacú; Cochran, Eric

    Here we present the phase behavior of a new type of coil-hyperbranched diblock copolymer: poly(styrene- b-acrylated epoxidized soybean oil), or PS-PAESO. PS-PAESO is an example of a biorenewable thermoplastic elastomer (bio-TPE). To date, we have shown that bio-TPEs can be economical commercial substitutes for their petrochemically derived analogues--such as poly(styrene- b-butadiene- b-styrene) (SBS)--in a range of applications including pressure sensitive adhesives and bitumen modification. From a polymer physics perspective, PS-PAESO is an interesting material in that it couples a linear coil-like block with a highly branched block. Thus in contrast to the past five decades of studies on linear AB diblock copolymers, coil-hyperbranched block copolymers are relatively unknown to the community and can be expected to deviate substantially from the standard ``universal'' phase behavior in the AB systems. To explore these new materials, we have constructed a library of PS-PAESO materials spanning a range of molecular weight and composition values. The phase transition behavior and the morphology information will be interpreted by isochronal temperature scanning in dynamic shear rheology, small angle X-ray scattering and the corresponding transmission electron microscopy.

  20. Structure of poly(styrene-b-ethylene-alt-propylene) diblock copolymer micelles in squalane. (United States)

    Choi, Soo-Hyung; Bates, Frank S; Lodge, Timothy P


    The temperature dependence of the micellar structures formed by poly(styrene-b-ethylene-alt-propylene) (SEP) diblock copolymers in squalane, a highly selective solvent for the PEP blocks, has been studied using dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS). Four SEP diblock copolymers were prepared by sequential anionic polymerization of styrene and isoprene, followed by hydrogenation of the isoprene blocks, to yield SEP(17-73), SEP(26-66), SEP(36-69), and SEP(42-60), where the numbers indicate block molecular weights in kDa. All four polymers formed well-defined spherical micelles. In dilute solution, DLS provided the temperature-dependent mean hydrodynamic radius, R(h), and its distribution, while detailed fitting of the SAXS profiles gave the core radius, R(c), the equivalent hard sphere radius, R(hs), and an estimate of the aggregation number, N(agg). In general, the micelles became smaller as the critical micelle temperature (CMT) was approached, which was well above the glass transition of the core block. As concentration increased the micelles packed onto body centered cubic lattices for all four copolymers, which underwent order-disorder transitions upon heating near the dilute solution CMTs. The results are discussed in terms of current understanding of block copolymer solution self-assembly, and particular attention is paid to the issue of equilibration, given the high glass transition temperature of the core block.


    The dispersion polymerization of styrene in supercritical CO2 utilizing CO2-philic random copolymers was investigated. The resulting high yield of polystyrene particles in the micron-size range was formed using various random copolymers as stabilizers. The p...

  2. Stereoregularity evolution of isobornyl acrylate and styrene copolymers by 2D NMR spectroscopy (United States)

    Khandelwal, Deepika; Hooda, Sunita; Brar, A. S.; Shankar, Ravi


    Isobornyl acrylate/styrene (B/S) copolymers of different compositions have been prepared by Atom Transfer Radical Polymerization (ATRP) using methyl-2-bromopropionate as an initiator and PMDETA/CuBr as catalyst under nitrogen atmosphere at 60 °C. Copolymer compositions calculated from 1H NMR spectra are used to determine the reactivity ratios of monomers. Linear Kelen-Tudos (KT) and non-linear error in variable methods (EVM) have been employed for determination of monomer reactivity ratios in copolymers. The reactivity ratios obtained from KT and EVM are found to be rB = 0.41 ± 0.08, rS = 0.92 ± 0.13 and rB = 0.41 and rS = 0.93 respectively. These copolymers have been analyzed for their stereochemical structure using various 1D (1H, 13C{1H}, DEPT) and 2D (HSQC, TOCSY, NOESY, HMBC) NMR techniques. 2D HSQC and TOCSY NMR experiments are employed to resolve the highly overlapped and complex 1H and 13C{1H} NMR spectra of the copolymers. Spatial coupling of different types of protons are resolved by 2D NOESY NMR spectra. The configurational and compositional sequences of β-methylene carbons are assigned upto tetrad level whereas methine carbon is assigned as triad level of compositional sequences. The quaternary carbon of styrene and carbonyl carbon of isobornyl acrylate have been assigned as triad level of compositional sequences and are further confirmed by 2D HMBC NMR spectra.

  3. Recycling cycle of materials applied to acrylonitrile-butadiene-styrene/policarbonate blends with styrene-butadiene-styrene copolymer addition (United States)

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


    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.

  4. Mechanical and Electrical Properties of Styrene-Isoprene-Styrene Copolymer Doped with Expanded Graphite Nanoplatelets

    Directory of Open Access Journals (Sweden)

    Zdenko Špitalský


    Full Text Available The molecular dynamics of a triblock copolymer and of expanded graphite nanoplatelets were investigated. Composites were prepared using the solution technique. The effects of filler addition and of filler-matrix interactions were investigated using dielectric relaxation spectroscopy (DRS and dynamic mechanical analysis (DMA. Only one relaxation was observed by DRS, which was associated with the relaxation of the main polymer chain. Both DRS and DMA demonstrated that the addition of the filler does not cause a significant change in either the temperature of the relaxation or its activation energy, which suggests the presence of weak interactions between the filler and matrix. The storage modulus of the composites increased with increasing filler content. The composite containing 8% filler exhibited a storage modulus increase of approximately 394% in the rubber area. Using the DC electrical conductivity measurements, the electrical percolation threshold was determined to be approximately 5%. The dielectric permittivity and conductivity in the microwave region were determined, confirming that percolating behavior and the critical threshold concentration.

  5. Matrix-assisted laser desorption/ionization sample preparation optimization for structural characterization of poly(styrene-co-pentafluorostyrene) copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Tisdale, Evgenia; Kennedy, Devin; Wilkins, Charles, E-mail:


    Graphical abstract: -- Highlights: •We optimized sample preparation for MALDI TOF poly(styrene-copentafluorostyrene) co-polymers. •Influence of matrix choice was investigated. •Influence of matrix/analyte ratio was examined. •Influence of analyte/salt ratio (for Ag+ salt) was studied. -- Abstract: The influence of the sample preparation parameters (the choice of the matrix, matrix:analyte ratio, salt:analyte ratio) was investigated and optimal conditions were established for the MALDI time-of-flight mass spectrometry analysis of the poly(styrene-co-pentafluorostyrene) copolymers. These were synthesized by atom transfer radical polymerization. Use of 2,5-dihydroxybenzoic acid as matrix resulted in spectra with consistently high ion yields for all matrix:analyte:salt ratios tested. The optimized MALDI procedure was successfully applied to the characterization of three copolymers obtained by varying the conditions of polymerization reaction. It was possible to establish the nature of the end groups, calculate molecular weight distributions, and determine the individual length distributions for styrene and pentafluorostyrene monomers, contained in the resulting copolymers. Based on the data obtained, it was concluded that individual styrene chain length distributions are more sensitive to the change in the composition of the catalyst (the addition of small amount of CuBr{sub 2}) than is the pentafluorostyrene component distribution.

  6. Volume shrinkage and rheological studies of epoxidised and unepoxidised poly(styrene-block-butadiene-block-styrene) triblock copolymer modified epoxy resin-diamino diphenyl methane nanostructured blend systems. (United States)

    George, Sajeev Martin; Puglia, Debora; Kenny, Josè M; Parameswaranpillai, Jyotishkumar; Vijayan P, Poornima; Pionteck, Jűrgen; Thomas, Sabu


    Styrene-block-butadiene-block-styrene (SBS) copolymers epoxidised at different epoxidation degrees were used as modifiers for diglycidyl ether of the bisphenol A-diamino diphenyl methane (DGEBA-DDM) system. Epoxy systems containing modified epoxidised styrene-block-butadiene-block-styrene (eSBS) triblock copolymer with compositions ranging from 0 to 30 wt% were prepared and the curing reaction was monitored in situ using rheometry and pressure-volume-temperature (PVT) analysis. By controlling the mole percent of epoxidation, we could generate vesicles, worm-like micelles and core-shell nanodomains. At the highest mole percent of epoxidation, the fraction of the epoxy miscible component in the triblock copolymer (epoxidised polybutadiene (PB)) was maximum. This gave rise to core-shell nanodomains having a size of 10-15 nm, in which the incompatible polystyrene (PS) becomes the core, the unepoxidised PB becomes the shell and the epoxidised PB interpenetrates with the epoxy phase. On the other hand, the low level of epoxidation gave rise to bigger domains having a size of ∼1 μm and the intermediate epoxidation level resulted in a worm-like structure. This investigation specifically focused on the importance of cure rheology on nanostructure formation, using rheometry. The reaction induced phase separation of the PS phase in the epoxy matrix was carefully explored through rheological measurements. PVT measurements during curing were carried out to understand the volume shrinkage of the blend, confirming that shrinkage behaviour is related to the block copolymer phase separation process during curing. The volume shrinkage was found to be maximum in the case of blends with unmodified SBS, where a heterogeneous morphology was observed, while a decrease in the shrinkage was evidenced in the case of SBS epoxidation. It could be explained by two effects: (1) solubility of the epoxidised block copolymer in the DGEBA leads to the formation of nanoscopic domains upon

  7. Method of uranium reclamation from aqueous systems by reactive ion exchange. [US DOE patent application; anion exchange resin of copolymerized divinyl-benzene and styrene having quarternary ammonium groups and bicarbonate ligands (United States)

    Maya, L.


    A reactive ion exchange method for separation and recovery of values of uranium, neptunium, plutonium, or americium from substantially neutral aqueous systems of said metals comprises contacting said system with an effective amount of a basic anion exchange resin of copolymerized divinyl-benzene and styrene having quarternary ammonium groups and bicarbonate ligands to achieve nearly 100% sorption of said actinyl ion onto said resin and an aqueous system practically free of said actinyl ions. The method is operational over an extensive range of concentrations from about 10/sup -6/ M to 1.0 M actinyl ion and a pH range of about 4 to 7. The method has particulr application to treatment of waste streams from Purex-type nuclear fuel reprocessing facilities and hydrometallurgical processes involving U, Np, P, or Am.

  8. Thermotropic properties of phosphatidylcholine nanodiscs bounded by styrene-maleic acid copolymers. (United States)

    Dominguez Pardo, J J; Dörr, J M; Renne, M F; Ould-Braham, T; Koorengevel, M C; van Steenbergen, M J; Killian, J A


    Styrene-maleic acid copolymers (SMA) have been gaining interest in the field of membrane research due to their ability to solubilize membranes into nanodics. The SMA molecules act as an amphipathic belt that surrounds the nanodiscs, whereby the hydrophobic styrene moieties can insert in between the lipid acyl chains. Here we used SMA variants with different styrene-to-maleic acid ratio (i.e. 2:1, 3:1 and 4:1) to investigate how lipid packing in the nanodiscs is affected by the presence of the polymers and how it depends on polymer composition. This was done by analyzing the thermotropic properties of a series of saturated phosphatidylcholines in nanodiscs using laurdan fluorescence and differential scanning calorimetry. In all cases it was found that the temperature of the main phase transition (Tm) of the lipids in the nanodiscs is downshifted and that its cooperativity is strongly reduced as compared to the situation in vesicles. These effects were least pronounced for lipids in nanodiscs bounded by SMA 2:1. Unexpected trends were observed for the calorimetric enthalpy of the transition, suggesting that the polymer itself contributes, possibly by rearranging around the nanodiscs when the lipids adopt the fluid phase. Finally, distinct differences in morphology were observed for nanodiscs at relatively high polymer concentrations, depending on the SMA variant used. Overall, the results suggest that the extent of preservation of native thermodynamic properties of the lipids as well as the stability of the nanodiscs at high polymer concentrations is better for SMA 2:1 than for the other SMA variants. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

  9. Conventional and atom transfer radical copolymerization of phenoxycarbonylmethyl methacrylate-styrene and thermal behavior of their copolymers

    Directory of Open Access Journals (Sweden)


    Full Text Available The atom transfer radical polymerization (ATRP of phenoxycarbonylmethyl methacrylate (PCMMA with styrene (St were performed in bulk at 110°C in the presence of ethyl 2-bromoacetate, cuprous(Ibromide (CuBr, and N,N,N’,N”,N”-pentamethyldiethyltriamine. Also, a series conventional free-radical polymerization (CFRP of PCMMA and styrene were carried out in the presence of 2,2’-azobisisobutyronitrile in 1,4-dioxane solvent at 60°C. The structure of homo and copolymers was characterized by IR, 1H and 13C-NMR techniques. The composition of the copolymers was calculated by 1H-NMR spectra. The average-molecular weight of the copolymers were investigated by Gel Permeation Chromatography (GPC. For copolymerization system, their monomer reactivity ratios were obtained by using both Kelen-Tüdõs and Fineman-Ross equations. Thermal analysis measurements of homo- and copolymers prepared CFRP and ATRP methods were measured by TGA-50 and DSC-50. Blends of poly(PCMMA and poly(St obtained via ATRP method have been prepared by casting films from dichlorormethane solution. The blends were characterized by differential scanning calorimetry. The initial decomposition temperatures of the resulting copolymers increased with increasing mole fraction of St.

  10. Synthesis and Characterization of Amphiphilic Graft Copolymers of Poly (1,3dioxolane) Macromonomers with Styrene and Methyl Methacrylate (United States)

    Bendaikha, H.; Clisson, G.; Khoukh, A.; François, J.; Kada, S. Ould; Krallafa, A.


    Methacrylate-terminated Poly (1,3dioxolane) (PDXL) macromonomers were synthesized by cationic ring-opening polymerization in the presence of 2-hydroxypropyl methacrylate (2-HPMA) as transfer agent. Molecular weights and polydispersity index of the PDXL macromonomers were evaluated by size exclusion chromatography (SEC) and 1H-NMR. Copolymerizations of PDXL macromonomers with styrene (St) and methyl methacrylate (MMA) were carried out using various feed molar ratios. Monomer reactivity ratios between the macromonomers and the comonomers were estimated from the copolymerization results. Glass transition temperatures of the copolymers were found to decrease with an increase in the amount of PDXL in the copolymers.

  11. Functionalization of cross-linked poly(styrene) in the preparation of a PET target material

    Energy Technology Data Exchange (ETDEWEB)

    Zippi, E.M.; Grover, John; Valiulis, M.B.; Tibbets, Cynthia [Louisiana State Univ., Shreveport, LA (United States). Dept. of Chemistry and Physics; Kabalka, G.W. [Tennessee Univ., Knoxville, TN (United States). Dept. of Chemistry


    In an effort to prepare an improved carbon-rich target material for the generation of [{sup 13}N]ammonia for use in PET, styrene was polymerized and cross-linked with various percentages of divinylbenzene(DVB). The resulting copolymers were then sulfonated and nitrated and the degree of substitution was determined by elemental analysis. As expected, increased levels of DVB sterically hindered substitution of the aromatic ring. (Author).

  12. Influence of Poly(styrene-co-maleic acid) Copolymer Structure on the Properties and Self-Assembly of SMALP Nanodiscs. (United States)

    Hall, Stephen C L; Tognoloni, Cecilia; Price, Gareth J; Klumperman, Bert; Edler, Karen J; Dafforn, Tim R; Arnold, Thomas


    Polymer stabilized nanodiscs are self-assembled structures composed of a polymer belt that wraps around a segment of lipid bilayer, and as such are capable of encapsulating membrane proteins directly from the cell membrane. To date, most studies on these nanodiscs have used poly(styrene-co-maleic acid) (SMA) with the term SMA-lipid particles (SMALPs) coined to describe them. In this study, we have determined the physical and thermodynamic properties of such nanodiscs made with two different SMA copolymers. These include a widely used and commercially available statistical poly(styrene-co-maleic acid) copolymer (coSMA) and a reversible addition-fragmentation chain transfer synthesized copolymer with narrow molecular weight distribution and alternating styrene and maleic acid groups with a polystyrene tail, (altSMA). We define phase diagrams for each polymer, and show that, regardless of polymer topological structure, self-assembly is driven by the free energy change associated with the polymers. We also show that nanodisc size is polymer dependent, but can be modified by varying polymer concentration. The thermal stability of each nanodisc type is similar, and both can effectively solubilize proteins from the E. coli membrane. These data show the potential for the development of different SMA polymers with controllable properties to produce nanodiscs that can be optimized for specific applications and will enable more optimized and widespread use of the SMA-based nanodiscs in membrane protein research.

  13. Inner Stucture of Thin Films of Lamellar Poly(styrene-b-butadiene) Diblock Copolymers as revealed by Grazing-Incidence Small-Angle Scattering

    DEFF Research Database (Denmark)

    Busch, Peter; Posselt, Dorthe; Smilgies, Detlef-Matthias


    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 ...

  14. Microesferas poliméricas magnéticas à base de estireno e divinilbenzeno com morfologia casca e núcleo Magnetic polymeric microspheres based on styrene and divinylbenzene with core-shell morphology

    Directory of Open Access Journals (Sweden)

    Washington J. F. Formiga


    Full Text Available Microesferas poliméricas com propriedades magnéticas à base de estireno (STY e divinilbenzeno (DVB foram sintetizadas usando a técnica de polimerização em suspensão em duas etapas. Na primeira, foram preparados os núcleos poliméricos à base de STY e DVB e magnetita. Na segunda, os núcleos foram previamente inchados em uma emulsão de STY e DVB e novamente polimerizados para a formação da casca. Foram variados o método de adição da emulsão e o tempo de inchamento. Os materiais obtidos foram caracterizados quanto ao tamanho de partícula por peneiramento, análise termogravimétrica (TGA, microscopia eletrônica de varredura (SEM e magnetometria de amostra vibrante (VSM. Os métodos avaliados na formação da casca de poli(estireno-co-divinilbenzeno produziram partículas com diâmetro médio maior do que o núcleo. Este resultado indica a formação de morfologia casca e núcleo. O controle morfológico só foi obtido com as resinas RR48/1 e RR48/3. O método onde a emulsão de estireno e divinilbenzeno foi adicionada em etapa única, seguida de 48 horas de inchamento do núcleo a 10 °C (RR48/1, forneceu o maior rendimento (64%. Além disso, todas as resinas casca-núcleo foram sensíveis ao estímulo magnético realizado por um ímã, atestando assim que foram produzidas resinas com propriedades magnéticas.Magnetic polymeric microspheres based on styrene (STY and divinylbenzene (DVB were synthesized in two steps. Firstly, the polymeric core, constituted by STY, DVB and magnetite, was prepared by suspension polymerization. Then, the core was swollen in a STY and DVB emulsion. Subsequently, a second suspension polymerization was carried out in order to form a shell. The emulsion addition method and the swelling time were varied. The particle size, morphology, thermal stability and magnetic properties of the microspheres were studied by sieving, thermogravimetric analysis (TGA, scanning electron microscopy (SEM and vibrating

  15. Estimation of the Surface Properties of Styrene-Acrylonitrile Random Copolymers from Contact Angle Measurements. (United States)

    Adão; Saramago; Fernandes


    The surface free energy per unit area of a solid, gamma(S), is a fundamental property of materials and determines their surface and interfacial behavior in processes like wetting and adhesion. In this study the gamma(S) of a series of styrene-acrylonitrile random copolymers is evaluated. Three different approaches are used to determine the components in which the surface free energy can be decomposed. Using the geometric and the harmonic mean approach, the dispersive, gamma(d), and polar, gamma(p), components of the solid surface free energy were determined and compared to the Lifshitz-van der Waals, gamma(LW), and acid-base, gamma(AB), components using the approach developed by C. J. van Oss et al. (1987, Adv. Colloid Interface Sci. 28, 35). The acid-base approach was also used to evaluate the work of adhesion of the test liquids: water, glycerol, and thiodiglycol. It was found that the contact angles of these liquids follow closely the predictions of Cassie equation. The evaluation of the surface free energy components on one hand and the relative magnitude of the work of adhesion components on the other hand, suggest that below 50% of acrylonitrile the polystyrene repeating units are preferentially at the surface. Above 50% of acrylonitrile the segregation of the low-energy homopolymer at the surface decreases. Copyright 1999 Academic Press.

  16. Nanostructured Double Hydrophobic Poly(Styrene-b-Methyl Methacrylate) Block Copolymer Membrane Manufactured Via Phase Inversion Technique

    KAUST Repository

    Karunakaran, Madhavan


    In this paper, we demonstrate the formation of nanostructured double hydrophobic poly(styrene-b-methyl methacrylate) (PS-b-PMMA) block copolymer membranes via state-of-the-art phase inversion technique. The nanostructured membrane morphologies are tuned by different solvent and block copolymer compositions. The membrane morphology has been investigated using FESEM, AFM and TEM. Morphological investigation shows the formation of both cylindrical and lamellar structures on the top surface of the block copolymer membranes. The PS-b-PMMA having an equal block length (PS160K-b-PMMA160K) exhibits both cylindrical and lamellar structures on the top layer of the asymmetric membrane. All membranes fabricated from PS160K-b-PMMA160K shows an incomplete pore formation in both cylindrical and lamellar morphologies during the phase inversion process. However, PS-b-PMMA (PS135K-b-PMMA19.5K) block copolymer having a short PMMA block allowed us to produce open pore structures with ordered hexagonal cylindrical pores during the phase inversion process. The resulting PS-b-PMMA nanostructured block copolymer membranes have pure water flux from 105-820 l/ and 95% retention of PEG50K

  17. Chitosan/polyanion surface modification of styrene–butadiene–styrene block copolymer membrane for wound dressing

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Jen Ming, E-mail: [Department of Chemical and Materials Engineering, Chang Gung University, Kwei-Shan, Tao-Yuan 333, Taiwan (China); Yang, Jhe-Hao [Department of Electronic Engineering, Chang Gung University, Kwei-Shan, Tao-Yuan 333, Taiwan (China); Huang, Huei Tsz [Department of Chemical and Materials Engineering, Chang Gung University, Kwei-Shan, Tao-Yuan 333, Taiwan (China)


    The surface of styrene–butadiene–styrene block copolymer (SBS) membrane is modified with tri-steps in this study. At first, two step modified SBS membrane (MSBS) was prepared with epoxidation and ring opening reaction with maleated ionomer. Then chitosan was used as the polycation electrolyte and sodium alginate, poly(γ-glutamic acid) (PGA) and poly(aspartic acid) (PAsp) were selected as polyanion electrolytes to deposit on the surfaces of MSBS membrane by the layer-by-layer self-assembly (LbL) deposition technique to get three [chitosan/polyanion] LbL modified SBS membranes, ([CS/Alg], [CS/PGA] and [CS/PAsp]). From the quantitative XPS analysis and water contact angle measurement, it is found that the order of wettability and the content of functional group percentages of COO{sup −} and -O=C-N- on the three [CS/polyanion] systems are [CS/Alg] > [CS/PGA] > [CS/PAsp]. Performances of water vapor transmission rates, fibronectin adsorption, antibacterial assessment and 3T3 fibroblast cell growth on [CS/Alg], [CS/PGA] and [CS/PAsp] membranes were also evaluated. With the evaluation of water vapor transmission rate, these [CS/Alg], [CS/PGA] and [CS/PAsp] membranes are sterile semipermeable with water evaporation at about 82 ± 8 g/day · m{sup 2}. It is found that the amount of fibronectin adsorption on the three [CS/polyanion] systems is significantly determined by the sum of the functional group of COO{sup −} and -O=C-N- on the surfaces of [CS/Alg], [CS/PGA] and [CS/PAsp] systems. The results are inverse with the sum of the functional group of COO{sup −} and -O=C-N- on the three [CS/polyanion]. From the cytotoxicity test and cell adhesion and proliferation assay of 3T3 fibroblasts on the three [CS/polyanion] systems, it revealed that the cells not only remained viable but they also proliferated on the surfaces of [CS/Alg], [CS/PGA] and [CS/PAsp]. The bactericidal activity was found on [CS/Alg], [CS/PGA] and [CS/PAsp]. The transport of bacterial through

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

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Sun-Young [Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, 29 Geumgu-gil, Jeongeup-si, Jeollabuk-do 580-185 (Korea, Republic of); Department of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 120-749 (Korea, Republic of); Song, Ju-Myung; Sohn, Joon-Yong [Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, 29 Geumgu-gil, Jeongeup-si, Jeollabuk-do 580-185 (Korea, Republic of); Shul, Yong-Gun [Department of Chemical and Biomolecular Engineering, Yonsei University, 50 Yonsei-ro, Seodaemun-gu, Seoul 120-749 (Korea, Republic of); Shin, Junhwa, E-mail: [Advanced Radiation Technology Institute, Korea Atomic Energy Research Institute, 29 Geumgu-gil, Jeongeup-si, Jeollabuk-do 580-185 (Korea, Republic of)


    Highlights: • The c-SBS films were prepared using a gamma ray or electron beam. • The crosslinking degree of the c-SBS films were increased with the irradiation dose. • The prepared c-SBS films were sulfonated with various concentration of CSA. • The sulfonation of the c-SBS film is largely dependent on the concentration of CSA. • The sulfonation process is progressed from the surface to the inner part of c-SBS film. -- Abstract: 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.

  19. Shape Memory Polymer Composites of Poly(styrene-b-butadiene-b-styrene Copolymer/Liner Low Density Polyethylene/Fe3O4 Nanoparticles for Remote Activation

    Directory of Open Access Journals (Sweden)

    Yongkun Wang


    Full Text Available Magnetically sensitive shape memory poly(styrene-b-butadiene-b-styrene copolymer (SBS/liner low density polyethylene (LLDPE composites filled with various contents of Fe3O4 nanoparticles were prepared. The influence of the Fe3O4 nanoparticles content on the thermal properties, mechanical properties, fracture morphology, magnetic behavior, and shape memory effect of SBS/LLDPE/Fe3O4 composites was systematically studied in this paper. The results indicated that homogeneously dispersed Fe3O4 nanoparticles ensured the uniform heat generation and transfer in the alternating magnetic field, and endowed the SBS/LLDPE/Fe3O4 composites with an excellent magnetically responsive shape memory effect. When the shape memory composites were in the alternating magnetic field (f = 60 kHz, H = 21.21 kA·m−1, the best shape recovery ratio reached 99%, the shape retention ratio reached 99.4%, and the shape recovery speed increased significantly with the increment of Fe3O4 nanoparticles. It is anticipated that tagging products with this novel shape memory composite is helpful for the purpose of an intravascular delivery system in Micro-Electro-Mechanical System (MEMS devices.

  20. The structure and dynamics of thin poly(styrene)-b-(polybutadiene) copolymer films studied by x-ray scattering (United States)

    Song, Sanghoon; Byun, Youngsuk; Kim, Jeeun; Eom, Daeyong; Cha, Wonsuk; Kim, Hyunjung


    We have investigated the structure and dynamics of thin diblock copolymer films of poly(styrene)-b-poly(butadiene) using x-ray reflectivity, diffuse scattering, grazing incidence small angle scattering (GISAXS), and x-ray photon correlation spectroscopy (XPCS), respectively. The measurements were performed at temperatures below and above the order-disorder transition temperature (ODT) of bulk with different film thicknesses. The x-ray reflectivity and GISAXS results show that the structural changes appear at lower temperature than ODT of bulk. These results will be discussed with the findings from the XPCS.

  1. Grafting of copolymer styrene maleic anhydride on poly(ethylene terephthalate) film by chemical reaction and by plasma method

    Energy Technology Data Exchange (ETDEWEB)

    Bigan, Muriel; Bigot, Julien [Laboratoire de Chimie Organique et Macromoleculaire (UMR 8009), Universite des Sciences et Technologies de Lille, 59655 Villeneuve d' Ascq Cedex (France); Mutel, Brigitte [Laboratoire de Genie des Procedes d' Interactions Fluides reactifs-Materiaux (UPRES-EA 3751), Batiment C5, Universite des Sciences et Technologies de Lille, 59655 Villeneuve d' Ascq Cedex (France)], E-mail:; Coqueret, Xavier [Laboratoire Reactions Selectives et Applications (UMR-CNRS 6519) Universite de Reims Champagne-Ardennes, B.P. 1039, 51687 Reims Cedex 2 (France)


    This work deals with the chemical grafting of a styrene maleic anhydride copolymer on the surface of a previously hydrolyzed polyethylene terephthalate (PET) film 12 {mu}m thick via covalent bond. Two different ways are studied. The first one involves an activation of the hydrolyzed PET by the triethylamine before the grafting step. In the second one, the copolymer reacts with the 4-dimethylaminopyridine in order to form maleinyl pyridinium salt which reacts with alcohol function of the hydrolyzed PET. Characterization and quantification of the grafting are performed by Fourier transform infrared spectroscopy. Factorial experiment designs are used to optimize the process and to estimate experimental parameters effects. The opportunity to associate the chemical process to a cold remote nitrogen plasma one is also examined.

  2. Vegetable-Oil-Based Hyperbranched Polyester-Styrene Copolymer Containing Silver Nanoparticle as Antimicrobial and Corrosion-Resistant Coating Materials

    Directory of Open Access Journals (Sweden)

    Manawwer Alam


    Full Text Available Pongamia oil (PO was converted to Pongamia oil hydroxyl (POH via epoxidation process. The esterification of POH with linolenic acid was carried out to form hyperbranched polyester (HBPE, and further styrenation was performed at the conjugated double bond in the chain of linolenic acid. After styrenation, silver nanoparticle was added in different weight percentages (0.1–0.4 wt%. The structural elucidation of POH, HBPE, and HBPE-St was carried out by FT-IR, 1H-NMR, and 13C-NMR spectroscopic techniques. Physicochemical and physicomechanical analyses were performed by standard method. Thermal behavior of the HBPE-St was analyzed by using thermogravimetric analysis (TGA and differential scanning calorimetry (DSC. The coatings of HBPE-St were prepared on mild steel strips. The anticorrosive behavior of HBPE-St resin-based coatings in acid, saline, and tap water was evaluated, and the molecular weight of HBPE-St was determined by gel permeation chromatography (GPC. The antibacterial activities of the HBPE-St copolymers were tested in vitro against bacteria and fungi by disc diffusion method. The HBPE-St copolymers exhibited good antibacterial activities and can be used as antimicrobial and corrosion-resistant coating materials.

  3. The effectiveness of styrene-maleic acid (SMA) copolymers for solubilisation of integral membrane proteins from SMA-accessible and SMA-resistant membranes

    NARCIS (Netherlands)

    Swainsbury, David J. K.; Scheidelaar, Stefan; Foster, Nicholas; van Grondelle, Rienk; Killian, J. Antoinette; Jones, Michael R.


    Solubilisation of biological lipid bilayer membranes for analysis of their protein complement has traditionally been carried out using detergents, but there is increasing interest in the use of amphiphilic copolymers such as styrene maleic acid (SMA) for the solubilisation, purification and

  4. Anodic Stripping Voltammetry for the Determination of Trace Cr(VI) with Graphite/Styrene-Acrylonitrile Copolymer Composite Electrodes. (United States)

    Sari, Trisna K; Jin, Jiye; Zein, Rahmiana; Munaf, Edison


    A square-wave anodic stripping voltammetry (SWASV) for the determination of trace amounts of hexavalent chromium Cr(VI) at a graphite/styrene-acrylonitrile (Graphite-SAN) copolymer composite electrode is described. This method involves a preconcentration step whereby the trace Cr(VI) was cathodically reduced to Cr(III) on an electrode surface in an acetate buffer (pH 5), followed by an anodic stripping technique with a square-wave voltammetric mode. It has been shown that the analytical sensitivity is significantly improved at the Graphite-SAN copolymer composite electrode in comparison with the conventional glassy carbon electrode, due to the strong interaction between Cr(III) and the nitrile end group of the SAN copolymer. The SWASV response was characterized with respect to the pH, deposition potential, possible interferences, etc. Under the optimal conditions, the stripping peak height linearly increased with the concentration of Cr(VI) in a range from 0 to 150 ng mL(-1) with a correlation coefficient of 0.997, and a detection limit of 4.2 ng mL(-1) was achieved based on signal-to-noise ratio of about 3. The Graphite-SAN composite electrode exhibited some interesting advantages, such as high mechanical rigid, easy surface renewable, higher sensitivity and better peak resolution in comparison with the results at conventional glassy carbon electrodes. They have been applied to the determination of Cr(VI) in real water samples with satisfactory recoveries.

  5. [Determination of lead, cadmium, mercury, chromium and arsenic in acrylonitrile-butadiene-styrene copolymer using microwave digestion-ICP-MS]. (United States)

    Wang, Ying-Feng; Shi, Yan-Zhi; Zhang, Hua; Chen, Yu-Hong; Lau, John; Wilbur, Steven; Li, Ping


    A method was studied for the analysis of Cr, As, Cd, Hg and Pb in acrylonitrile-butadiene-styrene copolymer by using ICP-MS. The instrument parameters were optimized and the introduction system was developed systematically. The sample is decomposed by microwave digestion. The digestion condition was optimized concerning digestion system, proportion of acids and digestion procedure, which affords reference for the preparation of the same kinds of polymer samples. The detection limits of the method for all sample elements were 0.7-6.5 ng x g(-1), the recoveries were 89.8%-110.8%, and the RSDs were 2.8%-11.3%. The analytical method presented was characterized with good precision and accuracy, simplicity, rapidness, low limits of detection and no matrix matching requirements.

  6. Feasibility of Using Foamed Styrene Maleic Anhydride (SMA) Co-polymer in Wood Based Composites


    Mustafa Zor; Nurgul Tankut; Alper Kiziltas; Douglas Gardner; Hikmet Yazici


    Wood plastic composites (WPCs) have often been used in consumer applications, automotive industry and exterior construction. WPCs consist mostly of wood and thermoplastic polymer. WPCs can have superior outdoor durability and much lower maintenance costs than regular wood. WPCs can be used instead of wood. Styrene maleic anhydride (SMA) is used in plastic composites for the automotive industry and also in engineering applications. SMA wood composites, as one of the WPCs using wood fibers as r...

  7. Synthesis of New Blue Fluorescent Polymerizable 1,8-Naphthalimides and Their Copolymers with Styrene as Sensors for Fe(III Cations

    Directory of Open Access Journals (Sweden)

    Ivo Grabchev


    Full Text Available The synthesis, characterization, and functional properties of two new polymerizable 1,8-naphthalimides (MDs have been described. Their copolymers with styrene designed to act as a fluorescence PET chemosensor have been investigated. The study also reports the influence of different metal cations (Ag+, Mg2+, Cu2+, Sr2+, Co2+, Pb2+, and Fe3+ on the fluorescence intensity of both low and high molecular weight fluorophores.

  8. Preparation and bactericidal effect of composites based on crosslinked copolymers containing silver nanoparticles

    Directory of Open Access Journals (Sweden)

    Luiz C. de S. Maria


    Full Text Available Commercial copolymers based on styrene and divinylbenzene containing sulfonic acid groups were used as support for the incorporation of silver nanoparticles. These nanoparticles were obtained in situ by the reduction of Ag+ by using hydroxylamine in the presence of a protective agent. These materials were characterized with determination of the silver content and their morphological characteristics. The antibacterial activity of the final products against Escherichia coli was evaluated and the results show that the synthesized copolymers had antibacterial effect varying from 54 to 100%. The most efficient composite was made with small, well distributed particles.

  9. Determination of Human-Health Pharmaceuticals in Filtered Water by Chemically Modified Styrene-Divinylbenzene Resin-Based Solid-Phase Extraction and High-Performance Liquid Chromatography/Mass Spectrometry (United States)

    Furlong, Edward T.; Werner, Stephen L.; Anderson, Bruce D.; Cahill, Jeffery D.


    In 1999, the Methods Research and Development Program of the U.S. Geological Survey National Water Quality Laboratory began the process of developing a method designed to identify and quantify human-health pharmaceuticals in four filtered water-sample types: reagent water, ground water, surface water minimally affected by human contributions, and surface water that contains a substantial fraction of treated wastewater. Compounds derived from human pharmaceutical and personal-care product use, which enter the environment through wastewater discharge, are a newly emerging area of concern; this method was intended to fulfill the need for a highly sensitive and highly selective means to identify and quantify 14 commonly used human pharmaceuticals in filtered-water samples. The concentrations of 12 pharmaceuticals are reported without qualification; the concentrations of two pharmaceuticals are reported as estimates because long-term reagent-spike sample recoveries fall below acceptance criteria for reporting concentrations without qualification. The method uses a chemically modified styrene-divinylbenzene resin-based solid-phase extraction (SPE) cartridge for analyte isolation and concentration. For analyte detection and quantitation, an instrumental method was developed that used a high-performance liquid chromatography/mass spectrometry (HPLC/MS) system to separate the pharmaceuticals of interest from each other and coextracted material. Immediately following separation, the pharmaceuticals are ionized by electrospray ionization operated in the positive mode, and the positive ions produced are detected, identified, and quantified using a quadrupole mass spectrometer. In this method, 1-liter water samples are first filtered, either in the field or in the laboratory, using a 0.7-micrometer (um) nominal pore size glass-fiber filter to remove suspended solids. The filtered samples then are passed through cleaned and conditioned SPE cartridges at a rate of about 15

  10. [Electrokinetic chromatographic properties of amphiphilic copolymer poly (styrene-co-methacrylic acid) self-assembled micelle pseudostationary phase]. (United States)

    Ma, Xinyu; Ni, Xinjiong; Lu, Jie; Xing, Xiaoping; Cao, Yuhua; Cao, Guangqun


    The amphiphilic copolymer poly (styrene-co-methacrylic acid) (P (St-co-MAA)) with molar ratios of 6:4 and 7:3 self-assembled to form micelles. The polymeric micelles were used as pseudostationary phase (PSP) in micellar electrokinetic chromatography ( MEKC). Their physicochemical properties and MEKC performance were investigated as well in the present work. The critical micelle concentration ( CMC) , polarity, surface charge density and hydrodynamic diameter were used to characterize the solution physicochemical properties, while the methylene group selectivity was evaluated with n-alkylphenone homologous series. The time window and linear solvation energy relationship (LSER) analysis were used to characterize the MEKC retention behavior and the selectivity. All of these were compared with poly (methyl methacrylate-co-methacrylic acid) (P (MMA-co-MAA)) with the molar ratio of 7:3 and sodium dodecyl sulfate (SDS) micellar systems. The results showed that P ( St-co-MAA) system had the minimum CMC, the widest time window and the best methylene group selectivity. LSER analysis results showed that the hydrophobic effect was the most important interaction between solutes and PSPs, and the hydrogen-bonding acidity was the second significant factor on selectivity and MEKC retention behavior. P (St-co-MAA) system, especially with the molar ratio of 7 :3, had the highest effective parameter in LSER and showed a high separation selectivity of PSP.

  11. Protons conductive membranes from sulfonated styrenic copolymers; Membranas conductoras de protons a partir de copolimeros estirenicos sulfonados

    Energy Technology Data Exchange (ETDEWEB)

    Brum, F.J.B.; Silva, M.A.G.; Amico, S.C.; Malfatti, C.F.; Forte, M.M.C. [Universidade Federal do Rio Grande do Sul (EE/UFRGS), Porto Alegre, RS (Brazil). Escola de Engenharia], e-mail:; Vargas, J.V.C. [Universidade Federal do Parana (DEM/UFPR), Curitiba, PR (Brazil). Dept. de Engenharia Mecanica


    Fuel cells working with polymeric electrolyte known as Proton Exchange Membrane Fuel Cell (PEMFC) have become a promising source for energy generation since they can produce high density electric current in an effective way. In this work, a polymeric precursor based on sulfonated styrenic copolymer (RHS) was used with the aim of producing ion-exchange membranes thermally stable at 80 deg C and over. Films of RHS and poly(vinylalcohol) (PVA) mixtures with different polyelectrolyte content were prepared, using glutaraldehyde as a crosslinking agent and antimonic acid. The films or membranes were analyzed by infrared and electrochemical impedance spectroscopy, differential scanning calorimetry, thermogravimetry and water absorption content. The impedance studies showed that the ionic conductivity of the RHS/PVA membranes was highly dependent on the electrolyte polymer in a way that the higher the content, the higher the membrane ionic conductivity. The RHS66{sub G}1 showed ionic conductivity similar to the Nafion membrane analyzed at the same conditions. (author)

  12. Styrene-spaced copolymers including anthraquinone and β-O-4 lignin model units: synthesis, characterization and reactivity under alkaline pulping conditions. (United States)

    Megiatto, Jackson D; Cazeils, Emmanuel; Ham-Pichavant, Frédérique; Grelier, Stéphane; Gardrat, Christian; Castellan, Alain


    A series of random copoly(styrene)s has been synthesized via radical polymerization of functionalized anthraquinone (AQ) and β-O-4 lignin model monomers. The copolymers were designed to have a different number of styrene spacer groups between the AQ and β-O-4 lignin side chains aiming at investigating the distance effects on AQ/β-O-4 electron transfer mechanisms. A detailed molecular characterization, including techniques such as size exclusion chromatography, MALDI-TOF mass spectrometry, and (1)H, (13)C, (31)P NMR and UV-vis spectroscopies, afforded quantitative information about the composition of the copolymers as well as the average distribution of the AQ and β-O-4 groups in the macromolecular structures. TGA and DSC thermal analysis have indicated that the copolymers were thermally stable under regular pulping conditions, revealing the inertness of the styrene polymer backbone in the investigation of electron transfer mechanisms. Alkaline pulping experiments showed that close contact between the redox active side chains in the copolymers was fundamental for an efficient degradation of the β-O-4 lignin model units, highlighting the importance of electron transfer reactions in the lignin degradation mechanisms catalyzed by AQ. In the absence of glucose, AQ units oxidized phenolic β-O-4 lignin model parts, mainly by electron transfer leading to vanillin as major product. By contrast, in presence of glucose, anthrahydroquinone units (formed by reduction of AQ) reduced the quinone-methide units (issued by dehydration of phenolic β-O-4 lignin model part) mainly by electron transfer leading to guaiacol as major product. Both processes were distance dependent.

  13. The individual and cumulative effect of brominated flame retardant and polyvinylchloride (PVC) on thermal degradation of acrylonitrile-butadiene-styrene (ABS) copolymer. (United States)

    Brebu, Mihai; Bhaskar, Thallada; Murai, Kazuya; Muto, Akinori; Sakata, Yusaku; Uddin, Md Azhar


    Acrylonitrile-butadiene-styrene (ABS) copolymers without and with a polybrominated epoxy type flame retardant were thermally degraded at 450 degrees C alone (10 g) and mixed with polyvinylchloride (PVC) (8 g/2 g). Gaseous and liquid products of degradation were analysed by various gas chromatographic methods (GC with TCD, FID, AED, MSD) in order to determine the individual and cumulative effect of bromine and chlorine on the quality and quantity of degradation compounds. It was found that nitrogen, chlorine, bromine and oxygen are present as organic compounds in liquid products, their quantity depends on the pyrolysed polymer or polymer mixture. Bromophenol and dibromophenols were the main brominated compounds that come from the flame retardant. 1-Chloroethylbenzene was the main chlorine compound observed in liquid products. It was also determined that interactions appear at high temperatures during decomposition between the flame retardant, PVC and the ABS copolymer.

  14. The effectiveness of styrene-maleic acid (SMA) copolymers for solubilisation of integral membrane proteins from SMA-accessible and SMA-resistant membranes. (United States)

    Swainsbury, David J K; Scheidelaar, Stefan; Foster, Nicholas; van Grondelle, Rienk; Killian, J Antoinette; Jones, Michael R


    Solubilisation of biological lipid bilayer membranes for analysis of their protein complement has traditionally been carried out using detergents, but there is increasing interest in the use of amphiphilic copolymers such as styrene maleic acid (SMA) for the solubilisation, purification and characterisation of integral membrane proteins in the form of protein/lipid nanodiscs. Here we survey the effectiveness of various commercially-available formulations of the SMA copolymer in solubilising Rhodobacter sphaeroides reaction centres (RCs) from photosynthetic membranes. We find that formulations of SMA with a 2:1 or 3:1 ratio of styrene to maleic acid are almost as effective as detergent in solubilising RCs, with the best solubilisation by short chain variants (membranes was uniformly low, but could be increased through a variety of treatments to increase the lipid:protein ratio. However, proteins isolated from such membranes comprised clusters of complexes in small membrane patches rather than individual proteins. We conclude that short-chain 2:1 and 3:1 formulations of SMA are the most effective in solubilising integral membrane proteins, but that solubilisation efficiencies are strongly influenced by the size of the target protein and the density of packing of proteins in the membrane. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

  15. 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

    Energy Technology Data Exchange (ETDEWEB)

    Lucena, M.C.C.; Soares, S.A. [Ceara Univ., Fortaleza, CE (Brazil). Dept. de Quimica Organica e Inorganica]. E-mail:;; Soares, J.B. [Ceara Univ., Fortaleza, CE (Brazil). Dept. de Engenharia de Transportes]. E-mail:


    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)

  16. Preparação e caracterização de microesferas poliméricas magnéticas à base de estireno, divinilbenzeno e acetato de vinila Preparation and characterization of magnetic polymeric microspheres based on styrene, divinylbenzene and vinyl acetate

    Directory of Open Access Journals (Sweden)

    Jacira A. Castanharo


    Full Text Available Microesferas poliméricas magnéticas à base de estireno (STY, divinilbenzeno (DVB, acetato de vinila (VAc e ferro foram preparadas via polimerização em suspensão e semi-suspensão. Foram estudadas as influências da concentração de VAc adicionado na polimerização e da presença de ferro sobre as características das partículas poliméricas. Estas foram caracterizadas por espectroscopia vibracional na região do infravermelho por transformada de Fourier (FT-IR, análise termogravimétrica (TGA/DTGA, microscopia óptica por reflexão (MO, microscopia eletrônica de varredura (SEM e magnetometria de amostra vibrante (VSM. Foram obtidas com sucesso microesferas poliméricas com propriedades magnéticas à base de estireno, divinilbenzeno e acetato de vinila. Estes materiais apresentaram bom controle morfológico esférico e partículas de ferro aglomeradas por toda a superfície da microesfera. O maior rendimento de microesferas magnéticas foi encontrado na faixa de 288 μm. Apresentaram também boas propriedades magnéticas (22,62 a 73,75 emu.g-1 com comportamento próximo de materiais superparamagnéticos e boa estabilidade térmica (444 °C.Magnetic polymeric microspheres based on styrene (STY, divinylbenzene (DVB, vinyl acetate (VAc and iron were prepared through suspension and semi-suspension polymerization. An investigation was made of the influence from the concentration of VAc added to the polymerization and the presence of iron on the properties of the polymeric particles. These particles were characterized by Fourier transform infrared spectroscopy (FTIR, thermogravimetric analysis (TGA/DTGA, reflection optical microscopy (OM, scanning electron microscopy (SEM and vibrating sample magnetometry (VSM. Polymeric microspheres with magnetic properties based on styrene, divinylbenzene and vinyl acetate were obtained. These materials showed good control of the spheres morphology and aggregated iron particles throughout the microsphere

  17. DMFC Performance of Polymer Electrolyte Membranes Prepared from a Graft-Copolymer Consisting of a Polysulfone Main Chain and Styrene Sulfonic Acid Side Chains

    Directory of Open Access Journals (Sweden)

    Nobutaka Endo


    Full Text Available Polymer electrolyte membranes (PEMs for direct methanol fuel cell (DMFC applications were prepared from a graft-copolymer (PSF-g-PSSA consisting of a polysulfone (PSF main chain and poly(styrene sulfonic acid (PSSA side chains with various average distances between side chains (Lav and side chain lengths (Lsc. The polymers were synthesized by grafting ethyl p-styrenesulfonate (EtSS on macro-initiators of chloromethylated polysulfone with different contents of chloromethyl (CM groups, and by changing EtSS content in the copolymers by using atom transfer radical polymerization (ATRP. The DMFC performance tests using membrane electrode assemblis (MEAs with the three types of the PEMs revealed that: a PSF-g-PSSA PEM (SF-6 prepared from a graft copolymer with short average distances between side chains (Lav and medium Lsc had higher DMFC performance than PEMs with long Lav and long Lsc or with short Lav and short Lsc. SF-6 had about two times higher PDmax (68.4 mW/cm2 than Nafion® 112 at 30 wt % of methanol concentration. Furthermore, it had 58.2 mW/cm2 of PDmax at 50 wt % of methanol concentration because of it has the highest proton selectivity during DMFC operation of all the PSF-g-PSSA PEMs and Nafion® 112.

  18. Synthesis and characterization of sulfonated polymers for ionomeric membranes based on styrene copolymers; Sintese e caracterizacao de precursores sulfonados para membranas polimericas a base de copolimeros estirenicos

    Energy Technology Data Exchange (ETDEWEB)

    Becker, C.M.; Forte, M.M.C.; Amico, S.C. [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Escola de Engenharia. Lab. de Materiais Polimericos (LAPOL)], e-mail:, e-mail:, e-mail:; Vargas, J.V.C. [Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil). Dept. de Engenharia Mecanica], e-mail:


    Polymer electrolyte membrane fuel cell (PEMFC) have emerged strongly as a viable alternative for power source owing to their high energy efficiency and environmental friendliness. Currently, Nafion is the most frequently used membrane even though it has a high cost. The objective of this work is to synthesize sulfonated polymers, based on styrene copolymers, with different sulfonation degrees as an alternative material for fuel cell membranes. Acetyl sulfate was used to carry out the sulfonation and the resulting polymers were characterized by Fourier Transform Infra-red (FTIR), thermogravimetric analysis (TGA) and degree of substitution or sulfonation (DS). The polyelectrolytes were evaluated regarding their ion exchange capacity (IEC) and conductivity. The results demonstrated that increasing the sulfonic acid content of the polymer results in higher IEC, conductivity and water uptake. (author)

  19. Nanocomposites of PA6/ABS blends compatibilized with styrene-maleic anhydride copolymer;Nanocompositos de blendas de PA6/ABS compatibilizadas com copolimero estireno-anidrido maleico

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Amanda D. de, E-mail: [Universidade Federal de Sao Carlos (PPG-CEM/UFSCar), SP (Brazil). Programa de Pos-Graduacao em Ciencia e Engenharia de Materiais; Araujo, Edcleide M. [Universidade Federal de Campina Grande (UFCG), PB (Brazil); Pessan, Luiz A. [Universidade Federal de Sao Carlos (DEMa/UFSCar), SP (Brazil). Dept. de Engenharia de Materiais


    To achieve a balance between stiffness and toughness, ternary nanocomposites based on blends of polyamide 6 (PA6) and acrylonitrile-butadiene-styrene (ABS) were prepared by the melt intercalation using the organoclay Cloisite{sup R} 30B (OMMT) and the styrene-maleic anhydride copolymer (SMA) as compatibilizer. Four blending sequences were used to prepare studied systems and their mechanical properties studied through the Young's modulus and notched Izod impact. It was observed that the materials prepared by all blending sequences studied showed an increase in the Young's modulus compared to the neat PA6. However, a decrease in the toughness was observed for the systems with the addition of the organoclay. The DRX results showed an intercalated structure for the some systems that used ABS in their compositions. HDT measurements of the nanocomposites showed an increase in this property compared to the neat PA6. The use of nanoclay lead to a reinforcement of the polymeric matrix. (author)

  20. Spatial distribution of stabilizer-derived nitroxide radicals during thermal degradation of poly(acrylonitrile-butadiene-styrene) copolymers: a unified picture from pulsed ELDOR and ESR imaging. (United States)

    Jeschke, Gunnar; Schlick, Shulamith


    Double Electron-Electron Resonance (DEER) provides information on the spatial distribution of radicals on the length scale of a few nanometres, while Electron Spin Resonance Imaging (ESRI) provides information on a length scale of millimetres with a resolution of about 100 micrometres. Despite the gap between these length scales, results from the two techniques are found to complement and support each other in the characterization of the identity and distribution of nitroxide radicals derived from the Hindered Amine Stabilizer (HAS) Tinuvin 770 in poly(acrylonitrile-butadiene-styrene) (ABS) copolymers. DEER measurements demonstrate that there is no significant formation of biradicals from the bifunctional HAS, and provide the distributions of local radical concentrations. These distributions are poorly resolved for model-free analysis of the DEER data by the Tikhonov regularization; the resolution was significantly improved by utilizing information obtained by ESRI. DEER data can be fitted with only one adjustable parameter, namely the average radical concentration, if 1D and 2D spectral--spatial ESRI results on both the spatial distribution of nitroxides and their distribution between the acrylonitrile--styrene-rich (SAN) and butadiene-rich (B) microphases are considered.

  1. Synthesis of triblock and random copolymers of 4- acetoxystyrene and styrene by living atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Gao, Bo; Chen, Xianyi; Ivan, Bela


    Triblock copolymers containing polystyrene (PSt) and poly(4-acetoxystyrene) (PAcOSt) segments have been prepared by atom transfer radical polymerization (ATRP). In the first step one of the two monomers was polymerized in bulk using the initiating system alpha,alpha'-dibromo-p-xylene/CuBr/2...... weights and narrow molecular weight distributions. Polymerization of a mixture of equal molar amounts of the two monomers yielded a random copolymer with narrow molecular weight distribution....

  2. Poly(styrene-b-2-(N,N-dimethylamino)ethyl methacrylate) diblock copolymers: Micellization and application in the synthesis of photoluminescent CdS nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Basu, Saswati; Mondal, Samiran [Department of Chemistry, Visva-Bharati University, Santiniketan 731 235 (India); Chatterjee, Uma, E-mail: [Polymer Science Unit, Indian Association for the Cultivation of Sciences, Kolkata 700 032 (India); Mandal, Debabrata, E-mail: [Department of Chemistry, Visva-Bharati University, Santiniketan 731 235 (India)


    Fluorescence studies on amphiphilic diblock copolymers of styrene and 2-(N,N-dimethylamino)ethyl methacrylate using 1,8-anilinonaphthalenesulfonate (ANS) as fluorescent probe revealed the formation of stable micelles at extremely low polymer concentrations of {approx}0.05%. The micellar microenvironment was characterized by an average polarity of E{sub T}(30) = 44-48 kcal mol{sup -1}, similar to the moderately polar solvents, and extremely high microviscosity. Increase in hydrophilic: hydrophobic ratio of the copolymers resulted in an increase in the average polarity and decrease in microviscosity. The micelles proved to be excellent hosts for the synthesis and stabilization of photoluminescent CdS nanoparticles with a high degree of quantum confinement and broad photoluminescence, dominated by trap-state emission. Moreover, the size and size-related steady-state optical properties of CdS nanoparticles were significantly dependent on the microenvironment of the host micelle. In contrast, the photoluminescence dynamics of the nanoparticles, involving time-scales from 100 ps to 100 ns, are similar in all cases. Interestingly, the nanoparticles exhibit a large time-dependent Stokes shift, 75% of which is complete within the first {approx}100 ps after the excitation. The extremely rapid Stokes shift is attributed to the decay of the initially formed band-edge excitons in a time-scale too fast to be affected by the microenvironment surrounding the particle.

  3. Surfactant-Free RAFT Emulsion Polymerization of Styrene Using Thermoresponsive macroRAFT Agents: Towards Smart Well-Defined Block Copolymers with High Molecular Weights

    Directory of Open Access Journals (Sweden)

    Steffen Eggers


    Full Text Available The combination of reversible addition–fragmentation chain transfer (RAFT and emulsion polymerization has recently attracted much attention as a synthetic tool for high-molecular-weight block copolymers and their micellar nano-objects. Up to recently, though, the use of thermoresponsive polymers as both macroRAFT agents and latex stabilizers was impossible in aqueous media due to their hydrophobicity at the usually high polymerization temperatures. In this work, we present a straightforward surfactant-free RAFT emulsion polymerization to obtain thermoresponsive styrenic block copolymers with molecular weights of around 100 kDa and their well-defined latexes. The stability of the aqueous latexes is achieved by adding 20 vol % of the cosolvent 1,4-dioxane (DOX, increasing the phase transition temperature (PTT of the used thermoresponsive poly(N-acryloylpyrrolidine (PAPy macroRAFT agents above the polymerization temperature. Furthermore, this cosolvent approach is combined with the use of poly(N,N-dimethylacrylamide-block-poly(N-acryloylpiperidine-co-N-acryloylpyrrolidine (PDMA-b-P(APi-co-APy as the macroRAFT agent owning a short stabilizing PDMA end block and a widely adjustable PTT of the P(APi-co-APy block in between 4 and 47 °C. The temperature-induced collapse of the latter under emulsion polymerization conditions leads to the formation of RAFT nanoreactors, which allows for a very fast chain growth of the polystyrene (PS block. In dynamic light scattering (DLS, as well as cryo-transmission electron microscopy (cryoTEM, moreover, all created latexes indeed reveal a high (temperature stability and a reversible collapse of the thermoresponsive coronal block upon heating. Hence, this paper pioneers a versatile way towards amphiphilic thermoresponsive high-molecular-weight block copolymers and their nano-objects with tailored corona switchability.

  4. Effect of concentration and humidity on the formation of porous polymer films using Styrene Butadiene Co-Polymer (United States)

    Jose, Renu; Sujith, A.; Predeep, P.


    Honeycomb structured porous materials from complex polymers are formed using water droplet templating method. In the present work microporous films were prepared from styrene butadiene rubber (SBR) using emulsion technique. The pore sizes can be easily tuned by changing the concentration and the humidity condition. The pore size is characterized by optical microscope and Scanning electron microscope (SEM). These films can be used for various applications in optoelectronics, photonics, catalysis, tissue engineering, bioanalytical purposes etc.

  5. Investigations on the Phase Diagram and Interaction Parameter of Poly(styrene-b-1,3-cyclohexadiene) Copolymers

    KAUST Repository

    Misichronis, Konstantinos


    A series of linear diblock copolymers containing polystyrene (PS) and poly(1,3-cyclohexadiene) (PCHD) with high 1,4-microstructure (>87%) was synthesized by anionic polymerization and high vacuum techniques. Microphase separation in the bulk was examined by transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) and compared to computational analysis of the predicted morphological phase diagram for this system. Because of the high conformational asymmetry between PS and PCHD, these materials self-assemble into typical morphologies expected for linear diblock copolymer systems and atypical structures. Rheological measurements were conducted and revealed order–disorder transition temperatures (TODT), for the first time for PS-b-PCHD copolymers, resulting in a working expression for the effective interaction parameter χeff = 32/T – 0.016. Furthermore, we performed computational studies that coincide with the experimental results. These copolymers exhibit well-ordered structures even at high temperatures (∼260 °C) therefore providing a better insight concerning their microphase separation at the nanoscale which is important for their potential use in nanotechnology and/or nanolithography applications.

  6. Magnetic and dielectric properties of sulfonated (S) poly[(styrene)-(ethylene-co-butylene)]-styrene (SEBS) block copolymer/magnetic metal oxide nanocomposites synthesized via an in-situ precipitation method (United States)

    Peddini, Sateesh Kumar

    Block copolymer/magnetic metal oxide nanocomposites were synthesized by growing metal oxide nanoparticles (cobalt ferrite, CoFe2O 4 and iron oxide, alpha-Fe2O3) in sulfonated (s) poly (styrene) (PS) block domains of sulfonated poly [(styrene)-(ethylene-co-butylene)-(styrene)] (SEBS) BCP preformed films via an in-situ precipitation method by dissolving the salts of respective metal chloride (s) in a suitable solvent that selectively swells the sPS regions. Inorganic uptake was determined using thermogravimetric analysis (TGA), and it was observed that none of the samples incorporated more than 5 wt % of the inorganic component. Dynamical mechanical analysis was used to observe the changes in the glass transition temperatures (T g) in both blocks of the BCP by plotting tan delta vs. temperature responses in tensile mode on all samples. The results showed that the T g of the sPS block domains increased with sulfonation level and further increased with the incorporation of both nanoparticles in the same blocks, indicating that growth of nanoparticles takes place only in sPS blocks. The crystalline structure of the nanoparticles was observed using wide angle X-ray diffractometry (WAXD), and it was determined that cobalt iron oxide nanoparticles in 20 mole % sulfonated SEBS exhibited an inverse spinel structure confirming the structure to be CoFe2O4. And with iron oxide nanoparticles in 10 mole % sulfonated SEBS exhibiting a hematite (alpha-Fe2O 3) phase. Transmission electron microscopy (TEM) was used to investigate the particle size and distribution of nanoparticles in sBCP matrices at all sulfonation levels. Select area electron diffraction in TEM was used to determine crystalline structures of individual nanoparticles to compare with the structure observed from WAXD. The changes in thickness of interfaces between the individual PS and EB block domains with increase in sulfonation of PS blocks were investigated semi-quantitatively using tapping mode atomic force

  7. Synthesis and evaluation of copolymer based on cardanol and styrene on the stability of asphaltenes; Sintese e avaliacao de copolimero a base de cardanol e estireno sobre a estabilidade dos asfaltenos

    Energy Technology Data Exchange (ETDEWEB)

    Loureiro, Tatiana S.; Spinelli, Luciana S., E-mail: [Universidade Federal do Rio de Janeiro (UFRJ), Rio de Janeiro, RJ (Brazil). Instituto de Macromoleculas


    The destabilization of asphaltenes in crude oil mainly happens due to variations in pressure, temperature and oil composition, causing significant losses. Polymers containing specific groups can be used as asphaltenes stabilizers and thus, avoid your precipitation, or as asphaltenes flocculants to assist the removal of suspended particles in a particular oil. The monitoring of asphaltenes precipitation is usually evaluated by tests with variation in stability of asphaltenes in function of adding a flocculant solvent. In this work, it was evaluated the influence of a synthesized copolymer based on cardanol and styrene on the stability of asphaltenes. The stability of asphaltenes was monitored by precipitation tests induced by a flocculant agent (n-heptane), using an ultraviolet-visible (UV-Vis) spectrometer. The structural characterization of copolymer was performed by FTIR and {sup 1}H NMR. The results showed that copolymer can act as asphaltene flocculant. (author)

  8. Influence of the composition of hydroxypropyl cellulose/maleic acid-alt-styrene copolymer blends on their properties as matrix for drug release

    Directory of Open Access Journals (Sweden)


    Full Text Available Poly(carboxylic acid-polysaccharide compositions have been found suitable for obtaining drug formulations with controlled release, most formulations being therapeutically efficacious, stable, and non-irritant. The influence of the characteristics of the aqueous solutions from which the polymer matrix is prepared (i.e. the total concentration of polymer in solutions and the mixing ratio between the partners, hydroxypropyl cellulose, HPC and maleic acid-alternating-styrene copolymer, MAc-alt-S on the kinetics of some drugs release in acidic environment (pH = 2 has been followed by ‘in vitro’ dissolution tests. It has been established that the kinetics of procaine hydrochloride release from HPC/MAc-alt-S matrix depends on its composition; the diffusion exponent, n is close to 0.5 for matrices where one of the components is in large excess and n~0.02 for middle composition range. The lower value of diffusion exponent for middle composition range could be caused by the so called ‘burst effect’, therefore the kinetic evaluation is difficult.

  9. Effects of content and surface hydrophobic modification of BaTiO3 on the cooling properties of ASA (acrylonitrile-styrene-acrylate copolymer) (United States)

    Xiang, Bo; Zhang, Jun


    For the field of cool material, barium titanate (BaTiO3, BT) is still a new member that needs to be further studied. Herein, the effects of both content and surface hydrophobic modification of BT on the cooling properties of acrylonitrile-styrene-acrylate copolymer (ASA) were detailedly investigated, aiming to fabricate composited cool material. Butyl acrylate (BA) was employed to convert the surface of BT from hydrophilic to hydrophobic. The addition of unmodified BT could significantly improve the solar reflectance of ASA, especially when the addition amount is 3 vol%, the near infrared (NIR) reflectance increased from 22.02 to 72.60%. However, serious agglomeration occurred when the addition amount increased to 5 vol% and therefore led to a relatively smaller increase in solar reflectance and an obvious decline in impact strength. After surface hydrophobic modification, the modified BT (M-BT) presented better dispersibility in ASA matrix, which contributed to the improvement of both solar reflectance and impact strength. In addition, the temperature test provided a more sufficient and intuitive way to evaluate the cooling effect of the composited cool materials, and a significant decrease (over 10 °C) could be achieved in the temperature test when M-BT particles were introduced.

  10. One-step preparation of superhydrophobic acrylonitrile-butadiene-styrene copolymer coating for ultrafast separation of water-in-oil emulsions. (United States)

    Deng, Wanshun; Long, Mengying; Zhou, Qiannan; Wen, Ni; Deng, Wenli


    Superhydrophobic membranes with opposite wettability toward water and oil are able to separate water-in-oil emulsions. By constructing porous and hierarchal-structured superhydrophobic coating on filter paper, we hope a quick separation process could be achieved due to the acceleration of both demulsification and penetration process. Here, superhydrophobic coatings were prepared by simply spraying environmental and cost-effective acrylonitrile-butadiene-styrene copolymer (ABS) colloid in dichloromethane onto filter paper. The morphologies and wettability of the obtained coatings were carefully studied. Moreover, the separation performances in dealing with various surfactant-stabilized water-in-oil emulsions (SSWOE) were also investigated to verify our hypothesis. The morphologies of the ABS coatings varied with its weight concentration in dichloromethane and they changed from porous and plain surface into porous and hierarchal-structured surface. Besides, the hydrophobicity of the above coatings varied form hydrophobic to superhydrophobic. Moreover, the resulted superhydrophobic membranes show great separation capability in separating various span 80-stabilized water-in-oil emulsions with oil filtrate purities larger than 99.90% and huge penetration fluxes whose maximum is over 13,000L/(m(2)h). Thus, we envision that such membrane can be a practical candidate in dealing with water-in-oil emulsions to obtain pure oils. Copyright © 2017. Published by Elsevier Inc.

  11. Analysis of acrylonitrile, 1,3-butadiene, and related compounds in acrylonitrile-butadiene-styrene copolymers for kitchen utensils and children's toys by headspace gas chromatography/mass spectrometry. (United States)

    Ohno, Hiroyuki; Kawamura, Yoko


    A headspace gas chromatography/mass spectrometry method was developed for the simultaneous determination of the residual levels of acrylonitrile (AN), 1,3-butadiene (1,3-BD), and their related compounds containing propionitrile (PN) and 4-vinyl-1-cyclohexene (4-VC) in acrylonitrile-butadiene-styrene (ABS) copolymers for kitchen utensils and children's toys. A sample was cut into small pieces, then N,N-dimethylacetamide and an internal standard were added in a sealed headspace vial. The vial was incubated for 1 h at 90 degrees C and the headspace gas was analyzed by gas chromatography/mass spectrometry. The recovery rates of the analytes were 93.3-101.8% and the coefficients of variation were 0.3-6.5%. In ABS copolymers, the levels were 0.3-50.4 microg/g for AN, ND-4.5 microg/g for PN, 0.06-1.58 microg/g for 1,3-BD, and 1.1-295 microg/g for 4-VC. The highest level was found for 4-VC, which is a dimer of 1,3-BD, and the next highest was for AN, which is one of the monomers of the ABS copolymer. Furthermore, the method was also applied to acrylonitrile-styrene (AS) copolymers and polystyrenes (PS) for kitchen utensils, and nitrile-butadiene rubber (NBR) gloves. In AS copolymers, AN and PN were detected at 16.8-54.5 and 0.8-6.9 microg/g, respectively. On the other hand, the levels in PS and NBR samples were all low.


    Directory of Open Access Journals (Sweden)

    V. F. Lebedev


    Full Text Available Summary. In the polymerization of butadiene with styrene heat removal is the main factor limiting the output of the cascade reactor. Thus the residence time of the monomers in the reactor exceeds significantly the time necessary to complete the process on the basis of kinetic regularities. To increase the output of the mixture the distribution in the reactor cascade is made. It is necessary to distribute the flow of mixture through the reactor of the cascade to have the resulting polymer of the same viscosity at the outlet of each reactor. The algorithm of distribution of the mixture in the reactor cascade with regard to the synthesis parameters (temperature in the reactor and the feed rate of the mixture, the ratio of the modifier and the initiator in the complex, the number of reactors and a determined dynamic viscosity is developed. In accordance with the developed algorithm the calculation of the velocity of the mixture feed in each reactor of the cascade is made. It is shown that the flow of mixture in each polymerization unit depends on the overall output of the installation and the number of reactors in the cascade. The algorithm for the distribution of the initial mixture in the reactor cascade is developed to provide maximum output of the installation and set the quality of the obtained polymer. To determine the degree of conversion of monomers and temperature conditions of the process of polymerization under the calculated speed of the feed mixture in the first polymerization cascade the basic technological parameters of the polymerization process in real time mode, the calculation using a mathematical model is made. The analysis of the simulation results shows that during the first hour, the concentration of monomers does not exceed of 0.085 mol/l, which corresponds to the degree of conversion of monomer to 99 %, while the temperature in the reactor corresponds to the optimal mode - from 65 to 85 0C.

  13. Synthesis of Novel μ-Star Copolymers with Poly(N-Octyl Benzamide) and Poly(ε-Caprolactone) Miktoarms through Chain-Growth Condensation Polymerization, Styrenics-Assisted Atom Transfer Radical Coupling, and Ring-Opening Polymerization. (United States)

    Huang, Chih-Feng; Aimi, Junko; Lai, Kuan-Yu


    Star copolymers are known to phase separate on the nanoscale, providing useful self-assembled morphologies. In this study, the authors investigate synthesis and assembly behavior of miktoarm star (μ-star) copolymers. The authors employ a new strategy for the synthesis of unprecedented μ-star copolymers presenting poly(N-octyl benzamide) (PBA) and poly(ε-caprolactone) (PCL) arms: a combination of chain-growth condensation polymerization, styrenics-assisted atom transfer radical coupling, and ring-opening polymerization. Gel permeation chromatography, mass-analyzed laser desorption/ionization mass spectrometry, and (1) H NMR spectroscopy reveal the successful synthesis of a well-defined (PBA11 )2 -(PCL15 )4 μ-star copolymer (Mn,NMR ≈ 12 620; Đ = 1.22). Preliminary examination of the PBA2 PCL4 μ-star copolymer reveals assembled nanofibers having a uniform diameter of ≈20 nm. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Preparation, characterization and thermal properties of styrene maleic anhydride copolymer (SMA)/fatty acid composites as form stable phase change materials

    Energy Technology Data Exchange (ETDEWEB)

    Sari, Ahmet; Alkan, Cemil; Karaipekli, Ali; Oenal, Adem [Department of Chemistry, Gaziosmanpasa University, 60240, Tokat (Turkey)


    Fatty acids such as stearic acid (SA), palmitic acid (PA), myristic acid (MA) and lauric acid (LA) are promising phase change materials (PCMs) for latent heat thermal energy storage (LHTES) applications, but high cost is the major drawback of them, limiting their utility area in thermal energy storage. The use of fatty acids as form stable PCMs will increase their feasibilities in practical applications due to the reduced cost of the LHTES system. In this regard, a series of styrene maleic anhydride copolymer (SMA)/fatty acid composites, SMA/SA, SMA/PA, SMA/MA, and SMA/LA, were prepared as form stable PCMs by encapsulation of fatty acids into the SMA, which acts as a supporting material. The encapsulation ratio of fatty acids was as much as 85 wt.% and no leakage of fatty acid was observed even when the temperature of the form stable PCM was over the melting point of the fatty acid in the composite. The prepared form stable composite PCMs were characterized using optic microscopy (OM), viscosimetry and Fourier transform infrared (FT-IR) spectroscopy methods, and the results showed that the SMA was physically and chemically compatible with the fatty acids. In addition, the thermal characteristics such as melting and freezing temperatures and latent heats of the form stable composite PCMs were measured by using the differential scanning calorimetry (DSC) technique, which indicated they had good thermal properties. On the basis of all the results, it was concluded that form stable SMA/fatty acid composite PCMs had important potential for practical LHTES applications such as under floor space heating of buildings and passive solar space heating of buildings by using wallboard, plasterboard or floors impregnated with a form stable PCM due to their satisfying thermal properties, easy preparation in desired dimensions, direct usability without needing additional encapsulation thereby eliminating the thermal resistance caused by the shell and, thus, reducing the cost of

  15. Modified hydrogenated PBLH copolymer synthesis with styrene for proton exchange membranes fuel cell application; Derivados de PBLH hidrogenado na sintese de copolimeros com estireno, para a producao de membranas cationicas para celulas a combustivel

    Energy Technology Data Exchange (ETDEWEB)

    Ferraz, Fernando A.; Oliveira, Angelo R.S.; Rodrigues, Maraiza F.; Groetzner, Mariana B.; Cesar-Oliveira, Maria Aparecida F. [Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil). Dept. de Quimica. Lab. de Polimeros Sinteticos (LABPOL)]. E-mails:;;;;; Cantao, Mauricio P. [Instituto de Tecnologia para o Desenvolvimento (LACTEC), Curitiba, PR (Brazil)]. E-mail:


    Polymers used as electrolyte in fuel cells are expected to have functional groups in their structure which are responsible for proton conductivity. Since the use of hydroxylated liquid polybutadiene (PBLH) has not been mentioned in the literature as an ion exchange membrane for fuel cell application (PEMFC), and its structure can be modified for a later sulfonation, it has been studied. In this work, PBLH was modified through a hydrogenation reaction. Furthermore, hydrogenated polymeric esters were obtained by esterification and transesterification reactions (PBLH- estearate and PBLH- methacrylate). Reacting the PBLH methacrylate with styrene, it was generated a copolymer with appropriated structure for sulfonation, justifying researches for fuel cell. (author)

  16. Synthesis of crosslinked poly(styrene-co-divinylbenzene-co ...

    Indian Academy of Sciences (India)


    molecular weight distribution have unique properties which make them interesting and find applications in numerous ... late (SPM, Poly Sciences), sodium dodecyl sulfate (SDS,. Merck), sodium bicarbonate (Sisco) and ... of double distilled water and 0⋅1 g of sodium bicarbonate was added. A stirring rate of 360 rpm and a ...

  17. Síntese e caracterização de copolímeros à base de metacrilato de metila e divinilbenzeno com propriedades magnéticas Synthesis and characterization of copolymers based on methyl methacrylate and divinylbenzene with magnetic properties

    Directory of Open Access Journals (Sweden)

    Cristiane N. Costa


    Full Text Available Neste trabalho, foram sintetizados materiais binários baseados em copolímeros de metacrilato de metila reticulados com divinilbenzeno contendo partículas de ferro com propriedades magnéticas pela técnica de polimerização em suspensão. Foram estudados os efeitos da concentração de ferro adicionado na polimerização, da razão molar MMA/DVB, do tipo de agente de suspensão e da velocidade de agitação na formação do copolímero. Os copolímeros foram caracterizados quanto à morfologia, à estabilidade térmica, ao teor de ferro incorporado, à distribuição de tamanho de partículas, às propriedades magnéticas, à área superficial, ao volume e ao tamanho de poros. Foram obtidas microesferas poliméricas com propriedades magnéticas que apresentaram bom controle morfológico esférico e partículas de ferro aglomeradas por toda a superfície da microesfera. As análises de propriedades magnéticas mostraram que os materiais obtidos não apresentaram ciclos de histerese, estando assim próximos de um material com propriedades superparamagnéticas, com magnetização de saturação entre 8,0 e 13,0 emu.g-1.In this work, copolymers based on methyl methacrylate and divinylbenzene containing iron with magnetic properties were produced using the suspension polymerization method. An investigation was performed of the effect from the concentration of iron added to the polymerization, the MMA/DVB molar ratio in the copolymer formation, type of suspension agent and stirring speed on the synthesis of the copolymers. The copolymers morphology, thermal stability, contents of embedded iron, particle size distribution, magnetic properties, surface area, volume and pore size were evaluated. Polymeric microspheres with magnetic properties were successfully obtained. These materials showed good control of the spherical shape and agglomeration of iron particles under the surface of the microsphere. The analysis of magnetic properties pointed to

  18. Methyl Methacrylate and Alpha-Methyl Styrene: New Strategy for Synthesis of Bloc Copolymers for Use in Potential Biomedical Applications Generated by an Ecologic Catalyst Called Maghnite (Algerian MMT

    Directory of Open Access Journals (Sweden)

    Moulkheir Ayat


    Full Text Available A new model for synthesis of the plastics, block copolymers were prepared from methyl methacrylate (MMA and alpha-methyl styrene (α-MS by cationic copolymerization in the presence of a new and efficient catalyst of “Maghnite-Na” at 0 °C in bulk. In this paper, the copolymerization of α-MS and MMA was induced in heterogeneous phase catalyzed by Maghnite-Na was investigated under suitable conditions. The “Maghnite-Na” is a montmorillonite sheet silicate clay, with exchanged sodium cations to produce Na-Montmorillonite (Na+-MMT obtained from Tlemcen, Algeria, was investigated to remove heavy metal ion from wastewater as an efficient catalyst for cationic polymerization of many vinylic and heterocyclic monomers. The synthesized copolymer were characterized by Nuclear Magnetic Resonance (NMR-1H, NMR-13C, FT-IR spectroscopy, Differential Scanning Calorimetry (DSC, and Gel Permeation Chromatography (GPC to elucidate structural characteristics and thermal properties of the resulting copolymers. The structure compositions of “MMT”, “H+-MMT” and “Na+-MMT” have been developed. The effect of the MMA/α-MS molar ratio on the rate of copolymerization, the amount of catalyst, temperature and time of copolymerization on yield of copolymers was studied. The yield of copolymerization depends on the amount of Na+-MMT used and the reaction time. The kinetic studies indicated that the polymerization rate is first order with respect to monomer concentration. A possible mechanism of this cationic polymerization is discussed based on the results of the 1H-NMR Spectroscopic analysis of these model reactions. A cationic mechanism for the reaction studies showed that monomer was inserted into the growing chains. Copyright © 2016 BCREC GROUP. All rights reserved Received: 2nd May 2015; Revised: 24th February 2016; Accepted: 15th March 2016 How to Cite: Ayat, M., Belbachir, M., Rahmouni, A. (2016. Methyl Methacrylate and Alpha-Methyl Styrene: New


    Block copolymers of polystyrene and poly(t-butyl acrylate) were prepared using atom transfer radical polymerization techniques. These polymers were synthesized with a CuBr/N,N,N,NThe effectiveness of styrene-maleic acid (SMA) copolymers for solubilisation of integral membrane proteins from SMA-accessible and SMA-resistant membranes.

    NARCIS (Netherlands)

    Swainsbury, David J K; Scheidelaar, S.|info:eu-repo/dai/nl/413333418; Foster, Nicolas; Van Grondelle, Rienk; Killian, J.A.|info:eu-repo/dai/nl/071792317; Jones, Michael R.


    Solubilisation of biological lipid bilayer membranes for analysis of their protein complement has traditionally been carried out using detergents, but there is increasing interest in the use of amphiphilic copolymers such asstyrene maleic acid (SMA) for the solubilisation, purification and

  1. Analysis of Mechanical and Thermogravimetric Properties of Composite Materials Based on PVA/MWCNT and Styrene-Acrylic Copolymer/MWCNT (United States)

    Volynets, N. I.; Poddubskaya, O. G.; Demidenko, M. I.; Lyubimov, A. G.; Kuzhir, P. P.; Suslyaev, V. I.; Pletnev, M. A.; Zicans, Janis


    Mechanical and thermogravimetric properties of polymer composite materials with various concentrations of multiwalled carbon nanotubes effectively shielding radiation in the radio frequency (20 Hz - 1 MHz) and microwave (26-36 GHz) frequency ranges are studied. As a matrix, widely available polymeric materials, such as polyvinyl acetate and styrene-acrylate, were used in the form of dispersions. From the analysis of the obtained experimental data, it was shown that the introduction of carbon nanotubes into the polymer matrix makes it possible to increase mechanical properties and thermal stability of composite materials.

  2. Complexation of AB+, AB+C, ACB+, and A(B+-stat-C) block copolymer micelles with poly(styrene sulfonate) as models for tunable gene delivery vectors (United States)

    Laaser, Jennifer; Jiang, Yaming; Lohmann, Elise; Reineke, Theresa; Lodge, Timothy

    We investigate the complexation of poly(styrene sulfonate) with micelles with mixed cationic/hydrophilic coronas as models for tunable gene delivery vectors. The micelles are self-assembled from AB+, AB+C, ACB+, and A(B+-stat-C) block polymer architectures, where the hydrophobic A blocks (poly(styrene)) form the micelle cores, and the cationic B blocks (poly(dimethylamino ethyl methacrylate)) and hydrophilic, nonionic C blocks (poly(poly(ethylene glycol) methyl ether methacrylate)) form the coronas. We find that hydrophilic units do not change the colloidal stability of the complexes, and complexes based on all four micelle architectures form broad, multimodal size distributions. While complexes based on the AB+, AB+C, and ACB+polymer architectures are kinetically trapped at low ionic strength, however, those based on the A(B+-stat-C) architecture rapidly rearrange into single-micelle complexes when the linear polyanion is in excess. This suggests that the randomly-placed hydrophilic units break up the ion pairing between the cationic and anionic chains and promote formation of over-charged complexes. Design of the micelle architecture may thus provide a powerful way control the structure and stability of micelle-polyelectrolyte complexes for gene delivery applications.

  3. 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

    Energy Technology Data Exchange (ETDEWEB)

    Nam, Sang Ho; Kim, Yu Na [Mokpo National University, Muan (Korea, Republic of)


    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

  4. Silicon-containing soybean-oil-based copolymers. Synthesis and properties. (United States)

    Sacristán, Marta; Ronda, Joan C; Galià, Marina; Cádiz, Virginia


    New silicon-containing soybean-oil-based copolymers were prepared from soybean oil, styrene, divinylbenzene, and p-trimethylsilylstyrene by cationic polymerization using boron trifluoride etherate as initiator. Soxhlet extraction and NMR spectroscopy indicate that the copolymers consist of a cross-linked network plasticized with varying amounts of oligomers and unreacted oil. This soluble fraction increases when the SiST content in the feed increases, according to a lower reactivity of this monomer. The thermal, dynamomechanical, and flame-retardant properties of these materials were examined. Thermosets with glass transition temperatures ranging from 50 to 62 degrees C, which are thermally stable below 350 degrees C, and with LOI values from 22.6 to 29.7 were obtained. Their properties suggest that these materials may prove to be useful alternatives for current non-renewable-based thermosets and that the flame-retardant properties of vegetable-oil-based thermosets can be improved by adding covalently bonded silicon to the polymer.

  5. Utility of chromatographic and spectroscopic techniques for a detailed characterization of poly(styrene-b-isoprene) miktoarm star copolymers with complex architecture

    KAUST Repository

    Šmigovec Ljubič, Tina


    We analyzed various miktoarm star copolymers of the PS(PI) x type (x = 2, 3, 5, 7), which consist of one long polystyrene (PS) arm (82 or 105 kDa) and various numbers of short polyisoprene (PI) arms (from 11.3 to 39.7 kDa), prepared by anionic polymerization and selective chlorosilane chemistry. The length of the PI arm in stars decreases with the number of arms, so that the chemical compositions of all PS(PI) x samples were comparable. Our aim was to determine the purity of samples and to identify exactly the constituents of individual samples. For this purpose we used a variety of separation techniques (size-exclusion chromatography (SEC), reversed-phase liquid-adsorption chromatography (RP-LAC), and two-dimensional liquid chromatography (2D-LC)) and characterization techniques (UV-MALS-RI multidetection SEC system, NMR, and MALDI-TOF MS). The best separation and identification of the samples\\' constituents were achieved by RP-LAC, which separates macromolecules according to their chemical composition, and a subsequent analysis of the off-line collected fractions from the RP-C18 column by SEC/UV-MALS-RI multidetection system. The results showed that all PS(PI) x samples contained the homo-PS and homo-PI in minor amounts and the high-molar-mass (PS) y(PI) z (y > 1) species, the content of which is higher in the samples PS(PI) 5 and PS(PI) 7 than in the samples PS(PI) 2 and PS(PI) 3. The major constituent of the PS(PI) 2 sample was the one with the predicted structure. On the other hand, the major components of the PS(PI) x (x = 3, 5, and 7) samples were the stars consisting of a smaller number of PI arms than predicted from the functionalities of chlorosilane coupling agents. These results are in agreement with the average chemical composition of samples determined by proton NMR spectroscopy and characterization of the constituents by MALDI-TOF MS. © 2012 American Chemical Society.

  6. Polimerizacija, toplinska stabilnost i mehanizam razgradnje kopolimera (metakril-dicikloheksiluree i (metakril-diizopropiluree sa stirenom i α-metilstirenom (Polymerization, Thermal Stability and Degradation Mechanism of (Methacryl-Dicyclohexylurea and (Methacryl-Diisopropylurea Copolymers with Styrene and α-Methylstyrene

    Directory of Open Access Journals (Sweden)

    Vuković, R.


    Full Text Available This paper describes the polymerization of N-acryl-N,N'-dicyclohexylurea (A-DCU, N-methacryl- N,N'-dicyclohexylurea (MA-DCU and N-methacryl-N,N'-diisopropylurea (MA-DiPrU monomers with styrene (St and α-methylstyrene (α-MeSt, thermal stability and degradation mechanism of prepared copolymers. Free-radical initiated polymerization was performed to low conversion by using dibenzoyl peroxyde (Bz2O2 in butanone at 70 °C under nitrogen stream. It was found that the pendant group in (methacrylic monomers have high influence to the polymerization as well as to the copolymer properties. A-DCU readily homopolymerized and copolymerized with St and r1,A-DCU = 0.72 and r2,α-MeSt= 0.07, while MA-DCU does not homopolymerized or copolymerized with α-MeSt under the same conditions, but copolymerized with St to randomly composed copolymers after a long heating of comonomers. Copolymers A-DCU with α-MeSt prepared under different monomer-to monomer-ratios in the feed have random composition with an azeotropic point at ratio of 0.75 (A-DCU to 0.25 (St. The initial rate of copolymerization indicates that the rate increases almost linearly with the increase of ratio of A-DCU in the comonomer feed. Reactivity ratios determined by the Kelen-Tüdös method are: r1,A-DCU = 0.72 and r2,α-MeSt = 0.07. Molar mass of copolymers increased from 8.5 to 30 (kg mol-1 when mole ratio of A-DCU to α-MeStin the feed increased from 0.1 to 0.9. Poly(A-DCU and copolymers with α-MeSt decomposed by two-step mechanism. Under TGA (nitrogen,10 °C min-1 conditions in the first step between 180 °C and 250 °C a quantitative yield of cyclohexylisocyanate (C6H11NCO separated by a decomposition of dicyclohexylurea (DCU. The thermally stable residue represented poly(acryl-cyclohexylamide, poly(A-CHA, and copolymer with α-MeSt, poly(A-CHA-co-α-MeSt. Glass transition temperature (Tg of poly(A-DCU was at 184 °C and Tg of residue, poly(A-CHA, was at 161 °C. Tg's of the copolymers are

  7. (Methacrylic Acid-Co-Divinylbenzene) Resin as Filler

    African Journals Online (AJOL)

    divinylbenzene) resin (PMD) as a new filler-binder for direct compression tablets. Methods: Powder properties of PMD and MCC were characterized. Tablets made from PMD and MCC with and without propranolol hydrochloride were evaluated for ...

  8. (Methacrylic Acid-Co-Divinylbenzene) Resin as Filler- Binder for

    African Journals Online (AJOL)

    divinylbenzene) resin (PMD) as a new filler-binder for direct compression tablets. Methods: Powder properties of PMD and MCC were characterized. Tablets made from PMD and MCC with and without propranolol hydrochloride were evaluated for ...

  9. Crystallization analysis fractionation of poly(ethylene-co-styrene) produced by metallocene catalysts

    KAUST Repository

    Kamal, Muhammad Shahzad


    Ethylene homo polymer and ethylene-styrene copolymers were synthesized using Cp2ZrCl2 (1)/methyl aluminoxane (MAO) and rac-silylene-bis (indenyl) zirconium dichloride (2)/MAO catalyst systems by varying styrene concentration and reaction conditions. Crystallization analysis fractionation (CRYSTAF), DSC, FTIR and 1H NMR spectroscopy were used for characterizing the synthesized polymers. Interestingly, styrene was able to increase the activity of 1/MAO and 2/MAO catalyst systems at low concentrations, but at higher concentrations the activity decreases. The 1/MAO system at low and high pressure was unable to incorporate styrene, and the final product was pure polyethylene. On the other hand, with 2/MAO polymerization of ethylene and styrene yielded copolymer containing both styrene and ethylene. Results obtained from CRYSTAF and DSC reveal that on using 1/MAO system at high pressure, the resulting polymer in the presence of styrene has similar crystallinity as the polymer produced without styrene. Using both 1/MAO at low pressure and 2/MAO leads to decrease in crystallinity with increase in styrene concentration, even though the former does not incorporate styrene. © 2013 Springer-Verlag Berlin Heidelberg.

  10. 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

    Directory of Open Access Journals (Sweden)

    Renato Turchet


    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.

  11. Impacts of Repeat Unit Structure and Copolymer Architecture on Thermal and Solution Properties in Homopolymers, Copolymers, and Copolymer Blends (United States)

    Marrou, Stephen Raye

    Gradient copolymers are a relatively new type of copolymer architecture in which the distribution of comonomers gradually varies over the length of the copolymer chain, resulting in a number of unusual properties derived from the arrangement of repeat units. For example, nanophase-segregated gradient copolymers exhibit extremely broad glass transition temperatures (Tgs) resulting from the wide range of compositions present in the nanostructure. This dissertation presents a number of studies on how repeat unit structure and copolymer architecture dictate bulk and solution properties, specifically taking inspiration from the gradient copolymer architecture and comparing the response from this compositionally heterogeneous material to other more conventional materials. The glass transition behavior of a range of common homopolymers was studied to determine the effects of subunit structure on Tg breadth, observing a significant increase in T g breadth with increasing side chain length in methacrylate-based homopolymers and random copolymers. Additionally, increasing the composition distribution of copolymers, either by blending individual random copolymers of different overall composition or synthesizing random copolymers to high conversion, resulted in significant increases to Tg breadth. Plasticization of homopolymers and random copolymers with low molecular weight additives also served to increase the Tg breadth; the most dramatic effect was observed in the selective plasticization of a styrene/4-vinylpyridine gradient copolymer with increases in T g breadth to values above 100 °C. In addition, the effects of repeat unit structure and copolymer architecture on other polymer properties besides Tg were also investigated. The intrinsic fluorescence of styrene units in styrene-containing copolymers was studied, noting the impact of repeat unit structure and copolymer architecture on the resulting fluorescence spectra in solution. The impact of repeat unit structure on

  12. Rheological Behavior of Entangled Polystyrene-Polyhedral Oligosilsesquioxane (POSS) Copolymer

    National Research Council Canada - National Science Library

    Wu, Jian; Mather, Patrick T; Haddad, Timothy S; Kim, Gyeong-Man


    ...: random copolymers of polystyrene (PS) and styryl-based polyhedral oligosilsesquioxane (POSS), R7(Si8O12)(C6H4CH=CH2), with R = isobutyl (iBu). A series of styrene-styryl POSS random copolymers with 0, 6, 15, 30, 50 wt...

  13. EPR investigation on radiation-induced graft copolymerization of styrene onto polyethylene: Energy transfer effects

    Energy Technology Data Exchange (ETDEWEB)

    Salih, M.A. [Dipartimento di Chimica Generale, Universita di Pavia, 27100 Pavia (Italy); Buttafava, A. [Dipartimento di Chimica Generale, Universita di Pavia, 27100 Pavia (Italy); Ravasio, U. [Dipartimento di Chimica Generale, Universita di Pavia, 27100 Pavia (Italy); Dipartimento di Ingegneria Nucleare, Politecnico di Milan (Italy); Mariani, M. [Dipartimento di Ingegneria Nucleare, Politecnico di Milan (Italy); Faucitano, A. [Dipartimento di Chimica Generale, Universita di Pavia, 27100 Pavia (Italy)]. E-mail:


    In this paper, energy transfer phenomena concerning the in-source graft copolymerization of styrene onto LDPE were investigated through the EPR analysis of the radical intermediates. The model solution experiments have shown a substantial deviation of the experimental G (radicals) values with respect to the additivity law, which reflect the negative effect of the styrene monomer concentration on the initiation rate of the graft copolymerization. The EPR measurements performed on polyethylene-co-styrene graft copolymers of various composition following low-temperature vacuum gamma irradiation have confirmed the decrease of the total radical yields with increasing the styrene concentration. The effect was partly attributed to the heterogeneity of the graft copolymer matrix and to the lack of molecular mobility in the solid state at low temperature, which prevents the attainment of the favourable geometrical configurations in intermolecular energy and charge transfer events.

  14. Interaction between poly(vinyl pyridine) and poly(2,6-dimethyl-1,4-phenylene oxide) : A copolymer blend miscibility study

    NARCIS (Netherlands)

    de Wit, Joost; van Ekenstein, Gert Alberda; ten Brinke, Gerrit


    The phase behavior of blends of poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) with random copolymers of styrene and 2-vinyl pyridine, Poly(S-co-2VP), as well as with random copolymers of styrene and 4-vinyl pyridine, Poly(S-co-4VP), has been investigated in order to estimate the values of the

  15. Synthesis of segmented (pb(ps-block-pb)(n)) and (pb(san-block- pb)(n)) block-copolymers via polymeric thermal iniferters

    NARCIS (Netherlands)

    Kroeze, E; ten Brinke, G.; Hadziioannou, G


    A technique is described for the synthesis of segmented poly(butadiene-block-styrene) block copolymers and segmented poly(butadiene-block-(styrene-co-acrylonitrile)) block copolymers through polybutadiene-based thermal iniferters. Dihydroxy- and dicarboxy-terminated polybutadienes were transformed

  16. Development of microporous drug-releasing films cast from artificial nanosized latexes of poly(styrene-co-methyl methacrylate) or poly(styrene-co-ethyl methacrylate). (United States)

    Otto, Daniel P; Vosloo, Hermanus C M; Liebenberg, Wilna; de Villiers, Melgardt M


    Two sets of copolymers comprising of styrene and either methyl or ethyl methacrylate as comonomer were conveniently synthesized by microemulsion copolymerization. The purified materials were characterized by GPC-MALLS and were shown to form artificial nanolatexes in THF. ATR-FTIR analysis revealed differences in copolymer composition and based on the copolymer properties, a selection of copolymers was chosen to cast drug-loaded, microporous films that exhibit microencapsulation of drug agglomerates. The contact angles of the copolymers suggested potential applications in medical devices to prevent the formation of bacterial biofilms that commonly result in infections. Additionally, the different copolymeric films showed two phases of drug release characterized by a rapid initial drug release followed by a zero-order phase. Depending on the application, one could select the copolymer films that best suited the application i.e. for short-term drug release applications such as urinary catheters or long-term applications such as artificial implants.

  17. Effect of planar extension on the structure and mechanical properties of polystyrene-poly(ethylene-¤co¤-butylene)-polystyrene triblock copolymers

    DEFF Research Database (Denmark)

    Daniel, C.; Hamley, I.W.; Mortensen, K.


    Two thermoplastic poly(styrene)-poly(ethylene-co-butylene) -poly(styrene) triblock copolymers containing either spherical or cylindrical poly(styrene) microdomains were pre-oriented through extensional flow. Small angle neutron scattering (SANS) measurements revealed that the pre-oriented triblock...

  18. Inverse vulcanization of sulfur with divinylbenzene: Stable and easy processable cathode material for lithium-sulfur batteries (United States)

    Gomez, Iñaki; Mecerreyes, David; Blazquez, J. Alberto; Leonet, Olatz; Ben Youcef, Hicham; Li, Chunmei; Gómez-Cámer, Juan Luis; Bondarchuk, Oleksandr; Rodriguez-Martinez, Lide


    Lithium-Sulfur (Li-S) battery technology is one of the promising candidates for next generation energy storage systems. Many studies have focused on the cathode materials to improve the cell performance. In this work we present a series of poly (S-DVB) copolymers synthesised by inverse vulcanization of sulfur with divinylbenzene (DVB). The poly (S-DVB) cathode shows excellent cycling performances at C/2 and C/4 current rates, respectively. It was demonstrated poly (S-DVB) copolymer containing 20% DVB did not influence the electrochemical performance of the sulfur material, compared to elemental sulfur as high specific capacities over ∼700 mAh g-1 at 500 cycles were achieved at C/4 current rate, comparable to conventional carbon-based S cathodes. However, the use of copolymer network is assumed to act firstly as sulfur reservoir and secondly as mechanical stabilizer, enhancing significantly the cycling lifetime. The Li-poly (S-DVB) cell demonstrated an extremely low degradation rate of 0.04% per cycle achieving over 1600 cycles at C/2 current rate.

  19. Synthesis of SAN-PB-SAN triblock copolymers via a ''living'' copolymerization with macro-photoiniferters

    NARCIS (Netherlands)

    Kroeze, E; de Boer, B.; ten Brinke, G.; Hadziioannou, G


    A technique is described for the synthesis of poly((styrene-co-acrylonitrile)-block-butadiene-block-(styrene-co-acrylonitrile)) (SAN-PB-SAN) triblock copolymers through polybutadiene-based photo-iniferters. Dihydroxy- and dicarboxy-terminated polybutadienes were transformed into the

  20. Functionalized Nanochannels from Self-Assembled and Photomodified Poly(Styrene-b-Butadiene-b-Styrene). (United States)

    Sutisna, Burhannudin; Polymeropoulos, George; Musteata, Valentina; Sougrat, Rachid; Smilgies, Detlef-M; Peinemann, Klaus-Viktor; Hadjichristidis, Nikolaos; Nunes, Suzana P


    Membranes are prepared by self-assembly and casting of 5 and 13 wt% poly(styrene-b-butadiene-b-styrene) (PS-b-PB-b-PS) copolymers solutions in different solvents, followed by immersion in water or ethanol. By controlling the solution-casting gap, porous films of 50 and 1 µm thickness are obtained. A gradient of increasing pore size is generated as the distance from the surface increased. An ordered porous surface layer with continuous nanochannels can be observed. Its formation is investigated, by using time-resolved grazing incident small angle X-ray scattering, electron microscopy, and rheology, suggesting a strong effect of the air-solution interface on the morphology formation. The thin PS-b-PB-b-PS ordered films are modified, by promoting the photolytic addition of thioglycolic acid to the polybutadiene groups, adding chemical functionality and specific transport characteristics on the preformed nanochannels, without sacrificing the membrane morphology. Photomodification increases fivefold the water permeance to around 2 L m(-2) h(-1) bar(-1) , compared to that of the unmodified one. A rejection of 74% is measured for methyl orange in water. The membranes fabrication with tailored nanochannels and chemical functionalities can be demonstrated using relatively lower cost block copolymers. Casting on porous polyacrylonitrile supports makes the membranes even more scalable and competitive in large scale. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. The effect of heat treatment on the internal structure of nanostructured block copolymer films

    DEFF Research Database (Denmark)

    Sepe, Alessandro; Hoppe, E T; Jaksch, S


    We report on the temperature dependence of the nanostructure of thin block copolymer films, as studied using in situ grazing-incidence small-angle x-ray scattering (GISAXS). We focus on spin-coated poly(styrene-b-butadiene) diblock copolymer thin films featuring lamellae perpendicular to the subs...

  2. Rheological Behavior of Entangled Polystyrene-Polyhedral Oligosilsesquioxane (POSS) Copolymer (Postprint)

    National Research Council Canada - National Science Library

    Wu, Jian; Mather, Patrick T; Haddad, Timothy S; Kim, Gyeong-Man


    ...: random copolymers of polystyrene (PS) and styryl-based polyhedral oligosilsesquioxane (POSS), R7(Si8O12)(C6H4CH=CH2), with R = isobutyl (iBu). A series of styrene-styryl POSS random copolymers with 0, 6, 15, 30, 50 wt...

  3. Fast & scalable pattern transfer via block copolymer nanolithography

    DEFF Research Database (Denmark)

    Li, Tao; Wang, Zhongli; Schulte, Lars


    A fully scalable and efficient pattern transfer process based on block copolymer (BCP) self-assembling directly on various substrates is demonstrated. PS-rich and PDMS-rich poly(styrene-b-dimethylsiloxane) (PS-b-PDMS) copolymers are used to give monolayer sphere morphology after spin-casting of s...... on long range lateral order, including fabrication of substrates for catalysis, solar cells, sensors, ultrafiltration membranes and templating of semiconductors or metals....

  4. Surface modification of poly(styrene-b-(ethylene-co-butylene)-b-styrene) elastomer via photo-initiated graft polymerization of poly(ethylene glycol)

    Energy Technology Data Exchange (ETDEWEB)

    Li Xiaomeng [State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Luan Shifang, E-mail: [State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Yang Huawei; Shi Hengchong; Zhao Jie; Jin Jing [State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Yin Jinghua, E-mail: [State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022 (China); Stagnaro, Paola [Istituto per Io Studio delle Macromolecole, Consiglio Nazionale delle Ricerche, Via de Marini 6, 16149 Genova (Italy)


    Poly(styrene-b-(ethylene-co-butylene)-b-styrene) (SEBS) copolymer biomedical elastomer was covalently grafted with poly(ethylene glycol) methyl ether methacrylate (PEGMA) via a photo-initiated graft polymerization technique. The surface graft polymerization of SEBS with PEGMA was verified by ATR-FTIR and XPS. Effect of graft polymerization parameters, i.e., monomer concentration, UV irradiation time and initiator concentration on the grafting density was investigated. Comparing with the virgin SEBS film, the PEGMA-modified SEBS film presented an enhanced wettability and a larger surface energy. Besides, the surface grafting of PEGMA imparted excellent anti-platelet adhesion and anti-protein adsorption to the SEBS surface.

  5. Stereoselective Copolymerization of Styrene with Terpenes Catalyzed by an Ansa-Lanthanidocene Catalyst: Access to New Syndiotactic Polystyrene-Based Materials

    Directory of Open Access Journals (Sweden)

    Eva Laur


    Full Text Available The copolymerization of bio-renewable β-myrcene or β-farnesene with styrene was examined using an ansa-neodymocene catalyst, affording two series of copolymers with high styrene content and unprecedented syndioregularity of the polystyrene sequences. The incorporation of terpene in the copolymers ranged from 5.6 to 30.8 mol % (β-myrcene and from 2.5 to 9.8 mol % (β-farnesene, respectively. NMR spectroscopy and DSC analyses suggested that the microstructure of the copolymers consists of 1,4- and 3,4-poly(terpene units randomly distributed along syndiotactic polystyrene chains. The thermal properties of the copolymers are strongly dependent on the terpene content, which is easily controlled by the initial feed. The terpolymerization of styrene with β-myrcene in the presence of ethylene was also examined.

  6. Removal of naphthalene from aqueous systems by poly(divinylbenzene) and poly(methyl methacrylate-divinylbenzene) resins. (United States)

    da Silva, Carla M F; Rocha, Quéren da C; Rocha, Paulo Cristiano S; Louvisse, Ana Maria T; Lucas, Elizabete F


    Treatment of the oily wastewater from crude oil extraction is a growing challenge due to rising concern for the environment. Polyaromatic hydrocarbons (PAHs) deserve special attention because of their high toxicity. There is a need to develop processes able to minimize the discharge of these compounds and analytic techniques to monitor the levels of PAHs in aqueous media. In this study poly(methyl methacrylate-divinylbenzene) (MMA-DVB) and poly(divinylbenzene) (DVB) were assessed with respect to their capacity to retain naphthalene (NAF) in continuous flow and batch processes (adsorption equilibrium and kinetics). The analytic techniques applied were gas chromatography and spectrofluorimetry, which was adapted for quantification of NAF. The batch adsorption studies showed that DVB is more efficient in adsorption than MMA-DVB, and the Freundlich model and pseudo-second-order model better fitted the equilibrium data and adsorption kinetics, respectively. The elution results showed that both resins are highly efficient in removing NAF, with DVB outperforming MMA-DVB. However, MMA is cheaper raw material, making MMA-DVB more competitive for treatment of oily wastewater. The resins were regenerated by eluting about 7.2 and 2.5 L of methanol:water (70:30 v/v), respectively for DVB and MMA-DVB. Regarding to the useful life after regeneration, the resins presented a reduction about 30%, relating to zero concentration of NAF. Copyright © 2015 Elsevier Ltd. All rights reserved.

  7. Nanoparticle Network Formation in Nanostructured and Disordered Block Copolymer Matrices

    Directory of Open Access Journals (Sweden)

    Khan Saad


    Full Text Available Abstract Incorporation of nanoparticles composed of surface-functionalized fumed silica (FS or native colloidal silica (CS into a nanostructured block copolymer yields hybrid nanocomposites whose mechanical properties can be tuned by nanoparticle concentration and surface chemistry. In this work, dynamic rheology is used to probe the frequency and thermal responses of nanocomposites composed of a symmetric poly(styrene-b-methyl methacrylate (SM diblock copolymer and varying in nanoparticle concentration and surface functionality. At sufficiently high loading levels, FS nanoparticle aggregates establish a load-bearing colloidal network within the copolymer matrix. Transmission electron microscopy images reveal the morphological characteristics of the nanocomposites under these conditions.

  8. Amphiphilic copolymers based on PEG-acrylate as surface active water viscosifiers : Towards new potential systems for enhanced oil recovery

    NARCIS (Netherlands)

    Raffa, Patrizio; Broekhuis, Antonius A.; Picchioni, Francesco


    With the purpose of investigating new potential candidates for enhanced oil recovery (EOR), amphiphilic copolymers based on Poly(ethylene glycol) methyl ether acrylate (PEGA) have been prepared by Atom Transfer Radical Polymerization (ATRP). A P(PEGA) homopolymer, a block copolymer with styrene

  9. Reactive blending of poly(styrene-maleic) anhydride with poly(phenylene oxide) by addition of `-amino-polystyrene

    NARCIS (Netherlands)

    Koning, Cor; Ikker, Andreas; Ikker, A.; Borggreve, Rein; Leemans, Luc; Möller, Martin; Moller, M.


    -(3-Aminopropyl-l-amino)polystyrene (-amino-PS) was melt-blended with styrene/maleic anhydride copolymers (SMA) containing 28 wt% maleic anhydride groups. The terminal primary amino group can react with the maleic anhydride monomer units in SMA, forming imides. The resulting product turned out to be

  10. Protonated Montmorillonite Maghnite-H+ Clay Used as Green Non-toxic Catalyst for the Synthesis of Biocompatible poly (DXL -co- Styrene.

    Directory of Open Access Journals (Sweden)

    N. HAMAM


    Full Text Available Copolymerization of 1,3-Dioxolane (DXL with Styrene (St catalyzed by Maghnite-H+ a montmorillonite sheet silicate clay exchanged with protons, was investigated. The cationic ring opening polymerization was initiated by Maghnite-H+ in bulk. The copolymer obtained was characterized by 1H-NMR, DSC and IR spectroscopy. The studies done, such as the effect of the amount of Maghnite-H+ on the syntheses of poly (DXL -co- Styrene.

  11. Effects of surfactants on the properties of mortar containing styrene/methacrylate superplasticizer. (United States)

    Negim, El-Sayed; Kozhamzharova, Latipa; Khatib, Jamal; Bekbayeva, Lyazzat; Williams, Craig


    The physical and mechanical properties of mortar containing synthetic cosurfactants as air entraining agent are investigated. The cosurfactants consist of a combination of 2% dodecyl benzene sodium sulfonate (DBSS) and either 1.5% polyvinyl alcohol (PVA) or 1.5% polyoxyethylene glycol monomethyl ether (POE). Also these cosurfactants were used to prepare copolymers latex: styrene/butyl methacrylate (St/BuMA), styrene/methyl methacrylate (St/MMA), and styrene/glycidyl methacrylate (St/GMA), in order to study their effects on the properties of mortar. The properties of mortar examined included flow table, W/C ratio, setting time, water absorption, compressive strength, and combined water. The results indicate that the latex causes improvement in mortar properties compared with cosurfactants. Also polymer latex containing DBSS/POE is more effective than that containing DBSS/PVA.

  12. Effects of Surfactants on the Properties of Mortar Containing Styrene/Methacrylate Superplasticizer (United States)

    Negim, El-Sayed; Kozhamzharova, Latipa; Khatib, Jamal; Bekbayeva, Lyazzat; Williams, Craig


    The physical and mechanical properties of mortar containing synthetic cosurfactants as air entraining agent are investigated. The cosurfactants consist of a combination of 2% dodecyl benzene sodium sulfonate (DBSS) and either 1.5% polyvinyl alcohol (PVA) or 1.5% polyoxyethylene glycol monomethyl ether (POE). Also these cosurfactants were used to prepare copolymers latex: styrene/butyl methacrylate (St/BuMA), styrene/methyl methacrylate (St/MMA), and styrene/glycidyl methacrylate (St/GMA), in order to study their effects on the properties of mortar. The properties of mortar examined included flow table, W/C ratio, setting time, water absorption, compressive strength, and combined water. The results indicate that the latex causes improvement in mortar properties compared with cosurfactants. Also polymer latex containing DBSS/POE is more effective than that containing DBSS/PVA. PMID:24955426

  13. Effects of Surfactants on the Properties of Mortar Containing Styrene/Methacrylate Superplasticizer

    Directory of Open Access Journals (Sweden)

    El-Sayed Negim


    Full Text Available The physical and mechanical properties of mortar containing synthetic cosurfactants as air entraining agent are investigated. The cosurfactants consist of a combination of 2% dodecyl benzene sodium sulfonate (DBSS and either 1.5% polyvinyl alcohol (PVA or 1.5% polyoxyethylene glycol monomethyl ether (POE. Also these cosurfactants were used to prepare copolymers latex: styrene/butyl methacrylate (St/BuMA, styrene/methyl methacrylate (St/MMA, and styrene/glycidyl methacrylate (St/GMA, in order to study their effects on the properties of mortar. The properties of mortar examined included flow table, W/C ratio, setting time, water absorption, compressive strength, and combined water. The results indicate that the latex causes improvement in mortar properties compared with cosurfactants. Also polymer latex containing DBSS/POE is more effective than that containing DBSS/PVA.

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


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


    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...

  15. Copolymerization kinetics of methyl methacrylate-styrene obtained by PLP-MALDI-ToF-MS. (United States)

    Willemse, Robin X E; van Herk, Alex M


    The combination of MALDI-ToF-MS and pulsed laser polymerization has been used to study the propagation rate coefficients for the copolymer system styrene-methyl methacrylate. For the first time, complete information regarding mode of termination, reactivity of photoinitiator-derived radicals, copolymer molecular mass, chemical composition, and copolymerization rates is obtained interrelated. The polymerizations were carried out in bulk with varying styrene concentrations at a temperature of 15.2 degrees C by an excimer pulsed laser with varying frequencies. Both chemical composition distributions and molecular weight distributions were determined by MALDI-ToF-MS. The data were fitted to the implicit penultimate unit model and have resulted in new point estimates of the monomer and radical reactivity ratios for the copolymer system styrene-methyl methacrylate: r(St) = 0.517, r(MMA) = 0.420, s(St) = 0.296, s(MMA) = 0.262. Comparison between Monte Carlo simulations and the obtained results further confirmed the very successful combination of pulsed laser copolymerization experiments with MALDI-ToF-MS. The obtained results are believed to be the most accurate and complete set of copolymerization parameters to date.

  16. Preparation of polystyrene-poly(ethylene glycol) diblock copolymer by "living" free radical polymerization

    DEFF Research Database (Denmark)

    Chen, Xianyi; Gao, Bo; Kops, Jørgen


    Amphiphilic diblock copolymer containing segments of polystyrene and monomethoxypoly(ethylene glycol) (PS-b-PEG) was synthesised by a novel method. Initially, the adduct (BZ-TEMPO) obtained by reacting benzoyl peroxide, styrene, and 2,2,6,6-tetramethyl-piperidinyl-1-oxy (TEMPO) was isolated...... terminated with a TEMPO unit (MPEG-TEMPO), which was further used to prepare the diblock copolymer PS-b-PEG by 'living' free radical polymerisation of styrene. The product was purified and identified by H-1 n.m.r. and GPC. However, large amounts of homopolystyrene was also formed by simultaneous thermal...

  17. Chain exchange in block copolymer micelles (United States)

    Lu, Jie; Bates, Frank; Lodge, Timothy


    Block copolymer micelles are aggregates formed by self-assembly of amphiphilic copolymers dispersed in a selective solvent, driven by unfavorable interactions between the solvent and the core-forming block. Due to the relatively long chains being subject to additional thermodynamic and dynamic constraints (e.g., entanglements, crystallinity, vitrification), block copolymer micelles exhibit significantly slower equilibration kinetics than small molecule surfactants. As a result, details of the mechanism(s) of equilibration in block copolymer micelles remain unclear. This present works focuses on the chain exchange kinetics of poly(styrene-b-ethylenepropylene) block copolymers in squalane (C30H62) using time-resolved small angle neutron scattering (TR-SANS). A mixture of h-squalane and d-squalane is chosen so that it contrast matches a mixed 50/50 h/d polystyrene micelle core. When the temperature is appropriate and isotopically labeled chains undergo mixing, the mean core contrast with respect to the solvent decreases, and the scattering intensity is therefore reduced. This strategy allows direct probing of chain exchange rate from the time dependent scattering intensity I(q, t).

  18. Random Copolymer Effect in Self-Assembled Hydrogen-Bonded P(S-co-4VP)(PDP) Side-Chain Polymers

    NARCIS (Netherlands)

    de Wit, Joost; van Ekenstein, Gert Alberda; Polushkin, Evgeny; Korhonen, Juuso; Ruokolainen, Janne; ten Brinke, Gerrit


    Random copolymers of styrene and 4-vinylpyridine P(S(1-x)-co-4VP(x)) were synthesized to study the effect of the random copolymer "repulsion" on the self-assembly in hydrogen-bonded complexes with pentadecylphenol (one PDP molecule per 4VP group). The major trends observed as a function of the

  19. Surface morphology of PS-PDMS diblock copolymer films

    DEFF Research Database (Denmark)

    Andersen, T.H.; Tougaard, S.; Larsen, N.B.


    Spin coated thin films (∼400 Å) of poly(styrene)–poly(dimethylsiloxane) (PS–PDMS) diblock copolymers have been investigated using X-ray Photoelectron Spectroscopy and Atomic Force Microscopy. Surface segregation of the poly(dimethylsiloxane) blocks was studied for five diblock copolymers which...... by use of peak shape analysis of the X-ray Photoelectron Spectra via the Tougaard Method. The amount of dimethylsiloxane in the uppermost part of the films was quantified as a function of annealing time and temperature. For annealing above the PS glass transition temperature, surface segregation...... of the dimethylsiloxane chain-ends occurs for all the studied PS–PDMS diblock copolymers. At room temperature, surface segregation takes place only when the amount of dimethylsiloxane in the diblock copolymers is small....

  20. Controlling sub-microdomain structure in microphase-ordered block copolymers and their nanocomposites (United States)

    Bowman, Michelle Kathleen

    Block copolymers exhibit a wealth of morphologies that continue to find ubiquitous use in a diverse variety of mature and emergent (nano)technologies, such as photonic crystals, integrated circuits, pharmaceutical encapsulents, fuel cells and separation membranes. While numerous studies have explored the effects of molecular confinement on such copolymers, relatively few have examined the sub-microdomain structure that develops upon modification of copolymer molecular architecture or physical incorporation of nanoscale objects. This work will address two relevant topics in this vein: (i) bidisperse brushes formed by single block copolymer molecules and (ii) copolymer nanocomposites formed by addition of molecular or nanoscale additives. In the first case, an isomorphic series of asymmetric poly(styrene-b -isoprene-b-styrene) (S1IS2) triblock copolymers of systematically varied chain length has been synthesized from a parent SI diblock copolymer. Small-angle x-ray scattering, coupled with dynamic rheology and self-consistent field theory (SCFT), reveals that the progressively grown S2 block initially resides in the I-rich matrix and effectively reduces the copolymer incompatibility until a critical length is reached. At this length, the S2 block co-locates with the S1 block so that the two blocks generate a bidisperse brush (insofar as the S1 and S2 lengths differ). This single-molecule analog to binary block copolymer blends affords unique opportunities for materials design at sub-microdomain length scales and provides insight into the transition from diblock to triblock copolymer (and thermoplastic elastomeric nature). In the second case, I explore the distribution of molecular and nanoscale additives in microphase-ordered block copolymers and demonstrate via SCFT that an interfacial excess, which depends strongly on additive concentration, selectivity and relative size, develops. These predictions are in agreement with experimental findings. Moreover, using a

  1. Design of block copolymer membranes using segregation strength trend lines

    KAUST Repository

    Sutisna, Burhannudin


    Block copolymer self-assembly and non-solvent induced phase separation are now being combined to fabricate membranes with narrow pore size distribution and high porosity. The method has the potential to be used with a broad range of tailor-made block copolymers to control functionality and selectivity for specific separations. However, the extension of this process to any new copolymer is challenging and time consuming, due to the complex interplay of influencing parameters, such as solvent composition, polymer molecular weights, casting solution concentration, and evaporation time. We propose here an effective method for designing new block copolymer membranes. The method consists of predetermining a trend line for the preparation of isoporous membranes, obtained by computing solvent properties, interactions and copolymer block sizes for a set of successful systems and using it as a guide to select the preparation conditions for new membranes. We applied the method to membranes based on poly(styrene-b-ethylene oxide) diblocks and extended it to newly synthesized poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) terpolymers. The trend line method can be generally applied to other new systems and is expected to dramatically shorten the path of isoporous membrane manufacture. The PS-b-P2VP-b-PEO membrane formation was investigated by in situ Grazing Incident Small Angle X-ray Scattering (GISAXS), which revealed a hexagonal micelle order with domain spacing clearly correlated to the membrane interpore distances.

  2. Synthesis and Characterization of Organotin Containing Copolymers: Reactivity Ratio Studies

    Directory of Open Access Journals (Sweden)

    Mohamed H. El-Newehy


    Full Text Available Organotin monomers containing dibutyltin groups – dibutyltin citraconate (DBTC as a new monomer and dibutyltin maleate (DBTM – were synthesized. Free radical copolymerizations of the organotin monomers with styrene (ST and butyl acrylate (BA were performed. The overall conversion was kept low (≤15% wt/wt for all studied samples and the copolymers composition was determined from tin analysis using the Gillman and Rosenberg method. The reactivity ratios were calculated from the copolymer composition using the Fineman-Ross (FR method. The synthesized monomers were characterized by elemental analysis, 1H-, 13C-NMR and FTIR spectroscopy.

  3. Polymers and block copolymers of fluorostyrenes by ATRP

    DEFF Research Database (Denmark)

    Hvilsted, Søren; Borkar, Sachin; Abildgaard, Lillian


    Fully or partly fluorinated polymers have many desirable and intriguing properties. In the framework of a larger program on design and control of new functional block copolymers we recently employed the Atom Transfer Radical Polymerization (ATRP) protocol on 2,3,4,5,6-pentafluorostyrene (FS). We...... materials based on 2,3,5,6-tetrafiuoro-4-methoxy-styrene (TFMS). TFMS homopolymers as well as diblock copolymers with FS are produced by ATRP. Both types of novel polymers were subsequently demethylated and different side chains introduced on the resulting hydroxy sites....

  4. Mechanism of Molecular Exchange in Copolymer Micelles (United States)

    Choi, Soo-Hyung; Lodge, Timothy; Bates, Frank


    Compared to thermodynamic structure, much less has been known about the kinetics of block copolymer micelles which should underlay the attainment of thermodynamic equilibrium. In this presentation, molecular exchange between spherical micelles formed by isotopically labeled diblock copolymers was investigated using time-resolved small-angle neutron scattering. Two pairs of structurally matched poly(styrene-b-ethylene-alt-propylene) (PS-PEP) were synthesized and dispersed in isotopic mixture of squalane, highly selective to PEP block. Each pair includes polymers with fully deuterated (dPS-PEP) and a normal (hPS-PEP) PS blocks. Temperature dependence of the micelle exchange rate R(t) is consistent with melt dynamics for the core polymer. Furthermore, R(t) is significantly sensitive to the core block length N due to the thermodynamic penalty associated with ejecting a core block into the solvent. This hypersensitivity, combined with modest polydispersity in N, leads to an approximately logarithmic decay in R(t).

  5. Sustainable Triblock Copolymers for Application as Thermoplastic Elastomers (United States)

    Ding, Wenyue; Wang, Shu; Ganewatta, Mitra; Tang, Chuanbing; Robertson, Megan

    Thermoplastic elastomers (TPEs), combining the processing advantages of thermoplastics with the flexibility and extensibility of elastomeric materials, have found versatile applications in industry, including electronics, clothing, adhesives, and automotive components. ABA triblock copolymers, in which A represents glassy endblocks and B the rubbery midblock, are commercially available as TPEs, such as poly(styrene-b-butadiene-b-styrene) (SBS) or poly(styrene-b-isoprene-b-styrene) (SIS). However, the commercial TPEs are derived from fossil fuels. The finite availability of fossil fuels and the environmental impact of the petroleum manufacturing have led to the increased interest in the development of alternative polymeric materials from sustainable sources. Rosin acids are promising replacement for the petroleum source due to their abundance in conifers, rigid molecular structures, and ease of functionalization. In this study, we explored the utilization of a rosin acid derivative, poly(dehydroabietic ethyl methacrylate) (PDAEMA), as a sustainable alternative for the glassy domain. The triblock copolymer poly(dehydroabietic ethyl methacrylate-b-n-butyl acylate-b-dehydroabietic ethyl methacrylate) (DnBD) was synthesized and characterized. DnBD exhibited tunable morphological and thermal properties. Tensile testing revealed elastomeric behavior.

  6. Improved synthesis of polystyrene-poly(ethylene oxide)-heparin block copolymers

    NARCIS (Netherlands)

    Vulic, I.; Loman, A.J.B.; Feijen, Jan; Okano, T.; Kim, S.W.


    A novel procedure for the synthesis of block copolymers composed of a hydrophobic block of polystyrene, a hydrophilic block of poly(ethylene oxide) and a bioactive block of nitrous acid-degraded heparin was developed. Amino-semitelechelic polystyrene was prepared by anionic polymerization of styrene

  7. Synthesis of Hydrophilic and Amphiphilic Acryl Sucrose Monomers and Their Copolymerisation with Styrene, Methylmethacrylate and α- and β-Pinenes

    Directory of Open Access Journals (Sweden)

    Maria Teresa Barros


    Full Text Available Herein, we report the synthesis of monomethacryloyl sucrose esters, and their successful free radical homo- and co-polymerisation with styrene, methylmethacrylate, α- and β-pinene. The chemical, physical, structural and surface chemical properties of these polymers, containing a hydrophobic olefin backbone and hydrophilic sugar moieties as side chains, have been investigated. Biodegradation tests of the copolymer samples by a microbial fungal culture (Aspergillus niger method showed good biodegradability. The chemical structure and surface chemistry of the synthesized homo- and co-polymers demonstrate their potential technological relevance as amphiphilic and biodegradable polymers.

  8. Electric-Field-Induced Alignment of Block Copolymer/Nanoparticle Blends

    Energy Technology Data Exchange (ETDEWEB)

    Liedel, Clemens [RWTH Aachen University; Schindler, Kerstin [RWTH Aachen University; Pavan, Mariela J. [Hebrew University of Jerusalem; Lewin, Christian [RWTH Aachen University; Pester, Christian W [ORNL; Ruppel, Markus A [ORNL; Urban, Volker S [ORNL; Shenhar, Roy [Hebrew University of Jerusalem; Boker, Alexander [RWTH Aachen University


    External electric fi elds readily align birefringent block-copolymer mesophases. In this study the effect of gold nanoparticles on the electric-fi eld-induced alignment of a lamellae-forming polystyrene- block -poly(2-vinylpyridine) copolymer is assessed. Nanoparticles are homogeneously dispersed in the styrenic phase and promote the quantitative alignment of lamellar domains by substantially lowering the critical field strength above which alignment proceeds. The results suggest that the electric-fi eldassisted alignment of nanostructured block copolymer/nanoparticle composites may offer a simple way to greatly mitigate structural and orientational defects of such fi lms under benign experimental conditions.

  9. Copper mediated controlled radical copolymerization of styrene and2-ethylhexyl acrylate and determination of their reactivity ratios.

    Directory of Open Access Journals (Sweden)

    Bishnu Prasad Koiry


    Full Text Available Copolymerization is an important synthetic tool to prepare polymers with desirable combination of properties which are difficult to achieve from the different homopolymers concerned. This investigation reports the copolymerization of 2-ethylhexyl acrylate (EHA and styrene using copper bromide (CuBr as catalyst in combination with N,N,N’,N,N- pentamethyldiethylenetriamine (PMDETA as ligand and 1-phenylethyl bromide (PEBr as initiator. Linear kinetic plot and linear increase in molecular weights versus conversion indicate that copolymerization reactions were controlled. The copolymer composition was calculated using 1H NMR studies. The reactivity ratio of styrene and EHA (r1 and r2 were determined using the Finemann-Ross (FR, inverted Finemann-Ross (FR and Kelen-Tudos (KT methods. Thermal properties of the copolymers were also studied by using TGA and DSC analysis.

  10. Synthesis and characterization of poly(styrene-co-methyl methacrylate); Sintese e caracterizacao do poli(estireno-co-metacrilato de metila)

    Energy Technology Data Exchange (ETDEWEB)

    Augustinho, Tiago R.; Abarca, Silvia A.C.; Machado, Ricardo A.F. [Departamento de Engenharia Quimica e Alimentos - Universidade Federal de Santa Catarina - UFSC, Florianopolis, SC (Brazil)


    Polystyrene (PS) is nowadays commonly used due its advantages over competitors. PS presents a lower cost when compared with Acrylonitrile Butadiene Styrene (ABS) and with Polyethylene Tere-phthalate (PET), and can be easier processed than polypropylene (PP). At expandable form (EPS), can be used as projective equipment, thermal insulation, floating boards, refrigerators, isothermal, and low cost applications such as packaging and disposable material. Searching for more resistant materials and with a low cost, researches with copolymers materials are being developed. In this study, copolymerization reactions were carried out by suspension polymerization using monomers styrene and methyl methacrylate (MMA) with styrene. Styrene was in the highest percentage in relation to the MMA. The MMA was selected because is a monomer that presents a higher resistance than PS. The copolymerization was confirmed by performing infrared spectroscopy (IR), nuclear magnetic resonance of hydrogen (RMN{sup 1}H), differential scanning calorimetry (DSC) and thermogravimetry (TGA). (author)

  11. Survey of volatile substances in kitchen utensils made from acrylonitrile–butadiene–styrene and acrylonitrile–styrene resin in Japan

    National Research Council Canada - National Science Library

    Abe, Yutaka; Yamaguchi, Miku; Mutsuga, Motoh; Kawamura, Yoko; Akiyama, Hiroshi


    Residual levels of 14 volatile substances, including 1,3‐butadiene, acrylonitrile, benzene, ethylbenzene, and styrene, in 30 kitchen utensils made from acrylonitrile–butadiene–styrene resin ( ABS ) and acrylonitrile–styrene resin...

  12. Helbredsrisici ved eksponering for styren i glasfiberplastindustrien

    DEFF Research Database (Denmark)

    Kolstad, Henrik Albert; Ebbehøj, Nielse; Bonde, Jens Peter


    This is a summary of the health risks of occupational styrene exposure based on recent reviews. We conclude about the exposure levels that there is strong evidence that styrene causes acute irritation of eyes and respiratory tract above 25 ppm, genotoxic effects above 10 ppm, and persistent nervous...... or relevant exposure levels. We recommend reconsideration of the current Danish threshold limit value of 25 ppm, biological monitoring of styrene exposed workers, and epidemiological analyses of styrene exposure levels and long-term health effects among employees of the Danish reinforced plastics industry....... system effects with for instance reduced psychological performance, colour discrimination and hearing level following long-term styrene exposure above 10 ppm. There is moderate evidence of a causal association with cancer, but data are not sufficient to allow us to pinpoint specific cancers at risk...

  13. Acquired dyschromatopsia among styrene-exposed workers. (United States)

    Gobba, F; Galassi, C; Imbriani, M; Ghittori, S; Candela, S; Cavalleri, A


    We investigated the occurrence of color vision loss in 75 styrene-exposed workers and in 60 referents. Color vision was evaluated by adopting the Lanthony D 15 desaturated panel, a test specifically suited to detect mild acquired dyschromatopsia. The results of the test were expressed as Color Confusion Index. Styrene exposure was evaluated with both environmental and biological monitoring. Airborne levels of the solvent were 3.2 to 549.5 mg/m3. In styrene-exposed workers color vision was significantly impaired when compared with referents matched for age. A significative correlation was found between environmental and urinary levels of styrene and Color Confusion Index excluding the influence of age in multiple regression analysis, indicating the possibility of a dose-effect relationship. The findings suggest that styrene can induce an early appearance of a dose-dependent color vision loss.

  14. Helbredsrisici ved eksponering for styren i glasfiberplastindustrien

    DEFF Research Database (Denmark)

    Kolstad, Henrik Albert; Ebbehøj, Nielse; Bonde, Jens Peter


    or relevant exposure levels. We recommend reconsideration of the current Danish threshold limit value of 25 ppm, biological monitoring of styrene exposed workers, and epidemiological analyses of styrene exposure levels and long-term health effects among employees of the Danish reinforced plastics industry.......This is a summary of the health risks of occupational styrene exposure based on recent reviews. We conclude about the exposure levels that there is strong evidence that styrene causes acute irritation of eyes and respiratory tract above 25 ppm, genotoxic effects above 10 ppm, and persistent nervous...... system effects with for instance reduced psychological performance, colour discrimination and hearing level following long-term styrene exposure above 10 ppm. There is moderate evidence of a causal association with cancer, but data are not sufficient to allow us to pinpoint specific cancers at risk...

  15. Micellization of St/MMA gradient copolymers: a general picture of structural transitions in gradient copolymer micelles. (United States)

    Zheng, Chao; Huang, Haiying; He, Tianbai


    In this work, a gradient copolymer of styrene (St) and methyl methacrylate (MMA) is synthesized via reversible addition-fragmentation chain transfer living radical polymerization and its micellization behaviors in an acetone and water mixture are investigated by transmission electron microscopy, light scattering, and NMR spectroscopy. Three different kinds of transitions were found to coexist in a single system for the first time: a unimers to micelles transition, a star-like micelles to crew-cut micelles transition resulting from the shrinkage of micelles, and morphological transitions from spherical micelles to cylindrical micelles to vesicles. Our findings provide a general picture of structural transitions and relaxation processes in gradient copolymer micelles, which can lead to the development of novel materials and applications based on gradient copolymers. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Synthesis of phthalimide and succinimide copolymers and their evaluation as flow improvers for an Egyptian waxy crude oil

    Directory of Open Access Journals (Sweden)

    A.M. Al-Sabagh


    Full Text Available This paper describes the synthesis, characterization and performance evaluation of three phthalimide and three succinimide copolymers of vinyl acetate, styrene and methyl methacrylate as flow improvers for waxy crude oil. The prepared copolymers were named as; (VAPh; (StPh; (MMAPh; (VAS; (StS and (MMAS. These copolymers were characterized by FTIR and 1H NMR spectroscopy. The molecular weights and nitrogen content of these copolymers were determined by using the GPC technique and the Kjeldhal method, respectively. The rheological properties of crude oil (with and without additives were studied. From the obtained results, it was remarked that the styrene phthalimide copolymer (StPh exhibited the maximum pour point depression (ΔPP500 ppm = 30. The results of the rheological flow properties showed that the Bingham yield values (τβ for crude oil without additives at 15, 27 and 39 °C were 0.286, 0.131 and 0.075 Pa respectively, whereas the τβ for the treated crude oil by the styrene phthalimide (StPh copolymer were 0.021, 0.0164 and 0.0081 Pa at 500 ppm at the same temperatures.

  17. Mechanism of isotactic styrene polymerization with a C 6F 5-substituted bis(phenoxyimine) titanium system

    KAUST Repository

    Caporaso, Lucia


    We report a combined, experimental and theoretical, study of styrene polymerization to clarify the regio- and stereocontrol mechanism operating with a C 6F 5-substituted bis(phenoxyimine) titanium dichloride complex. Styrene homopolymerization, styrene-propene and styrene-ethene-propene copolymerizations have been carried out to this aim. A combination of 13C NMR analysis of the chain-end groups and of the microstructure of the homopolymers and copolymers reveals that styrene polymerization is highly regioselective and occurs prevalently through 2,1-monomer insertion. DFT calculations evidenced that steric interaction between the growing chain and the monomer in the transition state insertion stage is at the origin of this selectivity. The formation of isotactic polystyrene with a chain-end like microstructure is rationalized on the base of a mechanism similar to that proposed for the syndiospecific propene polymerization catalyzed by bis(phenoxyimine) titanium dichloride complexes. Finally, a general stereocontrol mechanism operative in olefin polymerization with this class of complexes is proposed. © 2012 American Chemical Society.

  18. Study of the mechanical properties of Acrylonitrile Butadiene Styrene - High Impact Polystyrene blends with Styrene Ethylene Butylene Styrene


    PEYDRO Miguel Angel; JUAREZ David; Sanchez-Caballero, Samuel; PARRES Francisco


    A binary blend Acrylonitrile Butadiene Styrene ¿ High Impact Polystyrene (ABS-HIPS 50% wt) was prepared on a twin-screw extruder at 190-210 oC. The different mechanical properties were then analyzed using tensile strength and impact tests. The analysis of mechanical properties showed a decrease in elongation at break and impact strength. On the other hand, we have prepared ternary blends of ABS-HIPS- Styrene Ethylene Butylene Styrene (SEBS), varying the percentage of SEBS from 10 to 30 %wt us...

  19. Study of the Influence of adding styrene-ethylene/butadiene-styrene in acrylonitrile-butadiene-styrene and polyethylene blends


    M.A. Peydro; F. Parres; Navarro Vidal, Raúl; Sanchez-Caballero, Samuel


    This work studies the recovery of two grades of acrylonitrile butadiene styrene (ABS) contaminated with low-density polyethylene (LDPE), by adding styrene ethylene/butadiene styrene (SEBS). To simulate contaminated ABS, virgin ABS was mixed with 1, 2, 4, and 8% of LDPE and then extruded at 220°C. After this, the ABS with the highest percentage of LDPE (8%) was mixed with 1, 2, 4, and 8% of SEBS and then extruded. Different blends were mechanically, rheologically, optically, and dimensionally ...

  20. Directed assembly of non-equilibrium ABA triblock copolymer morphologies on nanopatterned substrates. (United States)

    Ji, Shengxiang; Nagpal, Umang; Liu, Guoliang; Delcambre, Sean P; Müller, Marcus; de Pablo, Juan J; Nealey, Paul F


    The majority of past work on directed assembly of block copolymers on chemically nanopatterned surfaces (or chemical patterns) has focused on AB diblock copolymers, and the resulting morphologies have generally corresponded to equilibrium states. Here we report a study on directed assembly of ABA triblock copolymers. Directed assembly of thin films of symmetric poly(methyl methacrylate-b-styrene-b-methyl methacrylate) (PMMA-b-PS-b-PMMA) triblock copolymers is shown to be capable of achieving a high degree of perfection, registration, and accuracy on striped patterns having periods, L(s), commensurate with the bulk period of the copolymer, L(o). When L(s) is incommensurate with L(o), the triblock copolymer domains can reach dimensions up to 55% larger or 13% smaller than L(o). The range over which triblock copolymers tolerate departures from a commensurate L(s) is significantly larger than that accessible with the corresponding diblock copolymer material on analogous directed assembly systems. The assembly kinetics of the triblock copolymer is approximately 3 orders of magnitude slower than observed in the diblock system. Theoretically informed simulations are used to interpret our experimental observations; a thermodynamic analysis reveals that triblocks can form highly ordered, non-equilibrium metastable structures that do not arise in the diblock.

  1. Synthesis and characterization of novel functional electrosterically stabilized colloidal particles prepared by emulsion polymerization using a strongly ionized amphiphilic diblock copolymer


    Priti S. Mohanty; Dietsch, Hervé; Rubatat, Laurent; Stradner, Anna; Matsumoto, K.; Matsuoka, H; Schurtenberger, Peter


    Amphiphilic diblock copolymers such as poly(styrene)-block-poly(styrene sulfonate) (PS-b-PSS) (Matsuoka, H.; Maeda, S.; Kaewsaiha, P.; Matsumoto, K. Langmuir 2004, 20, 7412), belong to a class of new polymeric surfactants that ionize strongly in aqueous media. We investigated their self-assembly behavior in aqueous solutions and used them as an emulsifier to prepare electrosterically stabilized colloidal particles of different diameters between 70 to 400 nm. We determined the size, size polyd...

  2. Cationic surfactants/copoly(styrene oxide-ethylene oxide) systems: A physico-chemical investigation

    Energy Technology Data Exchange (ETDEWEB)

    Taboada, Pablo [Laboratorio de Fisica de Coloides y Polimeros, Grupo de Sistemas Complejos, Departamento de Fisica de la Materia Condensada, Facultad de Fisica, Universidad de Santiago de Compostela (Spain)], E-mail:; Castro, Emilio [Laboratorio de Fisica de Coloides y Polimeros, Grupo de Sistemas Complejos, Departamento de Fisica de la Materia Condensada, Facultad de Fisica, Universidad de Santiago de Compostela (Spain); Barbosa, Silvia [Laboratorio de Fisica de Coloides y Polimeros, Grupo de Sistemas Complejos, Departamento de Fisica de la Materia Condensada, Facultad de Fisica, Universidad de Santiago de Compostela (Spain); Mosquera, Victor [Laboratorio de Fisica de Coloides y Polimeros, Grupo de Sistemas Complejos, Departamento de Fisica de la Materia Condensada, Facultad de Fisica, Universidad de Santiago de Compostela (Spain)


    The interactions between the diblock copolymer S{sub 15}E{sub 63} and the surfactants dodecyltrimethylammonium (DoTAB) and hexadecyltrimethylammoniun (CTAB) bromides have been investigated by dynamic light scattering, transmission electron microscopy and isothermal titration calorimetry. The surfactants with the same headgroup differentiate in their chain length. At 20 deg C, the block copolymer is associated into micelles with a hydrodynamic radius of 11.3 nm, which is composed of a hydrophobic styrene oxide (S) core and a water-swollen oxypolyethylene (PEO) corona. The different copolymer/surfactant systems have been studied at a constant copolymer concentration of 2.5 g dm{sup -3} and in a vast range of surfactant concentration, from 5.0 x 10{sup -6} up to 0.1 M. When DoTAB is added to the block copolymer solution, no important variations are observed in the apparent hydrodynamic radius up to a surfactant concentration of {approx}10{sup -2} M, for which this magnitude starts decreasing abruptly as a consequence of disruption of the copolymer micelles due to surfactant binding. This phenomenon is also observed for CTAB but at much lower concentrations ({approx}10{sup -5} M). This decrease is associated to repulsive electrostatic interactions between surfactant headgroups in the micelle. Complete disruption of the mixed aggregates occurs neither for DoTAB nor CTAB in the measured concentration range. Transmission electron microscopy has confirmed this behaviour. Titration calorimetric data of micellised DoTAB present a plateau region indicating no interaction between the copolymer and the surfactant at low surfactant concentrations, followed by an exothermic decrease as a consequence of starting copolymer micelle disruption. For CTAB, an endothermic maximum points out the existence of interactions between copolymer micelles and this surfactant. This maximum is followed by a steep decrease which reflects the disruption of the mixed surfactant/copolymer micelles up

  3. Morphology of biaxially stretched triblock copolymer gels using SAXS (United States)

    Krishnan, Arjun; Ghosh, Tushar; Spontak, Richard


    Gels of styrenic triblock copolymers swollen by a low-volatility, midblock-selective oil behave as high-strain, low-field dielectric elastomers in the design of electroactive polymeric actuators. A standard configuration of such devices involves stretching, or ``prestraining,'' the elastomer film biaxially. However, little is known about the effect of biaxial prestrain on copolymer morphology. In this study, small-angle X-ray scattering (SAXS) is used to probe the nanostructure of gels composed of poly[styrene-b-(ethylene-co-butylene)-b-styrene] and mineral oil by systematically changing the concentration of polymer from 5 to 30 wt% and the biaxial prestrain from 0 to 300%. In the azimuthally integrated intensity profiles, the form factor due to scattering from polystyrene microdomains correlates strongly with polymer concentration and does not change with the applied prestrain, indicating that the polystyrene crosslinks remain as polydisperse spheres. The structure factor data correlates with prestrain, and is fitted using the Percus-Yevick approximation for interacting spheres. While a hard sphere interaction model is sufficient for unstrained gels, we resort to a square shoulder hard sphere potential for strained samples.

  4. Grafting of styrene onto fluoropolymers films

    Energy Technology Data Exchange (ETDEWEB)

    Geraldes, Adriana N.; Zen, Heloisa A.; Parra, Duclerc F.; Lugao, Ademar B.; Linardi, Marcelo [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil). Centro de Quimica e Meio Ambiente], E-mail:


    Grafting of styrene onto poly(vinylidenefluoride) (PVDF) and poly(tetrafluoroethylene) (PTFE) films was studied for the synthesis of ion exchange membranes. Radiation-induced grafting of styrene onto PVDF and PTFE films was investigated by simultaneous method using a Co{sup 60} source. The films of PVDF and PTFE were irradiated at total dose of 20 to 120 kGy and chemical changes were monitored after contact with styrene. Films of PTFE and PVDF were immersed in styrene/toluene 1:1 and were submitted to gamma radiation. After irradiation the samples were evaluated at periods of 0, 7, 14, 21 and 28 days, at room temperature in order to measure the grafting degree. Results of infrared spectroscopic analysis (FTIR), differential scanning calorimetry (DSC), thermogravimetry analysis (TGA) and the degree of grafting (DOG) were evaluated. The characterization techniques showed that irradiated PVDF and PTFE films exhibited a much higher grafting degree at 120 kGy. (author)

  5. Fungal biodegradation of lignopolystyrene graft copolymers. [Pleurotus ostreatus; Phanerochaete chrysosporium; Trametes versicolor; Gloeophyllum trabeum

    Energy Technology Data Exchange (ETDEWEB)

    Milstein, O.; Gersonde, R.; Huttermann, A. (Forstbotanisches Inst. der Univ. Gottingen (Germany)); MengJiu Chen; Meister, J.J (Univ. of Detroit Mercy, MI (United States))


    White rot basidiomycetes were able to biodegrade styrene (1-phenylethene) graft copolymers of lignin containing different proportions of lignin and polystyrene (poly(1-phenylethylene)). The biodegradation tests were run on lignin-styrene copolymerization products which contained 10.3, 32.2, and 50.4{percent} (wt/wt) lignin. The polymer samples were incubated with the white rot fungi Pleurotus ostreatus, Phanerochaete chrysosporium, and Trametes versicolor and the brown rot fungus Gloeophyllum trabeum. White rot fungi degraded the plastic samples at a rate which increased with increasing lignin content in the copolymer sample. Both polystyrene and lignin components of the copolymer were readily degraded. Polystyrene pellets were not degradable in these tests. Degradation was verified for both incubated and control samples by weight loss, quantitative UV spectrophotometric analysis of both lignin and styrene residues, scanning electron microscopy of the plastic surface, and the presence of enzymes active in degradation during incubation. Brown rot fungus did not affect any of the plastics. White rot fungi produced and secreted oxidative enzymes associated with lignin degradation in liquid media during incubation with lignin-polystyrene copolymer.

  6. Perpendicularly Aligned, Anion Conducting Nanochannels in Block Copolymer Electrolyte Films

    Energy Technology Data Exchange (ETDEWEB)

    Arges, Christopher G.; Kambe, Yu; Suh, Hyo Seon; Ocola, Leonidas E.; Nealey, Paul F.


    Connecting structure and morphology to bulk transport properties, such as ionic conductivity, in nanostructured polymer electrolyte materials is a difficult proposition because of the challenge to precisely and accurately control order and the orientation of the ionic domains in such polymeric films. In this work, poly(styrene-block-2-vinylpyridine) (PSbP2VP) block copolymers were assembled perpendicularly to a substrate surface over large areas through chemical surface modification at the substrate and utilizing a versatile solvent vapor annealing (SVA) technique. After block copolymer assembly, a novel chemical vapor infiltration reaction (CVIR) technique selectively converted the 2-vinylpyridine block to 2-vinyl n-methylpyridinium (NMP+ X-) groups, which are anion charge carriers. The prepared block copolymer electrolytes maintained their orientation and ordered nanostructure upon the selective introduction of ion moieties into the P2VP block and post ion-exchange to other counterion forms (X- = chloride, hydroxide, etc.). The prepared block copolymer electrolyte films demonstrated high chloride ion conductivities, 45 mS cm(-1) at 20 degrees C in deionized water, the highest chloride ion conductivity for anion conducting polymer electrolyte films. Additionally, straight-line lamellae of block copolymer electrolytes were realized using chemoepitaxy and density multiplication. The devised scheme allowed for precise and accurate control of orientation of ionic domains in nanostructured polymer electrolyte films and enables a platform for future studies that examines the relationship between polymer electrolyte structure and ion transport.

  7. Highly conductive side chain block copolymer anion exchange membranes. (United States)

    Wang, Lizhu; Hickner, Michael A


    Block copolymers based on poly(styrene) having pendent trimethyl styrenylbutyl ammonium (with four carbon ring-ionic group alkyl linkers) or benzyltrimethyl ammonium groups with a methylene bridge between the ring and ionic group were synthesized by reversible addition-fragmentation radical (RAFT) polymerization as anion exchange membranes (AEMs). The C4 side chain polymer showed a 17% increase in Cl(-) conductivity of 33.7 mS cm(-1) compared to the benzyltrimethyl ammonium sample (28.9 mS cm(-1)) under the same conditions (IEC = 3.20 meq. g(-1), hydration number, λ = ∼7.0, cast from DMF/1-propanol (v/v = 3 : 1), relative humidity = 95%). As confirmed by small angle X-ray scattering (SAXS), the side chain block copolymers with tethered ammonium cations showed well-defined lamellar morphologies and a significant reduction in interdomain spacing compared to benzyltrimethyl ammonium containing block copolymers. The chemical stabilities of the block copolymers were evaluated under severe, accelerated conditions, and degradation was observed by (1)H NMR. The block copolymer with C4 side chain trimethyl styrenylbutyl ammonium motifs displayed slightly improved stability compared to that of a benzyltrimethyl ammonium-based AEM at 80 °C in 1 M NaOD aqueous solution for 30 days.

  8. Perforated layer structures in liquid crystalline block copolymers (United States)

    Tenneti, Kishore; Chen, Xiaofang; Li, Christopher; Tu, Yingfeng; Wan, Xinhua; Zhou, Qi-Feng; Sics, Igors; Hsiao, Benjamin


    Phase structures of a series of poly(styrene-block-(2,5-bis-(4- methoxyphenyl)oxycarbonyl)styrene) (PS-b-PMPCS) liquid crystalline “rod-coil” block copolymers (LCBCPs) were investigated using thermal analysis, X-ray analysis and transmission electron microscopy. In the low molecular weight asymmetric BCP system, perforated layer structures were observed where the excessive PS molecules punctured the PMPCS domains and these perforations uniquely possess tetragonal in- plane symmetry. In the high molecular weight system, these perforated layer structures were observed in symmetric samples. Randomly initiated perforations became more regular and uniform upon blending with PS homopolymer in symmetric BCPs. These regular perforations also possess tetragonal in-plane symmetry.

  9. Thermoplastic Dielectric Elastomer of Triblock Copolymer with High Electromechanical Performance. (United States)

    Ma, Zipeng; Xie, Yuhan; Mao, Jie; Yang, Xuxu; Li, Tiefeng; Luo, Yingwu


    Dielectric elastomer (DE) actuators have been shown to have promising applications as soft electromechanical transducers in many emerging technologies. The DE actuators, which are capable of large actuation strain over a wide range of excitation frequencies, are highly desirable. Here, the first single-component DE of a triblock copolymer with attractive electromechanical performance is reported. Symmetric poly(styrene-b-butyl acrylate-b-styrene) (SBAS) is designed and synthesized. The SBAS actuator exhibits about 100% static actuation area strain and excellent dynamic performance, as evidenced by a wide half bandwidth of 300 Hz and a very high specific power of 1.2 W g-1 within the excitation frequency range of 300-800 Hz. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. New highly fluorinated styrene-based materials with low surface energy prepared by ATRP

    DEFF Research Database (Denmark)

    Borkar, Sachin; Jankova Atanasova, Katja; Siesler, Heinz W


    2,3,5,6-Tetrafluoro-4-(2,2,3,3,3-pentafluoropropoxy)styrene (TF(F-5)S) and 2,3,5,6-tetrafluoro-4-(2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctaoxy)styrene (TF(F,5)S) are prepared by nucleophilic substitution of 2,3,4,5,6-pentafluorostyrene. The neat monomers are subjected to atom transfer...... radical polymerization (ATRP) at 110 degreesC to high conversions in relatively short times, 10-120 min; TF(F-5)S is additionally polymerized at 70 and 90 degreesC. Block copolymers with styrene are prepared by the macroinitiator approach. All polymers, in the number-average molecular weight range from...... than 10 mol %. The fluorinated side chains of P(TF(F-5)S) and P(TF(F-15)S) enrich the surface of thin films, which results in an advancing water contact angle of 117degrees and 122degrees, respectively. Both XPS analyses and contact angle measurements strongly imply that the fluorinated parts...

  11. The effect of salt on the morphologies of compositionally asymmetric block copolymer electrolytes (United States)

    Loo, Whitney; Maslyn, Jacqueline; Oh, Hee Jeung; Balsara, Nitash

    Block copolymer electrolytes are promising for applications in lithium metal solid-state batteries. Due to their ability to microphase separate into distinct morphologies, their ion transport and mechanical properties can be decoupled. The addition of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt to poly(styrene)-block-poly(ethylene oxide) (SEO) has been shown to increase microphase separation in symmetric block copolymer systems due to an increase in the effective interaction parameter (χeff) ; however the effect of block copolymer compositional asymmetry is not well-understood. The effect of compositional asymmetry on polymer morphology was investigated through small and wide angle X-ray scattering (SAXS/WAXS). The effective Flory-Huggins interaction parameter was extracted from the scattering profiles in order to construct a phase diagram to demonstrate the effect of salt and compositional asymmetry on block copolymer morphology.

  12. HPMA copolymers as surfactants in the preparation of biocompatible nanoparticles for biomedical application. (United States)

    Kelsch, Annette; Tomcin, Stephanie; Rausch, Kristin; Barz, Matthias; Mailänder, Volker; Schmidt, Manfred; Landfester, Katharina; Zentel, Rudolf


    In this work we describe the application of amphiphilic N-(2-hydroxypropyl)methacrylamide (HPMA)-based copolymers as polymeric surfactants in miniemulsion techniques. HPMA-based copolymers with different ratios of HPMA (hydrophilic) to laurylmethacrylate (LMA; hydrophobic) units were synthesized by RAFT polymerization and postpolymerization modification. The amphiphilic polymers can act as detergents in both the miniemulsion polymerization of styrene and the miniemulsion process in combination with solvent evaporation, which was applied to polystyrene and polylactide. Under optimized conditions, monodisperse colloids can be prepared. The most promising results could be obtained by using the block copolymer with a ratio of 90/10. Preliminary cell uptake studies showed that polymer-stabilized nanoparticles have only minor unspecific cellular internalization in HeLa cells. Furthermore, cytotoxicity assays showed no particle-attributed toxicity. In addition, the copolymer-stabilized particles preserved the shape and size in human blood serum as demonstrated by dynamic light scattering.

  13. Concentration Dependent Structure of Block Copolymer Solutions (United States)

    Choi, Soohyung; Bates, Frank S.; Lodge, Timothy P.


    Addition of solvent molecules into block copolymer can induce additional interactions between the solvent and both blocks, and therefore expands the range of accessible self-assembled morphologies. In particular, the distribution of solvent molecules plays a key role in determining the microstructure and its characteristic domain spacing. In this study, concentration dependent structures formed by poly(styrene-b-ethylene-alt-propylene) (PS-PEP) solution in squalane are investigated using small-angle X-ray scattering. This reveals that squalane is essentially completely segregated into the PEP domains. In addition, the conformation of the PS block changes from stretched to nearly fully relaxed (i.e., Gaussian conformation) as amounts of squalane increases. NRF

  14. Copolymerization of Carbon–carbon Double-bond Monomer (Styrene with Cyclic Monomer (Tetrahydrofuran

    Directory of Open Access Journals (Sweden)

    Sari Fouad


    Full Text Available We reported in this work that the cationic copolymerization in one step takes place between carbon–carbon double-bond monomer styrene with cyclic monomer tetrahydrofuran. The comonomers studied belong to different families: vinylic and cyclic ether. The reaction is initiated with maghnite-H+ an acid exchanged montmorillonite as acid solid ecocatalyst. Maghnite-H+ is already used as catalyst for polymerization of many vinylic and heterocyclic monomers. The oxonium ion of tetrahydrofuran and carbonium ion of styrene propagated the reaction of copolymerization. The acetic anhydride is essential for the maintenance of the ring opening of tetrahydrofuran and the entry in copolymerization. The temperature was kept constant at 40°C in oil bath heating for 6 hours. A typical reaction product was analyzed by 1H-NMR, 13C-NMR and IR and the formation of the copolymer was confirmed. The reaction was proved by matched with analysis. The maghnite-H+ allowed us to obtain extremely pure copolymer in good yield by following a simples operational conditions. Copyright © 2012 by BCREC UNDIP. All rights reservedReceived: 29th October 2012; Revised: 29th November 2012; Accepted: 29th November 2012[How to Cite: S. Fouad, M.I. Ferrahi, M. Belbachir. (2012. Copolymerization of Carbon–carbon Double-bond Monomer (Styrene with Cyclic Monomer (Tetrahydrofuran. Bulletin of Chemical Reaction Engineering & Catalysis, 7(2: 165-171. (doi:10.9767/bcrec.7.2.4074.165-171][How to Link / DOI: ] | View in 

  15. Nanostructured Organic-Inorganic Hybrid Films Prepared by the Sol-Gel Method from Self-Assemblies of PS-b-PAPTES-b-PS Triblock Copolymers


    Gamys, Ce Guinto; Beyou, Emmanuel; Bourgeat-Lami, Elodie; Alcouffe, Pierre; David, Laurent


    International audience; ABA-based triblock copolymers of styrene as block ends and gelable 3-acryloxypropyltriethoxysilane (APTES) as the middle block were successfully prepared through nitroxide-medi- ated polymerization (NMP). The copolymers were bulk self- assembled into films and the degree of phase separation between the two blocks was evaluated by differential scanning calorimetry (DSC). Their morphology was examined through small angle X-ray scattering (SAXS) and transmission electron ...

  16. Study the adsorption of sulfates by high cross-linked polystyrene divinylbenzene anion-exchange resin (United States)

    Fathy, Mahmoud; Moghny, Th. Abdel; Awadallah, Ahmed E.; El-Bellihi, Abdel-Hameed A.-A.


    In response to rising concerns about the effect of sulfate on water quality, human health, and agriculture, many jurisdictions around the world are imposing tighter regulations for sulfate discharge. This is driving the need for environmental compliance in industries like mining, metal processing, pulp and paper, sewage treatment, and chemical manufacturing. The sulfate removal from synthetic water by high cross-linked polystyrene divinylbenzene resin was studied at batch experiments in this study. The effect of pH, contact time, sulfates concentration, and adsorbent dose on the sulfate sequestration was investigated. The optimum conditions were studied on Saline water as a case study. The results showed that with increasing of the absorbent amount; contact time, and pH improve the efficiency of sulfate removal. The maximum sulfates uptake was obtained in pH and contact time 3.0 and 120 min, respectively. Also, with increasing initial concentration of sulfates in water, the efficiency of sulfate removal decreased. The obtained results in this study were matched with Freundlich isotherm and pseudo-second-order kinetic. The maximum adsorption capacity (Qm) and constant rate were found 0.318 (mg/g) and 0.21 (mg/g.min), respectively. This study also showed that in the optimum conditions, the sulfate removal efficiency from Saline water by 0.1 mg/L sulfates was 65.64 %. Eventually, high cross-linked polystyrene divinylbenzene resin is recommended as a suitable and low cost absorbent to sulfate removal from aqueous solutions.

  17. Effect of the structure of ethylene-propylene-diene-graft-polystyrene graft copolymers on morphology and mechanical properties of SAN/EPDM blends

    Directory of Open Access Journals (Sweden)


    Full Text Available Ethylene-propylene-diene-graft-polystyrene (EPDM-g-PS copolymers were synthesized to obtain different structures of graft copolymers with different graft lengths and graft densities. The structure of synthesized EPDM-g-PS copolymers was characterized by gel permeation chromatography (GPC and by Fourier transforms infrared spectroscopy (FTIR. These presynthesized graft copolymers were added (5 phr to styrene-acrylonitrile (SAN and ethylene-propylene-diene (EPDM blends, prepared to maintain the following SAN/EPDM ratios a 95/5 and b 90/10. SAN/EPDM blends were characterized by the determination of mechanical properties (tensile strength, elongation at break while their morphology was inspected by scanning electronic microscopy, SEM. The obtained results show that various structures of EPDM-g-PS copolymers influence the miscibility in SAN/EPDM blends. Optimal concentration of side branches of graft copolymers provide the finest morphology and enhance mechanical properties.

  18. Synthesis and characterization of novel organotin carboxylate maleimide monomers and copolymers

    Directory of Open Access Journals (Sweden)


    Full Text Available Two novel tributyltin carboxylate maleimide monomers, tributyltin(maleimidoacetate and tributyltin(4-maleimidobenzoate, were synthesized by condensation reaction of maleimidoacetic acid or 4-maleimidobenzoic acid with bis(tributyltin oxide. Copolymerization of these monomers with styrene was carried in dioxane at 70°C using asobisisobutyronitrile as free radical initiator. The structures of monomers and copolymers were confirmed by FT-IR (Fourier Transform Infrared, 1H and 13C NMR (nuclear magnetic resonance spectroscopy and elemental analysis. The copolymers were characterized by solubility and thermal analysis.

  19. Synthesis and kinetics studies of poly(styrene-b-vinylmethylsiloxane) and its thin film ordering by thermal and solvent annealing (United States)

    Chatterjee, Sourav; Uddin, Md Fakar; Lwoya, Baraka; Albert, Julie N. L.

    Nano-structured thin film materials are important materials that find uses in templating and membrane applications. Block copolymers (BCP) have gained considerable attention for next-generation lithographic masks due to their self-assemble into morphologies with periodic sub 20 nm feature sizes with high regularity and reproducibility. A novel synthetic block copolymer of poly(styrene-b-vinylmethylsiloxane) (PS-b-PVMS) was synthesized. Like poly(styrene-b-dimethylsiloxane), this polymer has a high Flory Huggins interaction parameter between blocks to minimize feature size. Furthermore, incorporation of the vinyl side group provides an opportunity for post-polymerization chemical modification to manipulate the interaction parameter or impart functionality for various applications. Synthesis and kinetic studies of PS-b-PVMS as well as PS and PVMS homopolymers will be presented. All polymers are well characterized by proton NMR and GPC. As proof of concept, we show that block copolymers having different block fractions self-assemble into the expected nanostructures (lamellae, cylinders, spheres). Thin film studies also will be presented showing how the ordering of PS-b-PVMS is affected by different solvent and thermal annealing conditions.

  20. Production and characterization of poly(styrene-co-methylmethacrylate);Producao e caracterizacao de poliestireno-co-metacrilato de metila

    Energy Technology Data Exchange (ETDEWEB)

    Augustinho, Tiago R.; Coan, Thais; Abarca, Silvia A.C.; Testoni, Alex A.S.; Baumgarten, Bruno P.; Machado, Ricardo A.F., E-mail: [Universidade Federal de Santa Catarina (UFSC), Florianopolis (Brazil). Dept. de Engenharia Quimica e Alimentos


    Polystyrene (PS) is a polymer used in diverse industrial segments. It is easy to process and has a low cost when compared to other materials. However, PS has low mechanical resistance, which limits its application in some areas. Thus, a methodology that is sufficiently used is the synthesis of a copolymer, formed of two or more monomers to get products that have characteristics that are not possible to obtain with only one monomer. In this work, the styrene and methyl methacrylate monomers had been carried through reactions of copolymerization by means of polymerization in suspension using (MMA) with styrene in a bigger percentage. MMA was selected for being a monomer that results in a polymeric configuration more resistant than the PS. The copolymerization was proven to occur by infra-red spectroscopy (IR) and Nuclear Magnetic Resonance (NMR). Different analyses were performed using different initiators, weight molar and conversion studies. (author)

  1. 21 CFR 177.1810 - Styrene block polymers. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Styrene block polymers. 177.1810 Section 177.1810... FOR HUMAN CONSUMPTION (CONTINUED) INDIRECT FOOD ADDITIVES: POLYMERS Substances for Use as Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1810 Styrene block polymers. The styrene...

  2. Polystyrene Chain Growth from Di-End-Functional Polyolefins for Polystyrene-Polyolefin-Polystyrene Block Copolymers

    Directory of Open Access Journals (Sweden)

    Chung Sol Kim


    Full Text Available Triblock copolymers of polystyrene (PS and a polyolefin (PO, e.g., PS-block-poly(ethylene-co-1-butene-block-PS (SEBS, are attractive materials for use as thermoplastic elastomers and are produced commercially by a two-step process that involves the costly hydrogenation of PS-block-polybutadiene-block-PS. We herein report a one-pot strategy for attaching PS chains to both ends of PO chains to construct PS-block-PO-block-PS directly from olefin and styrene monomers. Dialkylzinc compound containing styrene moieties ((CH2=CHC6H4CH2CH22Zn was prepared, from which poly(ethylene-co-propylene chains were grown via “coordinative chain transfer polymerization” using the pyridylaminohafnium catalyst to afford di-end functional PO chains functionalized with styrene and Zn moieties. Subsequently, PS chains were attached at both ends of the PO chains by introduction of styrene monomers in addition to the anionic initiator Me3SiCH2Li·(pmdeta (pmdeta = pentamethyldiethylenetriamine. We found that the fraction of the extracted PS homopolymer was low (~20% and that molecular weights were evidently increased after the styrene polymerization (ΔMn = 27–54 kDa. Transmission electron microscopy showed spherical and wormlike PS domains measuring several tens of nm segregated within the PO matrix. Optimal tensile properties were observed for the sample containing a propylene mole fraction of 0.25 and a styrene content of 33%. Finally, in the cyclic tensile test, the prepared copolymers exhibited thermoplastic elastomeric properties with no breakage up over 10 cycles, which is comparable to the behavior of commercial-grade SEBS.

  3. Survey of volatile substances in kitchen utensils made from acrylonitrile–butadiene–styrene and acrylonitrile–styrene resin in Japan


    Abe, Yutaka; Yamaguchi, Miku; Mutsuga, Motoh; Kawamura, Yoko; Akiyama, Hiroshi


    Residual levels of 14 volatile substances, including 1,3-butadiene, acrylonitrile, benzene, ethylbenzene, and styrene, in 30 kitchen utensils made from acrylonitrile–butadiene–styrene resin (ABS) and acrylonitrile–styrene resin (AS) such as slicers, picks, cups, and lunch boxes in Japan were simultaneously determined using headspace gas chromatography/mass spectroscopy (HS-GC/MS). The maximum residual levels in the ABS and AS samples were found to be 2000 and 2800 μg/g of styrene, respectivel...

  4. Chain exchange in triblock copolymer micelles (United States)

    Lu, Jie; Lodge, Timothy; Bates, Frank


    Block polymer micelles offer a host of technological applications including drug delivery, viscosity modification, toughening of plastics, and colloidal stabilization. Molecular exchange between micelles directly influences the stability, structure and access to an equilibrium state in such systems and this property recently has been shown to be extraordinarily sensitive to the core block molecular weight in diblock copolymers. The dependence of micelle chain exchange dynamics on molecular architecture has not been reported. The present work conclusively addresses this issue using time-resolved small-angle neutron scattering (TR-SANS) applied to complimentary S-EP-S and EP-S-EP triblock copolymers dissolved in squalane, a selective solvent for the EP blocks, where S and EP refer to poly(styrene) and poly(ethylenepropylene), respectively. Following the overall SANS intensity as a function of time from judiciously deuterium labelled polymer and solvent mixtures directly probes the rate of molecular exchange. Remarkably, the two triblocks display exchange rates that differ by approximately ten orders of magnitude, even though the solvophobic S blocks are of comparable size. This discovery is considered in the context of a model that successfully explains S-EP diblock exchange dynamics.

  5. Surface Modification of Poly(divinylbenzene) Microspheres via Thiol-Ene Chemistry and Alkyne-Azide Click Reactions

    NARCIS (Netherlands)

    Goldmann, Anja S.; Walther, Andreas; Nebhani, Leena; Joso, Raymond; Ernst, Dominique; Loos, Katja; Barner-Kowollik, Christopher; Barner, Leonie; Mueller, Axel H. E.; Müller, Axel H.E.


    We report the functionalization of cross-linked poly(divinylbenzene) (pDVB) microspheres using both thiol-ene chemistry and azide-alkyne click reactions. The RAFT technique was carried out to synthesize SH-functionalized poly(N-isopropylacrylimide) (pNIPAAm) and utilized to generate pNIPAAm

  6. Shear induced order in SEP diblock copolymer micelles: multiple BCC slip systems (United States)

    Torija, Maria A.; Choi, Soohyung; Bates, Frank S.; Lodge, Timothy P.


    Poly(styrene-b-ethylene-alt-propylene) (SEP) diblock copolymers are solvated by squalane leading to glassy poly(styrene) domains dispersed in a viscoelastic medium. For diblocks containing less than about 50% by weight poly(styrene) and at SEP concentrations greater than 6 w. % these mixtures self-assemble into glassy spherical microdomains that order on a body centered cubic (BCC) lattice. We have investigated how polycrystalline configurations respond to large amplitude oscillatory shear as a function of shear rate, strain amplitude and block copolymer composition. Structure was characterized by small-angle X-ray scattering measurements while simultaneously deforming the mixtures with an in-situ rheometer. All three slip systems associated with plastic deformation in BCC metals110,211,321, were identified with the x-ray beam oriented perpendicular to the shear plane. Higher shear rates and larger strain amplitudes produced more slip within the 211 system. These results represent one of the most comprehensive assessments of BCC structure in solvated copolymers and will be discussed within the context of the associated linear viscoelastic behavior.

  7. Fabrication of Bioactive Surfaces by Functionalization of Electroactive and Surface-Active Block Copolymers

    Directory of Open Access Journals (Sweden)

    Omotunde Olubi


    Full Text Available Biofunctional block copolymers are becoming increasingly attractive materials as active components in biosensors and other nanoscale electronic devices. We have described two different classes of block copolymers with biofuctional properties. Biofunctionality for block copolymers is achieved through functionalization with appropriate biospecific ligands. We have synthesized block copolymers of electroactive poly(3-decylthiophene and 2-hydroxyethyl methacrylate by atom transfer radical polymerization. The block copolymers were functionalized with the dinitrophenyl (DNP groups, which are capable of binding to Immunoglobulin E (IgE on cell surfaces. The block copolymers were shown to be redox active. Additionally, the triblock copolymer of α, ω-bi-biotin (poly(ethylene oxide-b-poly (styrene-b-poly(ethylene oxide was also synthesized to study their capacity to bind fluorescently tagged avidin. The surface-active property of the poly(ethylene oxide block improved the availability of the biotin functional groups on the polymer surfaces. Fluorescence microscopy observations confirm the specific binding of biotin with avidin.

  8. Silicone/Acrylate Copolymers (United States)

    Dennis, W. E.


    Two-step process forms silicone/acrylate copolymers. Resulting acrylate functional fluid is reacted with other ingredients to produce copolymer. Films of polymer were formed by simply pouring or spraying mixture and allowing solvent to evaporate. Films showed good weatherability. Durable, clear polymer films protect photovoltaic cells.

  9. Water soluble poly(styrene sulfonate)-b-poly(vinylidene fluoride)-b-poly(styrene sulfonate) triblock copolymer nanoparticles

    Czech Academy of Sciences Publication Activity Database

    Černoch, Peter; Černochová, Zulfiya; Petrova, Svetlana; Kaňková, Dana; Kim, J.-S.; Vasu, V.; Asandei, A. D.


    Roč. 6, č. 60 (2016), s. 55374-55381 ISSN 2046-2069 R&D Projects: GA MŠk(CZ) LH14038 Institutional support: RVO:61389013 Keywords : polystyrenesulfonate * poly(neopentyl styrenesulfonate) * PVDF Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.108, year: 2016

  10. Transport Properties of Sulfonated Poly (Styrene-b-isobutylene-b-styrene) Triblock Copolymers at High Ion-Exchange Capacities

    National Research Council Canada - National Science Library

    Winey, Karen I; Elabd, Yossef A; Napadensky, Eugene; Walker, Charles W


    ... (IEC), specifically at high IECs (up to -2 mequiv/g). The proton conductivity of S-SIBS was -1 order of magnitude higher than sulfonated polystyrene at similar IECs and 3-fold higher than Nafion 117 at an IEC of 2 mequiv/g...

  11. 21 CFR 177.1050 - Acrylonitrile/styrene copoly-mer modified with butadiene/styrene elastomer. (United States)


    ... milliliters of 3 percent acetic acid in a Pyrex glass pressure bottle. (3) The pyrex glass pressure bottle is... contain adjuvant substances required in its production. Such adjuvants may include substances generally...

  12. Compatibilization of blends of low density polyethylene and poly(vinyl chloride) by segmented EB(SAN-block-EB)(n) block copolymers

    NARCIS (Netherlands)

    Kroeze, E; ten Brinke, G.; Hadziioannou, G

    Hydrogenated segmented poly[butadiene-block-((styrene-co-acrylonitrile)-block-butadiene)(n)] block copolymers, which were developed by use of the polymeric iniferter technique, were tested for their compatibilizing capacities for (10/90) LDPE/PVC blends. The acrylonitrile content of the SAN blocks

  13. Silicon containing copolymers

    CERN Document Server

    Amiri, Sahar; Amiri, Sanam


    Silicones have unique properties including thermal oxidative stability, low temperature flow, high compressibility, low surface tension, hydrophobicity and electric properties. These special properties have encouraged the exploration of alternative synthetic routes of well defined controlled microstructures of silicone copolymers, the subject of this Springer Brief. The authors explore the synthesis and characterization of notable block copolymers. Recent advances in controlled radical polymerization techniques leading to the facile synthesis of well-defined silicon based thermo reversible block copolymers?are described along with atom transfer radical polymerization (ATRP), a technique utilized to develop well-defined functional thermo reversible block copolymers. The brief also focuses on Polyrotaxanes and their great potential as stimulus-responsive materials which produce poly (dimethyl siloxane) (PDMS) based thermo reversible block copolymers.

  14. Polystyrene cups and containers: styrene migration. (United States)

    Tawfik, M S; Huyghebaert, A


    The level of styrene migration from polystyrene cups was monitored in different food systems including: water, milk (0.5, 1.55 and 3.6% fat), cold beverages (apple juice, orange juice, carbonated water, cola, beer and chocolate drink), hot beverages (tea, coffee, chocolate and soup (0.0, 0.5, 1, 2, and 3.6% fat), take away foods (yogurt, jelly, pudding and ice-cream), as well as aqueous food simulants (3% acetic acid, 15, 50, and 100% ethanol) and olive oil. Styrene migration was found to be strongly dependent upon the fat content and storage temperature. Drinking water gave migration values considerably lower than all of the fatty foods. Ethanol at 15% showed a migration level equivalent to milk or soup containing 3.6% fat. Maximum observed migration for cold or hot beverages and take-away foods was 0.025% of the total styrene in the cup. Food simulants were responsible for higher migration (0.37% in 100% ethanol). A total of 60 food samples (yogurt, rice with milk, fromage, biogardes, and cheese) packed in polystyrene containers were collected from retail markets in Belgium, Germany, and the Netherlands. The level of styrene detected in the foods was always fat dependent.

  15. Catalytic dehydrogenations of ethylbenzene to styrene

    NARCIS (Netherlands)

    Kapteijn, F.; Makkee, M.; Nederlof, C.

    This research work on the catalytic dehydrogenation of ethylbenzene (EB) to styrene (ST) had a primary goal of developing improved catalysts for dehydrogenation processes both in CO2 as well as with O2 that can compete with the conventional dehydrogenation process in steam. In order to achieve this

  16. Graft Copolymerization and Characterization of Styrene with ...

    African Journals Online (AJOL)



    May 24, 2017 ... 1Department of Chemistry, Faculty of Science, Northwest University, P.M.B 3220, Kano, Nigeria. 2Department of Pure and ... In this study, styrene was successfully grafted onto chitosan by conventional free radical polymerization technique, using ..... radical species is very high, chain transfer and reaction ...

  17. Time-composition superpositioning in the rheological behavior of triblock copolymer/selective co-solvent blends (United States)

    Krishnan, Arjun; Bukovnik, Rudolf; Spontak, Richard


    Thermoplastic elastomers composed of styrenic triblock copolymers are of great importance in applications such as adhesives and vibration dampening due to their resilience and facile processing. The swelling of these polymers by adding midblock selective solvents or oligomers provides an easy route by which to modify the morphology and mechanical behavior of these systems. In this study we consider a ternary blend of a poly[styrene-b-(ethylene-co-butylene)-b-styrene] triblock copolymer and mixtures of two midblock selective co-solvents: a mineral oil that is liquid at ambient temperature, and a glassy tackifier resin that exhibits limited solubility in the midblock matrix. We use dynamic rheology to study the viscoelastic response of a wide variety of systems under oscillatory shear. The copolymer concentration is varied between 15 to 35 wt%, while the resin/oil ratio in the midblock-solvent matrix is independently varied. Frequency spectra acquired at ambient temperature display viscoelastic behavior that shifts in the frequency domain depending on the resin/oil ratio. At high oil loadings, the materials behave as physical gels. For each copolymer concentration, all the frequency data can be shifted by time-composition superpositioning to yield a single master-curve.

  18. Dynamics of Block Copolymer Nanocomposites

    Energy Technology Data Exchange (ETDEWEB)

    Mochrie, Simon G. J.


    A detailed study of the dynamics of cadmium sulfide nanoparticles suspended in polystyrene homopolymer matrices was carried out using X-ray photon correlation spectroscopy for temperatures between 120 and 180 °C. For low molecular weight polystyrene homopolymers, the observed dynamics show a crossover from diffusive to hyper-diffusive behavior with decreasing temperatures. For higher molecular weight polystyrene, the nanoparticle dynamics appear hyper-diffusive at all temperatures studied. The relaxation time and characteristic velocity determined from the measured hyper-diffusive dynamics reveal that the activation energy and underlying forces determined are on the order of 2.14 × 10-19 J and 87 pN, respectively. We also carried out a detailed X-ray scattering study of the static and dynamic behavior of a styrene– isoprene diblock copolymer melt with a styrene volume fraction of 0.3468. At 115 and 120 °C, we observe splitting of the principal Bragg peak, which we attribute to phase coexistence of hexagonal cylindrical and cubic double- gyroid structure. In the disordered phase, above 130 °C, we have characterized the dynamics of composition fluctuations via X-ray photon correlation spectroscopy. Near the peak of the static structure factor, these fluctuations show stretched-exponential relaxations, characterized by a stretching exponent of about 0.36 for a range of temperatures immediately above the MST. The corresponding characteristic relaxation times vary exponentially with temperature, changing by a factor of 2 for each 2 °C change in temperature. At low wavevectors, the measured relaxations are diffusive with relaxation times that change by a factor of 2 for each 8 °C change in temperature.

  19. Mechanical and optical effects of elastomer interaction in polypropylene modification: Ethylene-propylene rubber, poly-(ethylene-co-octene and styrene-butadiene elastomers

    Directory of Open Access Journals (Sweden)

    M. Gahleitner


    Full Text Available The interaction between binary combinations of three different elastomer classes commonly applied in impact modification of isotactic polypropylene (iPP was studied. Blends based on a homogeneous ethylene-propylene (EP random copolymer (EP-RACO and a heterophasic EP impact copolymer comprising ethylene-propylene rubber (EPR with different external elastomer types, one homogeneous ethylene-1-octene copolymer (EOC, and two hydrogenated styrenebutadiene-styrene triblock copolymers (SEBS with different styrene content, were prepared. The phase morphology, mobility as a function of temperature, mechanical and optical properties were studied. Special effects could be achieved for the combination of two different elastomer types. The results clearly demonstrate the possibility to achieve attractive property combinations in ternary systems consisting of a crystalline PP matrix and two different types of elastomer, EPR or EOC on the one hand and SEBS on the other hand. A combination of density matching and compatibilization effects allows reaching good low temperature impact strength together with a transparency close to matrix level when selecting a butadiene-rich SEBS type.


    Directory of Open Access Journals (Sweden)

    Nurul Hidayat Aprilita


    Full Text Available Capillary column with monolithic stationary phase was prepared from silanized fused-silica capillary of 200 µm I.D. by in situ free radical polymerization of divinylbenzene with glycidy methacrylate in the presence of decanol and tetrahydrofuran as porogens.  The hydrodynamic and chromatographic properties of this monolith, such as backpressure at different flow-rate, pore size distribution, van Deemter plot and the effect of varying gradient-rate were investigated.  Poly(glycidyl methacrylate-divinylbenzene monolithic capillary has been used successfully for the reversed-phase chromatographic separation of proteins.   Keywords: monolithic stationary phase, poly(glycidyl methacrylate-divinylbenzene, proteins

  1. Molecular exchange in block copolymer micelles: when corona chains overlap (United States)

    Lu, Jie; Lodge, Timothy; Bates, Frank; Choi, Soohyung


    The chain exchange kinetics of poly(styrene-b-ethylenepropylene) (PS-PEP) diblock copolymer micelles in squalane (C30H62) was investigated using time-resolved small angle neutron scattering (TR-SANS). The solvent is a mixture of h-squalane and d-squalane that contrast-matches a mixed 50/50 h/d PS micelle core. As isotope labeled chains exchange, the core contrast decreases, leading to a reduction in scattering intensity. This strategy therefore allows direct probing of the chain exchange rate. Separate copolymer micellar solutions containing either deuterium labeled (dPS) or normal (hPS) poly(styrene) core blocks were prepared and mixed at room temperature, below the core glass transition temperature. The samples were heated to several temperatures (around 100 °C) and monitored by TR-SANS every 5 min. As polymer concentration was increased from 1% to 15% by volume, we observed a significant slowing down of chain exchange rate. Similar retarded kinetics was found when part of the solvent in the 1% solution was replaced by homopolymer PEP (comparable size as corona block). Furthermore, if all the solvent is replaced with PEP, no exchange was detected for up to 3hr at 200 °C. These results will be discussed in terms of a molecular model for chain exchange Infineum, Iprime, NIST, ORNL

  2. Environmentally benign electroless nickel plating using supercritical carbon-dioxide on hydrophilically modified acrylonitrile-butadiene-styrene (United States)

    Tengsuwan, Siwach; Ohshima, Masahiro


    Electroless Ni-P plating using supercritical carbon dioxide (scCO2) in conjunction with copolymer-based hydrophilic modification was applied to an acrylonitrile-butadiene-styrene (ABS) substrate. The surface of ABS substrate was hydrophilically modified by blending with a multi-block copolymer, poly(ether-ester-amide)s (PEEA), in injection molding process. The substrate was then impregnated with Pd(II)-hexafluoroacetylacetonate, Pd(hfa)2, using scCO2, followed by the electroless plating reaction. ABS/PEEA substrates with different PEEA to ABS blend ratios and different volume ratios of butadiene to the styrene-acrylonitrile copolymer (SAN) matrix were prepared to investigate how the dispersed PEEA and butadiene domains affected the blend morphology and the adhesive strength of the plating metal-to-polymer contact. Increasing the PEEA copolymer to ABS blend ratio increased the mass transfer rate of the plating solution in the ABS substrate. Consequently, the metal-polymer composite layer became thicker, which increased the adhesive strength of the metal-to-polymer contact because of the anchoring effect. The butadiene domains appeared to attract the Pd catalyst precursor, and thus, the proportion of butadiene in the ABS matrix also affected the adhesive strength of the contact between the metal layer and the substrate. The ABS substrate was successfully plated with a Ni-P metal layer with an average adhesive strength of 9.1 ± 0.5 N cm-1 by choosing appropriate ABS/PEEA blend ratios and a Pd(hfa)2 concentration.

  3. Study of the thermal properties of Acrylonitrile Butadiene Styrene - High Impact Polystyrene blends with Styrene Ethylene Butylene Styrene


    PEYDRO Miguel Angel; JUAREZ David; Sanchez-Caballero, Samuel; PARRES Francisco


    A binary blend Acrylonitrile Butadiene Styrene ¿ High Impact Polystyrene (ABS-HIPS 50% wt) was prepared on a twin-screw extruder at 190-210 oC. The different properties were then analyzed using melt flow index (MFI), thermogravimetric analysis (TGA), and Fourier Transform Infrared spectroscopy (FTIR). FTIR analysis indicated heterogeneous distribution of the blend in injected pieces and SEM micrographs show heterogeneous distribution of both phase (ABS and HIPS). On the other hand, we have pr...

  4. Mechanical Properties of Phenolic Composites Reinforced with Flax-g-copolymers Prepared under Different Reaction Conditions - A Comparative Study

    Directory of Open Access Journals (Sweden)

    Susheel Kalia


    Full Text Available Graft copolymers of methyl methacrylate (MMA and its binary mixtures such as MMA + ethyl acrylate (EA, MMA + acrylonitrile (AN, MMA + acrylic acid (AA, MMA + vinyl acetate (VA, MMA + acrylamide (AAm and MMA + styrene (Sty with flax fiber have been prepared in air (IA and under the influence of microwave radiations (MWR. Synthesized flax-g-copolymers under two different reaction conditions were used as reinforcing material in the preparation of phenol-formaldehyde composites. Mechanical properties such as wear resistance, modulus of rupture (MOR, modulus of elasticity (MOE and stress at the limit of proportionality (SP were measured and a comparative studied has been made. It has been found that composites reinforced with flax-g-copolymers-MWR showed better mechanical properties in comparison to composites reinforced with flax-g-copolymers-IA

  5. Structure and Dynamics Ionic Block co-Polymer Melts: Computational Study (United States)

    Aryal, Dipak; Perahia, Dvora; Grest, Gary S.

    Tethering ionomer blocks into co-polymers enables engineering of polymeric systems designed to encompass transport while controlling structure. Here the structure and dynamics of symmetric pentablock copolymers melts are probed by fully atomistic molecular dynamics simulations. The center block consists of randomly sulfonated polystyrene with sulfonation fractions f = 0 to 0.55 tethered to a hydrogenated polyisoprene (PI), end caped with poly(t-butyl styrene). We find that melts with f = 0.15 and 0.30 consist of isolated ionic clusters whereas melts with f = 0.55 exhibit a long-range percolating ionic network. Similar to polystyrene sulfonate, a small number of ionic clusters slow the mobility of the center of mass of the co-polymer, however, formation of the ionic clusters is slower and they are often intertwined with PI segments. Surprisingly, the segmental dynamics of the other blocks are also affected. NSF DMR-1611136; NERSC; Palmetto Cluster Clemson University; Kraton Polymers US, LLC.

  6. Nitroxide-mediated radical ring-opening copolymerization: chain-end investigation and block copolymer synthesis. (United States)

    Delplace, Vianney; Harrisson, Simon; Tardy, Antoine; Gigmes, Didier; Guillaneuf, Yohann; Nicolas, Julien


    Well-defined, degradable copolymers are successfully prepared by nitroxide-mediated radical ring opening polymerization (NMrROP) of oligo(ethylene glycol) methyl ether methacrylate (OEGMA) or methyl methacrylate (MMA), a small amount of acrylonitrile (AN) and cyclic ketene acetals (CKAs) of different structures. Phosphorous nuclear magnetic resonance allows in-depth chain-end characterization and gives crucial insights into the nature of the copoly-mer terminal sequences and the living chain fractions. By using a small library of P(OEGMA-co-AN-co-CKA) and P(MMA-co-AN-co-CKA) as macroinitiators, chain extensions with styrene are performed to furnish (amphiphilic) block copolymers comprising a degradable segment. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Energy Technology Data Exchange (ETDEWEB)

    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


    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)

  8. Direct Synthesis of Polymer Nanotubes via Aqueous Dispersion Polymerization of Cyclodextrin/Styrene Complex. (United States)

    Chen, Xi; Liu, Lei; Huo, Meng; Zeng, Min; Peng, Liao; Feng, Anchao; Wang, Xiaosong; Yuan, Jinying


    We report a one-step synthesis of nanotubes by RAFT dispersion polymerization of cyclodextrin/styrene (CD/St) complexes directly in water. The resulted amphiphilic PEG-b-PS diblock copolymers self-assemble in situ into nanoparticles with various morphologies. Spheres, worms, lamellae, and nanotubes were controllably obtained. Because of the complexation, the swelling degree of polystyrene (PS) blocks by free St is limited, resulting limited mobility of PS chains. Consequently, kinetically trapped lamellae and nanotubes were obtained instead of spherical vesicles. During the formation of nanotubes, small vesicles firstly formed at the ends of the tape-like lamellae, then grew and fused into nanotubes with limited chain rearrangement. The introduction of host-guest interaction based on CDs enables the aqueous dispersion polymerization of water-immiscible monomers, and produces kinetically trapped nanostructures, which could be a powerful technique for nanomaterials synthesis. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Radiation-induced degradation of poly(styrene-co-methylmethacrylate) and blends of polystyrene and polymethylmethacrylate (United States)

    Torikai, Ayako; Harayama, Ken-Ichi; Hayashi, Nobutomo; Mitsuoka, Takuya; Fueki, Kenji


    The γ-ray-induced degradation of poly(styrene-co-methyl-methacrylate) [poly(St-co-MMA)] and blends of polystyrene (PSt) and polymethylmethacrylate (PMMA) was investigated by ultraviolet (UV), Fourier transform infrared (FTIR) spectroscopy and viscosity measurements. The optical density around 250 nm decreases linearly with the electron fraction of PSt in the blends, but this does not hold in case of the degradation of poly(St-co-MMA). Similar trends are seen for the decrease in the amount of ester groups, oxidation product formation and the number of chain scission (Cs). A protective effect due to the St component was observed in case of the degradation of poly(St-co-MMA), but it was not observed for the blends. The spatial extent of protection affected by St unit was deduced by assuming a random distribution of MMA and St throughout the copolymer molecule.

  10. Evaluation of some anionic exchange resins as potential tablet ...

    African Journals Online (AJOL)

    Purpose: To determine the potential of some anionic exchange resins as tablet disintegrants. Methods: Dowex1® x2, x4 and x8 resins (crosslinked copolymers of styrene and divinylbenzene with quaternary methyl amine functionality) were evaluated as disintegrant for dibasic calcium phosphate dihydrate tablets. The best ...

  11. Thermal degradation kinetics of polyketone based on styrene and carbon monoxide

    Energy Technology Data Exchange (ETDEWEB)

    Mu, Jiali, E-mail:; Fan, Wenjun; Shan, Shaoyun; Su, Hongying; Wu, Shuisheng; Jia, Qingming


    Highlights: • The PK were synthesized from carbon monoxide and styrene in the presence of PANI-PdCl{sub 2} catalyst and PdCl{sub 2} catalyst. • The structures and thermal behaviors of PK prepared by homogenous and the supported catalyst were investigated. • The microstructures of PK were changed in the supported catalyst system. • The alternating PK copolymer (PANI-PdCl{sub 2} catalyst) was more thermally stable than PK (PdCl{sub 2} catalyst). • The degradation activation energy values were estimated by Flynn–Wall–Ozawa method and Kissinger method. - Abstract: Copolymerization of styrene with carbon monoxide to give polyketones (PK) was carried out under homogeneous palladium catalyst and polyaniline (PANI) supported palladium(II) catalyst, respectively. The copolymers were characterized by {sup 1}H NMR, {sup 13}C NMR and GPC. The results indicated that the PK catalyzed by the supported catalyst has narrow molecular weight distribution (PDI = 1.18). For comparison purpose of thermal behaviors of PK prepared by the homogeneous and the supported catalyst, thermogravimetric (TG) analysis and derivative thermogravimetric (DTG) were conducted at different heating rates. The peak temperatures (396–402 °C) for PK prepared by the supported catalyst are higher than those (387–395 °C) of PK prepared by the homogeneous catalyst. The degradation activation energy (E{sub k}) values were estimated by Flynn–Wall–Ozawa method and Kissinger method, respectively. The E{sub k} values, as determined by two methods, were found to be in the range 270.72 ± 0.03–297.55 ± 0.10 kJ mol{sup −1}. Structures analysis and thermal degradation analysis revealed that the supported catalyst changed the microstructures of PK, resulting in improving thermal stability of PK.

  12. Preparation and biocompatibility of grafted functional β-cyclodextrin copolymers from the surface of PET films

    Energy Technology Data Exchange (ETDEWEB)

    Jiang, Yan, E-mail: [College of Materials Science and Engineering, Changzhou University, Changzhou 213164, Jiangsu (China); Liang, Yuan; Zhang, Hongwen [College of Materials Science and Engineering, Changzhou University, Changzhou 213164, Jiangsu (China); Zhang, Weiwei [College of Life Science, Agriculture and Forestry, Qiqihar University, Qiqihar 161006, Heilongjiang (China); Tu, Shanshan [College of Materials Science and Engineering, Changzhou University, Changzhou 213164, Jiangsu (China)


    The hydrophobic inert surface of poly(ethylene terephthalate) (PET) film has limited its practical bioapplications, in which case, better biocompatibility should be achieved by surface modification. In this work, the copolymer of functional β-cyclodextrin derivatives and styrene grafted surfaces was prepared via surface-initiated atom transfer radical polymerization (SI-ATRP) on initiator-immobilized PET. The structures, composition, properties, and surface morphology of the modified PET films were characterized by fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), contact angle measurement, and scanning electronic microscopy (SEM). The results show that the surface of PET films was covered by a thick targeted copolymer layer, and the hydrophobic surface of PET was changed into an amphiphilic surface. The copolymer-grafted surfaces were also shown good biocompatibility on which SGC-7901 A549 and A549/DDP cells readily attached and proliferated, demonstrating that the functional copolymer-grafted PET films could be a promising alternative to biomaterials especially for tissue engineering. - Highlights: • The PET film was grafted by functional β-CD copolymers, which owns amphiphilicity. • The surface of grafted PET film by copolymers enhanced the cell adhesion and growth. • The biocompatible PET film may be used in tissue engineering and cell cultivation.

  13. Enrichment of boron-10 by inverse-frontal chromatography using quaternized 4-vinylpyridine-divinylbenzene anion-exchange resin

    Energy Technology Data Exchange (ETDEWEB)

    Mardan, A. [Pinstech, Islamabad (Pakistan)


    In order to enrich {sup 10}B, 40 meter band migration of boric acid-mannitol with hydrochloric acid solution was performed by inverse frontal chromatography on a porous, 25% crosslinked, 38% quaternized 4-vinylpyridine-divinylbenzene resin. The maximum enrichment (R{sub L}) of {sup 10}B was 94.15%. The overall process parameters, namely slope coefficient (k) and separation coefficient (e), were found to be 0.1282 cm{sup {minus}1} and 0.02967, respectively.

  14. “Uncontrolled” Preparation of Disperse Poly(lactide)- block -poly(styrene)- block -poly(lactide) for Nanopatterning Applications

    Energy Technology Data Exchange (ETDEWEB)

    Vanderlaan, Marie E.; Hillmyer, Marc A. (UMM)


    We report the facile synthesis of well-defined ABA poly(lactide)-block-poly(styrene)-block-poly(lactide) (LSL) triblock copolymers having a disperse poly(styrene) midblock (Ð = 1.27–2.24). The direct synthesis of telechelic α,ω-hydroxypoly(styrene) (HO-PS-OH) midblocks was achieved using a commercially available difunctional free radical diazo initiator 2,2'-azobis[2-methyl-N-(2-hydroxyethyl)propionamide]. Poly(lactide) (PLA) end blocks were subsequently grown from HO-PS-OH macroinitiators via ring-opening transesterification polymerization of (±)-lactide using the most common and prevalent catalyst system available, tin(II) 2-ethylhexanoate. Fourteen LSL triblock copolymers with total molar masses Mn,total = 24–181 kg/mol and PLA volume fractions fPLA = 0.15–0.68 were synthesized and thoroughly characterized. The self-assembly of symmetric triblocks was analyzed in the bulk using small-angle X-ray scattering and in thin films using grazing incidence small-angle X-ray scattering and atomic force microscopy. We demonstrate both the bulk and thin film self-assembly of LSL disperse triblocks gave well-organized nanostructures with uniform domain sizes suitable for nanopatterning applications.

  15. Styrene polymerization in three-component cationic microemulsions

    Energy Technology Data Exchange (ETDEWEB)

    Perez-Luna, V.H.; Puig, J.E. (Universidad de Guadalajara (Mexico)); Castano, V.M. (Instituto de Fisica (Mexico)); Rodriguez, B.E.; Murthy, A.K.; Kaler, E.W. (Univ. of Delaware, Newark (USA))


    The polymerization of styrene in three-component dodecyltrimethylammonium bromide (DTAB) microemulsions is reported. The structure of the unpolymerized microemulsions, determined by conductimetry and quasielastic light scattering (QLS), is consistent with styrene-swollen micelles in equilibrium with regular micelles, both dispersed in an aqueous phase. Polymerization of these transparent microemulsions, monitored by QLS an dilatometry, produced stable, bluish monodisperse microlatices with particle radii ranging from 20 to 30 nm, depending on styrene content. Polymerization initiation appears to occur in the styrene-swollen micelles, and the polymer particles grow by recruiting monomer and surfactant from uninitiated droplets and small micelles.

  16. Macroporous Composite Cryogels with Embedded Polystyrene Divinylbenzene Microparticles for the Adsorption of Toxic Metabolites from Blood

    Directory of Open Access Journals (Sweden)

    Tanja Eichhorn


    Full Text Available Composite monolithic adsorbents were prepared by the incorporation of neutral polystyrene divinylbenzene (PS-DVB microparticles into macroporous polymer structures produced by cryogelation of agarose or poly(vinyl alcohol. The composite materials exhibited excellent flow-through properties. Scanning electron microscopy of the composite cryogels revealed that the microparticles were covered by thin films of poly(vinyl alcohol or agarose and thus were withheld in the monolith structure. Plain PS-DVB microparticles showed efficient adsorption of albumin-bound toxins related to liver failure (bilirubin and cholic acid and of cytokines (tumor necrosis factor-alpha and interleukin-6. The rates of adsorption and the amount of adsorbed factors were lower for the embedded microparticles as compared to the parent PS-DVB microparticles, indicating the importance of the accessibility of the adsorbent pores. Still, the macroporous composite materials showed efficient adsorption of albumin-bound toxins related to liver failure as well as efficient binding of cytokines, combined with good blood compatibility. Thus, the incorporation of microparticles into macroporous polymer structures may provide an option for the development of adsorption modules for extracorporeal blood purification.

  17. Styrene exposure during the manufacturing of reinforced fiberglass pipe

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, K.E.


    Considering the large number of employees exposed to airborne styrene during the manufacturing of reinforced fiberglass pipe and the absence of appropriate information to define airborne styrene exposure and the resulting levels of urinary mandelic acid, it was necessary that these parameters be evaluated in an actual industrial setting in order to appropriately monitor and control health hazards in the work place. Styrene measurements were collected at eight work stations over a 5-year period at the world's largest manufacturer of styrenated reinforced fiberglass pipe. Pre- and post-shift urinary mandelic acid was measured for 16 employees for 3-consecutive days. The data obtained were statistically analyzed to determine the mean styrene exposure at each work station and the relationship between airborne styrene and pre-and post-shift urinary mandelic acid. The results of this study indicated that both the pre- and post-shift urinary mandelic acid measurements can be utilized to confirm human exposure to styrene. Post-shift measurements are more reflective of daily variations in styrene exposure, whereas pre-shift urinary mandelic acid was found to correlate best to the long-term airborne styrene concentrations (r = 0.787). The prediction equations of NIOSH and ACGIH for the arithmetic mean airborne styrene concentration from post-shift mandelic acid were not valid for the low levels of styrene exposure and urinary mandelic acid concentrations found in this study. Significant changes in the post-shift to pre-shift urinary mandelic acid concentrations were observed.

  18. Lipid-induced degradation in biocompatible poly(Styrene-Isobutylene-Styrene) (SIBS) thermoplastic elastomer. (United States)

    Fittipaldi, Mauro; Grace, Landon R


    The thermoplastic elastomer Poly(Styrene-block-Isobutylene-block-Styrene) (SIBS) is highly biocompatible, which has led to its use in several commercially-available implants. However, lipid-induced degradation has been previously identified as a primary cause of failure in long-term SIBS implants subject to mechanical loading. Thus, understanding the mechanisms and extent of lipid-induced damage and the role of styrene-isobutylene ratio and molecular weight is critical to improving longevity of SIBS-based implants in order to fully exploit the biocompatibility advantages. Samples of four different SIBS formulations were fabricated via compression molding, immersed to lipid saturation contents from 5 to 80% by weight, and tested in uniaxial tension, stress relaxation, and dynamic creep modes. Degradation mechanisms were investigated via infrared spectroscopy, chromatography, and microscopy. No evidence of lipid-induced chemical interactions or chain scissoring was observed. However, a decrease in tensile strength, loss of dynamic creep performance and faster relaxation with increasing lipid content is attributed to strong internal straining. The magnitude of these losses is inversely proportional to both molecular weight and styrene content, suggesting that selection of these variables during the design phase should be based not only on the mechanical requirements of the application, but the expected degree of lipid exposure. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Otoacoustic emission sensitivity to exposure to styrene and noise. (United States)

    Sisto, R; Cerini, L; Gatto, M P; Gherardi, M; Gordiani, A; Sanjust, F; Paci, E; Tranfo, G; Moleti, A


    The ototoxic effect of the exposure to styrene is evaluated, also in the presence of simultaneous exposure to noise, using otoacoustic emissions as biomarkers of mild cochlear damage. Transient-evoked and distortion product otoacoustic emissions were recorded and analyzed in a sample of workers (15 subjects) exposed to styrene and noise in a fiberglass manufacturing facility and in a control group of 13 non-exposed subjects. Individual exposure monitoring of the airborne styrene concentrations was performed, as well as biological monitoring, based on the urinary concentration of two styrene metabolites, the Mandelic and Phenylglyoxylic acids. Noise exposure was evaluated using wearable phonometers, and hearing loss with pure tone audiometry. Due to their different job tasks, one group of workers was exposed to high noise and low styrene levels, another group to higher styrene levels, close to the limit of 20 ppm, and to low noise levels. A significant negative correlation was found between the otoacoustic emission levels and the concentration of the styrene urinary metabolites. Otoacoustic emissions, and particularly distortion products, were able to discriminate the exposed workers from the controls, providing also a rough estimate of the slope of the dose-response relation between otoacoustic levels and styrene exposure.

  20. Synthesis and antibacterial activities of cyclodimers of styrene oxides

    African Journals Online (AJOL)

    A simple synthetic procedure for preparation of 1,4-dioxanes or 1,3-dioxolanes from styrene oxides is described. Electron-donating groups on the aromatic ring of the styrene oxides were found to favour formation of 1,4-dioxanes while electron-withdrawing groups favoured formation of 1,3-dioxolanes. Antibacterial activities ...

  1. Spatial distribution of a midblock-associating homopolymer blended into a triblock copolymer

    Energy Technology Data Exchange (ETDEWEB)

    Lee, S.H.; Koberstein, J.T. (Univ. of Connecticut, Storrs, CT (United States). Dept. of Chemical Engineering); Quan, X. (AT T Bell Labs., Murray Hill, NJ (United States)); Gancarz, I. (Technical Univ. of Wroclaw (Poland)); Wignall, G.D. (Oak Ridge National Lab., TN (United States)); Wilson, F.C. (E.I. Du Pont de Nemours, Inc., Wilmington, DE (United States))


    The spatial distribution of midblock associating homopolymer confined within the lamellar microdomain structure of a triblock copolymer is probed with small angle neutron scattering experiments. The materials examined are poly(styrene-b-[saturated 1,2-butadiene]-b-styrene) triblock copolymers to which a low molecular weight poly(saturated 1,2-butadiene) homopolymer has been added. The butadienes are saturated with either hydrogen, deuterium, or mixtures of the two gases in order to vary their neutron scattering contrast with respect to polystyrene. The results of contrast matching experiments demonstrate that there is a strong tendency for the homopolymer to localize at the center of the midblock microdomain. Experimental scattering profiles are modeled using one-dimensional scattering density profiles in order to obtain a quantitative description of the blend morphologies. This modeling indicates that two distinct scenarios exist for homopolymer localization in a triblock copolymer: one wherein the microdomain structure contracts and a second wherein there is an expansion of the microdomain. Possible origins of this behavior are proposed on the basis of the consideration of the configuration available to the midblock sequence, that is, tie chains that traverse the midblock domain, or loops that enter and exit the midblock microdomain through the same interface.

  2. Evaluation of a new, macroporous polyvinylpyridine resin for processing plutonium using nitrate anion exchange

    Energy Technology Data Exchange (ETDEWEB)

    Marsh, S.F.


    Anion exchange in nitric acid is the major aqueous process used to recover and purify plutonium from impure scrap materials. Most strong-base anion exchange resins incorporate a styrene-divinylbenzene copolymer. A newly available, macroporous anion exchange resin based on a copolymer of 1-methyl-4-vinylpyridine and divinylbenzene has been evaluated. Comparative data for Pu(IV) sorption kinetics and capacity are presented for this new resin and two other commonly used anion exchange resins. The new resin offers high capacity and rapid sorption kinetics for Pu(IV) from nitric acid, as well as greatly stability to chemical and radiolytic degradation. 8 refs., 14 figs.

  3. Grafting of styrene onto polypropylene membranes

    Energy Technology Data Exchange (ETDEWEB)

    Zen, Heloisa A.; Geraldes, Adriana N.; Parra, Duclerc F.; Lugao, Ademar B. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)], E-mail:


    The grafting of styrene onto polypropylene (PP) by simultaneous radiation was carried out. The effects of absorbed dose and the pos radiation period on the grafting yield were investigated. The experiment comprised PP films with 40{mu}m thickness exposed to gamma ionizing radiation at room temperature and nitrogen atmosphere. The films were immersed in styrene/toluene and then irradiated at total dose of 40, 80 and 100 kGy. After irradiation the samples were evaluated at periods of 0, 7, 14, 21 and 28 days at room temperature in order to observe the behavior of grafting degree. Structural, chemical changes and surface morphologies of the modified PP films were characterized by infrared spectroscopic analysis (FTIR), differential scanning calorimetry analysis (DSC), thermogravimetric analysis (TGA) and the degree of grafting (DOG) was gravimetrically determined. The simultaneous radiation indicated the dependency of the percent graft on the absorbed dose. The DOG values are higher when the film was submitted at 100 kGy dose. The thermal stability shows a decrease in the degradation temperature of the modified samples in comparison with the pure polymer. (author)

  4. 75 FR 9438 - Americas Styrenics, LLC-Marietta Plant a Subsidiary of Americas Styrenics, LLLC Formerly Known as... (United States)


    ... Americas Styrenics LLC, including on- site leased workers from Pioneer Pipe Co., Marietta, Ohio. The notice... Employment and Training Administration Americas Styrenics, LLC-Marietta Plant a Subsidiary of Americas... Pioneer Pipe Co.: Marietta, OH; Amended Certification Regarding Eligibility To Apply for Worker Adjustment...

  5. Molecular Exchange in Ordered Diblock Copolymer Micelles (United States)

    Choi, Soo-Hyung; Lodge, Timothy; Bates, Frank


    Previously, molecular exchange between spherical micelles in dilute solution (1 vol% polymer) was investigated using time-resolved small-angle neutron scattering (TR-SANS). As the concentration of spherical micelles formed by the diblock copolymers increases, the micelles begin to overlap and eventually pack onto body-centered cubic (BCC) lattice. In this study, concentrated, ordered micelles (15 vol% polymers) prepared by dispersing isotopically labeled poly(styrene- b -ethylene-alt-propylene) in an isotopic squalane mixture was investigated to understand the micellar concentration dependence of the molecular exchange. Perfectly random mixing of isotopically labeled micelles on the BCC lattice was confirmed by SANS patterns where the interparticle contribution vanishes, resulting in an intensity that directly relates to the exchange kinetics. The measured molecular exchange process for the concentrated, ordered system is qualitatively consistent with the previous observations, but the rate is more than an order of magnitude slower than that for the dilute, disordered system. Infineum(IPrime), MRSEC(NSF), NIST.

  6. Molecular Exchange Dynamics in Block Copolymer Micelles (United States)

    Bates, Frank; Lu, Jie; Choi, Soohyung; Lodge, Timothy


    Poly(styrene-b-ethylene propylene) (PS-PEP) diblock copolymers were mixed with squalane (C30H62) at 1% by weight resulting in the formation of spherical micelles. The structure and dynamics of molecular exchange were characterized by synchrotron small-angle x-ray scattering (SAXS) and time resolved small-angle neutron scattering (TR-SANS), respectively, between 100 C and 160 C. TR-SANS measurements were performed with solutions initially containing deuterium labeled micelle cores and normal cores dispersed in a contrast matched squalane. Monitoring the reduction in scattering intensity as a function of time at various temperatures revealed molecular exchange dynamics highly sensitive to the core molecular weight and molecular weight distribution. Time-temperature superposition of data acquired at different temperatures produced a single master curve for all the mixtures. Experiments conducted with isotopically labeled micelle cores, each formed from two different but relatively mondisperse PS blocks, confirmed a simple dynamical model based on first order kinetics and core Rouse single chain relaxation. These findings demonstrate a dramatic transition to nonergodicity with increasing micelle core molecular weight and confirm the origins of the logarithmic exchange kinetics in such systems.

  7. Monodisperse microbeads of hypercrosslinked polystyrene for liquid and supercritical fluid chromatography (United States)

    Tsyurupa, M. P.; Blinnikova, Z. K.; Il'in, M. M.; Davankov, V. A.; Parenago, O. O.; Pokrovskii, O. I.; Usovich, O. I.


    Monodisperse styrene-divinylbenzene (1 wt %) copolymer microbeads are obtained via the elaborate method of high-productivity precipitation polymerization. The crosslinking of this copolymer with chloromethyl methyl ether in the presence of Friedel-Crafts catalyst yields porous hypercrosslinked polymers with degrees of crosslinking that range from 200 to 500%. Microbead sorbents are shown to be suited for selective stationary phases for high-performance liquid chromatography and supercritical fluid chromatography.

  8. Investigation of complexing ability of ionites with various groups to some heavy and transition metal ions

    Directory of Open Access Journals (Sweden)

    Yedil Yergozhin


    Full Text Available The physico-chemical and complexing properties of the sorbent based on chloromethylated styrene and divinylbenzene copolymer with nicotinamide groups and copolymers based on metacryloilaminobenzene acids with 2-methyl-5-vinylpyridineisomers are studied. By potentiometric titration method the constant of polyelectrolytes functional groups ionization, the composition and strength of the resulting complexes with ions of some heavy and transition metals are determined.

  9. The shape of cells adhering to sulfonated copolymer surfaces. (United States)

    Kowalczyńska, Hanna M; Nowak-Wyrzykowska, Małgorzata; Inkielman, Marcin; Stołowska, Liliana; Marciniak, Ewa


    We studied the shape of L1210 leukaemia cells adhering in a protein-free medium to sulfonated (styrene/methyl methacrylate) copolymer surfaces of two sulfonic group densities, and thus of differing wettability. The use of our image analysis method and the mathematical procedure [Kowalczynska, H.M. et al, Colloids Surfaces B: Biointerfaces, 30 (2003) 193-206.] allowed us to calculate the values of the so-called shape parameter, which quantitatively determines the three-dimensional cell shape. Here, we show that the values of the shape parameter of the adhering cells and the F-actin concentration, in the region near the cell-substratum interface, depend on the density of sulfonic groups present on the substratum surface.

  10. Biocompatibility and characterization of polylactic acid/styrene-ethylene-butylene-styrene composites. (United States)

    Tsou, Chi-Hui; Kao, Bo-Jyue; Yang, Ming-Chien; Suen, Maw-Cherng; Lee, Yi-Hsuan; Chen, Jui-Chin; Yao, Wei-Hua; Lin, Shang-Ming; Tsou, Chih-Yuan; Huang, Shu-Hsien; De Guzman, Manuel; Hung, Wei-Song


    Polylactic acid (PLA)/styrene-ethylene-butylene-styrene (SEBS) composites were prepared by melt blending. Differential scanning calorimetry (DSC) and wide angle X-ray diffraction (WXRD) were used to characterize PLA and PLA/SEBS composites in terms of their melting behavior and crystallization. Curves from thermal gravimetric analysis (TGA) illustrated that thermostability increased with SEBS content. Further morphological analysis of PLA/SEBS composites revealed that SEBS molecules were not miscible with PLA molecules in PLA/SEBS composites. The tensile testing for PLA and PLA/SEBS composites showed that the elongation at the break was enhanced, but tensile strength decreased with increasing SEBS content. L929 fibroblast cells were chosen to assess the cytocompatibility; the cell growth of PLA was found to decrease with increasing SEBS content. This study proposes possible reasons for these properties of PLA/SEBS composites.

  11. Neurobehavioral effects of acute styrene exposure in fiberglass boatbuilders

    Energy Technology Data Exchange (ETDEWEB)

    Letz, R.; Mahoney, F.C.; Hershman, D.L.; Woskie, S.; Smith, T.J. (Mount Sinai School of Medicine, New York, NY (USA))


    A field investigation of the effects of acute exposure to styrene among fiberglass boatbuilders was performed. Personal samples of styrene in breathing zone air and postshift urinary mandelic acid were collected for 105 workers exposed and not exposed to styrene in 6 fiberglass boatbuilding companies in New England. Three tests from the computerized Neurobehavioral Evaluation System (NES) were performed by the subjects in the morning before exposure to styrene, near midday, and at the end of the work day. Duration of exposure averaged 2.9 years (SD = 4.6), 8-hour TWA styrene exposure averaged 29.9 ppm (SD = 36.2), and urinary mandelic acid averaged 347 mg/g creatinine (SD = 465). Regression analyses indicated a statistically significant relationship between postshift performance on the Symbol-Digit test and both acute styrene exposure and mandelic acid. Other analyses comparing workers exposed to less than 50 ppm and greater than 50 ppm styrene also showed a significant effect on Symbol-Digit performance. All three NES tests showed test-retest correlation coefficients above .80, and ease of use for collection of neurobehavioral data under field conditions was demonstrated.

  12. Synthesis and Characterization of Poly (styrene-co-butyl acrylate)/Silica Aerogel Nanocomposites by in situ AGET ATRP: Investigating Thermal Properties (United States)

    Khezri, Khezrollah; Fazli, Yousef


    Hydrophilic silica aerogel nanoparticles surface was modified with hexamethyldisilazane. Then, the resultant modified nanoparticles were used in random copolymerization of styrene and butyl acrylate via activators generated by electron transfer for atom transfer radical polymerization. Conversion and molecular weight determinations were performed using gas and size exclusion chromatography respectively. Addition of modified nanoparticles by 3 wt% results in a decrease of conversion from 68 to 46 %. Molecular weight of copolymer chains decreases from 12,500 to 7,500 g.mol-1 by addition of 3 wt% modified nanoparticles; however, PDI values increase from 1.1 to 1.4. Proton nuclear magnetic resonance spectroscopy results indicate that the molar ratio of each monomer in the copolymer chains is approximately similar to the initial selected mole ratio of them. Increasing thermal stability of the nanocomposites is demonstrated by thermal gravimetric analysis. Differential scanning calorimetry also shows a decrease in glass transition temperature by increasing modified silica aerogel nanoparticles.

  13. 78 FR 55644 - Styrene, Copolymers with Acrylic Acid and/or Methacrylic Acid; Tolerance Exemption (United States)


    ... 20156) on behalf of Akzo Nobel Surface Chemistry, (909 Mueller Ave., Chattanooga, TN 37406) submitted a petition to EPA under the Federal Food, Drug, and Cosmetic Act (FFDCA), requesting an exemption from the..., (7140 Heritage Village Plaza, Gainesville, VA 20156) on behalf of Akzo Nobel Surface Chemistry, (909...

  14. SMA-SH: Modified styrene maleic acid copolymer for functionalization of lipid nanodiscs

    NARCIS (Netherlands)

    Lindhoud, S.; Dias Ribeiro De Carvalho, V.I.; Pronk, J.W.; Aubin-Tam, M.E.


    Challenges in purification and subsequent functionalization of membrane proteins often complicate their biochemical and biophysical characterization. Purification of membrane proteins generally involves replacing the lipids surrounding the protein with detergent molecules, which can affect protein

  15. Microphase separation of a symmetric poly(styrene-B-paramethylstyrene) diblock copolymer

    DEFF Research Database (Denmark)

    Bartels, V.T.; Abetz, V.; Mortensen, K.


    transition temperature T(MST) by approximately 7%. Also from a peak intensity analysis we determine T(MST) at approximately 180-degrees-C. The shape of the peak change at T(MST) and the indication of a second-order peak is observed, characteristic of a lamellar phase in the ordered regime. Intensity does...

  16. 21 CFR 177.1030 - Acrylonitrile/butadiene/styrene/methyl methacrylate copolymer. (United States)


    ... acetic acid, 50 percent ethanol, and n-heptane for 10 days at 120 °F. (2) The finished food-contact... to distilled water, 3 percent acetic acid and n-heptane at 190 °F for 2 hours, cooled to 120 °F (80... section may contain adjuvant substances required in its production. Such adjuvants may include substances...

  17. Structure and Piezoelectricity of Poly (styrene-co-acrylonitrile) Copolymer Doped with Different Dyes

    Czech Academy of Sciences Publication Activity Database

    Elhadidy, Hassan; Abdelhamid, M.I.; Aboelwafa, A.M.; Habib, A.


    Roč. 52, č. 12 (2013), s. 1277-1284 ISSN 0360-2559 R&D Projects: GA MŠk(CZ) ED1.1.00/02.0068; GA MŠk(CZ) EE2.3.20.0214 Institutional support: RVO:68081723 Keywords : DANS * DAST * Piezo- and pyro- electricity * SAN * structure * TDSC Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.481, year: 2012

  18. Influence of Architecture, Concentration, and Thermal History on the Poling of Nonlinear Optical Chromophores in Block Copolymer Domains

    Energy Technology Data Exchange (ETDEWEB)

    Leolukman, Melvina; Paoprasert, Peerasak; Wang, Yao; Makhija, Varun; McGee, David J.; Gopalan, Padma (UW)


    Factors affecting the electric-field-induced poling of nonlinear optical chromophores in block copolymer domains were investigated by encapsulating the chromophores in a linear-diblock copolymer [poly(styrene-b-4-vinylpyridine)] and linear-dendritic (poly(methyl methacrylate)-dendron) block copolymer via hydrogen bonding. Temperature-dependent Fourier transform infrared spectroscopy and morphology evaluation by X-ray scattering and transmission electron microscopy were used with in situ second harmonic generation to correlate domain architectures, processing conditions such as thermal history, and chromophore concentrations with poling efficiency. Poling of chromophores encapsulated in the minority domain (spheres or cylinders) of a linear-diblock copolymer was inhibited by the increasing chromophore concentration within the domain and the chemical nature of the majority domain. Chromophore encapsulation in the majority domain produced the most favorable conditions for poling as measured by in situ second harmonic generation. Thermal annealing of the linear-diblock copolymer/chromophore composites resulted in chromophore aggregation with a corresponding decrease in nonlinear optical activity. The linear-dendron/chromophore system presented the most effective architecture for spatially dispersing chromophores. These findings suggest that while well-ordered phase-separated systems such as block copolymers enhance chromophore isolation over homopolymer systems, a more effective approach is to explore polymer chains end functionalized with chromophores.

  19. Self-assembly of Si-containing block copolymers with high-segregation strength: toward sub-10nm features in directed self-assembly (United States)

    Reboul, C.; Fleury, G.; Aissou, K.; Brochon, C.; Cloutet, E.; Nicolet, C.; Chevalier, X.; Navarro, C.; Tiron, R.; Cunge, G.; Hadziioannou, G.


    Ordered microstructures with nanometrically defined periodicity offer promising opportunities in microelectronic applications for the production of advanced CMOS digital logic circuits. To produce the features and arrays inherent to such technologies, the combination of the "bottom-up" block copolymer self-assembly with "top-down" guiding templates has been successfully introduced leading to new technological breakthroughs. Among the materials used in the direct self-assembly methodology, poly(styrene-b-methylmethacrylate) systems have reached an unprecedented level of maturity which will lead to their introduction into the next technological nodes. However, this system suffers from deficiencies such as a low Flory Huggins parameter (X = 0.04 at 25°C) and a low chemical contrast as regards to the etching processes which could be problematic for targeting sub-22 nm features. Consequently we have developed new systems based on Si-containing block copolymers which are characterized by high segregation strength as well as strong chemical etching contrast. In this contribution, we focus on a poly(lactic acid) / poly(dimethylsiloxane) system exhibiting a cylindrical mesostructure. By controlling the surface energy at the interface between the substrate and the block copolymer domains, we show the possibility to control the orientation of the mesostructure with a methodology comparable to the one used for poly(styrene) / poly(methyl methacrylate) system but with random copolymers having distinct monomers than the block copolymers.

  20. Solution small-angle x-ray scattering as a screening and predictive tool in the fabrication of asymmetric block copolymer membranes

    KAUST Repository

    Dorin, Rachel Mika


    Small-angle X-ray scattering (SAXS) analysis of the diblock copolymer poly(styrene-b-(4-vinyl)pyridine) in a ternary solvent system of 1,4-dioxane, tetrahydrofuran, and N,N-dimethylformamide, and the triblock terpolymer poly(isoprene-b-styrene-b-(4-vinyl)-pyridine) in a binary solvent system of 1,4-dioxane and tetrahydrofuran, reveals a concentration-dependent onset of ordered structure formation. Asymmetric membranes fabricated from casting solutions with polymer concentrations at or slightly below this ordering concentration possess selective layers with the desired nanostructure. In addition to rapidly screening possible polymer solution concentrations, solution SAXS analysis also predicts hexagonal and square pore lattices of the final membrane surface structure. These results suggest solution SAXS as a powerful tool for screening casting solution concentrations and predicting surface structure in the fabrication of asymmetric ultrafiltration membranes from self-assembled block copolymers. (Figure presented) © 2012 American Chemical Society.

  1. Anionic Polymerization of Styrene and 1,3-Butadiene in the Presence of Phosphazene Superbases

    KAUST Repository

    Ntetsikas, Konstantinos


    The anionic polymerization of styrene and 1,3-butadiene in the presence of phosphazene bases (t-BuP4, t-BuP2 and t-BuP1), in benzene at room temperature, was studied. When t-BuP1 was used, the polymerization proceeded in a controlled manner, whereas the obtained homopolymers exhibited the desired molecular weights and narrow polydispersity (Ð < 1.05). In the case of t-BuP2, homopolymers with higher than the theoretical molecular weights and relatively low polydispersity were obtained. On the other hand, in the presence of t-BuP4, the polymerization of styrene was uncontrolled due to the high reactivity of the formed carbanion. The kinetic studies from the polymerization of both monomers showed that the reaction rate follows the order of [t-BuP4]/[sec-BuLi] >>> [t-BuP2]/[sec-BuLi] >> [t-BuP1]/[sec-BuLi] > sec-BuLi. Furthermore, the addition of t-BuP2 and t-BuP1 prior the polymerization of 1,3-butadiene allowed the synthesis of polybutadiene with a high 1,2-microstructure (~45 wt %), due to the delocalization of the negative charge. Finally, the one pot synthesis of well-defined polyester-based copolymers [PS-b-PCL and PS-b-PLLA, PS: Polystyrene, PCL: Poly(ε-caprolactone) and PLLA: Poly(L-lactide)], with predictable molecular weights and a narrow molecular weight distribution (Ð < 1.2), was achieved by sequential copolymerization in the presence of t-BuP2 and t-BuP1.

  2. Compatibility, Morphology, Mechanical Properties and Biodegradability of Poly(styrene-ethylene-propylenestyrene/ Modified Thermoplastic Starch Blends

    Directory of Open Access Journals (Sweden)

    Saaid Rahimi Bandarabadi


    Full Text Available The effect of modified starch on the properties of poly(styrene-ethylenepropylene- styrene tri-block copolymer was studied. Chemical treatment of starch with maleic anhydride was accomplished in an internal mixer in the presence of glycerol. The reaction was confirmed using Fourier infrared spectroscopy (FTIR and titration. The blend samples containing 10, 20, 30 and 50 wt% were obtained by melt blending and their mechanical, morphological and dynamic-mechanical properties were studied. Scanning electron microscopy (SEM images displayed droplet-matrix morphology and with increases in modified starch up to 50 wt% some partial co-continuous morphology was also observed. With increase of modified starch in the compound, the size of dispersed phase increased. DMTA results revealed that the partial compatibility was obtained because of slight difference between glass transition temperatures of two phases in the presence of modified starch. The peak of modified starch shifted to higher values and the differences between the two peaks decreased, indicating partial compatibility. Mechanical properties including tensile, elongation-at-break and modulus were also determined and the results showed that the mechanical properties of the sample were higher than those of neat TPS because of the higher compatibility. Tensile strength was decreased with increase in modified starch content due to the absence of strong interfacial adhesion. Moduli of the samples were increased with increase in modified starch content due to higher stiffness of starch. Biodegradability of the samples was evaluated by weight loss percentage using compost test. A rapid degradation was observed in the first 45 days and with increase of the modified starch content the degree of degradation was increased.

  3. Electrochemical Evaluation of a Recycled Copolymer Coating for Cultural Heritage Conservation Purposes

    Directory of Open Access Journals (Sweden)

    Marco Hernández-Escampa


    Full Text Available Acrylonitrile-butadiene-styrene (ABS is a well-known discard product from the industry. This copolymer can be dissolved in organic solvents, and thin films can be created by immersion. Two requirements for coatings used for cultural heritage conservation purposes are transparency and reversibility, both fulfilled by ABS films. The aim of this work was to characterize the copolymer and to evaluate the electrochemical properties of ABS coatings applied to copper. Such performance was compared to that of a commercial varnish commonly used in conservation. The results indicate high protection values of the ABS film, generating a potential application for this waste material. The electrochemical techniques included electrochemical noise, impedance spectroscopy, and potentiodynamic polarization.

  4. Preliminary study of styrene grafting on polyethylene films

    Energy Technology Data Exchange (ETDEWEB)

    Moraes, Gilberto de O.; Geraldes, Adriana N.; Zen, Heloisa A.; Parra, Duclerc F.; Lugao, Ademar B. [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)], E-mail:


    Grafting of styrene on polyethylene was carried out as a preliminary study. The experiments covered a range from 5 to 20 kGy and intended to evaluate the absorbed dose that led to the best degree of grafting (DOG) under industrial dose rate. PE films 0,065 mm thick were exposed several times to radiation at room temperature and nitrogen atmosphere. The films were immersed in the solution content styrene/solvent then irradiated (5 to 20 kGy) dose. As an exploratory experiment, styrene grafting was gravimetrically evaluated and characterized by infrared spectroscopy (FTIR).The degree of grafting (DOG) was calculated. Concentrations of methanol/ Styrene at the rate of 80:20 were favorable at low dose of 10 kGy. In presence of acid, best result was achieved at 15 kGy in the range of 5 to 20 kGy. (author)

  5. Relation between colour vision loss and occupational styrene exposure level


    Gong, Y; Kishi, R.; Katakura, Y; Tsukishima, E; Fujiwara, K.; Kasai, S; Satoh, T.; Sata, F; Kawai, T.


    Aims: To investigate the relation between colour vision loss and the exposure level of styrene. Exposure level included the current exposure concentration, past cumulative exposure, and the maximum exposure level in the past.

  6. Dynamic response of acrylonitrile butadiene styrene under impact loading

    National Research Council Canada - National Science Library

    Owolabi, Gbadebo; Peterson, Alex; Habtour, Ed; Riddick, Jaret; Coatney, Michael; Olasumboye, Adewale; Bolling, Denzell


    ... rateloading.Tensile tests were conducted on 3-D printed acrylonitrile butadiene styrene (ABS) at differentstrain rates, according to the ASTM D638 standard, to assess its strain rate sensitivity under quasi-staticloads...

  7. Solubilisation of griseofulvin, quercetin and rutin in micellar formulations of triblock copolymers E62P39E62 and E137S18E137. (United States)

    Ribeiro, Maria Elenir N P; Vieira, Icaro G P; Cavalcante, Igor Marques; Ricardo, Nágila M P S; Attwood, David; Yeates, Stephen G; Booth, Colin


    The solubilisation of two poorly soluble flavonoids, quercetin and rutin, in micellar solutions of mixtures of a block copolymer of ethylene oxide and styrene oxide (E(137)S(18)E(137)) with one of ethylene oxide and propylene oxide (E(62)P(39)E(62)) has been studied at 25 and 37 degrees C. Solubilisation capacities were higher than those for the model poorly water-soluble drug griseofulvin and comparable with published values for the solubilisation of rutin by beta-cyclodextrin.

  8. Block copolymer investigations (United States)

    Yufa, Nataliya A.

    The research presented in this thesis deals with various aspects of block copolymers on the nanoscale: their behavior at a range of temperatures, their use as scaffolds, or for creation of chemically striped surfaces, as well as the behavior of metals on block copolymers under the influence of UV light, and the healing behavior of copolymers. Invented around the time of World War II, copolymers have been used for decades due to their macroscopic properties, such as their ability to be molded without vulcanization, and the fact that, unlike rubber, they can be recycled. In recent years, block copolymers (BCPs) have been used for lithography, as scaffolds for nano-objects, to create a magnetic hard drive, as well as in photonic and other applications. In this work we used primarily atomic force microscopy (AFM) and transmission electron microscopy (TEM), described in Chapter II, to conduct our studies. In Chapter III we demonstrate a new and general method for positioning nanoparticles within nanoscale grooves. This technique is suitable for nanodots, nanocrystals, as well as DNA. We use AFM and TEM to demonstrate selective decoration. In Chapters IV and V we use AFM and TEM to study the structure of polymer surfaces coated with metals and self-assembled monolayers. We describe how the surfaces were created, exhibit their structure on the nanoscale, and prove that their macroscopic wetting properties have been altered compared to the original polymer structures. Finally, Chapters VI and VII report out in-situ AFM studies of BCP at high temperatures, made possible only recently with the invention of air-tight high-temperature AFM imaging cells. We locate the transition between disordered films and cylinders during initial ordering. Fluctuations of existing domains leading to domain coarsening are also described, and are shown to be consistent with reptation and curvature minimization. Chapter VII deals with the healing of PS-b-PMMA following AFM-tip lithography or

  9. Styrene-Associated Health Outcomes at a Windblade Manufacturing Plant (United States)

    McCague, Anna-Binney; Cox-Ganser, Jean M.; Harney, Joshua M.; Alwis, K. Udeni; Blount, Benjamin C.; Cummings, Kristin J.; Edwards, Nicole; Kreiss, Kathleen


    Background Health risks of using styrene to manufacture windblades for the green energy sector are unknown. Methods Using data collected from 355 (73%) current windblade workers and regression analysis, we investigated associations between health outcomes and styrene exposure estimates derived from urinary styrene metabolites. Results The median current styrene exposure was 53.6 mg/g creatinine (interquartile range: 19.5–94.4). Color blindness in men and women (standardized morbidity ratios 2.3 and 16.6, respectively) was not associated with exposure estimates, but was the type previously reported with styrene. Visual contrast sensitivity decreased and chest tightness increased (odds ratio 2.9) with increasing current exposure. Decreases in spirometric parameters and FeNO, and increases in the odds of wheeze and asthma-like symptoms (odds ratios 1.3 and 1.2, respectively) occurred with increasing cumulative exposure. Conclusions Despite styrene exposures below the recommended 400 mg/g creatinine, visual and respiratory effects indicate the need for additional preventative measures in this industry. PMID:26305283

  10. Toxicity of the components of styrene polymers: polystyrene, acrylonitrile-butadiene-styrene (ABS) and styrene-butadiene-rubber (SBR). Reactants and additives. (United States)

    Fishbein, L


    The toxicity of the components of styrene polymers, e.g., polystyrene, ABS and SBR, were reviewed with primary focus on the reactive monomers (except styrene) (e.g., acrylonitrile, butadiene) as well as on impurities and solvents such as benzene, hexane and methylethyl ketone, and additives such as phenyl-2-naphthylamine, di-n-butyl phthalate, and a number of peroxide initiators and flame retardants (e.g., 2,3-dibromopropanol, decadibromodiphenyl oxide and antimony trioxide). It is stressed that toxicity data are generally lacking for the majority of additives employed in the production of styrene polymers. Information is also lacking as to the numbers of individuals at potential risk and the extent of their exposure to the large number of additives employed.

  11. Designing block copolymer architectures for targeted membrane performance

    KAUST Repository

    Dorin, Rachel Mika


    Using a combination of block copolymer self-assembly and non-solvent induced phase separation, isoporous ultrafiltration membranes were fabricated from four poly(isoprene-b-styrene-b-4-vinylpyridine) triblock terpolymers with similar block volume fractions but varying in total molar mass from 43 kg/mol to 115 kg/mol to systematically study the effect of polymer size on membrane structure. Small-angle X-ray scattering was used to probe terpolymer solution structure in the dope. All four triblocks displayed solution scattering patterns consistent with a body-centered cubic morphology. After membrane formation, structures were characterized using a combination of scanning electron microscopy and filtration performance tests. Membrane pore densities that ranged from 4.53 × 1014 to 1.48 × 1015 pores/m 2 were observed, which are the highest pore densities yet reported for membranes using self-assembly and non-solvent induced phase separation. Hydraulic permeabilities ranging from 24 to 850 L m-2 h-1 bar-1 and pore diameters ranging from 7 to 36 nm were determined from permeation and rejection experiments. Both the hydraulic permeability and pore size increased with increasing molar mass of the parent terpolymer. The combination of polymer characterization and membrane transport tests described here demonstrates the ability to rationally design macromolecular structures to target specific performance characteristics in block copolymer derived ultrafiltration membranes. © 2013 Elsevier Ltd. All rights reserved.

  12. Computational Modeling of Polystyrene-b-(ethylene-co-butylene)-b-styrene and Mineral Oil Gels and Nanocomposites (United States)

    Chantawansri, T. L.; Berg, M.; Mrozek, R.; Stokes, K.; Henz, B.; Chung, P.; Beyer, F.; Lenhart, J.; Andzelm, J. W.


    There has been substantial interest in thermoplastic elastomer (TPE) gels composed of poly(styrene-b-(ethylene-co-butylene)-b-styrene)(SEBS) and hydrocarbon oils. Although the effects of adding nanoparticles on TPE gels is relatively unexplored, research in polymer nanocomposites have shown that the addition of nanoparticles enhanced physical properties. The microstructure of such a system is dependent on a variety of parameters such as block copolymer and nanoparticle concentrations, temperature, nanoparticle size, and nanoparticle interaction; thus to perform an extensive study of phase space, mesoscale modeling should be used in conjunction with the experimentation. To complement our experimental system, mesoscale modeling of this TPE gel and the corresponding nanocomposite are preformed using dynamic density functional theory and self consistent field theory through Materials Studio, where morphology of the system is studied as a function of various parameters and conditions. The validity of the computational methods has been confirmed for a number of experimental results, and subsequently has been used to explore a larger design space than is accessible solely through experimental methods.

  13. The Effect of Block Copolymer Adsorption on Thin Film Dewetting Kinetics (United States)

    Costa, A. C.; Oslanec, R.; Composto, R. J.; Vlcek, P.


    Using optical microscopy, the dewetting kinetics of thin polystyrene films from a solid substrate is studied as a function of block copolymer adsorption at the polymer/solid interface. The block copolymer is poly(styrene-block-methylmethacrylate) (PS-b-PMMA) which contains short MMA and long S blocks. The MMA block adsorbs to the silicon oxide surface, whereas the S block extends into the matrix polymer. The matrix is formed by a polystyrene (PS) homopolymer. The dewetting kinetics of PS films, with and without PS-b-PMMA, is investigated by measuring the hole diameter as a function of time, at constant temperature for various molecular weights and concentrations of PS-b-PMMA in the film. We find that the presence of adsorbing block copolymer at the polymer/solid interface can significantly retards the dewetting dynamics of thin polymer films by increasing the adhesion between the polymer film and the substrate. These macroscopic results are correlated with the molecular aspects of block copolymer adsorption, such as the volume fraction profile and the coverage of the adsorbed layer.

  14. Hybrid titanium dioxide/PS-b-PEO block copolymer nanocomposites based on sol-gel synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Gutierrez, J; Tercjak, A; Garcia, I; Peponi, L; Mondragon, I [' Materials-Technologies' Group, Departamento Ingenieria Quimica y Medio Ambiente, Escuela Politecnica, Universidad PaIs Vasco/Euskal Herriko Unibertsitatea, Plaza Europa 1, E-20018 Donostia-San Sebastian (Spain)], E-mail:


    The poly(styrene)-b-poly(ethylene oxide) (SEO) amphiphilic block copolymer, with two different molecular weights, has been used as a structure directing agent for generating nanocomposites of TiO{sub 2}/SEO via the sol-gel process. SEO amphiphilic block copolymers are designed with a hydrophilic PEO-block which can interact with inorganic molecules, as well as a hydrophobic PS-block which builds the matrix. The addition of different amounts of sol-gel provokes strong variations in the self-assembled morphology of TiO{sub 2}/SEO nanocomposites with respect to the neat block copolymer. As confirmed by atomic force microscopy (AFM), TiO{sub 2}/PEO-block micelles get closer, forming well-ordered spherical domains, in which TiO{sub 2} nanoparticles constitute the core surrounded by a corona of PEO-blocks. Moreover, for 20 vol% sol-gel the generated morphology changes to a hexagonally ordered structure for both block copolymers. The cylindrical structure of these nanocomposites has been confirmed by the two-dimensional Fourier transform power spectrum of the corresponding AFM height images. Affinity between titanium dioxide precursor and PEO-block of SEO allows us to generate hybrid inorganic/organic nanocomposites, which retain the optical properties of TiO{sub 2}, as evaluated by UV-vis spectroscopy.

  15. Molecular Dynamics Simulations of Silica-Filled Copolymers with Variable Sequence for Applications in Tire Treads (United States)

    Trazkovich, Alex J.; Hall, Lisa M.

    We simulate a simple nanocomposite relevant to tire tread compounds consisting of a single spherical nanoparticle surrounded by coarse-grained polymer chains. The polymers are composed of two different monomer types, which have different interaction strengths with the nanoparticle. The monomer sequence can be varied to model different copolymer configurations. We study the polymer end-to-end vector autocorrelation functions to obtain relaxation times of adsorbed and bulk polymer, showing how the interphase is affected by the polymer type and the monomer-nanoparticle interaction strengths. An understanding of the effect of copolymer sequence on the range of the polymer interphase and the magnitude of the effect on chain dynamics is critical to tire tread material design since the primary polymer component of modern tire tread is styrene-butadiene rubber (SBR) copolymer, which may be synthesized in primarily random or in various blocky copolymer configurations. Macromolecular adsorption to and desorption from filler surfaces has a significant effect on hysteresis, and in tire treads, hysteresis must be controlled to optimize the tradeoff between traction and rolling resistance. Superior tire tread materials must have high hysteresis under the operating conditions of traction while maintaining low hysteresis under the operating conditions of rolling resistance. An opportunity exists to control hysteresis through the use of SBR with specific monomer sequences.

  16. Copolymers of Vinyl-Containing Benzoxazine with Vinyl Monomers as Precursors for High Performance Thermosets

    Directory of Open Access Journals (Sweden)

    Tsutomu Takeichi


    Full Text Available A benzoxazine containing a vinyl group (P-4va was prepared by the reaction of phenol, 4-vinylaniline, and paraformaldehyde. A differential scanning calorimetry (DSC study revealed that ring-opening polymerization of the benzoxazine and chain polymerization of the vinyl group occurred in the same temperature range. When 2,2'-azobisisobutyronitrile was added as a radical initiator to P-4va, however, only the vinyl groups were polymerized at lower temperature, giving oligo(P-4va that contains pendent benzoxazine units. Radical copolymerization of P-4va with various vinyl monomers such as styrene, methyl methacrylate (MMA, and n-butyl acrylate (BuA was examined. The chemical structure of the copolymers was confirmed by FT-IR and 1H-NMR to be one of polyolefins bearing benzoxazine units as the pendant groups. The weight-average molecular weights of the copolymers determined by size exclusion chromatography were to be in the range of 1900–51,500 depending on the comonomers. DSC of the copolymers showed that the maxima of the exothermic peaks corresponding to the ring-opening polymerization of the pendent benzoxazine units were observed in the temperature range of 229–250 °C. Thermal cure up to 240 °C of the copolymer films afforded homogenous transparent films with improved thermal properties. Tough cured film was obtained by the copolymerization with MMA, while a tough and flexible film was obtained by the copolymerization with BuA.


    Directory of Open Access Journals (Sweden)

    G. T. Justino

    Full Text Available Abstract The high octane number of pyrolysis gasoline (PYGAS explains its insertion in the gasoline pool. However, its use is troublesome due to the presence of gum-forming chemicals which, in turn, can be removed via hydrogenation. The use of Langmuir-Hinshelwood kinetic models was evaluated for hydrogenation of styrene, a typical gum monomer, using Pd/9%Nb2O5-Al2O3 as catalyst. Kinetic models accounting for hydrogen dissociative and non-dissociative adsorption were considered. The availability of one or two kinds of catalytic sites was analyzed. Experiments were carried out in a semi-batch reactor at constant temperature and pressure in the absence of transport limitations. The conditions used in each experiment varied between 16 - 56 bar and 60 - 100 ºC for pressure and temperature, respectively. The kinetic models were evaluated using MATLAB and EMSO software. Models using adsorption of hydrogen and organic molecules on the same type of site fitted the data best.

  18. [Styrene migration into wine contained in polyester resin tanks]. (United States)

    Giffone, M; Brun, S


    The use of polyester resins in wine tanks manufacture or coating has widely spread during the past five years; this type of material has been and is still the source of organoleptic damage due to non polymerized sytrene migration into urine. Sytrene is a solvant often used in resin polymerization: it act as a reticulation agent of insaturated linear polyester. Polymerization at room temperature is allowed gy additives but has to be completed in warm air or in steam. An excess of styrene is often used for a polymerisation as complete as possible and remains on a free form. Then it migrates from the tank walls into the wine. For a better understanding of the styrene migration mechanism studies were performed on two levels: from small containers (4 l) kept in the laboratory and from tanks (30 hl) set up in an I.N.R.A. wine estate in all conditions usually realized in practice. Influence of time, temperature and alcohol content were studied. Styrene migration was interpreted as a diffusion phenomenom and styrene diffusion coefficients were calculated for several temperatures. Knowledge of these coefficients and of styrene content of the tank walls allow the prediction of a tank behaviour in time. Other substances that styrene were detected in wine and in tank walls, they are impurities either from resins like ethylbenzene, or from the catalyst like mesityl oxide. The lattest has never been mentioned in the litterature. From the results obtained it is possible to give some advices to manufacturers and users of polyester resin tanks, about the quality of raw materials, resins and additives along with the conditions carried and for their use and about the control of monomer styrene content in the walls of just manufactured tank.

  19. Spectrophotometric study of the interaction of methylene blue with poly(styrene-co-sodium styrene sulfonate

    Directory of Open Access Journals (Sweden)

    Souha Ben Mahmoud


    Full Text Available The interaction of the cationic phenothiazine dye, the Methylene Blue (MB with poly-(sodium styrene sulfonatef–co-(styrene1-f, (PSSNa f, has been investigated by spectrophotometric method. The polyelectrolyte induced metachromasy resulting in a blue shift of the absorption maxima of the dye, in agreement with the formation of dye H-aggregates. The stability of the PSSNa-MB complexes was studied as a function of polyelectrolyte chain length, polyelectrolyte electrostatic charge density f, polyelectrolyte concentration, NaCl salt addition, tetrahydrofurane (THF addition and THF treatment. The stoichiometry of PSSNa-MB complex evaluated by the molar ratio method was found 4:1 for the fully charged PSSNa f = 1. Reversal of metachromasy was observed upon salt and THF addition, while THF treatment does not affect the complex and allows recovering the initial complex. Finally, thermodynamic parameters of the interaction between the polyelectrolyte and the dye at different temperatures, namely free energy DG, the enthalpy DH and the entropy DS have been evaluated to determine the binding constant and as a consequence the stability of the complex. The metachromasy effect was found to be more high as the chemical charge f increases and reaches its maximum value f = 1, when operating at optimal conditions. So, the PSSNa f = 1-MB complex is the most stable in comparison to the others based on lower charge density PSSNa f.

  20. Polystyrene-co-Divinylbenzene PolyHIPE Monoliths in 1.0 mm Column Formats for Liquid Chromatography

    Directory of Open Access Journals (Sweden)

    Sidratul Choudhury


    Full Text Available The reversed phase liquid chromatographic (RP-HPLC separation of small molecules using a polystyrene-co-divinylbenzene (PS-co-DVB polyHIPE stationary phases housed within 1.0 mm i.d. silcosteel columns is presented within this study. A 90% PS-co-DVB polyHIPE was covalently attached to the walls of the column housing by prior wall modification with 3-(trimethoxysilyl propyl methacrylate and could withstand operating backpressures in excess of 200 bar at a flow rate of 1.2 mL/min. Permeability studies revealed that the monolith swelled slightly in 100% acetonitrile relative to 100% water but could nevertheless be used to separate five alkylbenzenes using a flow rate of 40 µL/min (linear velocity: 0.57 mm/s. Remarkable column-to-column reproducibility is shown with retention factor variation between 2.6% and 6.1% for two separately prepared columns.

  1. Reactive magnetic poly(divinylbenzene-co-glycidyl methacrylate) colloidal particles for specific antigen detection using microcontact printing technique. (United States)

    Eissa, Mohamed M; Mahbubor Rahman, Md; Zine, Nadia; Jaffrezic, Nicole; Errachid, Abdelhamid; Fessi, Hatem; Elaissari, Abdelhamid


    Epoxy-functionalized magnetic poly(divinylbenzene-co-glycidyl methacrylate) colloidal particles (mPDGs) were prepared by co-polymerization of 1,4-divinylbenzene and glycidyl methacrylate monomers. The reaction was conducted by batch emulsion polymerization in the presence of an oil in water magnetic emulsion as a seed. The chemical composition, morphology, iron oxide content, magnetic properties, particle size and colloidal stability of the prepared magnetic polymer particles were characterized using Fourier transform infrared spectroscopy, transmission electron microscopy, thermal gravimetric analysis, vibrating sample magnetometry, dynamic light scattering, and zeta potential determination, respectively. The prepared mPDGs were immobilized on a self-assembled monolayer of 3-aminopropyltriethoxysilane (APTES)/octadecyltrichlorosilane (OTS), which were patterned on glass using microcontact printing technique, forming mPDGs-APTES/OTS reactive surface. This construction (mPDGs-APTES/OTS) was used as a solid support for immunoassay. The immobilized magnetic particles were bioconjugated with monoclonal anti-human IL-10 antibody to provide specific and selective recognition sites for the recombinant human IL-10 protein (antigen). Fluorescence microscopic examination was carried out to follow this immunoassay using fluorescently labeled anti-human IL-10 antibody. The results obtained proved the successful use of mPDGs-APTES/OTS microcontact printed surfaces in an immunoassay, which can be exploited and integrated into microsystems in order to elaborate medical devices (e.g. biosensors) which could provide rapid analysis at high sensitivity with low volumes of analyte. Copyright © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

  2. Bentonite-based organoclays as innovative flame retardants agents for SBS copolymer. (United States)

    Franchini, M Comes; Fabbri, P; Frache, A; Ori, G; Messori, M; Siligardi, C; Ricci, A


    Two organophilic bentonites, based on nitrogen-containing compounds, have been synthesised via ion exchange starting from pristine bentonite with octadecyltrimethylammonium bromide (OTAB) and with synthetic melamine-derived N2,N4-dihexadecyl-1,3,5-triazine-2,4,6-triamine (DEDMEL). The chemical and morphological characterization of the organoclays was based on XRD, TEM, Laser Granulometry, X-Ray Fluorescence and CEC capacity. Copoly(styrene-butadiene-styrene)-nanocomposites (SBS-nanocomposites) were obtained by intercalation of the SBS-copolymer into these new organoclays by melt intercalation method. XRD and TEM analysis of the organoclays and of the micro/nano-composites obtained are presented. The effect of the organoclays on the SBS-nanocomposite's flammability properties was investigated using cone calorimeter. An encouraging decrease of 20% in the peak heat released rate (PHRR) has been obtained confirming the important role of melamine's based skeleton and its derived organoclays to act as effective fire retardants and for the improvement of this important functional property in SBS copolymers.

  3. Quantum chemistry investigation of secondary reaction kinetics in acrylate-based copolymers. (United States)

    Cuccato, Danilo; Mavroudakis, Evangelos; Moscatelli, Davide


    Recently, a growing amount of attention has been focused on the influence of secondary reactions on the free radical polymerization features and the properties and microstructure of the final polymer, particularly in the context of acrylate copolymers. One of the most challenging aspects of this research is the accurate determination of the corresponding reaction kinetics. In this paper, this problem is addressed using quantum chemistry. The reaction rate coefficients of various backbiting, propagation, and β-scission steps are estimated considering different chain configurations of a terpolymer system composed of methyl acrylate, styrene, and methyl methacrylate. The replacement of methyl acrylate radical units with styrene and methyl methacrylate globally decreases the backbiting probability and shifts the equilibrium toward the reactants, while the effect of replacing adjacent units is weaker and more dependent upon the specific substituting monomer. Propagation kinetics is affected primarily by the replacement of the radical units, while this effect appears to be particularly effective on midchain radical reactivity. The overall results clarify the different physicochemical behavior of chain-end, midchain, and short-branch radicals as a function of copolymer composition, providing new insights into free radical polymerization kinetics.

  4. The One-Pot Directed Assembly of Cylinder-Forming Block Copolymer on Adjacent Chemical Patterns for Bimodal Patterning. (United States)

    Chang, Tzu-Hsuan; Xiong, Shisheng; Liu, Chi-Chun; Liu, Dong; Nealey, Paul F; Ma, Zhenqiang


    The direct self-assembly of cylinder-forming poly(styrene-block-methyl-methacrylate) (PS-b-PMMA) block copolymer is successfully assembled into two orientations, according to the underlying guiding pattern in different areas. Lying-down and perpendicular cylinders are formed, respectively, depending on the design of chemical pattern: sparse line/space pattern or hexagonal dot array. The first chemical pattern composed of prepatterned cross-linked polystyrene (XPS) line/space structure has a period (LS ) equal to twice the intercylinder period of the block copolymer (L0 ). The PS-b-PMMA thin film on the prepared chemical template after thermal annealing forms a lying-down cylinder morphology when the width of the PS strips is less than the width of PS block in the PS-b-PMMA block copolymer. The morphology is only applicable at the discrete thickness of the PS-b-PMMA film. In addition to forming the lying-down cylinders directly on the XPS guiding pattern, the cylinder-forming block copolymer can also be assembled in a perpendicular way on the second guiding pattern (the hexagonal dot array). The block copolymer films are registered into two orientations in a single directed self-assembly process. The features of the assembled patterns are successfully transferred down to the silicon oxide substrate. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Directory of Open Access Journals (Sweden)

    Joner Oliveira Alves


    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.

  6. Energy Quenching Effects on Dry-Etching Durability of Alicyclic-Aliphatic Copolymers and Polymer Blends Enhanced by Polymer-Chain Entanglement (United States)

    Kushida, Masahito; Kawamoto, Kenryou; Harada, Kieko; Saito, Kyoichi; Sugita, Kazuyuki


    A correlation between the macromolecular structure and dry-etching durability is essential to design a resist of high performance. Ohnishi and ring parameters are known to be useful for estimating the durability, but some limitations are apparent, since the etching rate of a multicomponent matrix polymer is not only dependent on the composition. Previously, we have demonstrated that the etching rates of copolymers and polymer blends, which are composed of fragile aliphatic monomer and stable aromatic or alicyclic monomer units, are lower (the durabilities are higher) than the values calculated from those of the constituent homopolymers with the assumed wt% additivity. In this study, we prepared methyl methacrylate [MMA]/tricyclodecanyl methacrylate [TCDMA] copolymers of various compositions, and attempted to evaluate the dependence of etching rates on TCDMA content. The dependence was found to be inconsistent with those in the cases of α-methyl-styrene, 2-vinyl-naphthalene, and isobornyl methacrylate copolymers and polymer blends reported in the previous papers.

  7. Equilibrium and Nonequilibrium Nanoscale Ordering of Polystyrene-b-poly(N,N′-diethylaminoethyl methacrylate, a Block Copolymer Carrying Tertiary Amine Functional Groups

    Directory of Open Access Journals (Sweden)

    Pedro Navarro-Vega


    Full Text Available Poly(styrene-b-poly(N,N′-diethylaminoethyl methacrylate (PS-b-PDEAEM block copolymer was synthesized by RAFT free-radical polymerization using a trithiocarbonate type of chain transfer agent (CTA. Several block copolymer compositions were achieved maintaining low polydispersities by using PS as macro-CTA in the first step. Thin films of PS60%-b-PDEAEM40% were deposited over mica substrate, and its equilibrium and nonequilibrium nanostructures were studied. Lamellar (equilibrium, bicontinuous (nonequilibrium and detached nanoflakes (nonequilibrium, were obtained by using different annealing methods. Mixing nanocomposites of gold nanoparticles/PDEAEM in the block copolymer resulted in the formation of toroidal nanostructures confining gold nanoparticles to the core of those nanostructures. The same toroidal nanostructure was achieved by different annealing methods, including irradiation with UV light for 15 min. Electron micrographs show clearly this different type of arrays.

  8. LF-NMR study of effect the octadecylamine addition in the copolymerization process between acrylic acid and styrene monomers; Estudo por RMN de baixo campo do efeito da adicao de octadecilamina na copolimerizacao dos monomeros de acido acrilico e estireno

    Energy Technology Data Exchange (ETDEWEB)

    Pedroza, Oscar J.O.; Tavares, Maria I.B. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Inst. de Macromoleculas Professora Eloisa Mano]. E-mail:,


    The copolymer content at least two monomer units that are the repetitive unities in the polymeric chains. The use of Low Field Nuclear Magnetic Resonance (LF-NMR), MARAN ultra 23, was applied to measure the proton spin-lattice relaxation time values. The process of copolymerization between the acrylic acid (A) and the styrene (S) monomers was studied with the addition of the octadecylamine (D) in the acrylic acid monomer. These materials were submitted at reflux by 24 hours. After this process the polymerization was carried out at room temperature. The values of the relaxation parameter are showed in Table 1. The co polymerizations between acrylic acid and styrene monomers were influenced by the octadecylamine addition. The results showed that an increase in the amine concentration promotes flexibility in the final material. This can be explained in terms of chains size after amine addition, which promotes an increasing in the free space among the polymer chains. (author)

  9. New styrene-b-isobutylene-b-styrene (SIBS) glaucoma drainage implant (United States)

    Orozco, Marcia A.; Acosta, Ana C.; Espana, Edgar M.; Pinchuk, Leonard; Weber, Bruce; Davis, Stewart; Arrieta, Esdras; Dubovy, Sander; Fantes, Francisco; Aly, Mohamed; Zhou, Yonghua; Parel, Jean-Marie


    Purpose: To design and test the Miami-InnFocus Drainage Implant (MiDi) as a glaucoma shunt that is biocompatible, flexible, and significantly smaller than existing commercial implants in order to prevent postoperative hypotony, inflammation, scarring, erosion, and extrusion. Methods: A new biomaterial composed of styrene-b-isobutylene-b-styrene (SIBS) was used in a novel design for a glaucoma drainage implant. The implant consists of a tube 11mm long with an inner diameter of 70, 100, and 150 μm and outer diameter of 250 μm with a 1mm2 tab located 4.5mm from the proximal tip to prevent migration. The device was implanted in 15 New Zealand White rabbits for biocompatibility and efficacy testing. A similarly designed implant made of polydimethylsiloxane was implanted in 6 other animals as a pseudo-control. Typical GDI implantation technique was modified for this device. The proximal end of the new SIBS implant was inserted 2mm into the anterior chamber and the distal end placed in a subconjunctival space created by the surgeon. Biocompatibility of the device was studied by slit-lamp follow-up and intraocular pressure (IOP) measurements recorded periodically. Results: Biocompatibility of the MiDi was excellent. A low and diffuse bleb was observed with these devices. All SIBS tubes were patent 9 months after insertion. Immunostaining demonstrated non-continuous deposition of collagen with virtually no encapsulation. No macrophages or myofibroblast were visible around the SIBS polymer which was found more bioinert than the control PDMS. Conclusion: This newly designed glaucoma implant is clinically biocompatible in the rabbit model and maintained 100% patency at 9 months.

  10. Conceptual process design of extractive distillation processes for ethylbenzene/styrene separation

    NARCIS (Netherlands)

    Jongmans, Mark; Hermens, E.; Raijmakers, M.; Maassen, J.I.W.; Schuur, Boelo; de Haan, A.B.


    In the current styrene production process the distillation of the close-boiling ethylbenzene/styrene mixture to obtain an ethylbenzene impurity level of 100 ppm in styrene accounts for 75–80% of the energy requirements. The future target is to reach a level of 1–10 ppm, which will increase the

  11. Side chain alkylation of toluene with methanol over basic zeolites - novel production route towards styrene?

    NARCIS (Netherlands)

    Rep, M.; Rep, M.


    Styrene is an important monomer for the production of different types of (co-) polymers that are used in, e.g., toys, medical devices, food packaging, paper coatings etc. Styrene is produced with several different industrial processes. In 1998, the production of styrene monomer was approximately 21

  12. 40 CFR 721.9492 - Polymers of styrene, cyclohexyl methacrylate and substituted methacrylate. (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Polymers of styrene, cyclohexyl... Significant New Uses for Specific Chemical Substances § 721.9492 Polymers of styrene, cyclohexyl methacrylate...) The chemical substances identified generically as polymers of styrene, cyclohexyl methacrylate and...

  13. In vitro evolution of styrene monooxygenase from Pseudomonas putida CA-3 for improved epoxide synthesis

    NARCIS (Netherlands)

    Gursky, Lucas J.; Nikodinovic-Runic, Jasmina; Feenstra, K Anton; O'Connor, Kevin E.


    The styAB genes from Pseudomonas putida CA-3, which encode styrene monooxygenase, were subjected to three rounds of in vitro evolution using error-prone polymerase chain reaction with a view to improving the rate of styrene oxide and indene oxide formation. Improvements in styrene monooxygenase

  14. Advanced analytical methods for the structure elucidation of polystyrene-b-poly(n-butyl acrylate) block copolymers prepared by reverse iodine transfer polymerisation

    Energy Technology Data Exchange (ETDEWEB)

    Wright, Trevor Gavin; Pfukwa, Helen; Pasch, Harald, E-mail:


    Reverse iodine transfer polymerisation (RITP) is a living radical polymerisation technique that has shown to be feasible in synthesising segmented styrene-acrylate copolymers. Polymers synthesised via RITP are typically only described regarding their bulk properties using nuclear magnetic resonance spectroscopy and size exclusion chromatography. To fully understand the complex composition of the polymerisation products and the RITP reaction mechanism, however, it is necessary to use a combination of advanced analytical methods. In the present RITP procedure, polystyrene was synthesised first and then used as a macroinitiator to synthesise polystyrene-block-poly(n-butyl acrylate) (PS-b-PBA) block copolymers. For the first time, these PS-b-PBA block copolymers were analysed by a combination of SEC, in situ{sup 1}H NMR and HPLC. {sup 1}H NMR was used to determine the copolymer composition and the end group functionality of the samples, while SEC and HPLC were used to confirm the formation of block copolymers. Detailed information on the living character of the RITP process was obtained. - Highlights: • Comprehensive analysis of novel block copolymers. • Polymers were prepared for the first time by reverse iodine transfer polymerisation. • Combination of SEC, NMR, kinetic NMR, HPLC and comprehensive 2D-HPLC was used. • Detailed information about complex molecular composition and polymerisation kinetics was obtained.

  15. Highly selective dry etching of polystyrene-poly(methyl methacrylate) block copolymer by gas pulsing carbon monoxide-based plasmas (United States)

    Miyazoe, Hiroyuki; Jagtiani, Ashish V.; Tsai, Hsin-Yu; Engelmann, Sebastian U.; Joseph, Eric A.


    We propose a very selective PMMA removal method from poly(styrene-block-methyl methacrylate) (PS-b-PMMA) copolymer using gas pulsing cyclic etching. Flow ratio of hydrogen (H2) added to carbon monoxide (CO) plasma was periodically changed to control etch and deposition processes on PS. By controlling the process time of each etch and deposition step, full PMMA removal including etching of the neutral layer was demonstrated at 28 nm pitch, while PS thickness remained intact. This is more than 10 times higher etch selectivity than conventional continuous plasma etch processes using standard oxygen (O2), CO-H2 and CO-O2-based chemistries.

  16. Preparation of poly(glycidylmethacrylate-divinylbenzene) weak acid cation exchange stationary phases with succinic anhydride, phthalic anhydride, and maleic anhydride for ion chromatography. (United States)

    Liu, Junwei; Wang, Yong; Wu, Shuchao; Zhang, Peimin; Zhu, Yan


    In this work, poly(glycidylmethacrylate-divinylbenzene) microspheres were prepared and applied for the preparation of weak acid cation exchange stationary phases. Succinic anhydride, phthalic anhydride, and maleic anhydride were selected as carboxylation reagents to prepare three weak acid cation exchangers by direct chemical derivatization reaction without solvent or catalyst. The diameters and dispersity of the microspheres were characterized by scanning electron microscopy; the amount of accessible epoxy groups and mechanical stability were also measured. The weak acid cation exchangers were characterized by Fourier transform infrared spectroscopy; the content of carboxyl groups was measured by traditional acid base titration method. The chromatographic properties were characterized and compared by separating alkali, alkaline earth metal ions and ammonium and polar amines. The separation properties enhanced in the order of succinic anhydride, phthalic anhydride, and maleic anhydride modified poly(glycidylmethacrylate-divinylbenzene) cation exchangers. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. 21 CFR 175.125 - Pressure-sensitive adhesives. (United States)


    .... Butadiene-acrylonitrile copolymer. Butadiene-acrylonitrile-styrene copolymer. Butadiene-styrene copolymer.... Isobutylene-styrene copolymer. Petrolatum. Polybutene-1. Polybutene, hydrogenated; complying with the identity... contain not more than 1 percent by weight of triisopropanolamine). (c) Acrylonitrile copolymers identified...

  18. Lithium-Assisted Copolymerization of CO 2 /Cyclohexene Oxide: A Novel and Straightforward Route to Polycarbonates and Related Block Copolymers

    KAUST Repository

    Zhang, Dongyue


    A facile route toward alternating polycarbonates by anionic copolymerization of carbon dioxide (CO2) and cyclohexene oxide (CHO), using lithium halide or alkoxide as initiators and triisobutylaluminum (TiBA) as activator, is reported. α,ω-Heterobifunctional and α,ω-dihydroxypoly(cyclohexene carbonate)s (PCHC) as well as poly(CHC-co-CHO) copolymers with different carbonate composition could also be easily synthesized by adjusting the amount of TiBA or by adding inert lithium salts. The value of this initiating system also resides in the easy access to PSt-b-PCHC (PSt: polystyrene) and PI-b-PCHC (PI: polyisoprene) block copolymers which can be derived by mere one-pot sequential addition of styrene or dienes first and then of CO2 and CHO under the same experimental conditions. © 2016 American Chemical Society.

  19. Retardation of the dewetting process due to the addition of functional copolymers at polymer-polymer interfaces

    CERN Document Server

    Wunnicke, O; Lorenz-Haas, C; Leiner, V


    We studied the retardation of the dewetting process due to the addition of a functional copolymer in a polymer bilayer film. The model system consists of fully deuterated polystyrene (PS-d) on top of an amorphous polyamide (PA) sublayer on silicon substrates. Bilayer films were prepared with different content (0, 5, 10 and 30 vol. %) of a statistical copolymer (protonated styrene maleic anhydride acid (SMA2) containing 2% MA groups along the chain) being capable of forming hydrogen bonds with PA. The as-prepared as well as the annealed samples were investigated by neutron-reflectivity (NR) experiments, scanning force microscopy and optical microscopy. A significant retardation of dewetting is observed with the addition of SMA2. From model fits of NR curves the scattering length density profiles perpendicular to the sample surface were determined and an enrichment layer of SMA2 is detected. Retardation is explained by the intermixing of SMA2 and PS-d at the interface. (orig.)

  20. Simultaneous production of biobased styrene and acrylates using ethenolysis

    NARCIS (Netherlands)

    Spekreijse, J.; Notre, le J.E.L.; Haveren, van J.; Scott, E.L.; Sanders, J.P.M.


    Phenylalanine (1), which could be potentially obtained from biofuel waste streams, is a precursor of cinnamic acid (2) that can be converted into two bulk chemicals, styrene (3) and acrylic acid (4), via an atom efficient pathway. With 5 mol% of Hoveyda–Grubbs 2nd generation catalyst, 1 bar of

  1. Graft copolymerization and characterization of styrene with chitosan ...

    African Journals Online (AJOL)

    In this study, styrene was successfully grafted onto chitosan by conventional free radical polymerization technique, using potassium persulphate (KPS) as the initiator. The effect of various reaction conditions including chitosan:monomer weight ratio, polymerization temperature, reaction time and concentration of initiator ...

  2. Terpolymerization of 2-ethoxy ethylmethacrylate, styrene and maleic ...

    Indian Academy of Sciences (India)

    Terpolymerization of 2-ethoxyethyl methacrylate (2-EOEMA), styrene (St) and maleic anhydride (Ma) initiated by benzoyl peroxide was carried out in acetone as common solvent for three monomers. The structure and composition of terpolymer were determined by FTIR spectroscopy by recording analytical absorption bands ...

  3. Lignin poly(lactic acid) copolymers

    Energy Technology Data Exchange (ETDEWEB)

    Olsson, Johan Vilhelm; Chung, Yi-Lin; Li, Russell Jingxian; Waymouth, Robert; Sattely, Elizabeth; Billington, Sarah; Frank, Curtis W.


    Provided herein are graft co-polymers of lignin and poly(lactic acid) (lignin-g-PLA copolymer), thermoset and thermoplastic polymers including them, methods of preparing these polymers, and articles of manufacture including such polymers.

  4. Occupational Styrene Exposure on Auditory Function Among Adults: A Systematic Review of Selected Workers

    Directory of Open Access Journals (Sweden)

    Francis T. Pleban


    Full Text Available A review study was conducted to examine the adverse effects of styrene, styrene mixtures, or styrene and/or styrene mixtures and noise on the auditory system in humans employed in occupational settings. The search included peer-reviewed articles published in English language involving human volunteers spanning a 25-year period (1990–2015. Studies included peer review journals, case–control studies, and case reports. Animal studies were excluded. An initial search identified 40 studies. After screening for inclusion, 13 studies were retrieved for full journal detail examination and review. As a whole, the results range from no to mild associations between styrene exposure and auditory dysfunction, noting relatively small sample sizes. However, four studies investigating styrene with other organic solvent mixtures and noise suggested combined exposures to both styrene organic solvent mixtures may be more ototoxic than exposure to noise alone. There is little literature examining the effect of styrene on auditory functioning in humans. Nonetheless, findings suggest public health professionals and policy makers should be made aware of the future research needs pertaining to hearing impairment and ototoxicity from styrene. It is recommended that chronic styrene-exposed individuals be routinely evaluated with a comprehensive audiological test battery to detect early signs of auditory dysfunction. Keywords: auditory system, human exposure, ototoxicity, styrene

  5. Preparação de copolímeros à base de 2-vinilpiridina com propriedades bactericidas

    Directory of Open Access Journals (Sweden)

    Aline S. S. Valle


    Full Text Available We report the development of two copolymers based on 2-vinylpyridine, styrene and divinylbenzene (2Vpy-Sty-DVB with different porosity degrees. The copolymers were subsequently quaternized with methyl iodide. To prepare charge transfer complexes, the unmodified copolymers and their derivatives quaternized with methyl iodine were impregnated with iodine. The antibacterial properties of the polymers were evaluated in dilutions ranging from 10² to 10(7 cells/mL of the auxotrophic OHd5-K12 Escherichia coli strain. It was possible to obtain materials with complete antibacterial activity even in the highest cell concentrations tested.

  6. PVP-b-PEO block copolymers for stable aqueous and ethanolic graphene dispersions. (United States)

    Perumal, Suguna; Park, Kyung Tae; Lee, Hyang Moo; Cheong, In Woo


    The ability to disperse pristine (unfunctionalized) graphene is important for various applications, coating, nanocomposites, and energy related systems. Herein we report that amphiphilic copolymers of poly(4-vinyl pyridine)-block-poly(ethylene oxide) (PVP-b-PEO) are able to disperse graphene with high concentrations about 2.6mg/mL via sonication and centrifugation. Ethanolic and aqueous highly-ordered pyrolytic graphite (HOPG) dispersions with block copolymers were prepared and they were compared with the dispersions stabilized by P-123 Pluronic® (P123) and poly(styrene)-block-poly(ethylene oxide) (PS-b-PEO) synthesized. Transmission electron microscopy, scanning electron microscopy, atomic force microscopy, X-ray diffraction, Raman and UV-visible spectroscopic studies confirmed that PVP-b-PEO block copolymers are better stabilizers for HOPG graphene than P123 and PS-b-PEO. X-ray photoelectron spectroscopy and force-distance (F-d) curve analyses revealed that the nitrogen of vinyl pyridine plays a vital role in better attractive interaction with surface of graphene sheet. Thermogravimetric analysis showed that larger amount of PVP-b-PEO was adsorbed onto graphene with longer poly(4-vinyl pyridine) (PVP) block length and in aqueous medium, respectively, and which was consistent with electrical conductivity decreases. This study presents the dispersion efficiency of graphene using PVP-b-PEO varies substantially depending on the lengths of their hydrophobic (PVP) domains. Copyright © 2015 Elsevier Inc. All rights reserved.

  7. Synthesis and characterization of copolymers from hindered amines and vinyl monomers

    Directory of Open Access Journals (Sweden)

    Marcelo Aparecido Chinelatto


    Full Text Available New copolymers from hindered amines and vinyl monomers were synthesized by radical chain polymerization. To obtain polymeric HALS, acrylamide-(1ATP and acrylate-(4ATP monomers, derivatives from 2,2,6,6-tetramethylpiperidine and 2,2,6,6-tetramethyl-4-piperidinol were synthesized. The radical chain polymerization of 1ATP with styrene (Sty using 1-butanethiol (BTN resulted in a copolymer with 95 units of Sty and 15 units of 1ATP. The radical chain polymerization of 1ATP and vinyl acetate (VAc has produced only 1ATP homopolymer. In the chain polymerization of 4ATP with Sty or VAc, the hydrogen atom bonded to the nitrogen of 4ATP is labile enough to originate another radical at this site. The steric hindrance imposed by methyl groups on this bonding site hampers its reaction with other propagating species and the formation of a copolymer or network structure will be dependent on the size of the pendent group in the vinyl monomer.

  8. Electrically and chemically tunable soft-solid block copolymer structural color (Conference Presentation) (United States)

    Park, Cheolmin


    1D photonic crystals based on the periodic stacking of two different dielectric layers have been widely studied due to their potential use in low-power reflective mode displays, e-books and sensors, but the fabrication of mechanically flexible polymer structural color (SC) films, with electro-active color switching, remains challenging. Here, we demonstrate free-standing electric field tunable ionic liquid swollen block copolymer films. Placement of a polymer/ionic liquid (IL) film-reservoir adjacent to a self-assembled poly(styrene-block-quaternized 2vinyl pyridine) (PS-b-QP2VP) copolymer SC film allowed the development of R, G and B full-color SC block copolymer films by swelling of the QP2VP domains by the ionic liquid associated with water molecules. The IL-polymer/BCP SC film is mechanically flexible with excellent color stability over several days at ambient conditions. The selective swelling of the QP2VP domains could be controlled by both the ratio of the IL to a polymer in the gel-like IL reservoir layer and by an applied voltage in the range of -3V to +6V using a metal/IL reservoir/SC film/IL reservoir/metal capacitor type device.

  9. High-concentration graphene dispersion stabilized by block copolymers in ethanol. (United States)

    Perumal, Suguna; Lee, Hyang Moo; Cheong, In Woo


    This article describes a comprehensive study for the preparation of graphene dispersions by liquid-phase exfoliation using amphiphilic diblock copolymers; poly(ethylene oxide)-block-poly(styrene) (PEO-b-PS), poly(ethylene oxide)-block-poly(4-vinylpyridine) (PEO-b-PVP), and poly(ethylene oxide)-block-poly(pyrenemethyl methacrylate) (PEO-b-PPy) with similar block lengths. Block copolymers were prepared from PEO using the Steglich coupling reaction followed by reversible addition-fragmentation chain transfer (RAFT) polymerization. Graphite platelets (G) and reduced graphene oxide (rGO) were used as graphene sources. The dispersion stability of graphene in ethanol was comparatively investigated by on-line turbidity, and the graphene concentration in the dispersions was determined gravimetrically. Our results revealed that the graphene dispersions with PEO-b-PVP were much more stable and included graphene with fewer defects than that with PEO-b-PS or PEO-b-PPy, as confirmed by turbidity and Raman analyses. Gravimetry confirmed that graphene concentrations up to 1.7 and 1.8mg/mL could be obtained from G and rGO dispersions, respectively, using PEO-b-PVP after one week. Distinctions in adhesion forces of PS, VP, PPy block units with graphene surface and the variation in solubility of the block copolymers in ethanol medium significantly affected the stability of the graphene dispersion. Copyright © 2017 Elsevier Inc. All rights reserved.

  10. Composites copolymer-nanoparticule : courbure (United States)

    Hamdoun, B.; Ausserré, D.; Joly, S.


    The compression coefficient and the mean curvature coefficient of a composite of an A-B diblock copolymer charged with nanoparticles depend on the concentration of nanoparticles and on the dissymmetry of the copolymer chains. Concerning the curvature coefficient, a distinction must be done between an adiabatic and an isotherm coefficient when the copolymer chains are not symmetric or when Φ is not zero. Finally, the AB interfaces of the composite film present a spontaneous curvature that we calculate in the approximation of “small” nanoparticles. Les coefficients de compression et de courbure moyenne d'un composite de copolymères diblocs A-B et de nanoparticules dépendent de la concentration Φ en nanoparticules et de la dissymétrie du copolymères. Pour la courbure, on doit faire une distinction entre un coefficient adiabatique et un coefficient isotherme dès que le polymère n'est plus symétrique ou que Φ n'est plus nulle. Enfin, et surtout, les interfaces AB du composite présentent une courbure spontanée que nous calculons dans l'approximation des “petites” nanoparticules.

  11. Survey of volatile substances in kitchen utensils made from acrylonitrile-butadiene-styrene and acrylonitrile-styrene resin in Japan. (United States)

    Abe, Yutaka; Yamaguchi, Miku; Mutsuga, Motoh; Kawamura, Yoko; Akiyama, Hiroshi


    Residual levels of 14 volatile substances, including 1,3-butadiene, acrylonitrile, benzene, ethylbenzene, and styrene, in 30 kitchen utensils made from acrylonitrile-butadiene-styrene resin (ABS) and acrylonitrile-styrene resin (AS) such as slicers, picks, cups, and lunch boxes in Japan were simultaneously determined using headspace gas chromatography/mass spectroscopy (HS-GC/MS). The maximum residual levels in the ABS and AS samples were found to be 2000 and 2800 μg/g of styrene, respectively. The residual levels of 1,3-butadiene ranged from 0.06 to 1.7 μg/g in ABS, and three of 15 ABS samples exceeded the regulatory limit for this compound as established by the European Union (EU). The residual levels of acrylonitrile ranged from 0.15 to 20 μg/g in ABS and from 19 to 180 μg/g in AS. The levels of this substance in seven ABS and six AS samples exceeded the limit set by the U.S. Food and Drug Administration (FDA). Furthermore, the levels of acrylonitrile in three AS samples exceeded the voluntary standard established by Japanese industries. These results clearly indicate that the residual levels of some volatile compounds are still high in ABS and AS kitchen utensils and further observations are needed.

  12. Survey of volatile substances in kitchen utensils made from acrylonitrile–butadiene–styrene and acrylonitrile–styrene resin in Japan (United States)

    Abe, Yutaka; Yamaguchi, Miku; Mutsuga, Motoh; Kawamura, Yoko; Akiyama, Hiroshi


    Residual levels of 14 volatile substances, including 1,3-butadiene, acrylonitrile, benzene, ethylbenzene, and styrene, in 30 kitchen utensils made from acrylonitrile–butadiene–styrene resin (ABS) and acrylonitrile–styrene resin (AS) such as slicers, picks, cups, and lunch boxes in Japan were simultaneously determined using headspace gas chromatography/mass spectroscopy (HS-GC/MS). The maximum residual levels in the ABS and AS samples were found to be 2000 and 2800 μg/g of styrene, respectively. The residual levels of 1,3-butadiene ranged from 0.06 to 1.7 μg/g in ABS, and three of 15 ABS samples exceeded the regulatory limit for this compound as established by the European Union (EU). The residual levels of acrylonitrile ranged from 0.15 to 20 μg/g in ABS and from 19 to 180 μg/g in AS. The levels of this substance in seven ABS and six AS samples exceeded the limit set by the U.S. Food and Drug Administration (FDA). Furthermore, the levels of acrylonitrile in three AS samples exceeded the voluntary standard established by Japanese industries. These results clearly indicate that the residual levels of some volatile compounds are still high in ABS and AS kitchen utensils and further observations are needed. PMID:24936293

  13. Radiation grafting of glycidyl methacrylate and divinylbenzene onto polyethylene terephthalate fabrics for improving anti-dripping performance (United States)

    Chen, Xu; Wang, Yue; Dai, Guoliang; Peng, Jing; Li, Jiuqiang; Shi, Meiwu; Zhai, Maolin


    A new kind of anti-dripping polyethylene terephthalate (PET) fabric was successfully prepared by simultaneous gamma radiation-induced grafting polymerization of glycidyl methacrylate (GMA) and divinylbenzene (DVB) onto the surface of PET fabrics. The grafting yield (GY) and anti-dripping effect were optimized by changing the total absorbed dose, dose rate, concentration and the feed ratio of GMA and DVB. The grafting yield increased with the increase of absorbed dose and GMA monomer concentration, and decreased with the dose rate. It is confirmed that PET fabrics had been modified by Fourier transform infrared spectroscopy analysis. The tensile strength and elongation at break of modified PET fabrics were improved compared with original PET fabrics. The limiting oxygen index (LOI) of modified PET fabrics with the GY of 23-25% was 21.5, which was similar to that of unmodified PET fabrics. However, the anti-dripping performance of PET fabrics was improved remarkably after radiation modification due to the crosslinking of the sidechains grafted on the PET surface. This anti-dripping fabric may be promising for fire protective clothing.

  14. Nanopatterned block copolymers for use as vascular biomaterials (United States)

    Silverstein, Joshua S.

    Manipulation of surface topography or chemistry has been a growing trend in efforts to enhance the properties of medical devices. Understanding the interactions of biomolecules with nanoengineered surfaces is vital to assess the safety and efficacy of devices that incorporate these structures. In this dissertation, a model block copolymer (BCP) system based on poly(styrene)-block-poly(1,2-butadiene) was systematically modified using photochemical thiol-ene chemistry. Poly(1,2-butadiene) molecular weight and thiol-ene ratios were systematically varied based on a model monomer, boc-cysteamine, to determine the efficiency of the reaction. The results demonstrate the polydispersity index of modified BCPs significantly increased when low thiol-ene ratios were employed and sometimes induced gelation of the reacted polymers. Using a tenfold excess of thiol, functionalizations between 60-90% were obtained for an acid, amine, amide, and a pharmaceutical with a pendant thiol. Calorimetry showed a 30-60 °C increase in the glass transition temperature of the daughter polymers. Subsequently, films were cast from solvents found suitable to forming self-assembled BCP thin films. The synthetic and processing approach allows for the formation of nanopatterned block copolymer films with controlled chemistries from a single source material. The BCPs were further characterized using water contact angle measurements and atomic force microscopy in liquid. Significantly decreased contact angles were caused by selective swelling of charged BCP domains. Protein (fibrinogen, albumin, cytochrome C, immunoglobulin G) adsorption experiments were conducted under static and dynamic conditions with a quartz crystal microbalance with dissipation. The results indicate that nanopatterned chemistry and experimental conditions strongly impact adsorption dynamics. Adsorption behavior was dependent both on protein structure and the characteristics of the surface. Depending on the structural stability

  15. Effect of Grafting Density of Random Copolymer Brushes on Perpendicular Alignment in PS-b-PMMA Thin Films

    KAUST Repository

    Lee, Wooseop


    We modulated the grafting density (σ) of a random copolymer brush of poly(styrene-r-methyl methacrylate) on substrates to probe its effect on the formation of perpendicularly aligned lamellae of polystyrene-b-poly(methyl methacrylate) (PS-b-PMMA). Supported by coarse-grained simulation results, we hypothesized that an increase in σ will allow us to systematically tune the block copolymer interfacial interactions with the substrates from being preferential to one of the blocks to being neutral toward both blocks and will thereby facilitate enhanced regimes of perpendicularly aligned lamellae. We verified such a hypothesis by using a simple grafting-to approach to modify the substrates and characterized the thickness window for perpendicular lamellae as a function of brush thickness (or σ) on the grafted substrates using scanning force microscopy (SFM) images and grazing incidence small-angle X-ray scattering (GISAXS) measurements. The experimental results validated our hypothesis and suggested that the σ of random copolymer brushes can be used as an additional versatile parameter to modulate the interfacial interactions and the resulting alignment of block copolymer films.

  16. Unusual Emission of Polystyrene-Based Alternating Copolymers Incorporating Aminobutyl Maleimide Fluorophore-Containing Polyhedral Oligomeric Silsesquioxane Nanoparticles

    Directory of Open Access Journals (Sweden)

    Mohamed Gamal Mohamed


    Full Text Available In this study, we synthesized an unusual 2-aminobutyl maleimide isobutyl polyhedral oligomeric silsesquioxane (MIPOSS-NHBu monomer lacking conventional fluorescent groups. We then prepared poly(styrene-alt-2-aminobutyl maleimide isobutyl POSS [poly(S-alt-MIPOSS-NHBu] and poly(4-acetoxystyrene-alt-2-aminobutyl maleimide isobutyl POSS [poly(AS-alt-MIPOSS-NHBu] copolymers through facile free radical copolymerizations using azobisisobutyronitrile as the initiator and tetrahydrofuran as the solvent. A poly(4-hydroxystyrene-alt-2-aminobutyl maleimide isobutyl POSS [poly(HS-alt-MIPOSS-NHBu] copolymer was prepared through acetoxyl hydrazinolysis of poly(AS-alt-MIPOSS-NHBu. We employed 1H, 13C, and 29Si nuclear magnetic resonance spectroscopy; Fourier transform infrared spectroscopy; differential scanning calorimetry; and photoluminescence spectroscopy to investigate the structures and the thermal and optical properties of the monomers and novel POSS-containing alternating copolymers. Intramolecular hydrogen bonding between the amino and dihydrofuran-2,5-dione group and clustering of the locked C=O groups from the POSS nanoparticles in the MIPOSS-NHBu units restricted the intramolecular motion of the polymer chain, causing it to exhibit strong light emission. As a result, the MIPOSS-NHBu monomer and the poly(AS-alt-MIPOSS-NHBu copolymer both have potential applicability in the detection of metal ions with good selectivity.

  17. Polyethylene-Based Tadpole Copolymers

    KAUST Repository

    Alkayal, Nazeeha


    Novel well-defined polyethylene-based tadpole copolymers ((c-PE)-b-PS, PE: polyethylene, PS: polystyrene) with ring PE head and linear PS tail are synthesized by combining polyhomologation, atom transfer radical polymerization (ATRP), and Glaser coupling reaction. The -OH groups of the 3-miktoarm star copolymers (PE-OH)-b-PS, synthesized by polyhomologation and ATRP, are transformed to alkyne groups by esterification with propiolic acid, followed by Glaser cyclization and removal of the unreacted linear with Merrifield\\'s resin-azide. The characterization results of intermediates and final products by high-temperature size exclusion chromatography, H NMR spectroscopy, and differential scanning calorimetry confirm the tadpole topology.

  18. Composites copolymer-nanoparticule : courbure


    Hamdoun, B.; Ausserré, D.; Joly, S.


    Les coefficients de compression et de courbure moyenne d'un composite de copolymères diblocs A-B et de nanoparticules dépendent de la concentration Φ en nanoparticules et de la dissymétrie du copolymères. Pour la courbure, on doit faire une distinction entre un coefficient adiabatique et un coefficient isotherme dès que le polymère n'est plus symétrique ou que Φ n'est plus nulle. Enfin, et surtout, les interfaces AB du composite présentent une courbure spontanée que nous calculons dans l'appr...

  19. Removal of styrene from waste gas stream using a biofilter

    Directory of Open Access Journals (Sweden)

    B Bina


    Full Text Available Background: Styrene is produced in large quantities in the chemical industries and it has been listed among the 189 hazardous and toxic atmospheric contaminants under Clean Air Act Amendments, 1990, due to its adverse effects on human health. The biofiltration has been widely and efficiently applied during recent decades for the treatment of air streams contaminated by volatile organic compounds at low concentrations. Also this technology has been applied widely and efficiently in the removal of styrene from waste gas streams. Methods: Biofiltration of waste gas stream polluted by styrene vapor was investigated in a three-stage bench scale reactor. Yard waste compost using shredded hard plastics as a bulking agent in a 75:25 v/v mix of plastics:compost was used to packing biofilter. The system inoculation was achieved by adding thickened activated sludge obtained from municipal wastewater treatment plant and the effects of loading rate, inlet concentration, and empty bed retention time variations on the performance and operation of biofilter were studied. Results: Microbial acclimation to styrene was achieved with inlet concentration of 65 ± 11 ppm and bed contact time of 360 s after 57 days of operation. Under steady state conditions experimental results showed equal average removal efficiency of about 84% at loading rates of 60 and 80 g m-3 h-1 with empty bed retention time of 60 s. Maximum elimination capacity was obtained up to 81 g m-3 h-1 with organic loading rate of about 120 g m-3 h-1. Reduction in performance was observed at inlet concentrations of upper than 650 ppm related to organic loading rates up to 160 g m-3 h-1 and then removal efficiency was decreased sharply. Evaluation of the concentration profile along the bed height of column indicated that the most value of elimination capacity occurred in the first section of biofilter. Elimination capacity also showed higher performance when empty bed retention time was reduced to 30 s

  20. Main-chain supramolecular block copolymers. (United States)

    Yang, Si Kyung; Ambade, Ashootosh V; Weck, Marcus


    Block copolymers are key building blocks for a variety of applications ranging from electronic devices to drug delivery. The material properties of block copolymers can be tuned and potentially improved by introducing noncovalent interactions in place of covalent linkages between polymeric blocks resulting in the formation of supramolecular block copolymers. Such materials combine the microphase separation behavior inherent to block copolymers with the responsiveness of supramolecular materials thereby affording dynamic and reversible materials. This tutorial review covers recent advances in main-chain supramolecular block copolymers and describes the design principles, synthetic approaches, advantages, and potential applications.

  1. Styren a styren-7,8-oxid:metabolismus a analytické metody stanovení aduktů s proteiny

    Czech Academy of Sciences Publication Activity Database

    Jágr, Michal; Pacáková, V.; Petříček, Miroslav


    Roč. 103, č. 11 (2009), s. 902-910 ISSN 0009-2770 Institutional research plan: CEZ:AV0Z50200510 Keywords : styren * adducts * styren-7,8-oxid Subject RIV: EE - Microbiology, Virology Impact factor: 0.717, year: 2009

  2. Facile Synthesis of Multiblock Copolymers Containing Sequence-Controlled Peptides and Well-Defined Vinyl Polymers by Nitroxide-Mediated Polymerization. (United States)

    Nishimura, Shin-Nosuke; Higashi, Nobuyuki; Koga, Tomoyuki


    Precisely incorporating a wide range of structural and functional multiblocks along a polymer backbone is a significant challenge in polymer chemistry and offers promising opportunities to design highly ordered materials, including controlled polymer folding. Herein, a facile and versatile strategy for preparing functional multiblock copolymers composed of sequential peptides and well-defined vinyl polymers with a narrow polydispersity is reported. Cyclic oligopeptides have been developed that contain an alkoxyamine bond in the framework. By using this type of cyclic initiator, peptide-containing multiblock copolymers are successfully synthesized by nitroxide-mediated polymerization of styrene. To demonstrate the versatility of this method, radical (co)polymerizations were carried out for different monomers (p-chlorostyrene, 4-vinylpyridine, and styrene/acrylonitrile) and by three different cyclic peptide initiators with specific amino acid sequences. The resultant multiblock copolymer is foldable through intramolecular interactions between peptide blocks. It is believed that this approach will significantly advance the field of controlled polymer synthesis for complex structures and single-chain folding. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Effect of porosity and environment on the mechanical behavior of acrylic bone cement modified with acrylonitrile-butadiene-styrene particles: I. Fracture toughness. (United States)

    Vila, M M; Ginebra, M P; Gil, F J; Planell, J A


    The elastomeric copolymer acrylonitrile-butadiene-styrene (ABS) was added to a conventional acrylic bone cement matrix. The results obtained show that although strength and stiffness decreased with an increasing second phase volume fraction, ductility and toughness both increased. The crack propagation became stable for specimens containing over a 5% volume fraction of the second phase. The fracture toughness increased up to 60% when the amount of ABS reached 20% (v/v). For larger amounts linear elastic fracture mechanics techniques could not be used properly. The effects of porosity and environmental conditions on the mechanical behavior were also studied. The mechanisms that control the fracture process were investigated by means of scanning electron microscopy.

  4. Nanocomposites from block copolymer lamellar nanostructures and selective gold deposition. (United States)

    Diletto, Claudia; Morvillo, Pasquale; Di Girolamo, Rocco; Auriemma, Finizia; De Rosa, Claudio


    Innovative hybrid nanocomposites based on a nanostructured block copolymer (BCP) matrix whose lamellar nanodomains are selectively loaded with metal nanoparticles, have been prepared. A symmetric poly(styrene-b-methylmethacrylate) (PS-b-PMMA) amorphous BCP showing a lamellar morphology has been employed. Thin films of PS-b-PMMA were deposited by spin-coating or drop casting on indium thin oxide (ITO) substrate in order to achieve orientation of lamellae with the lamellar surface perpendicular to the substrate. The perpendicular orientation is related to the use of ITO substrate, which shows a neutral surface with non-preferential interactions with the PS and PMMA domains. Hybrid nanocomposites have been then prepared by selective incorporation of gold nanoparticles into the PS lamellar domain by using a simple method based on the selective deposition of thermally evaporated gold nanoparticles. This innovative approach can be very useful for the realization of nanocomposites that could be used as active layer in non-volatile OFET memory devices or very efficient organic solar cells, depending on the appropriate guest molecules.

  5. Dynamics of Chain Exchange in Block Copolymer Micelles (United States)

    Lodge, Timothy

    Block copolymer micelles are rarely at equilibrium. The primary reason is the large number of repeat units in the insoluble block, Ncore, which makes the thermodynamic penalty for extracting a single chain (``unimer exchange'') substantial. As a consequence, the critical micelle concentration (CMC) is rarely accessed experimentally; however, in the proximity of a critical micelle temperature (CMT), equilibration is possible. We have been using time-resolved small angle neutron scattering (TR-SANS) to obtain a detailed picture of the mechanisms and time scales for chain exchange, at or near equilibrium. Our model system is poly(styrene)-block-poly(ethylene-alt-propylene)) (PS-PEP), in the PEP-selective solvent squalane (C30H62) . Equivalent micelles with either normal (hPS) or perdeuterated (dPS) cores are initially mixed in a blend of isotopically substituted squalane, designed to contrast-match a 50:50 hPS:dPS core. Samples are then annealed at a target temperature, and chain exchange is revealed quantitatively by the temporal decay in scattered intensity. The rate of exchange as function of concentration, temperature, Ncore, Ncorona, and chain architecture (diblock versus triblock) will be discussed.

  6. Styrene-based shape memory foam: fabrication and mathematical modeling (United States)

    Yao, Yongtao; Zhou, Tianyang; Qin, Chao; Liu, Yanju; Leng, Jinsong


    Shape memory polymer foam is a promising kind of structure in the biomedical and aerospace field. Shape memory styrene foam with uniform and controlled open-cell structure was successfully fabricated using a salt particulate leaching method. Shape recovery capability exists for foam programming in both high-temperature compression and low-temperature compression (Shape recovery properties such as shape fixing property and shape recovery ratio were also characterized. In order to provide guidance for the future fabrication of shape memory foam, the theories of Gibson and Ashby as well as differential micromechanics theory were applied to predict Young’s modulus and the mechanical behavior of SMP styrene foams during the compression process.

  7. Effect of ultrasonic pretreatment on emulsion polymerization of styrene. (United States)

    Nagatomo, Daichi; Horie, Takafumi; Hongo, Chizuru; Ohmura, Naoto


    This study investigated the effect of pretreatment of ultrasonic irradiation on emulsion polymerization of styrene to propose a process intensification method which gives high conversion, high reaction rate, and high energy efficiency. The solution containing styrene monomer was irradiated by a horn mounted on the ultrasonic transducer with the diameter of 5mm diameter and the frequency of 28 kHz before starting polymerization. The pretreatment of ultrasound irradiation as short as 1 min drastically improved monomer dispersion and increased reaction rate even under the agitation condition with low rotational speed of impeller. Furthermore, the ultrasonic pretreatment resulted in higher monomer concentration in polymer particles and produced larger polymer particles than conventional polymerization without ultrasonic pretreatment. Copyright © 2016 Elsevier B.V. All rights reserved.

  8. Fall From High and Acute Styrene Exposure : A Case Report

    Directory of Open Access Journals (Sweden)

    Ferhat Ižcme


    Full Text Available Styrene is a benzene derivative of the aromatic hydrocarbon which is widely used in the manufacture of plastics industry, synthetic rubber and insulating materials. Its toxic effects occur by inhalation of its vapor or by direct contact. In acute intoxication irritation in the eye and skin may occur and chemical pneumonitis may develop in the lungs due to inhalation. It dissolves in ethanol, benzene, acetone and ether. Water solubility is low. In this paper we present the management of a patient who after falling down from the scaffold which is approximately 5 meters of height, a tin of styrene on the same scaffold spilled on him and we would like to draw attention to the need for decontamination chamber which is not available in the most of the emergency departments in our country.

  9. Acute behavioral effects of styrene exposure: a further analysis

    Energy Technology Data Exchange (ETDEWEB)

    Cherry, N.; Rodgers, B.; Venables, H.; Waldron, H.A.; Wells, G.G.


    Studies were carried out on two groups to styrene-based resin. Early morning urinary mandelic acid concentrations after two days without exposure correlated with reaction time measured on arrival at work. Men were found to differ considerably in their rate of clearance of mandelic acid-those with slow reaction times. After some months at reduced exposure, a small group of men with previously high mandelic acid concentrations has speeded up on the reaction time task.

  10. Micelles based on HPMA copolymers

    NARCIS (Netherlands)

    Talelli, M.; Rijcken, C.J.F.; Nostrum, C.F. van; Storm, G.; Hennink, W.E.

    Polymeric micelles have been under extensive investigation during the past years as drug delivery systems, particularly for anticancer drugs. They are formed by the self-assembly of amphiphilic block copolymers in aqueous solutions and have a spherical shape and a size in the nano-range (<200 nm).

  11. A poly(alkyl methacrylate-divinylbenzene-vinylbenzyl trimethylammonium chloride) monolithic column for solid-phase microextraction. (United States)

    Liu, Wan-Ling; Lirio, Stephen; Yang, Yicong; Wu, Lin-Tai; Hsiao, Shu-Ying; Huang, Hsi-Ya


    In this study, an organic polymer monolithic columns, which were prepared via in situ polymerization of alkyl methacrylate-ester (AMA), divinylbenzene (DVB) and vinylbenzyl trimethylammonium chloride (VBTA, charged monomer), were developed as adsorbent for solid-phase microextraction (SPME). Different parameters affecting the extraction efficiency for nine (9) non-steroidal anti-inflammatory drugs (NSAIDs) such as the ratio of the stearyl methacrylate (SMA) to DVB monomer, column length, sample pH, extraction flow rate and desorption solvent were investigated to obtain the optimal SPME condition. Also, the permeability for each poly(AMA-DVB-VBTA) monolithic column was investigated by adding porogenic solvent (poly(ethylene glycol), PEG). Using the optimized condition, a series of AMA-based poly(AMA-DVB-VBTA) monolith columns were developed to determine the effect the extraction efficiency of NSAIDs by varying the alkyl chain length of the methacrylate ester (methyl-, butyl-, octyl-, or lauryl-methacrylate; (MMA, BMA, OMA, LMA)). Results showed that decreasing the AMA chain length increases the extraction efficiency of some NSAIDs (i.e. sulindac (sul), naproxen (nap), ketoprofen (ket) and indomethacin (idm)). Among the poly(AMA-DVB-VBTA) monolithic columns, poly(BMA-DVB-VBTA) showed a highly repeatable extraction efficiency for NSAIDs with recoveries ranging from 85.0 to 100.2% with relative standard deviation (RSD) less than 6.8% (n=3). The poly(BMA-DVB-VBTA) can also be reused for at least 50 times without any significant effect in extraction efficiency for NSAIDs. Finally, using the established conditions, the poly(BMA-DVB-VBTA) was used to extract trace-level NSAIDs (100μgL(-1)) in river water with good recoveries ranging from 75.8 to 90.8% (RSD<14.9%). Copyright © 2015 Elsevier B.V. All rights reserved.


    Directory of Open Access Journals (Sweden)

    Ali KARA


    Full Text Available A modified suspension polymerization was used for the preparation of the mesoporous magnetic-poly(divinylbenzene-co-vinylimidazole (m-poly(DVB-VIM microbeads in size 53-212 μm of average diameter. The specific surface area and the DVB/VIM mol ratio of the microsphereswere determined as 29.47 m2/g and 1:4 mol/mol with Fe3O4, respectively. The physicochemical studies of adsorption of Ni(II ions from aqueous solutions such as pH, initial concentration, amountof mesoporous m-poly(DVB-VIM microbeads, contact time, and temperature onto the m-poly(DVBVIM microspheres were carried out. The maximum adsorption capacities of the m-poly(DVB-VIMmicrospheres towards Ni(II ions were determined as 13.51, 20.14, 21.00 and 23.62 mg/g at 277 K, 298 K, 318 K, and 338 K, respectively. The dynamic and equilibrium adsorption behaviours of the system were adequately described by the pseudo-second-order kinetic and the Langmuir isotherm models, respectively. Various thermodynamic parameters, such as the Gibbs’ free energy change (ΔGo, the standard enthalpy change (ΔHo and the standard entropy change (ΔSo were also determined. Morever, after use in the adsorption, the m-poly(DVB-VIM microbeads with paramagnetic property was separated from the via the applied magnetic force. These results indicate that the material studied could be used as a purifier for the removal of Ni(II ions from water and wastewater under magnetic field.

  13. Confined space hazards: combined exposure to styrene, fiberglass, and silica. (United States)

    Shields, P G; McCunney, R J; Chase, K H


    Work in confined spaces continues to present hazards to workers. The magnitude of this problem was recently addressed by the Occupational Safety and Health Administration in its Final Rule for "Permit-Required Control Spaces for General Industry" (29 CFR Parts 1910). Although illness and injury are typically due to asphyxiation, explosion, and drowning, toxic exposures also are an important risk. We describe herein four workers engaged in erosion-proofing enclosed chemical tanks with minimal ventilation and no respiratory protection. They were exposed to styrene-based solvents, styrene-based resins, silica, and fiberglass dust. Each experienced acute neurological effects and bronchitis. One worker developed a life-threatening pneumonia that resulted in numerous complications. The severity of the illness, which would likely not have otherwise occurred, resulted from impaired lung defense mechanisms due to the combined exposures. Several studies support the association of styrene exposure and respiratory illness that may be compounded by co-exposure to fiberglass in unique circumstances. To prevent the hazards of confined space, recommended procedures should be followed, including those established by the National Institute for Occupational Safety and Health and the Occupational Safety and Health Administration.

  14. Styrene biofiltration in a trickle-bed reactor

    Directory of Open Access Journals (Sweden)

    V. Novak


    Full Text Available The biological treatment of styrene waste gas in a trickle-bed filter (TBF was investigated. The bioreactor consisted of a two-part glass cylinder (ID 150 mm filled with 25 mm polypropylene Pall rings serving as packing material. The bed height was 1m. Although the laboratory temperature was maintained at 22 ºC, the water temperature in the trickle-bed filter was slightly lower (about 18 ºC.The main aim of our study was to observe the effect of empty-bed residence time (EBRT on bioreactor performance at a constant pollutant concentration over an extended time period. The bioreactor was inoculated with a mixed microbial consortium isolated from a styrene-degrading biofilter that had been running for the previous two years. After three weeks of acclimation period, the bioreactor was loaded with styrene (100 mg.m-3. EBRT was in the range of 53 s to 13 s. A maximum elimination capacity (EC of 11.3 gC.m-3.h-1 was reached at an organic loading (OL rate of 18.6 gC.m-3.h-1.

  15. Synthesis and characterization of novel functional electrosterically stabilized colloidal particles prepared by emulsion polymerization using a strongly ionized amphiphilic diblock copolymer. (United States)

    Mohanty, P S; Dietsch, H; Rubatat, L; Stradner, A; Matsumoto, K; Matsuoka, H; Schurtenberger, P


    Amphiphilic diblock copolymers such as poly(styrene)-block-poly(styrene sulfonate) (PS-b-PSS) (Matsuoka, H.; Maeda, S.; Kaewsaiha, P.; Matsumoto, K. Langmuir 2004, 20, 7412), belong to a class of new polymeric surfactants that ionize strongly in aqueous media. We investigated their self-assembly behavior in aqueous solutions and used them as an emulsifier to prepare electrosterically stabilized colloidal particles of different diameters between 70 to 400 nm. We determined the size, size polydispersity, effective charge, total dissociable charge, structural ordering, and phase behavior using light scattering, transmission electron microscopy (TEM), small-angle neutron scattering (SANS), and potentiometric titration. These experiments clearly demonstrated that all of the synthesized particles were nearly monodisperse (polydispersity indexpolyelectrolyte brush shell. Finally, these monodisperse particles were found to self-assemble into 3D ordered colloidal crystalline arrays at a low volume fraction (=0.00074) that diffract light in the visible region.

  16. Preparation, characterization and evaluation of proton-conducting hybrid membranes based on sulfonated hydrogenated styrene-butadiene and polysiloxanes for fuel cell applications

    Energy Technology Data Exchange (ETDEWEB)

    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)


    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)

  17. Chromosomal aberrations in lymphocytes of workers exposed to low levels of styrene

    Energy Technology Data Exchange (ETDEWEB)

    Nordenson, I.; Beckman, L.


    Chromosomal aberrations were studied in lymphocytes of 15 workers exposed to styrene and 13 controls. The average styrene concentration in the work room air was 24 ppm, and the levels of urinary mandelic acid were below 2 mmol/l. No significant increase in the rates of gaps and breaks was found. However, the rate of micronuclei was significantly increased, which indicates that the mitotic spindle mechanism may be more sensitive to styrene and its metabolites than DNA.

  18. Block Copolymer Adhesion Promoter: Effect of Non Adsorbing Block Length and Substrate Polarity (United States)

    Costa, Ana Claudia; Composto, Russell J.; Vlcek, Petr; Satija, Sushil; Ivkov, Robert


    Block copolymer adsorption to polar substrates is investigated using neutron reflectivity and forward recoil spectrometry. The adhesion promoter is poly (deuterated styrene-block-methylmethacrylate) (dPS-b-MMA) having a short and nearly constant MMA block, which adsorbs to the substrate. The non-adsorbing dPS block length, NdPS, is systematically varied from below to above the entanglement degree of polymerization (Ne). The dPS-b-MMA is blended with a PS matrix, which represents a nearly neutral environment for the dPS block. The substrates are silicon oxide and an organic monolayer of an amino terminated silane. Dewetting studies show that film stability increases as NdPS approaches Ne and as the substrate becomes more hydrophobic. These macroscopic results suggest that entanglements across the matrix/adsorbed layer interface and a strong MMA-substrate interaction can greatly improve thin film stability.

  19. Structural rearrangements in a lamellar diblock copolymer thin film during treatment with saturated solvent vapor (United States)

    Di, Zhenyu; Posselt, Dorthe; Smilgies, Detlef-M.; Papadakis, Christine M.


    We have investigated the structural changes in thin films of lamellar poly(styrene-b-butadiene) diblock copolymers during treatment with saturated cyclohexane vapor, a solvent slightly selective for polybutadiene. Using real-time, in-situ grazing-incidence small-angle X-ray scattering (GISAXS), the swelling and the rearrangement of the lamellae were investigated with a time resolution of a few seconds, and the underlying processes on the molecular level were identified. After a few minutes in vapor, a transient state with a more well-defined and more long-range ordered lamellar orientation was encountered. Additional parallel lamellae formed which we attribute to the increased degree of coiling of the polymers in the swollen state. Eventually, the film became disordered. These changes are attributed to the increased mobility of the swollen polymers and the gradually decreasing segment-segment interaction parameter in the film as solvent is absorbed. PMID:20305742

  20. Adsorption Profile of Basic Dye onto Novel Fabricated Carboxylated Functionalized Co-Polymer Nanofibers

    Directory of Open Access Journals (Sweden)

    Marwa F. Elkady


    Full Text Available Acrylonitrile-Styrene co-polymer was prepared by solution polymerization and fabricated into nanofibers using the electrospinning technique. The nanofiber polarization was enhanced through its surface functionalization with carboxylic acid groups by simple chemical modification. The carboxylic groups’ presence was dedicated using the FT-IR technique. SEM showed that the nanofiber attains a uniform and porous structure. The equilibrium and kinetic behaviors of basic violet 14 dye sorption onto the nanofibers were examined. Both Langmuir and Temkin models are capable of expressing the dye sorption process at equilibrium. The intraparticle diffusion and Boyd kinetic models specified that the intraparticle diffusion step was the main decolorization rate controlling the process.

  1. Synthesis and characterization of functional copolymer/organo-silicate nanoarchitectures through interlamellar complex-radical (coterpolymerization

    Directory of Open Access Journals (Sweden)


    Full Text Available The functional copolymers, having a combination of rigid/flexible linkages and an ability of complex-formation with interlayered surface of organo-silicate, and their nanocomposites have been synthesized by interlamellar complex-radical (coterpolymerization of intercalated monomer complexes of maleic anhydride (MA and itaconic acid (IA with dimethyl dodecylamine surface modified montmorillonite (organo-MMT (MA…DMDA-MMT and IA…DMDA-MMT n-butyl methacrylate (BMA and/or BMA/styrene monomer mixtures. The results of nanocomposite structure–composition– property relationship studies indicate that interlamellar complex-formation between anhydride/acid units and surface alkyl amine and rigid/flexible linkage balance in polymer chains are important factors providing the effective intercalation/ exfoliation of the polymer chains into the silicate galleries, the formation of nanostructural hybrids with higher thermal stability, dynamic mechanical behaviour and well dispersed morphology.

  2. Role of corona block in molecular exchange in block copolymer micelles (United States)

    Wang, En; Lu, Jie; Lodge, Timothy; Bates, Frank

    Self-assembled block polymer micelles are used in a variety of applications including drug delivery and viscosity modification as additives to motor lubricants. Previous work with dilute solutions of poly(styrene-b-ethylene-alt-propylene) (PS-PEP) diblock copolymer micelle has resulted in a theoretical model that accounts for the dramatic influence of the PS core block length and dispersity on chain exchange kinetics in squalane, a selective neutral solvent for PEP. This model, which accounts for the significant effect of core block length and its polydispersity on chain exchange kinetics, does not address the role of the corona block length. This presentation will describe the consequences of varying the size of the PEP corona block at constant core molecular weight on the rate of chain exchange based on time-resolved small-angle neutron scattering (TR-SANS) measurements. These results have informed an improved model that explicitly includes a corona term.

  3. Evaluation of acrylate-based block copolymers prepared by atom transfer radical polymerization as matrices for paclitaxel delivery from coronary stents. (United States)

    Richard, Robert E; Schwarz, Marlene; Ranade, Shrirang; Chan, A Ken; Matyjaszewski, Krzysztof; Sumerlin, Brent


    Acrylate-based block copolymers, synthesized by atom transfer radical polymerization (ATRP) processes, were evaluated as drug delivery matrices for the controlled release of paclitaxel from coronary stents. The polymers were multiblock copolymers consisting of poly(butyl acrylate) or poly(lauryl acrylate) soft blocks and hard blocks composed of poly(methyl methacrylate), poly(isobornyl acrylate), or poly(styrene) homo- or copolymers. Depending on the ratio of hard to soft blocks in the copolymers, coating formulations were produced that possessed variable elastomeric properties, resulting in stent coatings that maintained their integrity when assessed by scanning electron microscopy (SEM) imaging of overexpanded stents. In vitro paclitaxel release kinetics from coronary stents coated with these copolymers typically showed an early burst followed by sustained release behavior, which permitted the elution of the majority of the paclitaxel over a 10-day time period. It was determined that neither the nature of the polyacrylate (n-butyl or lauryl) nor that of the hard block appeared to affect the release kinetics of paclitaxel at a loading of 25% drug by weight, whereas some effects were observed at lower drug loading levels. Differential scanning calorimetry (DSC) analysis indicated that the paclitaxel was at least partially miscible with the poly(n-butyl acrylate) phase of those block copolymers. The copolymers were also evaluated for sterilization stability by exposing both the copolymer alone and copolymer/paclitaxel coated stents to e-beam radiation at doses of 1-3 times the nominal dose used for medical device sterilization (25 kGy). It was found that the copolymers containing blocks bearing quaternary carbons within the polymer backbone were less stable to the radiation and showed a decrease in molecular weight as determined by gel-permeation chromatography. Conversely, those without quaternary carbons showed no significant change in molecular weight when

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

    National Research Council Canada - National Science Library

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


    Ceramifiable styrene-butadiene (SBR)-based composites containing low-softening-point-temperature glassy frit promoting ceramification, precipitated silica, one of four thermally stable refractory fillers...

  5. Where Scattering and Computations Meet: Structure and Dynamics of Ionic Co-Polymers (United States)

    Perahia, Dvora


    Ion transporting polymers constitute vital components in clean energy generation and storage devices including electrolytic media in fuel cells and ion conducting separators in batteries. While different polymers are currently in use, achieving controlled ion transport and storage ability while retaining mechanical and chemical stability remains a challenge: under the conditions which optimize the transport and storage for specific application, either mechanical or chemical stabilities are compromised. Designing block-co-polymers with ion transporting blocks bound to blocks that enhance mechanical and chemical stability would mitigate the challenge. Tailoring block copolymers with blocks that exhibit various desired properties, results in a new set of open questions that pertain to new complex materials including defining the phase diagram and understanding the interfacial regions of the muliblocks. Here we present the first molecular-level computational insight of the behavior of a pentablock, A-B-C-B-A, co-polymer that consists of an A block of poly(t-butyl-styrene), a B block of ethylene-r-propylene and a C block of a randomly sulfonated styrene, in solution in comparison with neutron scattering data. Neutron studies have shown that in hydrophobic solvents this pentablock forms elongated micelles in dilute solutions where the ionic block dominates the solution structure. These studies provide ensemble average of structure and properties. The computational studies provided further molecular-level insight. Here we will discuss the interrelations between scattering results and computational studies to provide remarkable understanding of a complex ionic system. Pathways to advance this molecular understanding to an actual membrane will be then discussed. We thank DOE contact DE-FGO2-12ER46843 for support of this work.

  6. Determination of Loops to Bridges Ratio in Triblock Copolymers by Dielectric Relaxation Spectroscopy^# (United States)

    Karatasos, K.; Anastasiadis, S. H.; Kremer, F.; Watanabe, H.


    Dielectric spectroscopy over a broad frequency (10-2 Hz to 10^6 Hz) and temperature (-160 to 300^circC) range has been used to investigate the loops to bridges ratio in ordered triblock copolymers. We have utilized a specifically synthesized poly(styrene-b-1,4-isoprene-styrene) triblock having symmetrically inverted dipoles along the chain backbone of the middle block and the respective diblock precursor. The relaxation process observed for the triblock, with relaxation times identical to the block end-to-end vector relaxation of the diblock, corresponds to relaxation of the loop conformation in the ordered triblock. The weight fraction of loops in the ordered triblock, w_loops, is estimated from comparison of the dielectric loss and/or the dielectric strength of this process in the triblock to that in the diblock. This fraction is being investigated as a function of the sample history. Besides, the very slow relaxation, recently observed in ordered diblocks and attributed to relaxation of the conformal interfaces formed in the ordered state, is also clearly observed for ordered triblocks. # Part of this research was sponsored by NATO's Scientific Affairs Division in the framework of the Science for Stability Programme

  7. Thermal scanning probe lithography for the directed self-assembly of block copolymers (United States)

    Gottlieb, S.; Lorenzoni, M.; Evangelio, L.; Fernández-Regúlez, M.; Ryu, Y. K.; Rawlings, C.; Spieser, M.; Knoll, A. W.; Perez-Murano, F.


    Thermal scanning probe lithography (t-SPL) is applied to the fabrication of chemical guiding patterns for directed self-assembly (DSA) of block copolymers (BCP). The two key steps of the overall process are the accurate patterning of a poly(phthalaldehyde) resist layer of only 3.5 nm thickness, and the subsequent oxygen-plasma functionalization of an underlying neutral poly(styrene-random-methyl methacrylate) brush layer. We demonstrate that this method allows one to obtain aligned line/space patterns of poly(styrene-block-methyl methacrylate) BCP of 18.5 and 11.7 nm half-pitch. Defect-free alignment has been demonstrated over areas of tens of square micrometres. The main advantages of t-SPL are the absence of proximity effects, which enables the realization of patterns with 10 nm resolution, and its compatibility with standard DSA methods. In the brush activation step by oxygen-plasma exposure, we observe swelling of the brush. This effect is discussed in terms of the chemical reactions occurring in the exposed areas. Our results show that t-SPL can be a suitable method for research activities in the field of DSA, in particular for low-pitch, high-χ BCP to achieve sub-10 nm line/space patterns.

  8. Synthesis of cyclopentadienyl capped polyethylene and subsequent block copolymer formation via hetero Diels-Alder (HDA) chemistry. (United States)

    Espinosa, Edgar; Glassner, Mathias; Boisson, Christophe; Barner-Kowollik, Christopher; D'Agosto, Franck


    In the current contribution it is demonstrated - for the first time - that poly(ethylene) (M(n) = 1,400 as well as 2,800 g  ·  mol(-1) , PDI = 1.2) can be readily equipped with highly reactive cyclopentadienyl (Cp) end groups. The Cp terminal poly(ethylene) can subsequently be reacted in an efficient hetero Diels-Alder (HDA) reaction with macromolecules (poly(isobornyl acrylate) (M(n) = 4,600 g  ·  mol(-1) , PDI = 1.10) and poly(styrene) (M(n) = 6,300 g  ·  mol(-1) , PDI = 1.13) featuring strongly electron withdrawing thiocarbonyl thio end groups, prepared via reversible addition fragmentation chain transfer (RAFT) polymerization employing benzylpyridin-2-yldithioformate (BPDF) as transfer agent. The resulting block copolymers have been analyzed via high-temperature size exclusion chromatography (SEC) as well as nuclear magnetic resonance (NMR) spectroscopy. The current system allows for the removal of the excess of the non-poly(ethylene) containing segment via filtration of the poly(ethylene)-containing block copolymer. However, the reaction temperatures need to be judiciously selected. Characterization of the generated block copolymers at elevated temperatures can lead - depending on the block copolymer type - to the occurrence of retro Diels-Alder processes. The present study thus demonstrates that RAFT-HDA ligation can be effectively employed for the generation of block copolymers containing poly(ethylene) segments. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Styrene exposure and biologic monitoring in FRP boat production plants

    Energy Technology Data Exchange (ETDEWEB)

    Ikeda, M.; Koizumi, A.; Miyasaka, M.; Watanabe, T.


    A survey on styrene exposure was conducted in five small to medium-sized fiber-reinforced plastic (FRP) boat plants utilizing carbon felt dosimeters as personal and stationary samplers to measure 4h (TWA) exposure during workday afternoons. The heaviest exposure, up to 256 ppm by personal sampling and 174 ppm by stationary sampling, took place during the lamination on a mold to produce a boat shell, and the work inside narrow holds also resulted in exposures of a comparable degree. Styrene levels were much lower in other auxiliary works. The TWA of exposure in an entire boat production was estimated to be 40-50 ppm. Installation of several flexible hoses as an exhaust system was proved to be effective in decreasing the vapor concentration. Gas masks were also useful in reducing the exposure. Urine samples were collected from 96 male workers at the end of 8h work (4h in the morning and 4h in the afternoon) and also from 22 nonexposed male subjects, and analyzed for mandelic acid (MA), phenylglyoxylic acid (PhGA), and hippuric acid (HA). When the results of urinalyses were compared with 4-h styrene TWA as monitored by personal sampling, the best correlation was obtained with MA + PhGA/creatinine (the correlation coefficient, 0.88), followed by MA (0.84). For these two cases, regression lines and 95% confidence limits for the group means and for the individual values were calculated. The urinary level of MA, PhGA, and HA in the 22 nonexposed male subjects were also tabulated.

  10. Devulcanization of styrene butadiene (SBR) waste tire by controlled oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Rios, Rachel R.V.A.; Gontijo, Manuela; Ferraz, Vany P.; Lago, Rochel M.; Araujo, Maria Helena [Minas Gerais Univ., Belo Horizonte, MG (Brazil). Dept. de Quimica]. E-mail:


    This work describes the devulcanization of vulcanized SBR (Styrene Butadiene Rubber) based on controlled oxidation with nitric acid. IR, {sup 1}H and {sup 13}C-NMR, CHN elemental analyses, TG, GPC and TPD-MS (Temperature Programmed Decomposition-Mass Spectrometry) experiments suggest that nitric acid promotes two processes: devulcanization by oxidation of the sulfide crosslinks and oxidation of the carbon framework leading to the formation of -COOH and -NO{sub 2} groups. Under aggressive conditions (HNO{sub 3}, reflux) the polymer chain is strongly oxidized and fragmented to a highly oxygenated low molecular weight fraction, which is soluble in water. (author)

  11. 40 CFR 721.6920 - Butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted... (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Butyl acrylate, polymer with... acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted silane. (a... butyl acrylate, polymer with substituted methyl styrene, methyl methacrylate, and substituted silane...

  12. 76 FR 77709 - Butyl acrylate-methacrylic acid-styrene polymer; Tolerance Exemption (United States)


    ... AGENCY 40 CFR Part 180 Butyl acrylate-methacrylic acid-styrene polymer; Tolerance Exemption AGENCY...-propenoate and ethenylbenzene (CAS Reg. No. 25036-16-2); also known as butyl acrylate-methacrylic acid...-risk polymers are described in 40 CFR 723.250(d). Butyl acrylate-methacrylic acid-styrene polymer...


    The report gives results of emissions measurements carried out at a representative facility (Eljer Plumbingware in Wilson, NC) that manufactures polyester-resin-reinforced shower stalls and bathtubs by spraying styrene-based resins onto molds in vented, open, spray booths. Styren...


    This report is an addendum to a 1996 report, Assessment of Styrene Emission Controls for FRP/C and Boat Building Industries. It presents additional evaluation of the biological treatment of styrene emissions, Dow Chemical Company's Sorbathene solvent vapor recovery system, Occupa...

  15. 40 CFR 721.3800 - Formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol, ethylene... (United States)


    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Formaldehyde, condensated... Formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol, ethylene oxide adduct. (a... generically as formaldehyde, condensated polyoxyethylene fatty acid, ester with styrenated phenol, ethylene...

  16. Utilizing the phenol byproducts of coke production: 3. Phenols as coinhibitors of thermopolymerization during styrene production

    Energy Technology Data Exchange (ETDEWEB)

    I.I. Batura; A.F. Gogotov; V.I. Cherepanov; O.I. Baranov; A.A. Levchuk; M.V. Parilova [Irkutsk State Technical University, Irkutsk (Russian Federation)


    A new oligomerization procedure for phenol byproducts from coke production is experimentally studied. This method, oxidative combination, is intended to produce an effective coinhibitor of styrene thermopolymerization. When combined with a Mannich base, the new oligomer exhibits excellent inhibiting properties in the heat treatment of styrene and matches the effectiveness of imported inhibitors based on nitroxyl radicals. 15 refs., 1 tab.

  17. Exploiting Framework Flexibility of a Metal-Organic Framework for Selective Adsorption of Styrene over Ethylbenzene

    NARCIS (Netherlands)

    Mukherjee, S.; Joarder, B.; Desai, A.V.; Manna, B.; Krishna, R.; Ghosh, S.K.


    The separation of styrene and ethylbenzene mixtures is industrially important and is currently performed in highly energy-intensive vacuum distillation columns. The primary objective of our investigation is to offer an energy-efficient alternative for selective adsorption of styrene by a flexible

  18. Sequence-controlled copolymers of 2,3,4,5-pentafluorostyrene: Mechanistic insight and application to organocatalysis

    KAUST Repository

    O'Shea, John Paul


    A number of copolymers between styrene (St) or 4-azidomethylstyrene (N 3St) and 2,3,4,5,6-pentafluorostyrene (FSt) have been prepared by atom-transfer radical polymerization (ATRP) and conventional free radical polymerization (FRP). The mode of monomer alternation in copolymers has been established unambiguously using heteronuclear multiple bond correlation (HMBC) NMR. The degree and nature of monomer alternation was found to be strongly dependent on both the solvent (or lack thereof) and the polymerization initiator. These results are in contrast to previously published studies, which rely primarily on classic analysis of monomer reactivity ratios. We proceeded to independently functionalize the N3St and FSt moieties using orthogonal "click" chemistries: copper-catalyzed azide-alkyne cycloaddition (CuAAC) and fluoroarene-thiol coupling (FTC). An alternating copolymer bearing -NH2 and -SO3 - functional groups was found to be a competent organocatalyst for a Henry reaction between benzaldehyde and nitromethane. This journal is © 2014 The Royal Society of Chemistry.

  19. The development of novel Nexar block copolymer/Ultem composite membranes for C2-C4 alcohols dehydration via pervaporation. (United States)

    Zuo, Jian; Shi, Gui Min; Wei, Shawn; Chung, Tai-Shung


    Novel composite membranes comprising sulfonated styrenic Nexar pentablock copolymers were developed by dip-coating on poly(ether imide) hollow fibers for pervaporation dehydration of C2-C4 alcohols. The advantages of using block copolymers as the selective layer are (1) their effectiveness to synergize the physicochemical properties of different chemical and structural moieties and (2) tunable nanoscale morphology and nanostructure via molecular engineering. To achieve high-performance composite membranes, the effects of coating time, ion exchange capacity (IEC) of the copolymer, and solvent systems for coating were investigated. It is revealed that a minimum coating time of 30 s is needed for the formation of a continuous and less-defective top layer. A higher IEC value results in a membrane with a higher flux and lower separation factor because of enhanced hydrophilicity and stretched chain conformation. Moreover, the composite membranes prepared from hexane/ethanol mixtures show higher separation factors and lower fluxes than those from the hexane solvent owing to microdomain segregation induced by ethanol and a smooth and dense top selective layer. These hypotheses were verified by atomic force microscopy and positron annihilation spectroscopy. The newly developed composite membranes demonstrate impressive separation performance with fluxes exceeding 2 kg/m(2) h and separation factors more than 200 for isopropyl alcohol and n-butanol dehydration from 85/15 wt % alcohol/water feed mixtures at 50 °C.

  20. Phase behavior and ionic conductivity of concentrated solutions of polystyrene-poly(ethylene oxide) diblock copolymers in an ionic liquid. (United States)

    Simone, Peter M; Lodge, Timothy P


    Concentrated solutions of poly(styrene-b-ethylene oxide) (PS-PEO) diblock copolymers were prepared using the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide [EMI][TFSI] as the solvent. The self-assembled microstructures adopted by the copolymer solutions have been characterized using small-angle X-ray scattering. Lyotropic mesophase transitions were observed, with a progression from hexagonally packed cylinders of PEO, to lamellae, to hexagonally packed cylinders of PS upon increasing [EMI][TFSI] content. The change in lamellar domain spacing with ionic liquid concentration was found to be comparable to that reported for other block copolymers in strongly selective solvents. The ionic conductivity of the concentrated PS-PEO/[EMI][TFSI] solutions was measured via impedance spectroscopy, and ranged from 1 x 10(-7) to 1 x 10(-3) S/cm at temperatures from 25 - 100 degrees C. Additionally, the ionic conductivity of the solutions was found to increase with both ionic liquid concentration and molecular weight of the PEO blocks. The ionic conductivity of PEO homopolymer/[EMI][TFSI] solutions was also measured in order to compare the conductivity of the PS-PEO solutions to the expected limit for a lamellar sample with randomly oriented microstructure grains.

  1. Organocatalytic chemo- and regioselective oxyarylation of styrenes via a cascade reaction: remote activation of hydroxyl groups. (United States)

    Zhang, Yu-Chen; Jiang, Fei; Wang, Shu-Liang; Shi, Feng; Tu, Shu-Jiang


    The first organocatalytic oxyarylation of styrenes has been established through a cascade of vinylogous Michael addition/alkoxyl transfer reactions of o- or p-hydroxylstyrenes with quinone imine ketals. The process leads to a highly chemo- and regioselective oxyarylation of styrenes and provides access to m-alkylated anilines in generally high yields and excellent diastereoselectivity (up to 99% yield, >95:5 dr). An investigation of the reaction pathway revealed that the existence and position of the hydroxyl group of styrene played crucial roles in the cascade reaction, suggesting that the two reactants were simultaneously activated by binaphthyl-derived phosphoric acid via hydrogen bonding interactions and long-distance conjugative effects. In addition, the activating group of the hydroxyl functionality in the products can be easily removed or transformed, demonstrating the applicability and utility of this strategy in styrene oxyarylation and in the synthesis of styrene-based compounds.

  2. Human exposure to styrene. IV. Industrial hygiene investigations and biological monitoring in the polyester industry

    Energy Technology Data Exchange (ETDEWEB)

    Guillemin, M.P.; Bauer, D.; Martin, B.; Marazzi, A.


    An industrial hygiene study of 10 glassfiber reinforced polyester plants (including 90 workers) was undertaken to investigate the styrene exposure in this industry and to estimate biological limit values (BLV's) for the urinary metabolites of styrene: mandelic (MA) and phenylglyoxylic acids (PGA). Time weighted average (TWA) styrene exposures were found ranging from 2 to 200 ppm. The urinary elimination of metabolites correlated well with exposure and the BLV's corresponding to an 8-h exposure at 100 ppm were consistent with earlier laboratory findings (end-of-shift sample: MA 1640, PGA 510, MA + PGA 2150; next-morning sample: MA 330, PGA 330, MA + PGA 660 mg/g creat.). Total metabolites (MA + PGA) in the next-morning sample or mandelic acid in the end-of-shift sample are recommended for routine monitoring of exposure to styrene. The study revealed the need for further research on how to reduce styrene exposure in this industry.

  3. No acute behavioral effects of exposure to styrene: a safe level of exposure

    Energy Technology Data Exchange (ETDEWEB)

    Edling, C.; Ekberg, K.


    To determine whether exposure to low levels of styrene (below 110 mg/m3) causes acute behavioral effects and symptoms that may be related to concentrations of styrene in air or urinary mandelic acid or both, 12 men occupationally exposed to styrene were studied and compared with a reference group of 10 unexposed men. Simple reaction time was measured before and after work and information about symptoms was obtained by questionnaire. Active and passive sampling of airborne styrene was carried out and urinary mandelic acid concentrations were measured. Although the size of the study groups is small, the results indicate that exposure to styrene below 110 mg/m3 does not cause any acute adverse effects on the central nervous system.

  4. The effect of heat treatment on the internal structure of nanostructured block copolymer films

    Energy Technology Data Exchange (ETDEWEB)

    Sepe, A; Hoppe, E T; Jaksch, S; Magerl, D; Zhong, Q; Papadakis, C M [Technische Universitaet Muenchen, Physikdepartment, Fachgebiet Physik weicher Materie/Lehrstuhl fuer funktionelle Materialien, James-Franck-Strasse 1, 85747 Garching (Germany); Perlich, J [HASYLAB at DESY, Notkestrasse 85, 22603 Hamburg (Germany); Posselt, D [IMFUFA, Department of Science, Systems and Models, Roskilde University, PO Box 260, 4000 Roskilde (Denmark); Smilgies, D-M, E-mail: [Cornell High Energy Synchrotron Source (CHESS), Wilson Laboratory, Cornell University, Ithaca, NY 14853 (United States)


    We report on the temperature dependence of the nanostructure of thin block copolymer films, as studied using in situ grazing-incidence small-angle x-ray scattering (GISAXS). We focus on spin-coated poly(styrene-b-butadiene) diblock copolymer thin films featuring lamellae perpendicular to the substrate. In situ GISAXS measurements elucidate the structural changes during heat treatment at temperatures between 60 and 130 {sup 0}C. Thermal treatment below 100 {sup 0}C does not destroy the perpendicular lamellar order. In contrast, treatment between 105 and 120 {sup 0}C leads to a broad distribution of lamellar orientations which only partially recovers upon subsequent cooling. Treatment at 130 {sup 0}C leads to severe changes of the film structure. We attribute the change of behavior at 100 {sup 0}C to the onset of the glass transition of the polystyrene block and the related increase of long-range mobility. Our results indicate that the perpendicular lamellar orientation for high molar mass samples is not stable under all conditions.

  5. Solvent Size Dependent Structure Of Diblock Copolymer Micelles In N-alkane (United States)

    Lee, Sangho; Heo, Tae-Young; Choi, Soo-Hyung

    Block copolymers can self-assemble into micelles in selective solvents. Theoretical description for the micelle structure is described the balance between core block stretching and core block-solvent interaction with the assumption that the core is melt state. So, core block was stretched and solvent entropy effect(e.g.solvent penetration into core)was simplified at the theoretical models. However, we observed PS-PEP micelle in squalane that the core block was nearly fully relaxed. In this study, we investigate the micelle structure as a function of solvent size. Here, we use Poly(styrene-b-ethylene-alt-propylene) in selective solvent such as n-alkanes. Solvents are favorable for PEP corona block and unfavorable PS core block. As solvent size decreases, solvent easily can penetrate into core, however, interaction parameter increases systematic. Critical micelle temperature(CMT) and detailed micelle structure were measured by Small-Angle X-ray Scattering. Interestingly, we observed that the CMT decreases as solvent size decreases. The core block is fully relaxed by comparing with core radius and 20,PS. Almost each structure data overlapped as a function of CMT-T. This results show that block copolymer micelle can be controlled by solvent size and thus solvent entropy effect Ministry of Trade, Industry and Energy, Korea Evaluation Institute of Industrial Technology, Pohang Accelerator Laboratory (4C beam line).

  6. A series of poly(butylimidazolium) ionic liquid functionalized copolymers for anion exchange membranes (United States)

    Ouadah, Amina; Xu, Hulin; Luo, Tianwei; Gao, Shuitao; Wang, Xing; Fang, Zhou; Jing, Chaojun; Zhu, Changjin


    A new series of ionic liquid functionalized copolymers for anion exchange membranes (AEM) is prepared. Poly(butylvinylimidazolium)(b-VIB) is copolymerized with para-methyl styrene (p-MS) by the radical polymerization formed block copolymers b-VIB/p-MS, which is crosslinked with poly(diphenylether bibenzimidazole) (DPEBI) providing the desired materials b-VIB/p-MS/DPEBI. Structures are characterized via H1NMR, FTIR spectra and elemental analysis. The b-VIB blocks offer the anion conduction function while DPEBI moieties contribute to enhancing other properties. The prepared membranes display chloride conductivity as high as 19.5 mS/cm at 25 °C and 69.2 mS/cm at 100 °C-higher than that of the commercial membrane tokuyuama A201-. Their hydroxide conductivity reaches 35.7 Scm-1 at 25 °C and 73.1 Scm-1 at 100 °C. The membranes showed a linear Arrhenius behavior in the anion conduction, low activation energies and distinguished nanophase separation of hydrophilic/hydrophobic regions by the transmission electron microscopy (TEM) studies. Thermal investigations using TGA and DSC confirm that the membranes are stable up to 250 °C. Particularly, drastically alkaline stability due to no decrease in the hydroxide conductivity after 168 h of treatment with 2M KOH.

  7. 40 CFR 63.500 - Back-end process provisions-carbon disulfide limitations for styrene butadiene rubber by emulsion... (United States)


    ... disulfide limitations for styrene butadiene rubber by emulsion processes. 63.500 Section 63.500 Protection... limitations for styrene butadiene rubber by emulsion processes. (a) Owners or operators of sources subject to this subpart producing styrene butadiene rubber using an emulsion process shall operate the process...

  8. 40 CFR 721.7020 - Distillates (petroleum), C(3-6), polymers with styrene and mixed terpenes (generic name). (United States)


    ...), polymers with styrene and mixed terpenes (generic name). 721.7020 Section 721.7020 Protection of...), C(3-6), polymers with styrene and mixed terpenes (generic name). (a) Chemical substance and...), polymers with styrene and mixed terpenes (PMN P-89-676) is subject to reporting under this section for the...

  9. Preparation and characterization of nanocomposites of natural rubber with polystyrene and styrene-methacrylic acid copolymer nanoparticles

    Directory of Open Access Journals (Sweden)

    T. Nuruk


    Full Text Available Composites of natural rubber (NR/vinyl polymer nanoparticles as polystyrene (PS and poly(styrenemethacrylic acid (P(S-MAA were prepared by heterocoagulation technique. The polymer nanoparticles were prepared by emulsifier-free emulsion polymerizations at 70°C using potassium persulfate as initiator. Under acidic condition where positive charge was present on the NR latex (NRL surface, the nanoparticles having negative charge mainly from sulfate group of initiator were able to adsorb on the NRL surface, the electrostatic interaction being the driving force. The scanning electron micrographs showed that the polymer nanoparticles are homogenously distributed throughout NR matrix as nanoclusters with an average size of about 500 and 200 nm for PS and P(S-MAA, respectively. The mechanical properties of NR/PS and NR/P(S-MAA composite films were compared with the NR host. The nanocomposites, particularly when the polymer nanoparticles are uniformly dispersed, possess significantly enhanced mechanical properties strongly depending on the morphology of the nanocomposites.

  10. Resistivity and Its Anisotropy Characterization of 3D-Printed Acrylonitrile Butadiene Styrene Copolymer (ABS/Carbon Black (CB Composites

    Directory of Open Access Journals (Sweden)

    Jie Zhang


    Full Text Available The rapid printing of 3D parts with desired electrical properties enables numerous applications. Fused deposition modeling (FDM using conductive thermoplastic composites has been a valuable approach for such fabrication. The parts produced by FDM possess various controllable structural features, but the effects of the structural features on the electrical properties remain to be determined. This study investigated the effects of these features on the electrical resistivity and resistivity anisotropy of 3D-printed ABS/CB composites. The effects of the process parameters of FDM, including the layer thickness, raster width, and air gap, on the resistivity in both the vertical and horizontal directions for cubic samples were studied because the internal structure of the printed parts depended on those process parameters. The resistivities of printed parts in different parameter combinations were measured by an impedance analyzer and finite element models were created to investigate the relationship between the resistivity and the internal structure. The results indicated that the parameters remarkably affected the resistivity due to the influence of voids and the bonding condition between adjacent fibers. The resistivity in the vertical direction ranged from 70.40 ± 2.88 Ω·m to 180.33 ± 8.21 Ω·m, and the resistivity in the horizontal direction ranged from 41.91 ± 2.29 Ω·m to 58.35 ± 0.61 Ω·m at the frequency of 1 kHz. Moreover, by adjusting the resistivities in different directions, the resistivity anisotropy of the printed parts can be manipulated from 1.01 to 3.59. This research may serve as a reference to fabricate parts with sophisticated geometry with desired electrical resistivity and resistivity anisotropy.

  11. Aggregate structure and effect of phthalic anhydride modified soy protein on the mechanical properties of styrene-butadiene copolymer (United States)

    The aggregate structure of phthalic anhydride (PA) modified soy protein isolate (SPI) was investigated by estimating its fractal dimension from the equilibrated dynamic strain sweep experiments. The estimated fractal dimensions of the filler aggregates were less than 2, indicating that these partic...

  12. Drug targeting to tumors using HPMA copolymers

    NARCIS (Netherlands)

    Lammers, T.G.G.M.


    Copolymers based on N-(2-hydroxypropyl)methacrylamide (HPMA) are prototypic and well-characterized polymeric drug carriers that have been broadly implemented in the delivery of anticancer agents. HPMA copolymers circulate for prolonged periods of time, and by means of the Enhance Permeability and

  13. Syntheses and Post-Polymerization Modifications of Well-Defined Styrenic Polymers Containing Three-Membered Heterocyclic Functionalities (United States)

    McLeod, David Charles

    Macromolecules that contain electrophilic moieties, such as benzyl halides, activated esters, and epoxides, will readily undergo efficient nucleophilic substitution reactions with a wide variety of compounds under mild conditions, and are therefore ideally suited to act as "universal" precursors to functional materials. Epoxide-containing polymers derived from the radical polymerization of commercially-available glycidyl methacrylate are often employed in this role; however, methacrylic polymers suffer from certain limitations as a result of the incorporated ester groups, which are not stabile in the presence of strong nucleophiles, acids, bases, or esterase enzymes. Styrenic polymers that do not contain labile carbonyl moieties are usually the precursors of choice when high chemical stability is desired in the end product, but the production of functional materials from epoxide-containing styrenic polymers is relatively unexplored. In this dissertation, improved methods were developed for synthesizing 4-vinylphenyloxirane (4VPO) and 4-vinylphenyl glycidyl ether (4VPGE), two of the better-known epoxide-containing styrenic monomers, in high-yield and purity. Well-defined, epoxide-containing styrenic polymers with targeted molecular weights, narrow molecular weight distributions, and controlled architectures (specifically, linear and star-shaped homopolymers, as well as linear block copolymers with styrene) were produced from 4VPO and 4VPGE for the first time using reversible-deactivation radical polymerization techniques, such as low-catalyst-concentration atom transfer radical polymerization (LCC ATRP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization. The robust nature and utility of poly4VPO and poly4VPGE were then demonstrated by the efficient, ring-opening modification of the pendant epoxide groups with a structurally- and functionally-diverse array of alcohols under acidic conditions at ambient temperature. The macromolecular

  14. Ultrahigh Molecular Weight Linear Block Copolymers: Rapid Access by Reversible-Deactivation Radical Polymerization and Self- Assembly into Large Domain Nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Mapas, Jose Kenneth D.; Thomay, Tim; Cartwright, Alexander N.; Ilavsky, Jan; Rzayev, Javid


    Block copolymer (BCP) derived periodic nanostructures with domain sizes larger than 150 nm present a versatile platform for the fabrication of photonic materials. So far, the access to such materials has been limited to highly synthetically involved protocols. Herein, we report a simple, “user-friendly” method for the preparation of ultrahigh molecular weight linear poly(solketal methacrylate-b-styrene) block copolymers by a combination of Cu-wire-mediated ATRP and RAFT polymerizations. The synthesized copolymers with molecular weights up to 1.6 million g/mol and moderate dispersities readily assemble into highly ordered cylindrical or lamella microstructures with domain sizes as large as 292 nm, as determined by ultra-small-angle x-ray scattering and scanning electron microscopy analyses. Solvent cast films of the synthesized block copolymers exhibit stop bands in the visible spectrum correlated to their domain spacings. The described method opens new avenues for facilitated fabrication and the advancement of fundamental understanding of BCP-derived photonic nanomaterials for a variety of applications.

  15. The tonotopicity of styrene-induced hearing loss depends on the associated noise spectrum. (United States)

    Venet, Thomas; Campo, Pierre; Thomas, Aurélie; Cour, Chantal; Rieger, Benoît; Cosnier, Frédéric


    The neuropharmacological and cochleotoxic effects of styrene can exacerbate the impact of noise on the peripheral auditory receptor. The mechanisms through which co-exposure to noise and styrene impairs hearing are complex as the slowly developing cochleotoxic process can be masked in the short-term by the rapid pharmacological effect on the central nervous system. The current investigation was therefore designed to delineate the auditory frequency range sensitive to noise, to styrene, and to noise and styrene combined. In case of different frequency ranges targeted by noise and styrene, it would be possible to point out the main factor responsible for cases of deafness by looking at the location of the audiometric deficits. Male Brown-Norway rats were exposed to 600-ppm styrene, to an octave band noise centered at 8 kHz, or to both noise and styrene. The noise exposure was of two different types: impulse noise with a LEX,8h (equivalent continuous noise level averaged over 8 h) of 80 dB and continuous noise with a LEX,8 h of 85 dB SPL. Hearing was tested using a non-invasive technique based on distortion product otoacoustic emissions. Hearing data were completed with histological analysis of cochleae. The results showed that exposure to styrene alone caused outer hair cell losses in the apical cochlear region, which discriminates low frequencies. In contrast, noise-induced hearing loss was located at half an octave above the central frequency of the spectrum, around 10-12 kHz. Damage due to impulse noise was significantly exacerbated by styrene, and the noise spectrum defined the location of the cochlear trauma. Combined exposure caused greater cell losses than the sum of losses measured with the impulse noise and styrene alone. The fact that the tonotopicity of the styrene-induced damage depends on the associated noise spectrum complicates the diagnosis of styrene-related hearing loss with a tone-frequency audiometric approach. In conclusion, there is not really a

  16. Free radical (co)polymerization of methyl methacrylate and styrene in room temperature ionic liquids (United States)

    Zhang, Hongwei

    Conventional free radical polymerizations were carried out in a variety of room temperature ionic liquids (RTILs). Generally, methyl methacrylate (MMA) and styrene (St) were used as typical monomers to compare the polymerization behavior both in RTILs and in common volatile organic compound solvents (VOCs). In most cases, it was observed that both yields and molecular weights are enhanced in the RTIL. While we believe the "diffusion-controlled termination" mechanism makes the termination of the radical propagating chains difficult due to the highly viscous nature of RTIL, other researchers have suggested that the rapid polymerization rates are due to the high polarity of these reaction media. By employing more than a dozen RTILs with a wide range of anions and cations, we attempted to correlate the viscosity and polarity of the RTILs with the molecular weights and polymerization rates. This correlation was not successful, suggesting that other parameters may also play a role in affecting the polymerization behavior. Other kinds of polymerizations have also been attempted including nitroxide-mediated living radical polymerizations of St and MMA in 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM]PF6), and redox initiation system initiated polymerization of MMA through redox pair formed by cation of trihexyl-tetradecyl-phosphonium bis(2,4,4-trimethylpentyl) phosphinate ([H3TDP] [(PM3) 2P]) and BPO. The formation of PSt-b-PMMA by sequential monomer addition through the standard free radical polymerization mechanism, using BPO as initiator, can be realized in [BMIM]PF6 due to the insolubility of polymerized first block---PSt in [BMIM]PF6. The macroradicals wrapped inside the chain coils have prolonged lifetimes because of the diminished termination, which allow some of these radicals to initiate polymerization of MMA at room temperature to form diblock copolymer. Solvents effects on reactivity ratios for free radical statistical copolymerization have been

  17. New insights into the effects of styrene-butadiene-styrene polymer modifier on the structure, properties, and performance of asphalt binder: The case of AP-5 asphalt and solvent deasphalting pitch

    Energy Technology Data Exchange (ETDEWEB)

    Nciri, Nader, E-mail: [Department of Energy, Materials, and Chemical Engineering, Korea University of Technology and Education, 1600 Chungjeol-ro, Byeongcheon-myeon, Dongnam-gu, Cheonan-City, Chungnam-Province 330-708 (Korea, Republic of); Kim, Namho [Department of Architectural Engineering, Korea University of Technology and Education, 1600 Chungjeol-ro, Byeongcheon-myeon, Dongnam-gu, Cheonan-City, Chungnam-Province 330-708 (Korea, Republic of); Cho, Namjun, E-mail: [Department of Energy, Materials, and Chemical Engineering, Korea University of Technology and Education, 1600 Chungjeol-ro, Byeongcheon-myeon, Dongnam-gu, Cheonan-City, Chungnam-Province 330-708 (Korea, Republic of)


    This paper deals with the poorly understood effects of styrene-butadiene-styrene (SBS) copolymer on the bitumen performance. It focuses on determining the impact of various concentrations (e.g., 0, 4, 8, and 12 wt. %) of SBS on the attributes of two types of asphalt namely AP-5 asphalt and solvent deasphalting (SDA) pitch. The unmodified and modified binders were investigated in terms of their chemical compositions, microstructures, thermo-analytical behaviors, and physical properties. The intricate chemical compositions were evaluated by elemental analysis and thin layer chromatography-ionization detection (TLC-FID). Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR) spectroscopies, scanning electron microscopy (SEM), and X-ray diffraction (XRD) were utilized to examine the microstructures. Whereas, thermal characteristics were evaluated by thermogravimetric analysis (TGA/DTGA) and differential scanning calorimetry (DSC). The physical behaviors were monitored through the softening point, penetration, viscosity, and ductility tests. The findings showed that the blending of asphalt with different amounts of SBS resulted into different rheological behaviors. This was reflected from the difference in the SARA (i.e., saturates, aromatics, resins, and asphaltenes) compositions and colloidal instability indexes of the modified asphalts. SEM exhibited a continuous asphalt phase with distributed SBS particles, a continuous polymer phase with distributed asphalt globules, or two interconnected continuous phases. FT-IR, {sup 1}H {sup 13}C NMR, and XRD data revealed that the AP-5 asphalt and SDA pitch experienced a number of distinct structural changes. TGA/DSC studies determined the occurrence of diverse events during thermal treatment. It is concluded that the degree of SBS modification depends strongly on SARA composition and polymer content. If the polymers are molded at higher concentrations along with aromatics-rich SDA pitches, then the mixtures

  18. Creating Active Device Materials for Nanoelectronics Using Block Copolymer Lithography. (United States)

    Cummins, Cian; Bell, Alan P; Morris, Michael A


    The prolonged and aggressive nature of scaling to augment the performance of silicon integrated circuits (ICs) and the technical challenges and costs associated with this has led to the study of alternative materials that can use processing schemes analogous to semiconductor manufacturing. We examine the status of recent efforts to develop active device elements using nontraditional lithography in this article, with a specific focus on block copolymer (BCP) feature patterning. An elegant route is demonstrated using directed self-assembly (DSA) of BCPs for the fabrication of aligned tungsten trioxide (WO₃) nanowires towards nanoelectronic device application. The strategy described avoids conventional lithography practices such as optical patterning as well as repeated etching and deposition protocols and opens up a new approach for device development. Nanoimprint lithography (NIL) silsesquioxane (SSQ)-based trenches were utilized in order to align a cylinder forming poly(styrene)-block-poly(4-vinylpyridine) (PS-b-P4VP) BCP soft template. We outline WO₃ nanowire fabrication using a spin-on process and the symmetric current-voltage characteristics of the resulting Ti/Au (5 nm/45 nm) contacted WO₃ nanowires. The results highlight the simplicity of a solution-based approach that allows creating active device elements and controlling the chemistry of specific self-assembling building blocks. The process enables one to dictate nanoscale chemistry with an unprecedented level of sophistication, forging the way for next-generation nanoelectronic devices. We lastly outline views and future research studies towards improving the current platform to achieve the desired device performance.

  19. Creating Active Device Materials for Nanoelectronics Using Block Copolymer Lithography

    Directory of Open Access Journals (Sweden)

    Cian Cummins


    Full Text Available The prolonged and aggressive nature of scaling to augment the performance of silicon integrated circuits (ICs and the technical challenges and costs associated with this has led to the study of alternative materials that can use processing schemes analogous to semiconductor manufacturing. We examine the status of recent efforts to develop active device elements using nontraditional lithography in this article, with a specific focus on block copolymer (BCP feature patterning. An elegant route is demonstrated using directed self-assembly (DSA of BCPs for the fabrication of aligned tungsten trioxide (WO3 nanowires towards nanoelectronic device application. The strategy described avoids conventional lithography practices such as optical patterning as well as repeated etching and deposition protocols and opens up a new approach for device development. Nanoimprint lithography (NIL silsesquioxane (SSQ-based trenches were utilized in order to align a cylinder forming poly(styrene-block-poly(4-vinylpyridine (PS-b-P4VP BCP soft template. We outline WO3 nanowire fabrication using a spin-on process and the symmetric current-voltage characteristics of the resulting Ti/Au (5 nm/45 nm contacted WO3 nanowires. The results highlight the simplicity of a solution-based approach that allows creating active device elements and controlling the chemistry of specific self-assembling building blocks. The process enables one to dictate nanoscale chemistry with an unprecedented level of sophistication, forging the way for next-generation nanoelectronic devices. We lastly outline views and future research studies towards improving the current platform to achieve the desired device performance.

  20. Low level occupational exposure to styrene: its effects on DNA damage and DNA repair. (United States)

    Wongvijitsuk, Sirilak; Navasumrit, Panida; Vattanasit, Udomratana; Parnlob, Varabhorn; Ruchirawat, Mathuros


    The present study aimed to evaluate the effects of styrene exposure at levels below the recommended standards of the Threshold Limit Value (TLV-TWA(8)) of 20 ppm (ACGIH, 2004) in reinforced-fiberglass plastics workers. Study subjects comprised 50 exposed workers and 40 control subjects. The exposed workers were stratified by styrene exposure levels, i.e. group I (20 ppm, >84.40 mg/m(3)). The mean styrene exposure levels of exposed workers were significantly higher than those of the control workers. Biomarkers of exposure to styrene, including blood styrene and the urinary metabolites, mandelic acid (MA) and phenylglyoxylic acid (PGA), were significantly increased with increasing levels of styrene exposure, but were not detected in the control group. DNA damage, such as DNA strand breaks, 8-hydroxydeoxyguanosine (8-OHdG), and DNA repair capacity, were used as biomarkers of early biological effects. DNA strand breaks and 8-OHdG/10(5)dG levels in peripheral leukocytes of exposed groups were significantly higher compared to the control group (Prisk from occupational styrene exposure, even at levels below the recommended TLV-TWA(8) of 20 ppm. Copyright © 2010 Elsevier GmbH. All rights reserved.

  1. A multicenter study on the audiometric findings of styrene-exposed workers. (United States)

    Morata, Thais C; Sliwinska-Kowalska, Mariola; Johnson, Ann-Christin; Starck, Jukka; Pawlas, Krystyna; Zamyslowska-Szmytke, Ewa; Nylen, Per; Toppila, Esko; Krieg, Edward; Pawlas, Natalia; Prasher, Deepak


    The objective of this study was to evaluate hearing loss among workers exposed to styrene, alone or with noise. This cross-sectional study was conducted as part of NoiseChem, a European Commission 5th Framework Programme research project, by occupational health institutes in Finland, Sweden, and Poland. Participants' ages ranged from 18-72 years (n = 1620 workers). Participants exposed to styrene, alone or with noise, were from reinforced fiberglass products manufacturing plants (n = 862). Comparison groups were comprised of workers noise-exposed (n = 400) or controls (n = 358). Current styrene exposures ranged from 0 to 309 mg/m(3), while mean current noise levels ranged from 70-84 dB(A). Hearing thresholds of styrene-exposed participants were compared with Annexes A and B from ANSI S3.44, 1996. The audiometric thresholds of styrene exposed workers were significantly poorer than those in published standards. Age, gender, and styrene exposure met the significance level criterion in the multiple logistic regression for the binary outcome 'hearing loss' (P = 0.0000). Exposure to noise (risk factor for hearing loss, and styrene-exposed workers should be included in hearing loss prevention programs.

  2. Leaching of styrene and other aromatic compounds in drinking water from PS bottles. (United States)

    Ahmad, Maqbool; Bajahlan, Ahmad S


    Bottled water may not be safer, or healthier, than tap water. The present studies have proved that styrene and some other aromatic compounds leach continuously from polystyrene (PS) bottles used locally for packaging. Water sapmles in contact with PS were extracted by a preconcentration technique called as "purge and trap" and analysed by gas chromatograph-mass spectrometer (GC/MS). Eleven aromatic compounds were identified in these studies. Maximum concentration of styrene in PS bottles was 29.5 microg/L. Apart from styrene, ethyl benzene, toluene and benzene were also quantified but their concentrations were much less than WHO guide line values. All other compounds were in traces. Quality of plastic and storage time were the major factor in leaching of styrene. Concentration of styrene was increased to 69.53 microg/L after one-year storage. In Styrofoam and PS cups studies, hot water was found to be contaminated with styrene and other aromatic compounds. It was observed that temperature played a major role in the leaching of styrene monomer from Styrofoam cups. Paper cups were found to be safe for hot drinks.

  3. Technoeconomic evaluation of bio-based styrene production by engineered Escherichia coli. (United States)

    Claypool, Joshua T; Raman, D Raj; Jarboe, Laura R; Nielsen, David R


    Styrene is an important commodity chemical used in polymers and resins, and is typically produced from the petrochemical feedstocks benzene and ethylene. Styrene has recently been produced biosynthetically for the first time using engineered Escherichia coli, and this bio-based route may represent a lower energy and renewable alternative to petroleum-derived styrene. However, the economics of such an approach has not yet been investigated. Using an early-stage technoeconomic evaluation tool, a preliminary economic analysis of bio-based styrene from C(6)-sugar feedstock has been conducted. Owing to styrene's limited water solubility, it was assumed that the resulting fermentation broth would spontaneously form two immiscible liquid phases that could subsequently be decanted. Assuming current C(6) sugar prices and industrially achievable biokinetic parameter values (e.g., product yield, specific growth rate), commercial-scale bio-based styrene has a minimum estimated selling price (MESP) of 1.90 USD kg(-1) which is in the range of current styrene prices. A Monte Carlo analysis revealed a potentially large (0.45 USD kg(-1)) standard deviation in the MESP, while a sensitivity analysis showed feedstock price and overall yield as primary drivers of MESP.

  4. Trends in occupational exposure to styrene in the European glass fibre-reinforced plastics industry. (United States)

    Van Rooij, J G M; Kasper, A; Triebig, G; Werner, P; Jongeneelen, F J; Kromhout, H


    This study presents temporal trends of styrene exposure for workers in the European glass fibre-reinforced plastics (GRP) industry during the period 1966-2002. Data of personal styrene exposure measurements were retrieved from reports, databases and peer-reviewed papers. Only sources with descriptive statistics of personal measurements were accepted. The styrene exposure data cover personal air samples and biological monitoring data, that is, urinary styrene metabolites (mandelic acid and/or phenylglyoxylic acid) and styrene in blood. Means of series of measurements were categorized by year, country, production process, job and sampling strategy. Linear mixed models were used to identify temporal trends and factors affecting exposure levels. Personal exposure measurements were available from 60 reports providing data on 24145 1-8-h time-weighted average shift personal air samples. Available data of biological exposure indicators included measurements of mandelic acid in post-shift urine (6361 urine samples being analysed). Trend analyses of the available styrene exposure data showed that the average styrene concentration in the breathing zone of open-mould workers in the European GRP industry has decreased on average by 5.3% per year during the period 1966-1990 and by only 0.4% annually in the period after 1990. The highest exposures were measured in Southern Europe and the lowest exposures in Northern Europe with Central Europe in between. Biological indicators of styrene (mandelic acid in post-shift urine) showed a somewhat steeper decline (8.9%), most likely because urine samples were collected in companies that showed a stronger decrease of styrene exposure in air than GRP companies where no biological measurements were carried out.

  5. Highly efficient copper(II) ion sorbents obtained by calcium carbonate mineralization on functionalized cross-linked copolymers. (United States)

    Mihai, Marcela; Bunia, Ion; Doroftei, Florica; Varganici, Cristian-Dragos; Simionescu, Bogdan C


    A new type of Cu(II) ion sorbents is presented. These are obtained by CaCO3 mineralization from supersaturated solutions on gel-like cross-linked polymeric beads as insoluble templates. A divinylbenzene-ethylacrylate-acrylonitrile cross-linked copolymer functionalized with weakly acidic, basic, or amphoteric functional groups has been used, as well as different initial inorganic concentrations and addition procedures for CaCO3 crystal growth. The morphology of the new composites was investigated by SEM and compared to that of the unmodified beads, and the polymorph content was established by X-ray diffraction. The beads, before and after CaCO3 mineralization, were tested as sorbents for Cu(II) ions. The newly formed patterns on the bead surface after Cu(II) sorption were observed by SEM, and the elemental distribution on the composites and the chemical structure of crystals after interaction with Cu(II) were investigated by EDAX elemental mapping and by FTIR-ATR spectroscopy, respectively. The sorption capacity increased significantly after CaCO3 crystals growth on the weak anionic bead surface (up to 1041.5 mg Cu(II) /g sample) compared to that of unmodified beads (491.5 mg Cu(II) /g sample). © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Block copolymer membranes for aqueous solution applications

    KAUST Repository

    Nunes, Suzana Pereira


    Block copolymers are known for their intricate morphology. We review the state of the art of block copolymer membranes and discuss perspectives in this field. The main focus is on pore morphology tuning with a short introduction on non-porous membranes. The two main strategies for pore formation in block copolymer membranes are (i) film casting and selective block sacrifice and (ii) self-assembly and non-solvent induced phase separation (SNIPS). Different fundamental aspects involved in the manufacture of block copolymer membranes are considered, including factors affecting the equilibrium morphology in solid films, self-assembly of copolymer in solutions and macrophase separation by solvent-non-solvent exchange. Different mechanisms are proposed for different depths of the SNIPS membrane. Block copolymer membranes can be prepared with much narrower pore size distribution than homopolymer membranes. Open questions and indications of what we consider the next development steps are finally discussed. They include the synthesis and application of new copolymers and specific functionalization, adding characteristics to respond to stimuli and chemical environment, polymerization-induced phase separation, and the manufacture of organic-inorganic hybrids.

  7. Simulation of styrene polymerization reactors: kinetic and thermodynamic modeling

    Directory of Open Access Journals (Sweden)

    A. S. Almeida


    Full Text Available A mathematical model for the free radical polymerization of styrene is developed to predict the steady-state and dynamic behavior of a continuous process. Special emphasis is given for the kinetic and thermodynamic models, where the most sensitive parameters were estimated using data from an industrial plant. The thermodynamic model is based on a cubic equation of state and a mixing rule applied to the low-pressure vapor-liquid equilibrium of polymeric solutions, suitable for modeling the auto-refrigerated polymerization reactors, which use the vaporization rate to remove the reaction heat from the exothermic reactions. The simulation results show the high predictive capability of the proposed model when compared with plant data for conversion, average molecular weights, polydispersity, melt flow index, and thermal properties for different polymer grades.

  8. Preparation of acrylonitrile butadiene styrene fibers by pulse electrospinning

    Directory of Open Access Journals (Sweden)

    Dilyara Igimbayeva


    Full Text Available The paper represents the results on the preparation of polymer fibers of acrylonitrile butadiene styrene (ABS with the addition of iron as a modifying additives by pulse electrospinning. The virtue of the method of pulse electrospinning in comparison with classical electrospinning is to obtain fibers with a controlled length. To study the morphology of the fibers obtained samples were used the optical and scanning electron microscopy. To prove the presence of iron inside the fibers methods of elemental analysis and electron paramagnetic resonance were used. The technique and optimal conditions for obtaining fibers have been determined. The effect of technological parameters, concentrations of polymer solutions and modifying additives on the structure and morphology of the fibers were shown.

  9. Reactive processing of recycled polycarbonate/acrylonitrile butadiene styrene. (United States)

    Jung, Woo-Hyuk; Choi, Yeon-Sil; Moon, Jung-Min; Tortorrela, Nathan; Beatty, Charles L; Lee, Jang-Oo


    Cellular phone housings were ground to make original particulates using a knife mill. Foams and adhesives with a lighter density than water were removed from ground mixtures using a sink-float process in water; ground metals, button rubbers, and wires were separated from desired materials by using a sink float process in salt All housing materials, consisting of seven thermoplastics included in cellular phone housings, showed better tensile properties than pure housing materials made of polycarbonate/acrylonitrile butadiene styrene, but they only had about half of the impact strength. In contrast, the low impact strength for all housing materials was improved by adding 25 wt % polyethylene elastomer and/or 2.4 wt % ground epoxy circuit boards for batch mixing. Impact strengths, tensile strengths, and the energy absorption ability of all housing materials were improved by adding 5.4wt% glycidyl methacrylate for twin screw extrusion.

  10. Interacting Blends of Novel Unsaturated Polyester Amide Resin with Styrene

    Directory of Open Access Journals (Sweden)

    Hasmukh S. Patel


    Full Text Available Novel unsaturated poly (ester-amide resins (UPEAs were prepared by the reaction between an epoxy resin, namely diglycidyl ether of bisphenol–A (DGEBA and unsaturated aliphatic bisamic acids using a base catalyst. These UPEAs were then blended with a vinyl monomer namely, Styrene (STY. to produce a homogeneous resin syrup. The curing of these UPEAs-STY. resin blends was carried out by using benzoyl peroxide (BPO as a catalyst and was monitored by using a differential scanning calorimeter (DSC. The glass fibre reinforced composites (i.e. laminates of these UPEA-STY. resin blends were fabricated using the DSC data. The chemical, mechanical and electrical properties of the glass fibre composites have also been evaluated. The unreinforced cured samples of the UPEA-STY. resin blends were also analyzed by thermogravimetry (TGA.

  11. Impaired colour discrimination among workers exposed to styrene: relevance of a urinary metabolite.


    Eguchi, T.; Kishi, R.; Harabuchi, I; Yuasa, J; Arata, Y; Katakura, Y; Miyake, H.


    OBJECTIVES--To survey the loss of colour vision among Japanese workers who have been exposed to styrene concentrations currently considered low (about 20 ppm). Also to assess the effects of styrene by examination of the nature of the relation between disorder of colour vision and age, alcohol consumption, and other variables. METHODS--Colour discrimination was examined in 64 male workers exposed to styrene (mean age; 38.0, mean exposed years; 7.0) and in 69 controls (mean age; 38.0). A standa...

  12. Injectible bodily prosthetics employing methacrylic copolymer gels

    Energy Technology Data Exchange (ETDEWEB)

    Mallapragada, Surya K.; Anderson, Brian C.


    The present invention provides novel block copolymers as structural supplements for injectible bodily prosthetics employed in medical or cosmetic procedures. The invention also includes the use of such block copolymers as nucleus pulposus replacement materials for the treatment of degenerative disc disorders and spinal injuries. The copolymers are constructed by polymerization of a tertiary amine methacrylate with either a (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) polymer, such as the commercially available Pluronic.RTM. polymers, or a poly(ethylene glycol) methyl ether polymer.

  13. AFM study of excimer laser patterning of block-copolymer: Creation of ordered hierarchical, hybrid, or recessed structures

    Energy Technology Data Exchange (ETDEWEB)

    Švanda, Jan; Siegel, Jakub; Švorčík, Vaclav; Lyutakov, Oleksiy, E-mail:


    Highlights: • Combination of bottom-up (BCP separation) and top-down (laser patterning) technologies allows obtaining hierarchical structures. • Surface morphologies were determined by the order of patterning steps (laser modification, annealing, surface reconstruction). • Tuning the order of steps enables the reorientation of BCP domain at large scale, fabrication of hierarchical, hybrid or recessed structures. • The obtained structures can find potential applications in nanotechnology, plasmonics, information storage, sensors and smart surfaces. - Abstract: We report fabrication of the varied range of hierarchical structures by combining bottom-up self-assembly of block copolymer poly(styrene-block-vinylpyridine) (PS-b-P4VP) with top-down excimer laser patterning method. Different procedures were tested, where laser treatment was applied before phase separation and after phase separation or phase separation and surface reconstruction. Laser treatment was performed using either polarized laser light with the aim to create periodical pattern on polymer surface or non-polarized light for preferential removing of polystyrene (PS) part from PS-b-P4VP. Additionally, dye was introduced into one part of block copolymer (P4VP) with the aim to modify its response to laser light. Resulting structures were analyzed by XPS, UV–vis and AFM techniques. Application of polarized laser light leads to creation of structures with hierarchical, recessed or hybrid geometries. Non-polarized laser beam allows pronouncing the block copolymer phase separated structure. Tuning the order of steps or individual step conditions enables the efficient reorientation of block-copolymer domain at large scale, fabrication of hierarchical, hybrid or recessed structures. The obtained structures can find potential applications in nanotechnology, photonics, plasmonics, information storage, optical devices, sensors and smart surfaces.

  14. Thin Films of Block Copolymers/Homopolymer: Effect of Non-Adsorbing Block Length on the Interfacial Properties (United States)

    Costa, Ana Claudia; Composto, Russell J.; Vlcek, Petr; Geoghehan, Mark; Creton, Costantino


    We have addressed the effect of non-adsorbing block length of block copolymers on their interfacial properties. To this goal, a low volume fraction (5 vol.styrene-b-methylmethacrylate) (dPS-b-MMA) having a nearly constant adsorbing block length (NMMA 40) was added to a PS matrix, which represents a nearly neutral environment for the dPS block. Films with varying non-adsorbing block lengths (NdPS 90-940) were spin coated on silicon oxide surfaces. Neutron reflectivity and forward recoil spectrometry were used to measure the dPS-b-MMA interfacial excess (z*) and width (w). The results show that z* and w increases with NdPS. These results are interpreted using a self-consistent mean field model. Probe tack tests indicate that adhesion improves with NdPS and suggests that the entanglements across the matrix/adsorbed layer interface are partially responsible for enhanced thin film adhesion.

  15. Synthesis and Characterization of Novel Polymethylene-Based 3-Miktoarm Star Copolymers by Combining Polyhomologation with Other Living Polymerizations

    KAUST Repository

    Altaher, Maryam


    Polyethylene (PE) is produced in a huge scale globally and has plenty of desirable properties. It is used in coating, packaging, and artificial joint replacements. The growing need for high performance polyethylene led to the development of new catalysts, monomers and polymerizations. The synthesis of polymethylene (equivalent to polyethylene) by living polyhomologation opened the way to well-defined polymethylenes-based polymeric materials with controlled structure, molecular weight and narrow polydispersity. Such model polymers are substantial to study the structure-properties relationships. This research presents a new strategy based on the in situ formation of B-thexyl-silaboracyclic serving as initiating sites for the polyhomologation of dimethylsulfoxonium methylide. Combination with metal-free ring-opening polymerization (ROP) of ɛ-caprolactone (CL) and atom transfer radical polymerization (ATRP) of styrene led to three polymethylene-based 3-miktoarm stars copolymers PCL(PM-OH)2, Br-PCL(PM-OH)2 and PS(PM-OH)2.

  16. The influence of mechanical properties in the electrical breakdown in poly-styrene-ethylene-butadiene-styrene thermoplastic elastomer (United States)

    Kollosche, Matthias; Melzer, Michael; Becker, Andre; Stoyanov, Hristian; McCarthy, Denis N.; Ragusch, Hülya; Kofod, Guggi


    Dielectric elastomer actuators (DEA) are a class of eletro-active polymers with promising properties for a number of applications, however, such actuators are prone to failure. One of the leading failure mechanisms is the electrical breakdown. It is already well-known that the electro-mechanical actuation properties of DEA are strongly influenced by the mechanical properties of the elastomer and compliant electrodes. It was recently suggested that also the electrical breakdown in such soft materials is influenced by the mechanical properties of the elastomer. Here, we present stress-strain measurements obtained on two tri-block thermoplastic elastomers (SEBS 500040 and SEBS 500120, poly-styrene-ethylene-butadiene-styrene), with resulting large differences in mechanical properties, and compare them to measurements on the commonly used VHB 4910. Materials were prepared by either direct heat-pressing of the raw material, or by dissolving in toluene, centrifuging and drop-casting. Experiments showed that materials prepared with identical processing steps showed a difference in stiffness of about 20%, where centrifuged and drop-casted films were seen to be softer than heat-pressed films. Electric breakdown measurements showed that for identically processed materials, the stiffness seemed to be a strong indicator of the electrical breakdown strength. It was therefore found that processing leads to differences in both stiffness and electrical breakdown strength. However, unexpectedly, the softer drop-cast films had a much higher breakdown strength than the heatpressed films. We attribute this effect to impurities still present in the heat-pressed films, since these were not purified by centrifuging.

  17. Micellization and Dynamics of a Block Copolymer

    DEFF Research Database (Denmark)

    Hvidt, Søren


    ratios and temperature. The micellization process with increasing temperature has been followed by a number of techniques including differential scanning calorimetry, liquid chromatography, and surface tension measurements. Different micellization models have been tested for purified copolymers...

  18. Electrostatic control of block copolymer morphology (United States)

    Sing, Charles E.; Zwanikken, Jos W.; Olvera de La Cruz, Monica


    Energy storage is at present one of the foremost issues society faces. However, material challenges now serve as bottlenecks in technological progress. Lithium-ion batteries are the current gold standard to meet energy storage needs; however, they are limited owing to the inherent instability of liquid electrolytes. Block copolymers can self-assemble into nanostructures that simultaneously facilitate ion transport and provide mechanical stability. The ions themselves have a profound, yet previously unpredictable, effect on how these nanostructures assemble and thus the efficiency of ion transport. Here we demonstrate that varying the charge of a block copolymer is a powerful mechanism to predictably tune nanostructures. In particular, we demonstrate that highly asymmetric charge cohesion effects can induce the formation of nanostructures that are inaccessible to conventional uncharged block copolymers, including percolated phases desired for ion transport. This vastly expands the design space for block copolymer materials and is informative for the versatile design of battery electrolyte materials.

  19. Block copolymer structures in nano-pores (United States)

    Pinna, Marco; Guo, Xiaohu; Zvelindovsky, Andrei


    We present results of coarse-grained computer modelling of block copolymer systems in cylindrical and spherical nanopores on Cell Dynamics Simulation. We study both cylindrical and spherical pores and systematically investigate structures formed by lamellar, cylinders and spherical block copolymer systems for various pore radii and affinity of block copolymer blocks to the pore walls. The obtained structures include: standing lamellae and cylinders, ``onions,'' cylinder ``knitting balls,'' ``golf-ball,'' layered spherical, ``virus''-like and mixed morphologies with T-junctions and U-type defects [1]. Kinetics of the structure formation and the differences with planar films are discussed. Our simulations suggest that novel porous nano-containers can be formed by confining block copolymers in pores of different geometries [1,2]. [4pt] [1] M. Pinna, X. Guo, A.V. Zvelindovsky, Polymer 49, 2797 (2008).[0pt] [2] M. Pinna, X. Guo, A.V. Zvelindovsky, J. Chem. Phys. 131, 214902 (2009).

  20. Gyroid Membranes made from Nanoporous Blck Copolymers

    DEFF Research Database (Denmark)

    Szewczykowski, Piotr Plzemystaw; Vigild, Martin Etchells; Ndoni, Sokol


    Nanoporous materials are interesting and exciting materials in view of their many potential applications, especially as ultrafiltration membranes. One way of preparing nanoporous polymeric materials is to use block copolymers. Block copolymers have the great advantage that they organize them......-selves into different morphologies on the nano scale. Block copolymer synthesis controls the molecular weight and volume fraction of blocks, which determine the resulting nano-structures. From a membrane application point of view one very suitable morphology is the bicontinuous gyroid. Mechanical stability...... of the membrane and its nanoporosity is e.g. obtained by cross-linking the majority blocks and selectively etching the minority blocks. Here we report on ultrafiltration membranes prepared from a 1,2-polybutadiene-b-polydimethylsiloxane diblock copolymer with gyroid structure. Different experimental methods...

  1. Transmission electron microscopy of polymer blends and block copolymers (United States)

    Gomez, Enrique Daniel

    -consistent field theory (SCFT). The liquid-like nature of this system at room temperature makes traditional staining methods for the enhancement of contrast ineffective. As an alternative, we take advantage of the large inelastic scattering cross-section of soft materials to generate contrast in zero-loss TEM images. Independent spatially resolved thickness measurements enable quantification of electron scattering. This enabled a comparison between the TEM data and predictions based on SCFT without any adjustable parameters. The second example involves the utilization of energy-filtered transmission electron microscopy (EFTEM) to compute elemental maps by taking advantage of ionization events. Elemental mapping of lithium is used to determine the distribution of salt in nanostructured poly(styrene-block-ethylene oxide) (SEO) copolymer/lithium salt electrolytes. Surprisingly, the concentration of lithium within a poly(ethylene oxide) (PEO) domain is found to be inhomogeneous; the salt is localized to the middle of the channels. Self-consistent field theory simulations suggest that localization of lithium is due to chain stretching at the interface, which increases with molecular weight. EFTEM and SCFT results show that the segregation of lithium salt to the middle of the PEO lamellae is greater for higher molecular weight polymers. This is correlated with the ionic conductivity of the copolymer electrolyte, which is found to show a higher conductivity for thinner lithium lamellae.

  2. Silica reinforced triblock copolymer gels

    DEFF Research Database (Denmark)

    Theunissen, E.; Overbergh, N.; Reynaers, H.


    The effect of silica and polymer coated silica particles as reinforcing agents on the structural and mechanical properties of polystyrene-poly(ethylene/butylene)-polystyrene (PS-PEB-PS) triblock gel has been investigated. Different types of chemically modified silica have been compared in order...... to evaluate the influence of the compatibility between gel and filler. Time-resolved SANS and small-angle X-ray scattering (SAXS) shows that the presence of silica particles affects the ordering of the polystyrene domains during gelsetting. The scattering pattern of silica-reinforced gels reveals strong...... scattering at very low q, but no structure and formfactor information. However, on heating above the viscoelastic to plastic transition, the 'typical' scattering pattern of the copolymer gel builds-up. All reinforced gels are strengthened by the addition of the reinforcing agent. The transitions from...

  3. In-situ Polymerization of Styrene to Produce Polystyrene / Montmorillonite Nanocomposites

    National Research Council Canada - National Science Library

    Lahouari Mrah; Rachid Meghabar; Mohammed Belbachir


    .... CTAB-intercalated Mmt particles were easily dispersed and swollen in styrene monomer, PS/Mmt-CTAB nanocomposites were synthesized via in-situ polymerization, in-situ polymerization, this method...

  4. Exposure to styrene in fiberglass-reinforced plastic manufacture: still a problem. (United States)

    Papaleo, Bruno; Caporossi, Lidia; Bernardini, Francesca; Cristadoro, Luisa; Bastianini, Lucia; De Rosa, Mariangela; Capanna, Silvia; Marcellini, Laura; Loi, Francesco; Battista, Giuseppe


    The aim of the work is to define occupational exposure to styrene in fiberglass manufacture; the phase of stretching styrene resins needs some manual handling and leads workers to be exposed to styrene. We surveyed 20 workers in two companies manufacturing fiberglass, checking environmental levels and urinary concentrations of mandelic acid (MA), and phenylglioxylic acid (PGA). Workers completed a questionnaire collecting their medical history. Environmental monitoring showed some styrene concentrations higher than the threshold limit value-time-weighted average. Biological monitoring confirmed these findings and four workers had levels of urinary PGA and MA concentrations higher than the Biological Exposure Indices of the American Conference of Governmental Industrial Hygienists. This picture confirms that, even though the risk is known and the manufacturing cycle is well-defined, workers nevertheless risk exposure. More research is needed to optimize the work processes and the protection systems to lower this risk.

  5. Formation of styrene dependent on fermentation management during wheat beer production. (United States)

    Schwarz, Katrin J; Stübner, René; Methner, Frank-Jürgen


    Styrene is formed by the thermal decarboxylation of cinnamic acid during wort boiling or by enzymatic decarboxylation during fermentation. The enzymatic reactions proceed in parallel to the decarboxylation of ferulic- and p-cumaric acid to 4-vinylguaiacol and 4-vinylphenol by the same decarboxylase enzyme. However, the formation of styrene occurs much faster and all available cinnamic acid in wort was converted completely within a few hours. Moreover, the comparison of various manufacturing parameters shows that a higher fermentation temperature of 25 °C compared to 16 °C and an open fermentation management lead to a rapid decrease of styrene. This allows minimising the content of styrene in beer while maintaining the typical wheat beer flavours. Copyright © 2012 Elsevier Ltd. All rights reserved.

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

    National Research Council Canada - National Science Library

    G M Domínguez Almaraz; E Correa Gómez; JC Verduzco Juárez; JL Avila Ambriz


    ... (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...

  7. Responsive Copolymers for Enhanced Petroleum Recovery

    Energy Technology Data Exchange (ETDEWEB)

    McCormick, C.; Hester, R.


    The objectives of this work was to: synthesize responsive copolymer systems; characterize molecular structure and solution behavior; measure rheological properties of aqueous fluids in fixed geometry flow profiles; and to tailor final polymer compositions for in situ rheology control under simulated conditions. This report focuses on the synthesis and characterization of novel stimuli responsive copolymers, the investigation of dilute polymer solutions in extensional flow and the design of a rheometer capable of measuring very dilute aqueous polymer solutions at low torque.

  8. Updated evaluation of the migration of styrene monomer and oligomers from polystyrene food contact materials to foods and food simulants. (United States)

    Genualdi, Susan; Nyman, Patricia; Begley, Timothy


    Due to the 2011 labelling of styrene monomer as "reasonably anticipated to be a human carcinogen" by the National Institutes of Health's National Toxicology Program (NTP) and the controversy over whether styrene oligomers mimic the physiological effects of estrogen, an updated review of styrene monomer and oligomers in food and food contact materials (FCMs) was performed. The concentrations of styrene monomer and oligomers were determined in 24 polystyrene (PS) products and ranged from 9.3 to 3100 mg kg(-1) for the styrene monomer, 130-2900 mg kg(-1) for the sum of three styrene dimers, and 220-16,000 mg kg(-1) for the sum of six styrene trimers. Foods in contact with PS packaging had styrene monomer concentrations ranging from 2.6 to 163 ng g(-1); dimer concentrations from the limit of quantitation (LOQ) to 4.8 ng g(-1) and trimer concentrations were all below the LOQ (2 ng g(-1)). Diffusion coefficients (Dp) and partition coefficients (K) were also calculated for styrene dimers and trimers. The results presented here indicate that styrene monomer concentrations in foods have not significantly changed since the 1980s and monomer concentrations in food packaging quantified in this study were all below USFDA limits. Although styrene dimers and trimers are present in higher concentrations in PS FCMs than the monomer, their migration to food is limited because of their high K values (4 × 10(2) to 2 × 10(6)) and their low diffusion coefficients in PS products. Additionally, diffusion coefficients calculated using USFDA-recommended food simulants and Arrhenius plots describing the temperature dependence of styrene dimers and trimers can be used in future calculations of dietary intake of the styrene oligomers.

  9. Impact behaviour of acrylonitrile-butadiene-styrene after temperature and humidity load


    Hylova Lenka; Manas Miroslav


    This study deals with acrylonitrile-butadiene-styrene (ABS) which was subjected the drop-weight test before and after temperature and humidity load. ABS is an engineering plastic and also an important engineering terpolymer, which has butadiene part uniformly distributed through the acrylonitrile-styrene matrix and is commonly used in production of automotive interior components. The injection moulded ABS samples were subjected the penetration test at fall height 100 J before and after temper...

  10. Evolution of entanglements during the response to a uniaxial deformation of lamellar triblock copolymers and polymer glasses. (United States)

    Léonforte, F


    Using coarse-grained molecular-dynamics simulations, a generic styrene-block-butadiene-block-styrene triblock copolymer under lamellar conformation is used in order to investigate the mutual entanglement evolution when a structure of alternating glassy (S)/rubbery (B) layers is submitted to an imposed deformation. By varying the amount of loop chains between each phase, i.e., noncrossing chains, it is possible to generate different types of S/B interface definitions. A specific boundary driven tensile strain protocol has been developed in order to mimic "real" experiments and measure the stress-strain curve. The same protocol is also applied to a reference state consisting in a directed glassy homopolymers, as well as to an isotropic glassy polymer. The evolution of initial mutual entanglements from the undeformed samples during the whole deformation process is monitored. It is shown for all considered systems that initial entanglements mostly participate to the preyield regime of the stress-strain curve and that this network is debonded during the strain-hardening regime. For triblocks with a non-null amount of crossing chains, the lower the amount is, the longer the memory effect of the initial entanglement network in the postyield regime is. On the fly distributions of entanglements, which depart from the postyield regime, depict memory effects and long-time correlations during the strain-hardening regime. For triblocks, loop chains reinforce these effects.

  11. Immortal Ring-Opening Polymerization of rac-Lactide Using Polymeric Alcohol as Initiator to Prepare Graft Copolymer

    Directory of Open Access Journals (Sweden)

    Na Liu


    Full Text Available In the presence of a small molecular protic initiator, immortal ring-opening polymerization (ROP of lactide (LA is a highly efficient strategy to synthesize polylactide in a controllable manner, while using polymeric alcohol as an initiator has been less investigated. A series of polymeric alcohols (PS–OH composed of styrene and 4.3%–18% hydroxyl functional styrene (diethyl(hydroxy(4-vinylphenylmethylphosphonate, St–OH were synthesized through reversible addition-fragmentation transfer (RAFT polymerization. Using PS–OH as an initiator, the immortal ROP of rac-LA was catalyzed by dibutylmagnesium (MgnBu2 under various ratios of monomer to hydroxyl group within PS–OH to generate polystyrene-g-polylactide (PS–g–PLA copolymers with different graft lengths. After thermal annealing at 115 °C, the PLA domain aggregated to nanospheres among the PS continuum. The size of the nanospheres, varying from 130.1 to 224.2 nm, was related to the graft density and length of PS–g–PLA. Nanoporous films were afforded through chemical etching of the PLA component.

  12. Micro- and nanophase separations in hierarchical self-assembly of strongly amphiphilic block copolymer-based ionic supramolecules

    DEFF Research Database (Denmark)

    Ayoubi, Mehran Asad; Zhu, Kaizheng; Nyström, Bo


    By a selective complexation between different alkyltrimethylammonium amphiphiles (C8, C12 and C16) and three different diblock copolymer systems of poly(styrene)-b-poly(methacrylic acid) at various grafting densities X (X = number of alkyl chains per acidic group of the poly(methacrylic acid) PMAA...... block), a class of ionic supramolecules are successfully synthesized whose molecular architecture consists of a poly(styrene) PS block (Linear block) covalently connected to a strongly amphiphilic comb-like block (AmphComb block), i.e. Linear-b-AmphComb. In the melt state, these ionic supramolecules can...... show simultaneous microphase (between Linear and AmphComb blocks) and nanophase (within the AmphComb blocks) separations. This leads to the formation of various structure-in-structure two-scale hierarchical self-assemblies, including S-in-SLL, S-in-SBCC, S-in-C, S-in-L and C-in-L, where S, SLL, SBCC, C...

  13. Removal of Copper ions from aqueous solutions using polymer derivations of poly (styrene-alt-maleic anhydride

    Directory of Open Access Journals (Sweden)

    Naser Samadi


    Full Text Available In this study chelating resins have been considered to be suitable materials for the recovery of Copper (II ions in water treatments. Furthermore, these modified resins were reacted with 1,2-diaminoethane in the presence of ultrasonic irradiation for the preparation of a tridimensional chelating resin on the Nano scale for the recovery of Copper (II ions from aqueous solutions. This method which is used for removing and determining Copper (II ions using copolymers derived resins of poly (styrene-alternative-maleic anhydride (SMA and atomic absorption spectroscopy. The method is simple, sensitive, inexpensive and fast. The various parameters such as pH, contact time, concentrations of metal ions, mass of resin, and agitation speed were investigated on adsorption effect. The adsorption behavior of Copper (II ions were investigated by the synthesis of chelating resins at various pHs. The prepared resins showed a good tendency for removing the selected metal ions from aqueous solution, even at an acidic pH. Also, the prepared resins were examined for the removal of Copper (II ions from real samples such as industrial wastewater and were shown to be very efficient at adsorption in the cases of Copper (II ions. The pseudo-first-order, pseudo-second-order, and intra-particle diffusion kinetics equations were used for modeling of adsorption data and it was shown that pseudo-second-order kinetic equation could best describe the adsorption kinetics. The intra-particle diffusion study revealed that external diffusion might be involved in this case. The resins were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, and X-ray diffraction analysis.

  14. Genotoxicity of styrene oligomers extracted from polystyrene intended for use in contact with food

    Directory of Open Access Journals (Sweden)

    Makoto Nakai


    Full Text Available Here, we conducted in vitro genotoxicity tests to evaluate the genotoxicity of styrene oligomers extracted from polystyrene intended for use in contact with food. Styrene oligomers were extracted with acetone and the extract was subjected to the Ames test (OECD test guideline No. 471 and the in vitro chromosomal aberration test (OECD test guideline No. 473 under good laboratory practice conditions. The concentrations of styrene dimers and trimers in the concentrated extract were 540 and 13,431 ppm, respectively. Extraction with acetone provided markedly higher concentrations of styrene oligomers compared with extraction with 50% ethanol aqueous solution, which is the food simulant currently recommended for use in safety assessments of polystyrene by both the United States Food and Drug Administration and the European Food Safety Authority. And these high concentrations of styrene dimers and trimers were utilized for the evaluation of genotoxicity in vitro. Ames tests using five bacterial tester strains were negative both in the presence or absence of metabolic activation. The in vitro chromosomal aberration test using Chinese hamster lung cells (CHL/IU was also negative. Together, these results suggest that the risk of the genotoxicity of styrene oligomers that migrate from polystyrene food packaging into food is very low.

  15. The influence of chain stretching on the phase behavior of multiblock copolymer and comb copolymer melts

    NARCIS (Netherlands)

    Angerman, HJ; ten Brinke, G

    The subject of this paper is inspired by microphase-separated copolymer melts in which a small-scale structure is present inside one of the phases of a large-scale structure. Such a situation can arise in a diblock copolymer melt, if one of the blocks of the diblock is in itself a multiblock

  16. Interfacial structure and dynamics of polymeric materials. I. Perfluoropolyether lubricant on solid substrate. II. Two-dimensional self-assembly of linear-nanoparticle block copolymers (United States)

    Kim, Yoojin

    We have studied two systems of thin polymer films on solid surfaces. The first study has examined the effects of surface confinement in the backbone dynamics of a hard disk drive lubricant, Zdol, on silica and amorphous carbon surfaces. The second study has allowed us to investigate the effect of architecture on the block copolymer self-assembly at the air-water interface and on a solid surface in a straightforward fashion. Carbon-13 and fluorine-19 solid-state NMR techniques have been used to compare the various backbone dynamics of Zdol in the bulk and in ultra-thin films. On a silica surface, the conformational transition of one segment is found to slow down indicating that the interaction of Zdol with the surface hinders such motion. However, the amplitude of the C-F bond libration is slightly increased on the surface due to the elimination of the cohesive interaction with the neighboring molecules. The longer-range motions involving more than one segment in a cooperative fashion are detected by the 19F spin-spin relaxation time (T2) that decreases by two orders of magnitude in thin films. The 19F line width increase and the downfield shift suggest that backbone interacts with the active binding sites of the amorphous carbon surface via electron donation from the ether oxygen lone pairs. We have synthesized a series of poly(ethylene glycol)-b-(styrene- r-benzocyclobutene) block copolymers with different architectures. The linear block copolymer precursor and the linear-nanoparticle block copolymer resulting from selective intramolecular crosslinking of the benzocyclobutene units have exactly the same molecular weight and chemical composition, but different architectures. At the air-water interface, the block copolymers self-assemble into remarkably different surface aggregates. While the linear block copolymer forms disk-like surface assemblies, the linear-nanoparticle block copolymer exhibits long (>10 mum) worm-like aggregates whose length increases as a

  17. Solvent controlled ion association in structured copolymers: Molecular dynamics simulations in dilute solutions (United States)

    Aryal, Dipak; Perahia, Dvora; Grest, Gary S.


    Tailoring the nature of individual segments within ion containing block co-polymers is one critical design tool to achieve desired properties. The local structure including the size and distribution of the ionic blocks, as well as the long range correlations, are crucial for their transport ability. Here, we present molecular dynamics simulations on the effects of varying the concentrations of the ionizable groups on the conformations of pentablock ionomer that consist of a center block of ionic sulfonated styrene tethered to polyethylene and terminated by a bulky substituted styrene in dilute solutions. Sulfonation fractions f (0 ≤ f ≤ 0.55), spanning the range from ionomer to polyelectrolytes, were studied. Results for the equilibrium conformation of the chains in water and a 1:1 mixture of cyclohexane and heptane are compared to that in implicit poor solvents with dielectric constants ɛ = 1.0 and 77.73. In water, the pentablock collapses with the sulfonated groups on the outer surface. As f increases, the ionic, center block increasingly segregates from the hydrophobic regions. In the 1:1 mixture of cyclohexane and heptane, the flexible blocks swell, while the center ionic block collapses for f > 0. For f = 0, all blocks swell. In both implicit poor solvents, the pentablock collapses into a nearly spherical shape for all f. The sodium counterions disperse widely throughout the simulation cell for both water and ɛ = 77.73, whereas for ɛ = 1.0 and mixture of cyclohexane and heptane, the counterions largely condense onto the collapsed pentablock.

  18. Controlled Release of Imidacloprid from Poly Styrene-Diacetone - Nanoformulation (United States)

    Qian, Kun; Guo, Yanzhen; He, Lin


    Imidacloprid is a neonicotinoids insecticide, which is important for the cash crops such as tomato, rape and so on. The conventional formulation does not only increase the loss of pesticide but also leads to environmental pollution. Controlled-release formulations of pesticide are highly desirable not only for attaining the most effective utilization of the pesticide, but also for reducing environmental pollution. Pesticide imidacloprid was incorporated in poly (styrene-diacetone crylamide)-based formulation to obtain controlled release properties, and the imidacloprid nanocontrolled release formulation was characterized by infrared (IR) and field emission scanning electron microscope (FESEM). Factors related to loading efficiency, swelling and release behaviors of the formulation were investigated. It showed that the loading efficiency could reach about 40% (w/w). The values for the diffusion exponent "n" were in the range of 0.31-0.58, which indicated that the release of imidacloprid was diffusion-controlled. The time taken for 50% of the active ingredient to be released into water, T50, was also calculated for the comparison of formulations in different conditions. The results showed that the formulation with higher temperature and more diacetone crylamide had lower value of T50, which means a quicker release of the active ingredient. This study highlighted some pieces of evidence that improved pesticide incorporation and slower release were linked to potential interactions between the pesticide and the polymer.

  19. Fatigue Characteristics of 3D Printed Acrylonitrile Butadiene Styrene (ABS) (United States)

    Padzi, M. M.; Bazin, M. M.; Muhamad, W. M. W.


    Recently, the use of 3D printer technology has become significant to industries, especially when involving the new product development. 3D printing is a technology, which produces the 3D product or prototype using a layer-by-layer technique. However, there becomes less research on the mechanical performance of the 3D printed component. In the present work, fatigue characteristics of 3D printed specimen have been studied. Acrylonitrile butadiene styrene (ABS) has been chosen as a material research due to its wide applications. Two types of specimen used, which is the 3D printing and moulding specimens. Fused deposition modelling (FDM) technique was used to produce the specimens. The dog bone shape part was produced based on ASTM D638 standard and the tensile test has been carried out to get the mechanical properties. Fatigue test was carried out at 40%, 60% and 80% of the tensile strength. The moulded part shows higher fatigue cycles compared to 3D printed part for all loading percentages. Fatigue lives for 40%, 60% and 80%, were 911, 2645 and 26948 cycles, respectively. The results indicated that 3D printed part has a lower fatigue life, which may not suitable for industrial applications. However, the 3D printed part could be improved by using various parameters and may be introduced in low strength application.

  20. Polyamide copolymers having 2,5-furan dicarboxamide units

    Energy Technology Data Exchange (ETDEWEB)

    Chisholm, Bret Ja; Samanta, Satyabrata


    Polyamide copolymers, and methods of making and using polyamide copolymers, having 2,5-furan dicarboxamide units are disclosed herein. Such polymers can be useful for engineering thermoplastics having advantageous physical and/or chemical properties.

  1. Binary and ternary LLE data of the system (ethylbenzene + styrene + 1-ethyl-3-methylimidazolium thiocyanate) and binary VLE data of the system (styrene + 1-ethyl-3-methylimidazolium thiocyanate)

    NARCIS (Netherlands)

    Jongmans, Mark; Schuur, Boelo; de Haan, A.B.


    The distillation of close boiling mixtures may be improved by adding a proper affinity solvent, and thereby creating an extractive distillation process. An example of a close boiling mixture that may be separated by extractive distillation is the mixture ethylbenzene/styrene. The ionic liquid

  2. In Situ Investigation of the Adsorption of Styrene Phosphonic Acid on Cassiterite (110) Surface by Molecular Modeling

    National Research Council Canada - National Science Library

    Guichen Gong; Yuexin Han; Jie Liu; Yimin Zhu; Yanfeng Li; Shuai Yuan


    The flotation, adsorption and bonding mechanisms of styrene phosphonic acid (SPA) to cassiterite were studied using microflotation tests, zeta potential measurements, solution chemistry analysis and density functional theory...

  3. Occupational exposure to styrene in the fibreglass reinforced plastic industry: comparison between two different manufacturing processes. (United States)

    Tranfo, Giovanna; Gherardi, Monica; Paci, E; Gatto, Mariapia; Gordiani, A; Caporossi, Lidia; Capanna, Silvia; Sisto, Renata; Papaleo, B; Fiumalbi, Carla; Garofani, Patrizia


    Styrene is used in manufacturing fiberglass reinforced plastics: and occupational exposure was related to neurotoxicology and genotoxicity. The sum of the metabolites mandelic and phenylglyoxylic acids is the ACGIH biomarker for occupational exposure with a BEI of 400 mg/g of creatinine in end shift urine corresponding to a airborne styrene concentration of 85 mg/m3. There are two main molding processes, open and closed, the last more effective at controlling worker's styrene exposure. To compare the open molding process to the compression of fiber reinforced resin foils, a kind of closed molding, monitoring the styrene exposure of workers in two production sites (A and B). Environmental Monitoring was carried out by Radiello samplers and Biological Monitoring by means of the determination of MA and PGA with HPLC/MS/MS in 10 workers at Site A and 14 at Site B. The median values for styrene exposure resulted 31.1 mg/m3 for Site A and 24.4 mg/m for Site B, while the medians for the sum of the two metabolites in the end shift urine were 86.7 e 33.8 mg/g creatinine respectively. There is a significant linear correlation between personal styrene exposure and the excretion of styrene metabolites (R = 0.74). As expected the exposure markers of the workers of the two production sites resulted higher in the open process. The analytical results of both environmental and biological monitoring were all below the occupational exposure limits, confirming the efficacy of the protective devices.

  4. Oil recovery with vinyl sulfonic acid-acrylamide copolymers

    Energy Technology Data Exchange (ETDEWEB)

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


    An aqueous polymer flood containing sulfomethylated alkali metal vinyl sulfonate-acrylamide copolymers was proposed for use in secondary or tertiary enhanced oil recovery. The sulfonate groups on the copolymers sustain the viscosity of the flood in the presence of brine and lime. Injection of the copolymer solution into a waterflooded Berea core, produced 30.5 percent of the residual oil. It is preferred that the copolymers are partially hydrolyzed.

  5. Effect of annealing and UV-radiation time over micropore architecture of self-assembled block copolymer thin film

    Directory of Open Access Journals (Sweden)

    G. del C. Pizarro


    Full Text Available Block copolymers have been recognized as versatile materials to prepare nanoporous polymer films or membranes, but their potential has not been completely explored. This study focuses on the formation and characterization of nanoporous polymer films based on poly(styrene-block-(methylmethacrylate/methacrylic acid; (PS-b-MMA/MAA were obtained through atom transfer radical polymerization (ATRP, by using two different protocols: annealing and annealingirradiation; for improving the formation of microporous surface. The composition, crystallinity and structural order of the films were studied by Raman spectroscopy. The film polymer thickness was obtained through very high resolution ellipsometry (VHRE. Finally, atomic force microcopy (AFM and scanning electron microscopy (SEM techniques were used to detect changes in the porous-structure. These results show that the morphological properties of the block copolymer were affected via the modification of two variables, UV-radiation time and annealing. SEM and AFM micrographs showed that the morphology exhibit a porous ordered structure. Contact angle measurement suggests additional interactions between hydrophilic functional groups that influence the film wettability.

  6. Well-defined triblock copolymers of polyethylene with polycaprolactone or polystyrene using a novel difunctional polyhomologation initiator

    KAUST Repository

    Hadjichristidis, Nikolaos


    α,ω-Dihydroxy polyethylene was synthesized by polyhomologation of dimethylsulfoxonium methylide with 9-thexyl-9-BBN (9-BNN: 9-Borabicyclo[3.3.1]nonane), a novel difunctional initiator produced from 9-BBN and 2,3-dimethylbut-2-ene, with two active and one blocked sites, followed by hydrolysis/oxidation. The terminal hydroxy groups were either used directly as initiators, in the presence of 1-tert-butyl-2,2,4,4,4-pentakis(dimethylamino)-2λ5,4λ5-catenadi(phosphazene) (t-BuP2), for the ring opening polymerization of ɛ-caprolactone to afford polycaprolactone-b-polyethylene-b-polycaprolactone (PCL-b-PE-b-PCL) or after transformation to atom transfer radical polymerization initiating sites, for the polymerization of styrene to produce polystyrene-b-polyethylene-b-polystyrene (PSt-b-PE-b-PSt) triblock copolymers. Molecular characterization by 11B, 13C and 1H NMR as well as FTIR, and high temperature GPC (HT-GPC) confirmed the well-defined nature of the synthesized new difunctional initiator and triblock copolymers. Differential scanning calorimetry was used to determine the melting points of PE and PCL.

  7. Charge Transport in Conjugated Block Copolymers (United States)

    Smith, Brandon; Le, Thinh; Lee, Youngmin; Gomez, Enrique

    Interest in conjugated block copolymers for high performance organic photovoltaic applications has increased considerably in recent years. Polymer/fullerene mixtures for conventional bulk heterojunction devices, such as P3HT:PCBM, are severely limited in control over interfaces and domain length scales. In contrast, microphase separated block copolymers self-assemble to form lamellar morphologies with alternating electron donor and acceptor domains, thereby maximizing electronic coupling and local order at interfaces. Efficiencies as high as 3% have been reported in solar cells for one block copolymer, P3HT-PFTBT, but the details concerning charge transport within copolymers have not been explored. To fill this gap, we probed the transport characteristics with thin-film transistors. Excellent charge mobility values for electron transport have been observed on aluminum source and drain contacts in a bottom gate, bottom contact transistor configuration. Evidence of high mobility in ordered PFTBT phases has also been obtained following thermal annealing. The insights gleaned from our investigation serve as useful guideposts, revealing the significance of the interplay between charge mobility, interfacial order, and optimal domain size in organic block copolymer semiconductors.

  8. Photo-Induced Micellization of Block Copolymers

    Directory of Open Access Journals (Sweden)

    Satoshi Kuwayama


    Full Text Available We found novel photo-induced micellizations through photolysis, photoelectron transfer, and photo-Claisen rearrangement. The photolysis-induced micellization was attained using poly(4-tert-butoxystyrene-block-polystyrene diblock copolymer (PBSt-b-PSt. BSt-b-PSt showed no self-assembly in dichloromethane and existed as isolated copolymers. Dynamic light scattering demonstrated that the copolymer produced spherical micelles in this solvent due to irradiation with a high-pressure mercury lamp in the presence of photo-acid generators, such as bis(alkylphenyliodonium hexafluorophosphate, diphenyliodonium hexafluorophosphate, and triphenylsulfonium triflate. The 1H NMR analysis confirmed that PBSt-b-PSt was converted into poly(4-vinylphenol-block-PSt by the irradiation, resulting in self-assembly into micelles. The irradiation in the presence of the photo-acid generator also induced the micellization of poly(4-pyridinemethoxymethylstyrene-block-polystyrene diblock copolymer (PPySt-b-PSt. Micellization occurred by electron transfer from the pyridine to the photo-acid generator in their excited states and provided monodispersed spherical micelles with cores of PPySt blocks. Further, the photo-Claisen rearrangement caused the micellization of poly(4-allyloxystyrene-block-polystyrene diblock copolymer (PASt-b-PSt. Micellization was promoted in cyclohexane at room temperature without a catalyst. During micellization, the elimination of the allyl groups competitively occurred along with the photorearrangement of the 4-allyloxystyrene units into the 3-allyl-4-hydroxystyrene units.

  9. PEO-related block copolymer surfactants

    DEFF Research Database (Denmark)

    Mortensen, K.


    Non-ionic block copolymer systems based on hydrophilic poly(ethylene oxide) and more hydrophobic co-polymer blocks are used intensively in a variety of industrial and personal applications. A brief description on the applications is presented. The physical properties of more simple model systems ...... or lamellar nature. Shear has major effect on the crystalline texture, but seems not to change the thermodynamic stable phases significantly. (C) 2001 Elsevier Science B.V. All rights reserved.......Non-ionic block copolymer systems based on hydrophilic poly(ethylene oxide) and more hydrophobic co-polymer blocks are used intensively in a variety of industrial and personal applications. A brief description on the applications is presented. The physical properties of more simple model systems...... of such PEG-based block copolymers in aqueous suspensions are reviewed. Based on scattering experiments using either X-ray or neutrons, the phase behavior is characterized, showing that the thermo-reversible gelation is a result of micellar ordering into mesoscopic crystalline phases of cubic, hexagonal...

  10. 21 CFR 177.1980 - Vinyl chloride-propylene copolymers. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Vinyl chloride-propylene copolymers. 177.1980... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1980 Vinyl chloride-propylene copolymers. The vinyl chloride-propylene copolymers identified in paragraph (a) of this section may be safely...

  11. 21 CFR 177.1312 - Ethylene-carbon monoxide copolymers. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-carbon monoxide copolymers. 177.1312... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1312 Ethylene-carbon monoxide copolymers. The ethylene-carbon monoxide copolymers identified in paragraph (a) of this section may be safely...

  12. 21 CFR 177.1320 - Ethylene-ethyl acrylate copolymers. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-ethyl acrylate copolymers. 177.1320... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1320 Ethylene-ethyl acrylate copolymers. Ethylene-ethyl acrylate copolymers may be safely used to produce packaging materials, containers...

  13. 21 CFR 177.1350 - Ethylene-vinyl acetate copolymers. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-vinyl acetate copolymers. 177.1350 Section... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1350 Ethylene-vinyl acetate copolymers. Ethylene-vinyl acetate copolymers may be safely used as articles or components of articles...

  14. 21 CFR 177.1950 - Vinyl chloride-ethylene copolymers. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Vinyl chloride-ethylene copolymers. 177.1950... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1950 Vinyl chloride-ethylene copolymers. The vinyl chloride-ethylene copolymers identified in paragraph (a) of this section may be safely...

  15. 21 CFR 177.1310 - Ethylene-acrylic acid copolymers. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Ethylene-acrylic acid copolymers. 177.1310 Section... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1310 Ethylene-acrylic acid copolymers. The ethylene-acrylic acid copolymers identified in paragraph (a) of this section may be safely...

  16. 21 CFR 177.1211 - Cross-linked polyacrylate copolymers. (United States)


    ... polyacrylate copolymers consist of: (1) The grafted copolymer of cross-linked sodium polyacrylate identified as... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Cross-linked polyacrylate copolymers. 177.1211... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1211 Cross-linked polyacrylate...

  17. 21 CFR 181.32 - Acrylonitrile copolymers and resins. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Acrylonitrile copolymers and resins. 181.32 Section... Ingredients § 181.32 Acrylonitrile copolymers and resins. (a) Acrylonitrile copolymers and resins listed in this section, containing less than 30 percent acrylonitrile and complying with the requirements of...

  18. Preparation and evaluation of an adsorbent based on poly (muconic acid-co-divinylbenzene/ethylenedimethacrylate) for multiple monolithic fiber solid-phase microextraction of tetracycline antibiotics. (United States)

    Pei, Miao; Huang, Xiaojia


    To extract tetracycline antibiotics (TAs) effectively, a new adsorbent based on poly (muconic acid-co-divinylbenzene/ethylenedimethacrylate) monolith was fabricated and used as the extraction medium of multiple monolithic fiber solid-phase microextraction (MD/MF-SPME). The effect of the fabrication parameters on extraction efficiency was studied thoroughly. Elemental analysis, infrared spectroscopy, scanning electron microscopy and mercury intrusion porosimetry were used to check the physicochemical properties of the adsorbent. Some key parameters that affect the extraction performance of MD/MF-SPME for TAs were investigated systematically. Under the optimized experimental conditions, the prepared adsorbent could effectively extract the TAs through multiple interactions. At the same time, a simple and sensitive method for monitoring trace TAs in honey samples was developed by coupling MD/MF-SPME with high-performance liquid chromatography tandem mass spectrometry detection (MD/MF-SPME-HPLC-MS/MS). The limits of detection (S/N=3) for target compounds were in the range of 7.3-17.1ng/kg. The intra-day and inter-day precision (relative standard deviations, n=4, %) at 0.5μg/kg and 20.0μg/kg spiking concentrations were 5.0-9.5% and 3.6-10.0%, respectively. The mean recoveries of the target TAs in the real honey samples were between 70.5-111.0%. Copyright © 2017 Elsevier B.V. All rights reserved.


    Directory of Open Access Journals (Sweden)

    A. A. Sedykh


    Full Text Available Summary. In the prevention of gastric diseases flexible optical fiber harness with camera and lighting after its extraction from the stomach is subjected to disassembly and continuous sterilization. Protection flexible optical fiber tourniquet, disposable and transparent sheath reduces the duration of the disassembly and sterilization. As the material for the shell of the recommended developed by the Voronezh branch of the FSUE "NIISK" high-styrene block copolymers Styrotep-65. The aim of this work was the development of technologies for films, protective shells of TEC and estimation of their technical parameters. As a benchmark comparison was tested extruded film Styrotep-65. The orientation of the macromolecules of the polymer along the sleeve during extraction provided the anisotropy of the properties of the film along and across the sleeves. In the study of properties of solutions of thermoplastic elastomer is established that the increase in solution viscosity provides greater film thickness in a single dunking them in forms. We investigated the effect of the concentration of a solution Styrotep-65 in toluene and the speed of rotation of a spindle of a Brookfield viscometer PV-E on their viscosity. With increasing concentration of the polymer solution with 19,0 to 26.8 % of the mass. the level of viscosity was increased from 104 to 330 MPa•S. In the interval of increasing the rotational speed of the spindle from 2.0 to 10.0 rpm viscosity solutions is not dependent on the concentration increased due to manifestations of thixotropy. A further increase in the speed of rotation of the spindle 10 to 100 rpm did not affect the viscosity of the solutions. This is true for ideal fluids. Film cast on a horizontal surface of the cellophane from a 10 % toluene solution, was characterized by lower strength than extruded, but with a large elongation at break. Determined the impact of the multiplicity of dipping forms in solution and polymer solution

  20. Functional Nanoporous Polymers from Block Copolymer Precursors

    DEFF Research Database (Denmark)

    Guo, Fengxiao

    applications as, e.g., membranes for separation and purification, templates for nanostructured materials, sensors, substrates for catalysis, low dielectric constant materials, photonic materials, and depots for controlled drug delivery. The development of nanoporous polymers with well controlled pore wall......Abstract Self-assembly of block copolymers provides well-defined morphologies with characteristic length scales in the nanometer range. Nanoporous polymers prepared by selective removal of one block from self-assembled block copolymers offer great technological promise due to their many potential...... functionalities remains a great challenge due to the limitation of available polymer synthesis and the nanoscale confinement of the porous cavities. The main topic of this thesis is to develop methods for fabrication of functional nanoporous polymers from block copolymer precursors. A method has been developed...

  1. Functionalization of Block Copolymer Vesicle Surfaces

    Directory of Open Access Journals (Sweden)

    Wolfgang Meier


    Full Text Available In dilute aqueous solutions certain amphiphilic block copolymers self-assemble into vesicles that enclose a small pool of water with a membrane. Such polymersomes have promising applications ranging from targeted drug-delivery devices, to biosensors, and nanoreactors. Interactions between block copolymer membranes and their surroundings are important factors that determine their potential biomedical applications. Such interactions are influenced predominantly by the membrane surface. We review methods to functionalize block copolymer vesicle surfaces by chemical means with ligands such as antibodies, adhesion moieties, enzymes, carbohydrates and fluorophores. Furthermore, surface-functionalization can be achieved by self-assembly of polymers that carry ligands at their chain ends or in their hydrophilic blocks. While this review focuses on the strategies to functionalize vesicle surfaces, the applications realized by, and envisioned for, such functional polymersomes are also highlighted.

  2. [Bonding of MMA-BPO. DMPT resin to bovine tooth coated by poly (methyl methacrylate-co-p-styrene sulfonic acid)]. (United States)

    Kinoshita, T; Yamamoto, T; Nagata, K; Nakabayashi, N


    The objective of this study was to prepare a new type water-soluble bonding agent, methyl methacrylate (MMA)-p-styrene sulfonic acid copolymer (MS), and to investigate the effect of MS on bonding between resins and tooth substrates. MS is cross-linked with Ca2+ released from ground enamel and dentin and could be immobilized on their surface. A sample was prepared by bonding an acrylic rod with a BPO-amine catalyzed self-curing resin to ground enamel and dentin coated with an aqueous mixture of FeCl3 and 10 wt% MS. After immersion in water for 24 hrs, the tensile bond strength was measured. The bond strength to both enamel and dentin was only 2 MPa and adhesive failure occurred at the interface between cured MS and self-curing resin. This suggested that cured MS could adversely effect the polymerization of self-curing resins. A second treatment of cured MS on the tooth surface with metallic cations was carried out to minimize the amount of free sulfonic acids in the MS disturbing radical formation in self-curing resin. The second treatment improved the bond strength to 6 MPa.

  3. Process Window for Direct Recycling of Acrylonitrile-Butadiene-Styrene and High-Impact Polystyrene from Electrical and Electronic Equipment Waste. (United States)

    Vazquez, Yamila V; Barbosa, Silvia E


    The aim of this paper is to assess recycling process window of ABS (Acrylonitrile-Butadiene-Styrene) and HIPS (High impact Polystyrene) from WEEE (waste from electrical and electronic equipment) through a final properties/structure screening study on their blends. Main motivation is to evaluate which amount of one plastic WEEE can be included into the other at least keeping their properties. In this sense, a wider margin of error during sorting could be admitted to obtain recycling materials with similar technological application of recycled ABS and HIPS by themselves. Results are discussed in terms of final blend structure, focusing in the interaction, within blends, of copolymers phases and fillers presents in WEEE. The comparative analysis of mechanical performance and morphology of HIPS/ABS blends indicates that the addition of 50wt% HIPS to ABS even improves 50% the elongation at break maintaining the strength. On the opposite, HIPS maintains its properties with 20wt% of ABS added. This study allows enlarging composition process window of recycling plastic WEEE for similar applications. This could be a sustainable way to improve benefit of e-scrap with low costs and easy processability. In consequence, social interest in the recycling of this kind of plastic scrap could be encourage from either ecological or economical points of view. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. Micelles of poly(styrene-b-2-vinylpyridine-b-ethylene oxide) with blended polystyrene core and their application to the synthesis of hollow silica nanospheres. (United States)

    Liu, Dian; Sasidharan, Manickam; Nakashima, Kenichi


    Core-shell-corona (CSC) micelles of asymmetric triblock copolymer, poly(styrene-b-2-vinylpyridine-b-ethylene oxide) (PS-PVP-PEO), containing polystyrene homopolymer (homo-PS) in the core were successfully prepared in aqueous media. The influence of homo-PS contents over the formation of the micelles was investigated thoroughly by various techniques such as dynamic light scattering (DLS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and fluorescence spectroscopy. It was found that the size of the PS core of the micelle was increased by the addition of homo-PS as observed by DLS and TEM techniques. The SEM and TEM measurements confirm the spherical morphology of the micelles and enlargement of PS core over the addition of homo-PS. The increase in the PS core volume of the PS-PVP-PEO micelles is attributed to the insertion of homo-PS in the PS core. The micelles have also been demonstrated as facile soft templates for synthesis of hollow silica nanospheres. The average diameter of the spherical hollow particles could be tuned between 30.6 and 38.8 nm with cavity sizes ranging from 20.7 to 28.5 nm using tetramethoxysilane as silica precursors under mild acidic conditions. The facile synthesis of hollow silica using the CSC micelles with different homo-PS contents indicates that the hollow void size can be controlled within a range of several nanometers. Copyright © 2011 Elsevier Inc. All rights reserved.

  5. Characterization of free volume during vulcanization of styrene butadiene rubber by means of positron annihilation lifetime spectroscopy and dynamic mechanical test. (United States)

    Marzocca, A J; Cerveny, S; Salgueiro, W; Somoza, A; Gonzalez, L


    An experimental investigation was performed to study the effect on the free volume of the advance of the cross-linking reaction in a copolymer of styrene butadiene rubber by sulfur vulcanization. The dynamic modulus and loss tangent were evaluated over samples cured for different times at 433 K by dynamic mechanical tests over a range of frequencies between 5 and 80 Hz at temperatures between 200 and 300 K. Using the William-Landel-Ferry relationship, master curves were obtained at a reference temperature of 298 K and the coefficients c(0)(1) and c(0)(2) were evaluated. From these parameters the dependence of the free volume on the cure time is obtained. Positron annihilation lifetime spectroscopy was also used to estimate the size and number density of free volume sites in the material. The spectra were analyzed in terms of continuous distributions of free volume size. The results suggest an increase of the lower free volume size when cross linking takes place. Both techniques give similar results for the dependence of free volume on the time of cure of the polymer.

  6. Combinatorial Block Copolymer Ordering on Tunable Rough Substrates

    Energy Technology Data Exchange (ETDEWEB)

    Kulkarni, Manish M.; Yager, Kevin G.; Sharma, Ashutosh; Karim, Alamgir (IIT-India); (Akron); (BNL)


    Morphology control of block copolymer (BCP) thin films through substrate interaction via controlled roughness parameters is of significant interest for numerous high-tech applications ranging from solar cells to high-density storage media. While effects of substrate surface energy (SE) and roughness (R) on BCP morphology have been individually investigated, their synergistic effects have not been explored in any systematic manner. Interestingly, orientation response of BCP to changes in SE can be similar to what can be accomplished with variations in R. Here we present a novel approach for orienting lamellar BCP films of poly(styrene)-block-poly(methyl methacrylate) (PS-PMMA) on spin-coated xerogel (a dried gel of silica nanoparticle network) substrate with simultaneously tunable surface energy, {gamma}{sub s} {approx} 29-53 mJ/m{sup 2}, by UVO exposure and roughness, R{sub rms} {approx} 0.5-30 nm, by sol-gel processing steps of regulating the catalyst concentration and sol aging time. As in previous BCP orientation studies on 20 nm diameter monodisperse silica nanoparticle coated surface, we find a similar but broadened oscillatory BCP orientation behavior with film thickness due to the random rather than periodic rough surfaces. We also find that higher random roughness amplitude is not the necessary criteria for obtaining a vertical orientation of BCP lamellae. Rather, a high surface fractal dimension (D{sub f} > 2.4) of the rough substrate in conjunction with an optimal substrate surface energy {gamma}{sub s} {approx} 29 mJ/m{sup 2} results in 100% vertically oriented lamellar microdomains. The AFM measured film surface microstructure correlates well with the internal 3D BCP film structure probed by grazing incidence small-angle X-ray scattering (GISAXS) and rotational small-angle neutron scattering (SANS). In contrast to tunable self-assembled monolayer (SAM)-coated substrates, the xerogel films are very durable and retain their chemical properties over period

  7. Proton conducting sulphonated fluorinated poly(styrene) crosslinked electrolyte membranes

    Energy Technology Data Exchange (ETDEWEB)

    Soules, A.; Ameduri, B.; Boutevin, B.; David, G. [Institut Charles Gerhardt UMR CNRS 5253 Equipe, Ingenierie et Architectures Macromoleculaires,' ' Ecole Nationale Superieure de Chimie de Montpellier, 8 rue de l' Ecole Normale, 34296 Montpellier, Cedex 05 (France); Perrin, R. [CEA Le Ripault Departement des Materiaux, DMAT/SCMF/LSTP, BP16 - 37260 Monts (France); Gebel, G. [Structure et Proprietes des Architectures Moleculaires UMR 5819 (CEA-CNRS-UJF), INAC, SPrAM, CEA Grenoble, 17 Rue des Martyrs, 38054 Grenoble, Cedex 9 (France)


    Potential membranes for polymer electrolyte membrane fuel cell based on crosslinked sulphonated fluorinated polystyrenes (PS) were synthesised in two steps. First, azide-telechelic polystyrene was obtained by iodine transfer polymerisation of styrene in the presence of 1,6-diiodoperfluorohexane followed by azido chain-end functionalisation. Then azide-telechelic polystyrene was efficiently crosslinked with 1,10-diazido-1H,1H,2H,2H,9H,9H,10H,10H-perfluorodecane under UV irradiation. After 45 min only, almost completion of azide crosslinking could be achieved, resulting in crosslinked membranes with insoluble fractions higher than 95%. The sulphonation of the crosslinked membranes afforded ionic exchange capacities (IECs) ranging from 2.2 to 3.2 meq g{sup -1}. The hydration number was shown to be very high (from 30 to 75), depending on both the content of perfluorodecane and of sulphonic acid groups. The morphology of the membranes, assessed by small-angle X-ray scattering, was found to be a lamellar-type structure with two types of ionic domains. For the membrane that exhibited an IEC value of 2.2 meq.g{sup -1}, proton conductivity was in the same range as that of Nafion {sup registered} (120-135{sup -1}), whereas the membrane IEC value of 3.2 meq.g{sup -1} showed a proton conductivity higher than that of Nafion {sup registered} in liquid water from 25 to 80 C, though a high water uptake. (Copyright copyright 2011 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  8. Grafting titanium nitride surfaces with sodium styrene sulfonate thin films (United States)

    Zorn, Gilad; Migonney, Véronique; Castner, David G.


    The importance of titanium nitride lies in its high hardness and its remarkable resistance to wear and corrosion, which has led to its use as a coating for the heads of hip prostheses, dental implants and dental surgery tools. However, the usefulness of titanium nitride coatings for biomedical applications could be significantly enhanced by modifying their surface with a bioactive polymer film. The main focus of the present work was to graft a bioactive poly(sodium styrene sulfonate) (pNaSS) thin film from titanium nitride surfaces via a two-step procedure: first modifying the surface with 3-methacryloxypropyltrimethoxysilane (MPS) and then grafting the pNaSS film from the MPS modified titanium through free radical polymerization. X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) were used after each step to characterize success and completeness of each reaction. The surface region of the titanium nitride prior to MPS functionalization and NaSS grafting contained a mixture of titanium nitride, oxy-nitride, oxide species as well as adventitious surface contaminants. After MPS functionalization, Si was detected by XPS, and characteristic MPS fragments were detected by ToF-SIMS. After NaSS grafting, Na and S were detected by XPS and characteristic NaSS fragments were detected by ToF-SIMS. The XPS determined thicknesses of the MPS and NaSS overlayers were ∼1.5 and ∼1.7 nm, respectively. The pNaSS film density was estimated by the toluidine blue colorimetric assay to be 260 ± 70 ng/cm2. PMID:25280842

  9. Application of Lignin as Antioxidant in Styrene Butadiene Rubber Composite (United States)

    Liu, Shusheng; Cheng, Xiansu


    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.

  10. Co-polymer Films for Sensors (United States)

    Ryan, Margaret A. (Inventor); Homer, Margie L. (Inventor); Yen, Shiao-Pin S. (Inventor); Kisor, Adam (Inventor); Jewell, April D. (Inventor); Shevade, Abhijit V. (Inventor); Manatt, Kenneth S. (Inventor); Taylor, Charles (Inventor); Blanco, Mario (Inventor); Goddard, William A. (Inventor)


    Embodiments include a sensor comprising a co-polymer, the co-polymer comprising a first monomer and a second monomer. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is polystyrene and the second monomer is poly-2-vinyl pyridinium propylamine chloride. For some embodiments, the first monomer is poly-4-vinyl pyridine, and the second monomer is poly-4-vinyl pyridinium benzylamine chloride. Other embodiments are described and claimed.

  11. Electrochemical and spectroscopic characterization of poly (bithiophene + 2-methylfuran) copolymer (United States)

    Lamiri, Leila; Nessark, Belkacem; Habelhames, Farid; Sibous, Lakhdar


    In this work, Poly(bithiophene + 2-methylfuran) copolymer was successfully synthetized by an electrochemical polymerization of two monomers, bithiophene and 2-methylfuran in acetonitrile containing lithium perchlorate. The obtained copolymer was characterized via cyclic voltammetry, impedance spectroscopy, UV-visible, scanning electron microscope, conductivity and photocurrent measurements. The cyclic voltammetry study showed two redox couples characteristic of Poly (bithiophene + 2-methylfuran) copolymer. The impedance spectroscopy study revealed that the resistance of the copolymer film increases with the addition of 2-methylfuran. The photocurrent measurement showed good photoelectrochemical properties, making this copolymer an ideal candidate for photovoltaic cell applications.

  12. Final Technical Report - Autothermal Styrene Manufacturing Process with Net Export of Energy

    Energy Technology Data Exchange (ETDEWEB)

    Trubac, Robert , E.; Lin, Feng; Ghosh, Ruma: Greene, Marvin


    The overall objectives of the project were to: (a) develop an economically competitive processing technology for styrene monomer (SM) that would reduce process energy requirements by a minimum 25% relative to those of conventional technology while achieving a minimum 10% ROI; and (b) advance the technology towards commercial readiness. This technology is referred to as OMT (Oxymethylation of Toluene). The unique energy savings feature of the OMT technology would be replacement of the conventional benzene and ethylene feedstocks with toluene, methane in natural gas and air or oxygen, the latter of which have much lower specific energy of production values. As an oxidative technology, OMT is a net energy exporter rather than a net energy consumer like the conventional ethylbenzene/styrene (EB/SM) process. OMT plants would ultimately reduce the cost of styrene monomer which in turn will decrease the costs of polystyrene making it perhaps more cost competitive with competing polymers such as polypropylene.

  13. Occupational styrene exposure and acquired dyschromatopsia: A systematic review and meta-analysis. (United States)

    Choi, Ariel R; Braun, Joseph M; Papandonatos, George D; Greenberg, Paul B


    Styrene is a chemical used in the manufacture of plastic-based products worldwide. We systematically reviewed eligible studies of occupational styrene-induced dyschromatopsia, qualitatively synthesizing their findings and estimating the exposure effect through meta-analysis. PubMed, EMBASE, and Web of Science databases were queried for eligible studies. Using a random effects model, we compared measures of dyschromatopsia between exposed and non-exposed workers to calculate the standardized mean difference (Hedges'g). We also assessed between-study heterogeneity and publication bias. Styrene-exposed subjects demonstrated poorer color vision than did the non-exposed (Hedges' g = 0.56; 95%CI: 0.37, 0.76; P dyschromatopsia, suggesting a modest effect size with mild heterogeneity between studies. © 2017 Wiley Periodicals, Inc.

  14. Synthesis of amphiphilic diblock copolymer for surface modification of Ethylene-Norbornene copolymers

    DEFF Research Database (Denmark)

    Levinsen, Simon; Svendsen, Winnie Edith; Horsewell, Andy


    consisting of a bulk material compatible block and a hydrophilic block. To utilize the possibility of incorporating diblock copolymers into ethylenenorbornene copolymers, we have in this work developed a model poly(ethylene-1-butene) polymer compatible with the commercial available ethylene......-norbornene copolymer TOPAS. Through matching of the radius of gyration for the model polymer and TOPAS the miscibility was achieved. The poly(ethylene-1-butene) polymer was synthesized from a hydrogenated anionic polymerized polybutadiene polymer. As hydrophilic block poly(ethylene oxide) was subsequently added also......The aim of this work is to produce polymer modifiers in order to develop hydrophilic polymeric surfaces for use in microfluidics. The use of hydrophilic polymers in microfluidics will have many advantages e.g. preventing protein absorbance. Here we present an amphiphilic diblock copolymer...

  15. Molecular Interaction Control in Diblock Copolymer Blends and Multiblock Copolymers with Opposite Phase Behaviors (United States)

    Cho, Junhan


    Here we show how to control molecular interactions via mixing AB and AC diblock copolymers, where one copolymer exhibits upper order-disorder transition and the other does lower disorder-order transition. Linear ABC triblock copolymers possessing both barotropic and baroplastic pairs are also taken into account. A recently developed random-phase approximation (RPA) theory and the self-consistent field theory (SCFT) for general compressible mixtures are used to analyze stability criteria and morphologies for the given systems. It is demonstrated that the copolymer systems can yield a variety of phase behaviors in their temperature and pressure dependence upon proper mixing conditions and compositions, which is caused by the delicate force fields generated in the systems. We acknowledge the financial support from National Research Foundation of Korea and Center for Photofunctional Energy Materials.

  16. Measurement of styrene oxide in polystyrenes, estimation of migration to foods, and reaction kinetics and products in food simulants. (United States)

    Philo, M R; Fordham, P J; Damant, A P; Castle, L


    The concentration of styrene-7,8-oxide has been measured in nine base resins and 16 samples of polystyrene articles intended for food contact. The epoxide was not detected in the resins (limit of detection 0.5 mg/kg) but was found in 11 of the 16 packaging samples at up to 2.9 mg/kg. Assuming that the propensity of styrene oxide to migrate is the same as styrene monomer, and using existing survey data for styrene monomer in packaging and foods, the migration levels expected for styrene oxide were calculated. Estimates were from 0.002 to 0.15 microgram/kg styrene oxide in foods. The stability of styrene oxide in the four standard EU food simulants was studied at 40, 100, 150 and 175 degrees C, to establish the transformation products to be expected following migration testing. The half-life at 40 degrees C in distilled water, 15% aqueous ethanol, 3% aqueous acetic acid and olive oil was 15, 23, 2000 hr, respectively. The principal product was the diol from hydrolysis of the epoxide group. Ring opening in aqueous ethanol simulant gave the diol and also the glycol monoethyl ether. It is concluded that this instability of styrene oxide will reduce concentrations in foods, from an already low migration level to even lower levels with the formation of hydrolysis products that are less toxic than the parent epoxide.


    The paper gives results of an investigation of the impact of an ozone generator air cleaner on vapor-phase styrene concentrations in a full-scale indoor air quality test chamber. The time history of the concentrations of styrene and ozone is well predicted by a simulation model u...

  18. Kinetics and mechanism of styrene epoxidation by chlorite: role of chlorine dioxide. (United States)

    Leigh, Jessica K; Rajput, Jonathan; Richardson, David E


    An investigation of the kinetics and mechanism for epoxidation of styrene and para-substituted styrenes by chlorite at 25 °C in the pH range of 5-6 is described. The proposed mechanism in water and water/acetonitrile includes seven oxidation states of chlorine (-I, 0, I, II, III, IV, and V) to account for the observed kinetics and product distributions. The model provides an unusually detailed quantitative mechanism for the complex reactions that occur in mixtures of chlorine species and organic substrates, particularly when the strong oxidant chlorite is employed. Kinetic control of the reaction is achieved by the addition of chlorine dioxide to the reaction mixture, thereby eliminating a substantial induction period observed when chlorite is used alone. The epoxidation agent is identified as chlorine dioxide, which is continually formed by the reaction of chlorite with hypochlorous acid that results from ClO produced by the epoxidation reaction. The overall stoichiometry is the result of two competing chain reactions in which the reactive intermediate ClO reacts with either chlorine dioxide or chlorite ion to produce hypochlorous acid and chlorate or chloride, respectively. At high chlorite ion concentrations, HOCl is rapidly eliminated by reaction with chlorite, minimizing side reactions between HOCl and Cl2 with the starting material. Epoxide selectivity (>90% under optimal conditions) is accurately predicted by the kinetic model. The model rate constant for direct reaction of styrene with ClO2(aq) to produce epoxide is (1.16 ± 0.07) × 10(-2) M(-1) s(-1) for 60:40 water/acetonitrile with 0.20 M acetate buffer. Rate constants for para substituted styrenes (R = -SO3(-), -OMe, -Me, -Cl, -H, and -NO2) with ClO2 were determined. The results support the radical addition/elimination mechanism originally proposed by Kolar and Lindgren to account for the formation of styrene oxide in the reaction of styrene with chlorine dioxide.

  19. Photoluminescent nanocomposite materials based on SBMA copolymer and CdS (United States)

    Iovu, M.; Enachescu, M.; Culeac, I.; Verlan, V.; Robu, S.; Bojin, D.; Nistor, Iu.; Cojocaru, I.


    We present experimental results on copolymer-based nanocomposite made of styrene with butyl methacrylate (SBMA) (1:1) and inorganic semiconductor CdS. Thin film composite samples have been characterized by UV-Vis absorption and photoluminescent spectroscopy, as well as by transmission electron microscopy. Transmission electron microscope (TEM) examination confirms a relatively narrow distribution of CdS nanoclusters in the SBMA matrix, which covers the range 2-10 nm. On the other side, the average CdS particles size estimated from the position of first excitonic peak in the UV-Vis absorption spectrum was found to be 2.8 nm and 4.4 nm for two samples with different duration of thermal treatment, which is in good agreement with photoluminescence (PL) experimental data. The PL spectrum for CdS nanocrystals is dominated by near-band-edge emission. The relatively narrow line width (40-45 nm) of the main PL band suggests the nanoparticles having narrow size distribution. On the other side, relatively low PL emission from surface trap states at longer wavelengths were observed in the region 500-750 nm indicating on recombination on defects. Key words: nanocomposite, polymer matrix, photoluminescence,

  20. Synthesis of Well-Defined Polyethylene-Based 3-Miktoarm Star Copolymers and Terpolymers

    KAUST Repository

    Zhang, Zhen


    Novel polyethylene (PE)-based 3-miktoarm star copolymers A2B, (AB)2B and terpolymers (AC)2(BC) [A: PE; B, C: polystyrene (PS) or poly(methyl methacrylate) (PMMA)] were synthesized by combining boron chemistry, polyhomologation, and atom transfer radical polymerization (ATRP). 1,4-Pentadiene-3-yl 2-bromo-2-methylpropanoate was first synthesized followed by hydroboration with thexylborane to afford B-thexylboracyclanes, a multi-heterofunctional initiator with two initiating sites for polyhomologation and one for ATRP. After polyhomologation of dimethylsulfoxonium methylide the α,ω-dihydroxyl polyethylene (PE-OH)2-Br produced served as macroinitiator for the ATRP of styrene to afford (PE-OH)2-(PS-Br). Both (PE-OH)2-Br and (PE-OH)2-(PS-Br) were transformed to two new trifunctional macroinitiators (PE-Br)2-Br and (PE-Br)2-(PS-Br) through esterification reactions and used for the synthesis of (AB)2B and (AC)2(BC) 3-miktoarm star co/terpolymers. All intermediates and final products were characterized by 1H NMR, high temperature gel permeation chromatography (HT-GPC), and differential scanning calorimetry (DSC). The synthetic method is a general one and can be used for the synthesis of complex PE-based architectures by combination with other living/living-controlled polymerization techniques. © 2016 American Chemical Society.

  1. Unidirectional alignment of block copolymer templated porous films using solvent vapor annealing with soft shear (United States)

    Qiang, Zhe; Cavicchi, Kevin; Vogt, Bryan


    Porous films templated by block copolymers (BCPs) have been extensively investigated due to their potential numerous applications such as sorbents and nanolithography. However, in many cases, their performance critically depends on their nanostructural alignment and orientation. Achieving unidirectional alignment of these nanostructures over macroscopic dimensions is still challenging especially for BCPs with very high χ and Tg. Here, we illustrate a new method based on solvent vapor annealing with soft shear (SVA-SS), where a crosslinked poly(dimethylsiloxane) (PDMS) cap is simply adhered to the polymer films during SVA, to fabricate macroscopically aligned cylindrical structured mesoporous films using poly(styrene-block-N,N,-dimethyl-n-octadecylamine p-styrenesulfonate) (PS-b-PSS-DMODA) as the soft-template and phenolic resin as the precursor. The evolution of structures through the SVA-SS, thermal annealing and carbonization is determined by grazing incidence small angle x-ray scattering (GISAXS) and atomic force microscopy (AFM). Highly ordered mesoporous carbon films with S>0.8 can be obtained by this method. Potential applicability of this method to nanostructures besides cylinders, such as spheres and gyroid will be discussed.

  2. Lamellar Microdomains of Block-Copolymer-Based Ionic Supramolecules Exhibiting a Hierarchical Self-Assembly

    DEFF Research Database (Denmark)

    Ayoubi, Mehran Asad; Almdal, Kristoffer; Zhu, Kaizheng


    (Cn; n = 8, 12, and 16) trimethylammonium counterions (i.e., side chains) at various ion (pair) fractions X [i.e., counterion/side-chain grafting density; X = number of alkyl counterions (i.e., side chains) per acidic group of the parent PMAA block] these L-b-AC ionic supramolecules exhibit...... a spherical-in-lamellar hierarchical self-assembly. For these systems, (1) the effective Flory-Huggins interaction parameter between L- and AC-blocks chi'(Cn/x) was extracted, and (2) analysis of the lamellar microdomains showed that when there is an increase in X, alkyl counterion (i.e., side chain) length l......Based on a parent diblock copolymer of poly(styrene)-b-poly(methacrylic acid), PS-b-PMAA, linear-b-amphiphilic comb (L-b-AC) ionic supramolecules [Soft Matter 2013, 9, 1540-1555] are synthesized in which the poly(methacrylate) backbone of the ionic supramolecular AC-block is neutralized by alkyl...

  3. Self-assembly of block copolymer-based ionic supramolecules based upon multi-tail amphiphiles

    DEFF Research Database (Denmark)

    Asad Ayoubi, M.; Almdal, Kristoffer; Zhu, K.


    Utilising simple acid-base titration chemistry, a new family of Linear-b-Amphiphilic Comb (L-b-AC) ionic supramolecules [Soft Matter 2013, 9, 1540-1555] featuring multi-tail side-chains have been synthesized and examined by synchrotron SAXS. To three different parent diblock copolymers of poly......(styrene)-b-poly(methacrylic acid) PS-b-PMAA multi-tail ammonium side-chains of (C8)2-, (C8)4- or (C12)2-type were attached at various side-chain grafting densities (X), making it possible to separate effects of the details of the AC-block architecture from effects of the overall volume fraction of the AC block. The micro......-segregated morphologies of these systems include AC-block filled spherical microdomains in a liquid-like state (SPHLL), AC-block filled hexagonally-packed cylinders (CYL), alternating lamellar microlayers of AC- and L-blocks (LAM) and L-block filled hexagonally-packed cylinders (CYL*). For systems with the same parent...

  4. Increased frequency of lymphocyte micronuclei in workers producing reinforced polyester resin with low exposure to styrene

    Energy Technology Data Exchange (ETDEWEB)

    Hoegstedt, B.; Akesson, B.; Axell, K.; Gullberg, B.; Mitelman, F.; Pero, R.W.; Skerfving, S.; Welinder, H.


    A new micronucleus method based on the analysis of lymphocytes with preserved cytoplasm revealed an increased frequency of micronuclei in 38 workers employed in a plant producing styrene-modified polyester resin as compared to the frequency in 20 referents (5.9 vs 3.6%). The time-weighted average of the styrene concentration in the workroom air varied between 1 and 36 ppm (mean 13 ppm) during the last year and correlated well to low urinary levels of mandelic acid, which ranged from 9 to 316 mg/g of creatinine (mean 65 mg/g of creatinine).

  5. Impact behaviour of acrylonitrile-butadiene-styrene after temperature and humidity load

    Directory of Open Access Journals (Sweden)

    Hylova Lenka


    Full Text Available This study deals with acrylonitrile-butadiene-styrene (ABS which was subjected the drop-weight test before and after temperature and humidity load. ABS is an engineering plastic and also an important engineering terpolymer, which has butadiene part uniformly distributed through the acrylonitrile-styrene matrix and is commonly used in production of automotive interior components. The injection moulded ABS samples were subjected the penetration test at fall height 100 J before and after temperature and humidity load and the results were subsequently evaluated and discussed. It was found out that ABS after temperature and humidity load has lower impact resistance.

  6. Influence of the Nanoclay Cloisite 20A Incorporation on Properties of Acrylonitrile Butadiene Styrene (ABS) (United States)

    Sales, Jorge N.; Silva, Andressa A.; Valenzuela-Diaz, Francisco R.; Moura, Esperidiana A. B.

    This work aims to study the influence of the nanoclay Cloisite 20A incorporation on mechanical properties of ABS (acrylonitrile butadiene styrene). The incorporation of Cloisite 20A was made in two steps; firstly, a masterbatch was preparated and then, it was incorporated in ABS. The Cloisite 20A masterbatch using 40 % of nanoclay and 60 % of SAN (Styrene Acrylonitrile) was prepared in an adiabatic mill. After that, Cloisite 20A masterbarch at 1 and 5 % (wt) was added in ABS. The resulting nanocomposites were characterized by tensile tests and the correlation between properties was discussed.

  7. Kinetic study of the selective hydrogenation of styrene over a Pd egg-shell composite catalyst


    Betti,Carolina; Badano,Juan; Lederhos,Cecilia; Maccarrone, María; Carrara, Nicolás; Coloma, Fernando; Quiroga, Mónica; Vera, Carlos


    This is a study on the kinetics of the liquid-phase hydrogenation of styrene to ethylbenzene over a catalyst of palladium supported on an inorganic–organic composite. This support has a better mechanical resistance than other commercial supports, e.g. alumina, and yields catalysts with egg-shell structure and a very thin active Pd layer. Catalytic tests were carried out in a batch reactor by varying temperature, total pressure and styrene initial concentration between 353–393 K, 10–30 bar, an...

  8. Glycine/Glycolic acid based copolymers

    NARCIS (Netherlands)

    in 't Veld, P.J.A.; in 't Veld, Peter J.A.; Shen, Zheng-Rong; Shen, Z.; Takens, Gijsbert A.J.; Takens, G.A.J.; Dijkstra, Pieter J.; Feijen, Jan


    Glycine/glycolic acid based biodegradable copolymers have been prepared by ring-opening homopolymerization of morpholine-2,5-dione, and ring-opening copolymerization of morpholine-2,5-dione and glycolide. The homopolymerization of morpholine-2,5-dione was carried out in the melt at 200°C for 3 min

  9. Restructuring in block copolymer thin films

    DEFF Research Database (Denmark)

    Posselt, Dorthe; Zhang, Jianqi; Smilgies, Detlef-M.


    Block copolymer (BCP) thin films have been proposed for a number of nanotechnology applications, such as nanolithography and as nanotemplates, nanoporous membranes and sensors. Solvent vapor annealing (SVA) has emerged as a powerful technique for manipulating and controlling the structure of BCP ...

  10. Synthesis of fluorescent diblock copolymer nanoparticle supported ...

    Indian Academy of Sciences (India)


    Jun 9, 2017 ... using different techniques. The diblock copolymer (DBC) of. PCL is reviewed in this paper. In 2005, PCL-based liquid crys- talline DBC was synthesized and characterized thoroughly. [3]. A RAFT technique was adopted for the synthesis of PCL- based DBC [4]. A DBC between PCL and MMA was prepared.

  11. Nylon 46-polytetramethylene oxide segmented block copolymers

    NARCIS (Netherlands)

    Gaymans, R.J.; Schwering, P.; de Haan, J.L.


    Block copolymers were synthesized from amine-terminated polytetramethylene oxide (PMTO) (Mw 800 and 1130) and polyamide 4,6 salt. First prepolymers were prepared at 200–210°C in the presence of a solvent (pyrrolidone). The prepolymers were postcondensed at 255°C (where possible in the solid state)


    NARCIS (Netherlands)

    Hilberer, A; Gill, R.E; Herrema, J.K; Malliaras, G.G; Wildeman, J.; Hadziioannou, G

    In this article we review results obtained in our laboratory on the design and study of new light-emitting polymers. We are interested in the synthesis and characterisation of block copolymers with regularly alternating conjugated and non conjugated sequences. The blocks giving rise to luminescence

  13. Preparation of amphiphilic block copolymer containing triazene ...

    Indian Academy of Sciences (India)

    The lower rate constant in film state (film = 1.3 × 10−3 s-1), shows that the higher mobility of polymeric chains in solution allow a more rapid orientation, favourable to the triazene bond cleavage. The capability of block copolymer to form micelles in aqueous environment and implicitly, its critical micelle concentration (CMC) ...

  14. Structure–Conductivity Relationships in Ordered and Disordered Salt-Doped Diblock Copolymer/Homopolymer Blends

    Energy Technology Data Exchange (ETDEWEB)

    Irwin, Matthew T.; Hickey, Robert J.; Xie, Shuyi; So, Soonyong; Bates, Frank S.; Lodge, Timothy P. (UMM)


    We examine the relationship between structure and ionic conductivity in salt-containing ternary polymer blends that exhibit various microstructured morphologies, including lamellae, a hexagonal phase, and a bicontinuous microemulsion, as well as the disordered phase. These blends consist of polystyrene (PS, Mn ≈ 600 g/mol) and poly(ethylene oxide) (PEO, Mn ≈ 400 g/mol) homopolymers, a nearly symmetric PS–PEO block copolymer (Mn ≈ 4700 g/mol), and lithium bis(trifluoromethane)sulfonamide (LiTFSI). These pseudoternary blends exhibit phase behavior that parallels that of well-studied ternary polymer blends consisting of A and B homopolymers compatibilized by an AB diblock copolymer. The utility of this framework is that all blends have nominally the same number of ethylene oxide, styrene, Li+, and TFSI– units, yet can exhibit a variety of microstructures depending on the relative ratio of the homopolymers to the block copolymer. For the systems studied, the ratio r = [Li+]/[EO] is maintained at 0.06, and the volume fraction of PS homopolymer is kept equal to that of PEO homopolymer plus salt. The total volume fraction of homopolymer is varied from 0 to 0.70. When heated through the order–disorder transition, all blends exhibit an abrupt increase in conductivity. However, analysis of small-angle X-ray scattering data indicates significant structure even in the disordered state for several blend compositions. By comparing the nature and structure of the disordered states with their corresponding ordered states, we find that this increase in conductivity through the order–disorder transition is most likely due to the elimination of grain boundaries. In either disordered or ordered states, the conductivity decreases as the total amount of homopolymer is increased, an unanticipated observation. This trend with increasing homopolymer loading is hypothesized to result from an increased density of

  15. 21 CFR 177.1970 - Vinyl chloride-lauryl vinyl ether copolymers. (United States)


    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Vinyl chloride-lauryl vinyl ether copolymers. 177...-lauryl vinyl ether copolymers. The vinyl chloride-lauryl vinyl ether copolymers identified in paragraph... section vinyl chloride-lauryl vinyl ether copolymers consist of basic copolymers produced by the...

  16. Effect of monomer mixture composition on structure and chromatographic properties of poly(divinylbenzene-co-ethylvinylbenzene-co-2-hydroxyethyl methacrylate) monolithic rod columns for separation of small molecules. (United States)

    Smirnov, Konstantin N; Dyatchkov, Ivan A; Telnov, Maxim V; Pirogov, Andrey V; Shpigun, Oleg A


    Porous poly(divinylbenzene-co-ethylvinylbenzene-co-2-hydroxyethyl methacrylate) monoliths were synthesized via thermally initiated free-radical polymerization in confines of surface-vinylized glass columns (150 mm × 3 mm i.d.) and applied to the reversed-phase separation of low-molecular-weight aromatic compounds. In order to compensate for the polymer shrinkage during the synthesis and prevent the monolith from detachment from the column wall, polymerization was conducted under nitrogen pressure. The reaction proceeded at 60°C for 22 h. 2,2'-Azo-bis-isobutironitrile was used as the initiator and 1-dodecanol was used as the porogen. A series of monoliths with different monomer ratios were obtained. All the monoliths had high specific surface areas ranging from 370 to 490 m(2)/g. In the studied range of monomer mixture compositions, the mechanical stability of the stationary phase in water/acetonitrile eluents was found to be high enough and practically insensitive to the fraction of 2-hydroxyethyl methacrylate (HEMA). Increasing the molar fraction of HEMA from 10.5% to 14.7% resulted in the decrease of column permeability by two orders of magnitude (from 1.1×10(-12) to 1.8×10(-14) m(2)) and led to weaker retention of alkylbenzenes. The higher HEMA content was shown to reduce the plate height of the columns in the separation of small molecules from 160-490 μm to 40-76 μm. This was attributed mainly to the decrease of the domain size of the monoliths leading to lower eddy dispersion and mass transfer resistance in the column. Copyright © 2010 Elsevier B.V. All rights reserved.

  17. Chromatographic selectivity of poly(alkyl methacrylate-co-divinylbenzene) monolithic columns for polar aromatic compounds by pressure-driven capillary liquid chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Shu-Ling; Wang, Chih-Chieh; Fuh, Ming-Ren, E-mail:


    In this study, divinylbenzene (DVB) was used as the cross-linker to prepare alkyl methacrylate (AlMA) monoliths for incorporating π-π interactions between the aromatic analytes and AlMA-DVB monolithic stationary phases in capillary LC analysis. Various AlMA/DVB ratios were investigated to prepare a series of 30% AlMA-DVB monolithic stationary phases in fused-silica capillaries (250-μm i.d.). The physical properties (such as porosity, permeability, and column efficiency) of the synthesized AlMA-DVB monolithic columns were investigated for characterization. Isocratic elution of phenol derivatives was first employed to evaluate the suitability of the prepared AlMA-DVB columns for small molecule separation. The run-to-run (0.16–1.20%, RSD; n = 3) and column-to-column (0.26–2.95%, RSD; n = 3) repeatabilities on retention times were also examined using the selected AlMA-DVB monolithic columns. The π-π interactions between the aromatic ring and the DVB-based stationary phase offered better recognition on polar analytes with aromatic moieties, which resulted in better separation resolution of aromatic analytes on the AlMA-DVB monolithic columns. In order to demonstrate the capability of potential environmental and/or food safety applications, eight phenylurea herbicides with single benzene ring and seven sulfonamide antibiotics with polyaromatic moieties were analyzed using the selected AlMA-DVB monolithic columns. - Highlights: • First investigation on chromatographic selectivity of AlMA-DVB monolithic columns. • Good run-to-run/column-to-column repeatability (<3%) on AlMA-DVB monolithic columns. • Efficient separation of phenylurea herbicides and sulfonamides on AlMA-DVB columns.

  18. Poly(N-vinylcarbazole-co-divinylbenzene) monolith microextraction coupled to liquid chromatography-high resolution Orbitrap mass spectrometry to analyse benzodiazepines in beer and urine. (United States)

    Yao, Weixuan; Fan, Zhefeng; Zhang, Suling


    A poly(N-vinylcarbazole-co-divinylbenzene) (NVC/DVB) monolithic column was successfully prepared in a silanized capillary for microextraction of six benzodiazepines (BZPs) in complex samples. The polymerization was optimized primarily by changing the ratio of porogen content. The optimized polymer monolith had a homogeneous and continuous column bed, good permeability and mechanical stability. Poly(NVC/DVB) had good affinity to BZPs because of its through-pore structure and strong π-π stacking interactions derived from the rich benzene functional groups in the polymer. Potential factors that affect the extraction efficiency were studied in detail. In the optimized method, 3mL of sample (pH 2) was extracted with the polymer monolithic column and eluted with 80μL of methanol, and the eluent was analysed with ultra-high-performance liquid chromatography and quadrupole high resolution Orbitrap mass spectrometry (UHPLC/Q-Orbitrap MS). Under these conditions, the developed method gave the linear range of 0.005-0.5ng/mL for most of the six BZPs, whereas 0.05-0.5ng/mL for nitrazepam, 0.01-0.5ng/mL for lorazepam, respectively, with coefficients of determination (R(2))≥0.9991. The detection limits (LODs) were 1.08-6.04ng/L, and the quantification limits (LOQs) were 3.60-20.1ng/L. The method repeatability was investigated in terms of intra- and inter-day precision, which were indicated by relative standard deviations (RSDs) of ≤8.3% and ≤9.9%, respectively. Finally, the proposed method was successfully applied to detect BZPs in beer and human urine samples. The percentages of extraction recovery were 80.4-94.2% for beer and 79.6-95.2% for urine. Copyright © 2016 Elsevier B.V. All rights reserved.

  19. Analysis of protein phosphorylation by monolithic extraction columns based on poly(divinylbenzene) containing embedded titanium dioxide and zirconium dioxide nano-powders. (United States)

    Rainer, Matthias; Sonderegger, Harald; Bakry, Rania; Huck, Christian W; Morandell, Sandra; Huber, Lukas A; Gjerde, Douglas T; Bonn, Günther K


    The potential of an organic monolith with incorporated titanium dioxide (TiO(2)) and zirconium dioxide (ZrO(2)) nanoparticles was evaluated for the selective enrichment of phosphorylated peptides from tryptic digests. A pipette tip was fitted with a monolith based on divinylbenzene (DVB) of highly porous structure, which allows sample to pass through the monolithic bed. The enrichment of phosphopeptides was enhanced by increasing the pipetting cycles during the sample preparation and a higher recovery could be achieved with adequate buffer systems. A complete automated process was developed for enrichment of phosphopeptides leading to high reproducibility and resulting in a robust method designed to minimize analytical variance while providing high sensitivity at high sample throughput. The effect of particle size on the selectivity of phosphopeptides was investigated by comparative studies with nano- and microscale TiO(2) and ZrO(2) powders. Eleven phosphopeptides from alpha-casein digest could be recovered by an optimized mixture of microscale TiO(2)/ZrO(2) particles, whereas nine additional phosphopeptides could be retained by the same mixture of nano-structured material. When compared to conventional immobilized metal-ion affinity chromatography and commercial phosphorylation-enrichment kits, higher selectivity was observed in case of self fabricated tips. About 20 phosphopeptides could be retained from alpha-casein and five from beta-casein digests by using TiO(2) and ZrO(2) based extraction tips. Further selectivity for phosphopeptides was demonstrated by enriching a digest of in vitro phosphorylated extracellular signal regulated kinase 1 (ERK1). Two phosphorylated peptides of ERK1 could be identified by MALDI-MS/MS measurements and a following MASCOT database search.

  20. Enhanced Photophysical Properties of Nanopatterned Titania Nanodots/Nanowires upon Hybridization with Silica via Block Copolymer Templated Sol-Gel Process

    Directory of Open Access Journals (Sweden)

    Dinakaran Kannaiyan


    Full Text Available We fabricated titanium dioxide (TiO2-silica (SiO2 nanocomposite structures with controlled morphology by a simple synthetic approach using cooperative sol-gel chemistry and block copolymer (BCP self-assembly. Mixed TiO2-SiO2 sol-gel precursors were blended with amphiphilic poly(styrene-block-ethylene oxide (PS-b-PEO BCPs where the precursors were selectively incorporated into the hydrophilic PEO domains. Changing the volumetric ratio of TiO2-SiO2 sol-gel precursor from 5% to 20%, a stepwise structural inversion occurred from nanodot arrays to discrete nanowires. Template free hybrid inorganic nanostructures were produced after the removal of PS-b-PEO by irradiation of UV light. The morphological evolution and photophysical properties were investigated by microscopic studies, UV-visible absorption and photocatalytic properties.

  1. Non-woven fibrous materials with antibacterial properties prepared by tailored attachment of quaternized chitosan to electrospun mats from maleic anhydride copolymer. (United States)

    Ignatova, Milena; Petkova, Zhanina; Manolova, Nevena; Markova, Nadya; Rashkov, Iliya


    In order to impart antibacterial properties to microfibrous electrospun materials from styrene/maleic anhydride copolymers, quaternized chitosan derivatives (QCh) containing alkyl substituents of different chain lengths are covalently attached to the mats. A complete inhibition of the growth of bacteria, S. aureus (Gram-positive) and E. coli (Gram-negative), for a contact time of 30–120 min or a decrease of the bacterial titer by 2–3 log units is observed depending on the quaternization degree, the chain length of the alkyl substituent, and the molar mass of QCh. The modified mats are also effective in suppressing the adhesion of pathogenic S. aureus bacteria. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Striped, Ellipsoidal Particles by Controlled Assembly of Diblock Copolymers (United States)


    prediction has been experimentally verified by the observation of induced perpendicular orientation of poly- (styrene-b- methyl methacrylate ) (PS-b-PMMA...thermodynamically unstable or metastable morphologies.41−47 For example, a kinetically trapped morphology with axially stacked lamellae of poly(styrene-b...synthesized by sequential anionic polymerization using tetrahydrofur- an (THF) as a solvent at −78 °C with number average molar mass (Mn) values of the PS block

  3. Swelling of organoclays in styrene. Effect on flammability in polystyrene nanocomposites

    Directory of Open Access Journals (Sweden)


    Full Text Available In this work the effect of the compatibility between organoclays and styrene on the flammability of polystyrene/clay nanocomposites obtained through in situ incorporation was investigated. The reactions were carried out by bulk polymerization. The compatibility between organoclays and styrene was inferred from swelling of the organoclay in styrene. The nanocomposites were characterized by X-ray diffraction and Transmission Electron Microscopy. The heat release rate was obtained by Cone Calorimeter and the nanocomposites were tested by UL94 horizontal burn test. Results showed that intercalated and partially exfoliated polystyrene/clay nanocomposites were obtained depending on the swelling behavior of the organoclay in styrene. The nanocomposites submitted to UL94 burning test presented a burning rate faster than the virgin polystyrene (PS, however an increase of the decomposition temperature and an accentuated decrease on the peak of heat release of the nanocomposites were also observed compared to virgin PS. These results indicate that PS/clay nanocomposites, either intercalated or partially exfoliated, reduced the flammability approximately by the same extent, although reduced the ignition resistance of the PS.

  4. 0177 Exposure to styrene and the risk of cancer

    DEFF Research Database (Denmark)

    Christensen, Mette Skovgaard; Hansen, J; Ramlau-Hansen, Cecilia


    following occupational styrene exposure. METHOD: The cohort consists of 74 902 workers (84% men) in the Danish reinforced plastics industry, originating from 481 companies ever producing reinforced plastics in Denmark 1964-2009. We identified all workers in the National Supplementary Pension Fund Registry...

  5. Cyclodimerization of Stilbenes and Styrenes Catalyzed by Heteropolyacid Supported on Silica

    Directory of Open Access Journals (Sweden)

    B. Lantaño


    Full Text Available Several stilbenes and styrenes have been treated with heteropolyacid] (HPA supported over silice. The compounds obtained were characterized by 1H and 13C- NMR and the yields were compared with those obtained using H2SO4 (c and ethyl poliphosphate] (PPE.


    The report gives results of an evaluation of several conventional and novel emission control technologies that have been used or could be used to treat styrene emissions from open molding processes in fiberglass-reinforced plastics/composites (FRP/C) and fiberglass boat building ...

  7. Development of bioconjugated dye-doped poly(styrene-co-maleimide) nanoparticles as a new bioprobe

    CSIR Research Space (South Africa)

    Swanepoel, A


    Full Text Available -1 Journal of Materials Chemistry B Development of bioconjugated dye-doped poly(styrene-co- maleimide) nanoparticles as a new bioprobe A. Swanepoel, I. du Preez, T. Mahlangu, A. Chetty and B. Klumperman Abstract Fluorescent dye-doped poly...

  8. 40 CFR 721.3700 - Fatty acid, ester with styrenated phenol, ethylene oxide adduct. (United States)


    ... phenol, ethylene oxide adduct. 721.3700 Section 721.3700 Protection of Environment ENVIRONMENTAL..., ethylene oxide adduct. (a) Chemical substances and significant new uses subject to reporting. (1) The chemical substance identified generically as fatty acid, ester with styrenated phenol, ethylene oxide...

  9. Expanding Upon Styrene Biosynthesis to Engineer a Novel Route to 2-Phenylethanol. (United States)

    Machas, Michael S; McKenna, Rebekah; Nielsen, David R


    2-Phenylethanol (2PE) is a key molecule used in the fragrance and food industries, as well as a potential biofuel. In contrast to its extraction from plant biomass and/or more common chemical synthesis, microbial 2PE production has been demonstrated via both native and heterologous expression of the yeast Ehrlich pathway. Here, a novel alternative to this established pathway is systematically engineered in Escherichia coli and evaluated as a more robust and efficient route. This novel pathway is constructed via the modular extension of a previously engineered styrene biosynthesis pathway, proceeding from endogenous l-phenylalanine in five steps and involving four heterologous enzymes. This "styrene-derived" pathway boasts nearly a 10-fold greater thermodynamic driving force than the Ehrlich pathway, and enables reduced accumulation of acetate byproduct. When directly compared using a host strain engineered for l-phenylalanine over-production, preservation of phosphoenolpyruvate, and reduced formation of byproduct 2-phenylacetic acid, final 2PE titers via the styrene-derived and Ehrlich pathways reached 1817 and 1164 mg L-1 , respectively, at yields of 60.6 and 38.8 mg g-1 . Following optimization of induction timing and initial glucose loading, 2PE titers by the styrene-derived pathway approached 2 g L-1 - nearly a two-fold twofold increase over prior reports for 2PE production by E. coli employing the Ehrlich pathway. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Breath and blood levels of benzene, toluene, cumene and styrene in non-occupational exposure. (United States)

    Brugnone, F; Perbellini, L; Faccini, G B; Pasini, F; Maranelli, G; Romeo, L; Gobbi, M; Zedde, A


    Benzene, toluene, cumene and styrene were measured in the breath and blood of two groups of individuals. The first group included individuals belonging to a hospital staff, the second group included chemical workers who were not exposed to the abovementioned chemicals. The chemical workers were examined in plant infirmaries on the morning before the start of the workshift, and the hospital staff in the hospital infirmaries. One environmental air sample was taken in the infirmaries for each individual at the moment of the biological samplings. The environmental concentrations of benzene and styrene were significantly higher in the infirmaries of the chemical plant than in the infirmaries of the hospital. On the other hand, the environmental concentrations of toluene and cumene were not significantly different in the plant infirmaries and in the hospital infirmaries. In the hospital staff the alveolar concentrations of benzene, toluene and styrene were significantly lower than those in the chemical workers. In the hospital staff the blood concentrations of benzene, toluene and styrene were not significantly different from those in the chemical workers. Only the blood cumene concentration was significantly higher in the chemical workers. In hospital staff, smokers showed alveolar and blood concentrations of benzene and toluene that were significantly higher than those measured in the non smoker hospital staff. With reference to chemical workers, only alveolar benzene concentration was significantly higher in smokers than in non smokers.(ABSTRACT TRUNCATED AT 250 WORDS)

  11. Embryotoxic and teratogenic effects of styrene derivatives on sea urchin development. (United States)

    Pagano, G; Esposito, A; Giordano, G G; Hagström, B E


    The effects of styrene and some of its derivatives on the fertilization and differentiation of sea urchins was investigated. When one of the gametes was pretreated for a few minutes, it was ascertained that the test substances act on the haploid nucleus, producing specific changes in the differentiation of the embryo. By this test system directly acting, weak mutagens may be detected.

  12. Global styrene oligomers monitoring as new chemical contamination from polystyrene plastic marine pollution. (United States)

    Kwon, Bum Gun; Koizumi, Koshiro; Chung, Seon-Yong; Kodera, Yoichi; Kim, Jong-Oh; Saido, Katsuhiko


    Polystyrene (PS) plastic marine pollution is an environmental concern. However, a reliable and objective assessment of the scope of this problem, which can lead to persistent organic contaminants, has yet to be performed. Here, we show that anthropogenic styrene oligomers (SOs), a possible indicator of PS pollution in the ocean, are found globally at concentrations that are higher than those expected based on the stability of PS. SOs appear to persist to varying degrees in the seawater and sand samples collected from beaches around the world. The most persistent forms are styrene monomer, styrene dimer, and styrene trimer. Sand samples from beaches, which are commonly recreation sites, are particularly polluted with these high SOs concentrations. This finding is of interest from both scientific and public perspectives because SOs may pose potential long-term risks to the environment in combination with other endocrine disrupting chemicals. From SOs monitoring results, this study proposes a flow diagram for SOs leaching from PS cycle. Using this flow diagram, we conclude that SOs are global contaminants in sandy beaches around the world due to their broad spatial distribution. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Prognosis and determination of the threshold of chronic effect of carbon disulfide and styrene

    Energy Technology Data Exchange (ETDEWEB)

    Popov, T.; Zaprianov, Z.; Benchev, I.; Spasovski, M.


    Two series of studies were carried out: I--in workers exposed to four different mean annual CS/sub 2/ concentrations(6 mg/m3m3; 12 mg/m3; 51 mg/m3 and 247 mg/m3 and II series) in workers exposed to three styrene concentrations-(-I mg/m3; 40 mg/m3 and 400 mg/m3). The results obtained in series I show the role of the primary toxic effect (inhibition of oxidases with mixed function) and of the adaptation reactions to it with a view to accurate specifying the threshold of chronic CS/sub 2/ effect. The mathematical expression of the correlation between styrene concentration in air and blood, of phenyl-glyoxylic and mandelic acid in the urine of the exposed subjects enables the prognosis that the threshold of the noxious styrene effect is within the range of 150 mg/m3 to 250 mg/m3. A reduction on CS/sub 2/ MAC is proposed-(-from 10 mg/m3 to I mg/m3) and the correction of styrene MAC-(-from 5 mg/m3 to 30-50 mg/m3).

  14. Ionomeric membranes based on partially sulfonated poly(styrene) : synthesis, proton conduction and methanol permeation

    NARCIS (Netherlands)

    Picchioni, F.; Tricoli, V.; Carretta, N.


    Homogeneuosly sulfonated poly(styrene) (SPS) was prepared with various concentration of sulfonic acid groups in the base polymer. Membranes cast from these materials were investigated in relation to proton conductivity and methanol permeability in the temperature range from 20°C to 60°C. It was

  15. Development of Styrene-Grafted Polyurethane by Radiation-Based Techniques

    Directory of Open Access Journals (Sweden)

    Jin-Oh Jeong


    Full Text Available Polyurethane (PU is the fifth most common polymer in the general consumer market, following Polypropylene (PP, Polyethylene (PE, Polyvinyl chloride (PVC, and Polystyrene (PS, and the most common polymer for thermosetting resins. In particular, polyurethane has excellent hardness and heat resistance, is a widely used material for electronic products and automotive parts, and can be used to create products of various physical properties, including rigid and flexible foams, films, and fibers. However, the use of polar polymer polyurethane as an impact modifier of non-polar polymers is limited due to poor combustion resistance and impact resistance. In this study, we used gamma irradiation at 25 and 50 kGy to introduce the styrene of hydrophobic monomer on the polyurethane as an impact modifier of the non-polar polymer. To verify grafted styrene, we confirmed the phenyl group of styrene at 690 cm−1 by Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR-FTIR and at 6.4–6.8 ppm by 1H-Nuclear Magnetic Resonance (1H-NMR. Scanning Electron Microscope (SEM, X-ray Photoelectron Spectroscopy (XPS, Thermogravimetric Analysis (TGA and contact angle analysis were also used to confirm styrene introduction. This study has confirmed the possibility of applying high-functional composite through radiation-based techniques.

  16. Particle reinforced composites from acrylamide modified blend of styrene-butadiene and natural rubber (United States)

    Blends of styrene-butadiene rubber and natural rubber that provide balanced properties were modified with acrylamide and reinforced with soy protein particles. The rubber composites show improved mechanical properties. Both modified rubber and composites showed a faster curing rate. The crosslinking...

  17. Sorption of methylxanthines by different sorbents (United States)

    Dmitrienko, S. G.; Andreeva, E. Yu.; Tolmacheva, V. V.; Terent'eva, E. A.


    Sorption of caffeine, theophylline, theobromine, diprophylline, and pentoxyphylline on different sorbents (supercross-linked polystyrene, surface-modified copolymer of styrene and divinylbenzene Strata-X, and carbon nanomaterials Taunit and Diasorb-100-C16T) was studied in a static mode in an effort to find new sorbents suitable for sorption isolation and concentration of methylxanthines. The peculiarities of sorption of methylxanthines were explained in relation to the solution acidity, the nature of the sorbates and their concentration, the nature of the solvent, and the structural characteristics of the sorbents.

  18. Effect of the chemical composition of silver-containing nanocomposites based on polymer, silica, and activated carbon on their adsorption and catalytic properties (United States)

    Kotel'nikova, T. A.


    A series of silver-containing composites based on highly hydrophilic silica S-120, moderately hydrophilic activated carbon, and hydrophobic copolymer of styrene with divinylbenzene (Psb-1) is synthesized and studied using nonlinear gas chromatography, XRD, IR spectroscopy, and volumetric adsorption, and by optical means. The effect modifying an adsorbent with silver nanoparticles has on the structure, geometry, and chemistry of its surface, and the effects the concentration of metal, the nature of the matrix, the means of synthesis, and the size of nanoparticles have on its adsorption and catalytic properties, are studied. The surface plasmon resonance (SPR) effect is observed in some composites.

  19. Enhancement of Dry-Etching Durabilities by Energy or Etchant Quenching with aliphatic, aromatic and alicyclic homopolymer, polymer blends and copolymer (United States)

    Kushida, Masahito; Harada, Kieko; Saito, Kyoichi; Sugita, Kazuyuki


    Dry-etching rates for O2 reactive ion etching, O2 plasma etching, Ar sputter etching, and Ar ion beam etching were descending in the order of poly(methyl methacrylate) [PMMA], poly(isobornyl methacrylate) [PIBMA], poly(α-methyl styrene) [PMSt], and poly(2-vinylnaphthalene) [PVN]. 2-vinylnaphthalene monomer units were found to be more effective for enhancing dry-etching durability, which was defined as the reciprocal of etching rate, and for quenching the etching energy or etchants, than α-methyl styrene units. Dry-etching rates of PMMA, PMSt, and PVN homopolymers increased linearly proportional to reciprocal carbon atom content in a monomer units. However, dry-etching rates of polymer blends (PMMA/ PMSt, PMMA/ PVN) or copolymer (MMA-co-IBMA) did not follow the linear relationship, namely durabilities were larger than the value deduced from the reciprocal carbon atom content in a monomer units. The durability deviation from the estimated value was larger with PMMA/ PVN blends than that with PMMA/ PMSt blends, which means that the etching energy travels or etchants migrate for longer distance in the former blends.

  20. Renewable Pentablock Copolymers Containing Bulky Natural Rosin for Tough Bioplastics (United States)

    Rahman, Md Anisur; Ganewatta, Mitra S.; Lokupitiya, Hasala N.; Liang, Yuan; Stefik, Morgan; Tang, Chuanbing

    Renewable polymers have received significant attention due to environmental concerns on petrochemical counterparts. One of the most abundant natural biomass is resin acids. However, most polymers derived from resin acids are low molecular weight and brittle because of the high chain entanglement molecular weight resulted from the bulky hydrophenanthrene pendant group. It is well established that the brittleness can be overcome by synthesizing multi-block copolymers with low entanglement molecular weight components. We investigated the effects of chain architecture and microdomain orientation on mechanical properties of both tri and pentablock copolymers. We synthesized rosin-containing A-B-A-B-A type pentablock and A-B-A type triblock copolymers to improve their mechanical properties. Pentablock copolymers showed higher strength and better toughness as compared to triblock copolymers, both superior to homopolymers. The greater toughness of pentablock copolymers is due to the presence of the rosin based midblock chains that act as bridging chains between two polynorbornene blocks.

  1. Optical nanoimaging for block copolymer self-assembly. (United States)

    Yan, Jie; Zhao, Ling-Xi; Li, Chong; Hu, Zhe; Zhang, Guo-Feng; Chen, Ze-Qiang; Chen, Tao; Huang, Zhen-Li; Zhu, Jintao; Zhu, Ming-Qiang


    One approach toward optical nanoimaging involves sequential molecular localization of photoswitchable fluorophores to achieve high resolution beyond optical limit of diffraction. Block copolymer micelles assembled from polystryrene-block-poly(ethylene oxide) block copolymers (PSt-b-PEO) are visualized in optical nanoimaging by staining the polystyrene blocks with spiropyrans (SPs). SPs localized in hydrophobic phase of block copolymer micelles exhibit reversible fluorescence on-off switching at alternating irradiation of UV and visible light. Phase-selective distribution of SPs in block copolymer micelles enables optical nanoimaging of microphase structures of block copolymer self-assembly at 50-nm resolution. To date, this is the sturdiest realization of optical nanoimaging with subdiffraction resolution for solution self-assembly of block copolymers.

  2. Heterogeneous catalytic oxidative dehydrogenation of ethylbenzene to styrene with carbon dioxide

    Energy Technology Data Exchange (ETDEWEB)

    Badstube, T.; Papp, H. [Leipzig Univ. (Germany). Inst. fuer Technische Chemie; Kustrowski, P.; Dziembaj, R. [Jagiellonian Univ., Crakow (Poland). Faculty of Chemistry


    Alkaline promoted active carbon supported iron catalysts are very active in the oxidative dehydrogenation of ethylbenzene to styrene in the presence of carbon dioxide. The best results were obtained at 550 C for a Li-promoted catalyst with a conversion of ethylbenzene of 75% and a selectivity towards styrene of nearly 95%. These results are better than those obtained with industrial catalysts which perform the dehydrogenation process with an excess of water. The main product of the dehydrogenation reaction with CO{sub 2} was styrene, but the following by-products were detected - benzene and toluene. The selectivity towards toluene was always higher than towards benzene. We observed also the formation of carbon monoxide and water, which were produced with a constant molar ratio of about 0.8. The weight of the catalysts increased up to 20% during the reaction due to deposition of carbon. Using a too large excess of CO{sub 2} (CO{sub 2}/EB>10) was harmful for the styrene yield. The most favorable molar ratio of CO{sub 2} to EB was 10:1. No correlation between the molar ratios of reactants and the amount of deposited coke on the surface of catalysts was observed. The highest catalytic activity showed iron loaded D-90 catalysts which were promoted with alkali metals in a molar ratio of 1:10. Iron, nickel and cobalt loaded carbonized PPAN, PC, inorganic supports like Al{sub 2}O{sub 3}, SiO{sub 2}/ZrO{sub 2} or TiO{sub 2} respectively and commercial iron catalysts applied for styrene production did not show comparable catalytic activity in similar conditions. (orig.)

  3. Simulation of the styrene production process via catalytic dehydrogenation of ethylbenzene using CHEMCAD® process simulator

    Directory of Open Access Journals (Sweden)

    Amaury Pérez Sánchez


    Full Text Available Background: Process simulation has been extensively used in recent years to design, evaluate or optimize processes, systems and specific operations of the chemical industry and its related disciplines. Currently, CHEMCAD® constitute one of the most used process simulators because of the great number of chemical and petrochemical processes that can be simulated. Method: The simulation of the production process of styrene via catalytic dehydrogenation of ethyl-benzene is carried out by using the process simulator CHEMCAD® version 5.2.0, in order to determine the composition and mass flow-rate of each process involved in the production, as well as the main operating parameters of the equipment used. Two sensitivity studies were carried out: firstly, the influence of the temperature and pressure values applied at the LLV Separator on the amounts of ethyl-benzene and styrene to be obtained by the intermediate and top currents of this equipment; secondly, the influence of the operating pressure of the Distillation Column No. 1 (benzene-toluene column on the quantity of ethyl-benzene and styrene obtained at the bottom stream. The simulating software MATLAB® version 7.8.0 was used to process the results obtained. Results: Around 9234.436 kg/h of styrene is obtained in the last distillation column with 99.6% purity. Additionally, it was found that the water is the main impurity found on this stream, which represents 0.35% of the weight. Conclusions: The LLV Separator must operate at a low temperature (5 – 10 ºC and at a relatively high pressure (10 bar, whereas the Distillation Column No. 1 must work at a pressure near atmospheric (1.0 bar, or preferably under vacuum conditions in order to obtain the highest yields of styrene and ethyl-benzene.

  4. Preparation of Proteoglycan Mimetic Graft Copolymers. (United States)

    Kipper, Matt J; Place, Laura W


    Proteoglycans are proteins with pendant glycosaminoglycan polysaccharide side chains. The method described here enables the preparation of graft copolymers with glycosaminoglycan side chains, which mimic the structure and composition of proteoglycans. By controlling the stoichiometry, graft copolymers can be obtained with a wide range of glycosaminoglycan side-chain densities. The method presented here uses a three-step reaction mechanism to first functionalize a hyaluronic acid backbone, followed by reductive amination to couple the glycosaminoglycan side chain to the backbone, by the reducing end. Proteoglycan mimics like the ones proposed here could be used to study the structure-property relationships of proteoglycans and to introduce the biochemical and biomechanical properties of proteoglycans into biomaterials and therapeutic formulations.

  5. Hybrid, Nanoscale Phospholipid/Block Copolymer Vesicles

    Directory of Open Access Journals (Sweden)

    Bo Liedberg


    Full Text Available Hybrid phospholipid/block copolymer vesicles, in which the polymeric membrane is blended with phospholipids, display interesting self-assembly behavior, incorporating the robustness and chemical versatility of polymersomes with the softness and biocompatibility of liposomes. Such structures can be conveniently characterized by preparing giant unilamellar vesicles (GUVs via electroformation. Here, we are interested in exploring the self-assembly and properties of the analogous nanoscale hybrid vesicles (ca. 100 nm in diameter of the same composition prepared by film-hydration and extrusion. We show that the self-assembly and content-release behavior of nanoscale polybutadiene-b-poly(ethylene oxide (PB-PEO/1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylcholine (POPC hybrid phospholipid/block copolymer vesicles can be tuned by the mixing ratio of the amphiphiles. In brief, these hybrids may provide alternative tools for drug delivery purposes and molecular imaging/sensing applications and clearly open up new avenues for further investigation.

  6. Phase-Segregated Dendrigraft Copolymer Architectures

    Directory of Open Access Journals (Sweden)

    Lorena-Eugenia Sanchez Cadena


    Full Text Available Dendrigraft polymers have a multi-level branched architecture resulting from the covalent assembly of macromolecular building blocks. Most of these materials are obtained in divergent (core-first synthetic procedures whereby the molecule grows outwards in successive grafting reactions or generations. Two main types of dendrigraft polymers can be identified depending on the distribution of reactive sites over the grafting substrate: Arborescent polymers have a large and variable number of more or less uniformly distributed sites, while dendrimer-like star polymers have a lower but well-defined number of grafting sites strictly located at the ends of the substrate chains. An overview of the synthesis and the characterization of dendrigraft copolymers with phase-segregated morphologies is provided in this review for both dendrigraft polymer families. The tethering of side-chains with a different composition onto branched substrates confers unusual physical properties to these copolymers, which are highlighted through selected examples.

  7. Nanostructured Polysulfone-Based Block Copolymer Membranes

    KAUST Repository

    Xie, Yihui


    The aim of this work is to fabricate nanostructured membranes from polysulfone-based block copolymers through self-assembly and non-solvent induced phase separation. Block copolymers containing polysulfone are novel materials for this purpose providing better mechanical and thermal stability to membranes than polystyrene-based copolymers, which have been exclusively used now. Firstly, we synthesized a triblock copolymer, poly(tert-butyl acrylate)-b-polsulfone-b-poly(tert-butyl acrylate) through polycondensation and reversible addition-fragmentation chain-transfer polymerization. The obtained membrane has a highly porous interconnected skin layer composed of elongated micelles with a flower-like arrangement, on top of the graded finger-like macrovoids. Membrane surface hydrolysis was carried out in a combination with metal complexation to obtain metal-chelated membranes. The copper-containing membrane showed improved antibacterial capability. Secondly, a poly(acrylic acid)-b-polysulfone-b-poly(acrylic acid) triblock copolymer obtained by hydrolyzing poly(tert-butyl acrylate)-b-polsulfone-b-poly(tert-butyl acrylate) formed a thin film with cylindrical poly(acrylic acid) microdomains in polysulfone matrix through thermal annealing. A phase inversion membrane was prepared from the same polymer via self-assembly and chelation-assisted non-solvent induced phase separation. The spherical micelles pre-formed in a selective solvent mixture packed into an ordered lattice in aid of metal-poly(acrylic acid) complexation. The space between micelles was filled with poly(acrylic acid)-metal complexes acting as potential water channels. The silver0 nanoparticle-decorated membrane was obtained by surface reduction, having three distinct layers with different particle sizes. Other amphiphilic copolymers containing polysulfone and water-soluble segments such as poly(ethylene glycol) and poly(N-isopropylacrylamide) were also synthesized through coupling reaction and copper0-mediated

  8. Rapid ordering of block copolymer thin films. (United States)

    Majewski, Pawel W; Yager, Kevin G


    Block-copolymers self-assemble into diverse morphologies, where nanoscale order can be finely tuned via block architecture and processing conditions. However, the ultimate usage of these materials in real-world applications may be hampered by the extremely long thermal annealing times-hours or days-required to achieve good order. Here, we provide an overview of the fundamentals of block-copolymer self-assembly kinetics, and review the techniques that have been demonstrated to influence, and enhance, these ordering kinetics. We discuss the inherent tradeoffs between oven annealing, solvent annealing, microwave annealing, zone annealing, and other directed self-assembly methods; including an assessment of spatial and temporal characteristics. We also review both real-space and reciprocal-space analysis techniques for quantifying order in these systems.

  9. Ordering phenomena in ABA triblock copolymer gels

    DEFF Research Database (Denmark)

    Reynders, K.; Mischenko, N.; Kleppinger, R.


    Temperature and concentration dependencies of the degree of order in ABA triblock copolymer gels are discussed. Two factors can influence the ordering phenomena: the conformation of the midblocks (links of the network) and the polydispersity of the endblock domains (nodes of the network). The lat......Temperature and concentration dependencies of the degree of order in ABA triblock copolymer gels are discussed. Two factors can influence the ordering phenomena: the conformation of the midblocks (links of the network) and the polydispersity of the endblock domains (nodes of the network...... crystalline lattice with close-packed spheres or with cubic (presumably BCC) equilibrium morphology. The appearance of the latter is never detected in the gels with a stretched conformation of the midblock....

  10. A Cationic Smart Copolymer for DNA Binding

    Directory of Open Access Journals (Sweden)

    Tânia Ribeiro


    Full Text Available A new block copolymer with a temperature-responsive block and a cationic block was prepared by reversible addition-fragmentation chain transfer (RAFT polymerization, with good control of its size and composition. The first block is composed by di(ethylene glycol methyl ether methacrylate (DEGMA and oligo(ethylene glycol methyl ether methacrylate (OEGMA, with the ratio DEGMA/OEGMA being used to choose the volume phase transition temperature of the polymer in water, tunable from ca. 25 to above 90 °C. The second block, of trimethyl-2-methacroyloxyethylammonium chloride (TMEC, is positively charged at physiological pH values and is used for DNA binding. The coacervate complexes between the block copolymer and a model single strand DNA are characterized by fluorescence correlation spectroscopy and fluorescence spectroscopy. The new materials offer good prospects for biomedical application, for example in controlled gene delivery.

  11. Critical adsorption of copolymer tethered on selective surfaces (United States)

    Li, Hong; Qian, Chang-Ji; Luo, Meng-Bo


    Critical adsorption behaviors of flexible copolymer chains tethered to a flat homogeneous surface are studied by using Monte Carlo simulations. We have compared the critical adsorption temperature Tc, estimated by a finite-size scaling method, for different AB copolymer sequences with A the attractive monomer and B the inert monomer. We find that Tc increases with an increase in the fraction of monomers A, fA, in copolymers, and it increases with an increase in the length of block A for the same fA. In particular, Tc of copolymer (AnBn)r can be expressed as a function of the block length, n, and Tc of copolymer (AnB)r and (ABm)r can be expressed as a linear function of fA. Tc of random copolymer chains also can be expressed as a linear function of fA and it can be estimated by using weight-average of Tc of different diblocks in the random copolymer. However, the crossover exponent is roughly independent of AB sequence distributions either for block copolymers or for random copolymers.

  12. Adsorption-like Collapse of Diblock Copolymers


    Orlandini, E.; Seno, F.; Stella, A. L.


    A linear copolymer made of two reciprocally attracting N-monomer blocks collapses to a compact phase through a novel transition, whose exponents are determined with extensive MC simulations in two and three dimensions. In the former case, an identification with the statistical geometry of suitable percolation paths allows to predict that the number of contacts between the blocks grows like $N^{9/16}$. In the compact phase the blocks are mixed and, in two dimensions, also zipped, in such a way...

  13. Hydrogel networks based on ABA triblock copolymers. (United States)

    Tartivel, Lucile; Behl, Marc; Schroeter, Michael; Lendlein, Andreas


    Triblock copolymers from hydrophilic oligo(ethylene glycol) segment A and oligo(propylene glycol) segment B, providing an ABA structure (OEG-OPG-OEG triblock), are known to be biocompatible and are used as self-solidifying gels in drug depots. A complete removal of these depots would be helpful in cases of undesired side effects of a drug, but this remains a challenge as they liquefy below their transition temperature. Therefore we describe the synthesis of covalently cross-linked hydrogel networks. Triblock copolymer-based hydrogels were created by irradiating aqueous solutions of the corresponding macro-dimethacrylates with UV light. The degree of swelling, swelling kinetics, mechanical properties and morphology of the networks were investigated. Depending on precursor concentration, equilibrium degree of swelling of the films ranged between 500% and 880% and was reached in 1 hour. In addition, values for storage and loss moduli of the hydrogel networks were in the 100 Pa to 10 kPa range. Although OEG-OPG-OEG triblocks are known for their micellization, which could hamper polymer network formation, reactive OEG-OPG-OEG triblock oligomers could be successfully polymerized into hydrogel networks. The degree of swelling of these hydrogels depends on their molecular weight and on the oligomer concentration used for hydrogel preparation. In combination with the temperature sensitivity of the ABA triblock copolymers, it is assumed that such hydrogels might be beneficial for future medical applications - e.g., removable drug release systems.

  14. Surface hydrophilic modification of acrylonitrile-butadiene-styrene terpolymer by poly(ethylene glycol-co-1,4-cyclohexanedimethanol terephthalate): Preparation, characterization, and properties studies (United States)

    Chen, Tingting; Zhang, Jun


    Surface hydrophilic modified acrylonitrile-butadiene-styrene (ABS) terpolymer was prepared by melt blending with poly(ethylene glycol-co-1,4-cyclohexanedimethanol terephthalate) (PETG) random copolymer as the modifier. Attenuated total reflectance-Fourier transform-infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) were used for surface analysis. Through the contact angle measurement, the relationship between surface properties of the ABS/PETG blends and PETG content was investigated. Scanning electron microscope (SEM) and dynamical mechanical thermal analysis (DMTA) were used to characterize interface morphology and compatibility of the blends. The effect of PETG content on the mechanical and rheological properties was examined. The ATR-FTIR and XPS analysis suggested that the hydrophilic groups were enriched on the surface with increasing PETG content in the blend. The decrease of the water contact angle and the increase of the polarity for the blends with increasing PETG content indicated that the hydrophilic property of the blends was enhanced with increasing PETG content. The ABS/PETG blends were partially miscible. And the blends with ≤50 wt% PETG had better compatibility than the blends with above 50 wt% PETG. It was clear that below 50 wt% PETG, the PETG phase was dispersed in spherical form and the ABS phase was continuous. Above 50 wt% PETG, the PETG phase became continuous and the ABS phase was dispersed in irregular form. Moreover, the tensile strength and flexural strength of the blends were enhanced with increasing PETG content. The flexural modulus almost remained constant. And the impact strength was decreased when the content of PETG was increasing.

  15. Surface hydrophilic modification of acrylonitrile-butadiene-styrene terpolymer by poly(ethylene glycol-co-1,4-cyclohexanedimethanol terephthalate): Preparation, characterization, and properties studies

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Tingting; Zhang, Jun, E-mail:


    Highlights: • Surface hydrophilic modified ABS was prepared by melt blending with PETG. • O= C−O groups were enriched on the surface with increasing PETG content. • Hydrophilic property of the blends was enhanced with increasing PETG content. • Phase inversion behavior of the blends occurred around intermediate composition. • Tensile and flexural strength were enhanced with increasing PETG content. - Abstract: Surface hydrophilic modified acrylonitrile-butadiene-styrene (ABS) terpolymer was prepared by melt blending with poly(ethylene glycol-co-1,4-cyclohexanedimethanol terephthalate) (PETG) random copolymer as the modifier. Attenuated total reflectance-Fourier transform-infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) were used for surface analysis. Through the contact angle measurement, the relationship between surface properties of the ABS/PETG blends and PETG content was investigated. Scanning electron microscope (SEM) and dynamical mechanical thermal analysis (DMTA) were used to characterize interface morphology and compatibility of the blends. The effect of PETG content on the mechanical and rheological properties was examined. The ATR-FTIR and XPS analysis suggested that the hydrophilic groups were enriched on the surface with increasing PETG content in the blend. The decrease of the water contact angle and the increase of the polarity for the blends with increasing PETG content indicated that the hydrophilic property of the blends was enhanced with increasing PETG content. The ABS/PETG blends were partially miscible. And the blends with ≤50 wt% PETG had better compatibility than the blends with above 50 wt% PETG. It was clear that below 50 wt% PETG, the PETG phase was dispersed in spherical form and the ABS phase was continuous. Above 50 wt% PETG, the PETG phase became continuous and the ABS phase was dispersed in irregular form. Moreover, the tensile strength and flexural strength of the blends were enhanced with

  16. Convenient synthetic method of starch/lactic acid graft copolymer ...

    Indian Academy of Sciences (India)

    Copolymer of starch grafted with lactic acid (LA) could be directly prepared by reaction of cornstarch with lactic acid and with sodium hydroxide (NaOH) as the catalyst. The structure of starch/LA copolymer was characterized by IR, XRD, SEM and 1H-NMR. The effects of NaOH concentration, ratios of starch and LA, reaction ...

  17. Micellar structure of amphiphilic poly(2-oxazoline) diblock copolymers

    DEFF Research Database (Denmark)

    Papadakis, C.M.; Ivanova, R.; Lüdtke, K.


    Amphiphilic diblock copolymers from poly(2-oxazoline)s in aqueous solution can form micelles. By means of small-angle neutron scattering, we have found that poly[(n-nonyl-2-oxazoline)-b-(methyl-2-oxazoline)] {P[(NOx)-b-(MOx)]} diblock copolymers in aqueous solution form micelles of core-shell typ...

  18. Cryoelectron microscopy of block-copolymers in an organic solvent

    NARCIS (Netherlands)

    Oostergetel, G.T.; Esselink, F.J; Hadziioannou, G


    Solutions of the diblock copolymer polystyrene/poly-2-vinylpyridine (PS/P2VP) in toluene were studied by cryo-transmission electron microscopy following fast freezing of a thin film of the solution in liquid nitrogen. The block copolymer forms spherical micelles which can be visualized using phase

  19. Positively charged co-polymers for use as antimicrobial agents

    DEFF Research Database (Denmark)


    The present invention provides a positively charged co-polymer for use as an antimicrobial agent, wherein said positively charged co-polymer is composed of amino acids and/or derivatives thereof and wherein at least 75 molar percent of said amino acids are selected from the group consisting...

  20. From Block Copolymers to Nano-porous Materials

    DEFF Research Database (Denmark)

    Vigild, Martin Etchells; Ndoni, Sokol; Berg, Rolf Henrik


    Quantitative etching of the polydimethylsiloxane block in a series of polystyrene-polydimethylsiloxane (PS-PDMS) block copolymers is reported. Reacting the block copolymer with anhydrous hydrogen fluoride (HF) renders a nanoporous material with the remaining PS maintaining the original morphology...