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Sample records for acid-catalyzed polymerization reactions

  1. Development of Fluorous Lewis Acid-Catalyzed Reactions

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    Joji Nishikido

    2006-08-01

    Full Text Available Organic synthetic methodology in the 21st century aims to conform to the principles of green sustainable chemistry (GSC and we may expect that in the future, the realization of GSC will be an important objective for chemical industries. An important aim of synthetic organic chemistry is to implement waste-free and environmentally-benign industrial processes using Lewis acids as versatile as aluminum choride. A key technological objective of our work in this area has been to achieve a “catalyst recycling system that utilizes the high activity and structural features of fluorous Lewis acid catalysts”. Thus, we have developed a series of novel fluorous Lewis acid catalysts, namely the ytterbium(III, scandium(III, tin(IV or hafnium(IV bis(perfluoroalkanesulfonylamides or tris(perfluoro- alkanesulfonylmethides. Our catalysts are recyclable and effective for acylations of alcohols and aromatics, Baeyer-Villiger reactions, direct esterifications and transesterifications in a fluorous biphasic system (FBS, in supercritical carbon dioxide and on fluorous silica gel supports.

  2. Asymmetric Brønsted acid-catalyzed aza-Diels–Alder reaction of cyclic C-acylimines with cyclopentadiene

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    Magnus Rueping

    2012-10-01

    Full Text Available A new chiral Brønsted acid-catalyzed aza-Diels–Alder reaction of cyclic C-acylimines with cyclopentadiene has been developed. The reaction provides optically active aza-tetracycles in good yields with high diastereo- and enantioselectivities under mild reaction conditions.

  3. Negative resists for i-line lithography utilizing acid-catalyzed intramolecular dehydration reaction

    Science.gov (United States)

    Ueno, Takumi; Uchino, Shou-ichi; Hattori, Keiko T.; Onozuka, Toshihiko; Shirai, Seiichiro; Moriuchi, Noboru; Hashimoto, Michiaki; Koibuchi, S.

    1994-05-01

    Chemical amplification negative resist system composed of a novolak resin, a carbinol and an acid generator is investigated for i-line phase-shift lithography. The reaction in this resist is based on an acid-catalyzed intramolecular dehydration reaction. The dehydration products act as aqueous-base dissolution inhibitors, and carbinol compounds in unexposed areas work as dissolution promoters. The resist composed of a novolak resin, 1,4-bis((alpha) -hydroxyisopropyl) benzene (DIOL-1) and 2- naphthoylmethyltetramethylenesulfonium triflate (PAG-2) gives the best lithographic performance in terms of sensitivity and resolution. Line-and-space patterns of 0.275 micrometers are obtained using an i-line stepper (NA:0.45) in conjunction with a phase shifting mask.

  4. Investigation of the complex reaction coordinate of acid catalyzed amide hydrolysis from molecular dynamics simulations

    International Nuclear Information System (INIS)

    Zahn, Dirk

    2004-01-01

    The rate-determining step of acid catalyzed peptide hydrolysis is the nucleophilic attack of a water molecule to the carbon atom of the amide group. Therein the addition of the hydroxyl group to the amide carbon atom involves the association of a water molecule transferring one of its protons to an adjacent water molecule. The protonation of the amide nitrogen atom follows as a separate reaction step. Since the nucleophilic attack involves the breaking and formation of several bonds, the underlying reaction coordinate is rather complex. We investigate this reaction step from path sampling Car-Parrinello molecular dynamics simulations. This approach does not require the predefinition of reaction coordinates and is thus particularly suited for investigating reaction mechanisms. From our simulations the most relevant components of the reaction coordinate are elaborated. Though the C···O distance of the oxygen atom of the water molecule performing the nucleophilic attack and the corresponding amide carbon atom is a descriptor of the reaction progress, a complete picture of the reaction coordinate must include all three molecules taking part in the reaction. Moreover, the proton transfer is found to depend on favorable solvent configurations. Thus, also the arrangement of non-reacting, i.e. solvent water molecules needs to be considered in the reaction coordinate

  5. Graphene oxide for acid catalyzed-reactions: Effect of drying process

    Science.gov (United States)

    Gong, H. P.; Hua, W. M.; Yue, Y. H.; Gao, Z.

    2017-03-01

    Graphene oxides (GOs) were prepared by Hummers method through various drying processes, and characterized by XRD, SEM, FTIR, XPS and N2 adsorption. Their acidities were measured using potentiometric titration and acid-base titration. The catalytic properties were investigated in the alkylation of anisole with benzyl alcohol and transesterification of triacetin with methanol. GOs are active catalysts for both reaction, whose activity is greatly affected by their drying processes. Vacuum drying GO exhibits the best performance in transesterification while freezing drying GO is most active for alkylation. The excellent catalytic behavior comes from abundant surface acid sites as well as proper surface functional groups, which can be obtained by selecting appropriate drying process.

  6. Cooperative Effects Between Arginine and Glutamic Acid in the Amino Acid-Catalyzed Aldol Reaction.

    Science.gov (United States)

    Valero, Guillem; Moyano, Albert

    2016-08-01

    Catalysis of the aldol reaction between cyclohexanone and 4-nitrobenzaldehyde by mixtures of L-Arg and of L-Glu in wet dimethyl sulfoxide (DMSO) takes place with higher enantioselectivity (up to a 7-fold enhancement in the anti-aldol for the 1:1 mixture) than that observed when either L-Glu or L-Arg alone are used as the catalysts. These results can be explained by the formation of a catalytically active hydrogen-bonded complex between both amino acids, and demonstrate the possibility of positive cooperative effects in catalysis by two different α-amino acids. Chirality 28:599-605, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

  7. The acid-catalyzed hydrolysis of an α-pinene-derived organic nitrate: kinetics, products, reaction mechanisms, and atmospheric impact

    Science.gov (United States)

    Rindelaub, Joel D.; Borca, Carlos H.; Hostetler, Matthew A.; Slade, Jonathan H.; Lipton, Mark A.; Slipchenko, Lyudmila V.; Shepson, Paul B.

    2016-12-01

    data, product identification confirms that a unimolecular specific acid-catalyzed mechanism is responsible for organic nitrate hydrolysis under acidic conditions. The free energies and enthalpies of the isobutyl nitrate hydrolysis intermediates and products were calculated using a hybrid density functional (ωB97X-V) to support the proposed mechanisms. These findings provide valuable information regarding the organic nitrate hydrolysis mechanism and its contribution to the fate of atmospheric NOx, aerosol phase processing, and BSOA composition.

  8. A chiral Brønsted acid-catalyzed highly enantioselective Mannich-type reaction of α-diazo esters with in situ generated N-acyl ketimines.

    Science.gov (United States)

    Unhale, Rajshekhar A; Sadhu, Milon M; Ray, Sumit K; Biswas, Rayhan G; Singh, Vinod K

    2018-04-03

    A chiral phosphoric acid-catalyzed asymmetric Mannich-type reaction of α-diazo esters with in situ generated N-acyl ketimines, derived from 3-hydroxyisoindolinones has been demonstrated in this communication. A variety of isoindolinone-based α-amino diazo esters bearing a quaternary stereogenic center were afforded in high yields (up to 99%) with excellent enantioselectivities (up to 99% ee). Furthermore, the synthetic utility of the products has been depicted by the hydrogenation of the diazo moiety of adducts.

  9. Lewis Acid Catalyzed Asymmetric Three-Component Coupling Reaction: Facile Synthesis of α-Fluoromethylated Tertiary Alcohols.

    Science.gov (United States)

    Aikawa, Kohsuke; Kondo, Daisuke; Honda, Kazuya; Mikami, Koichi

    2015-12-01

    A chiral dicationic palladium complex is found to be an efficient Lewis acid catalyst for the synthesis of α-fluoromethyl-substituted tertiary alcohols using a three-component coupling reaction. The reaction transforms three simple and readily available components (terminal alkyne, arene, and fluoromethylpyruvate) to valuable chiral organofluorine compounds. This strategy is completely atom-economical and results in perfect regioselectivities and high enantioselectivities of the corresponding tertiary allylic alcohols in good to excellent yields. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Density functional theory analysis of the reaction pathway for methane oxidation to acetic acid catalyzed by Pd2+ in sulfuric acid.

    Science.gov (United States)

    Chempath, Shaji; Bell, Alexis T

    2006-04-12

    Density functional theory has been used to investigate the thermodynamics and activation barriers associated with the direct oxidation of methane to acetic acid catalyzed by Pd2+ cation in concentrated sulfuric acid. Pd2+ cations in such solutions are ligated by two bisulfate anions and by one or two molecules of sulfuric acid. Methane oxidation is initiated by the addition of CH4 across one of the Pd-O bonds of a bisulfate ligand to form Pd(HSO4)(CH3)(H2SO4)2. The latter species will react with CO to produce Pd(HSO4)(CH3CO)(H2SO4)2. The most likely path to the final products is found to be via oxidation of Pd(HSO4)(CH3)(H2SO4)2 and Pd(HSO4)(CH3CO)(H2SO4)2 to form Pd(eta2-HSO4)(HSO4)2(CH3)(H2SO4) and Pd(eta2-HSO4)(HSO4)2(CH3CO)(H2SO4), respectively. CH3HSO4 or CH3COHSO4 is then produced by reductive elimination from the latter two species, and CH(3)COOH is then formed by hydrolysis of CH3COHSO4. The loss of Pd2+ from solution to form Pd(0) or Pd-black is predicted to occur via reduction with CO. This process is offset, though, by reoxidation of palladium by either H2SO4 or O2.

  11. Nucleotide Selectivity in Abiotic RNA Polymerization Reactions

    Science.gov (United States)

    Coari, Kristin M.; Martin, Rebecca C.; Jain, Kopal; McGown, Linda B.

    2017-09-01

    In order to establish an RNA world on early Earth, the nucleotides must form polymers through chemical rather than biochemical reactions. The polymerization products must be long enough to perform catalytic functions, including self-replication, and to preserve genetic information. These functions depend not only on the length of the polymers, but also on their sequences. To date, studies of abiotic RNA polymerization generally have focused on routes to polymerization of a single nucleotide and lengths of the homopolymer products. Less work has been done the selectivity of the reaction toward incorporation of some nucleotides over others in nucleotide mixtures. Such information is an essential step toward understanding the chemical evolution of RNA. To address this question, in the present work RNA polymerization reactions were performed in the presence of montmorillonite clay catalyst. The nucleotides included the monophosphates of adenosine, cytosine, guanosine, uridine and inosine. Experiments included reactions of mixtures of an imidazole-activated nucleotide (ImpX) with one or more unactivated nucleotides (XMP), of two or more ImpX, and of XMP that were activated in situ in the polymerization reaction itself. The reaction products were analyzed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) to identify the lengths and nucleotide compositions of the polymerization products. The results show that the extent of polymerization, the degree of heteropolymerization vs. homopolymerization, and the composition of the polymeric products all vary among the different nucleotides and depend upon which nucleotides and how many different nucleotides are present in the mixture.

  12. Nucleotide Selectivity in Abiotic RNA Polymerization Reactions.

    Science.gov (United States)

    Coari, Kristin M; Martin, Rebecca C; Jain, Kopal; McGown, Linda B

    2017-09-01

    In order to establish an RNA world on early Earth, the nucleotides must form polymers through chemical rather than biochemical reactions. The polymerization products must be long enough to perform catalytic functions, including self-replication, and to preserve genetic information. These functions depend not only on the length of the polymers, but also on their sequences. To date, studies of abiotic RNA polymerization generally have focused on routes to polymerization of a single nucleotide and lengths of the homopolymer products. Less work has been done the selectivity of the reaction toward incorporation of some nucleotides over others in nucleotide mixtures. Such information is an essential step toward understanding the chemical evolution of RNA. To address this question, in the present work RNA polymerization reactions were performed in the presence of montmorillonite clay catalyst. The nucleotides included the monophosphates of adenosine, cytosine, guanosine, uridine and inosine. Experiments included reactions of mixtures of an imidazole-activated nucleotide (ImpX) with one or more unactivated nucleotides (XMP), of two or more ImpX, and of XMP that were activated in situ in the polymerization reaction itself. The reaction products were analyzed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) to identify the lengths and nucleotide compositions of the polymerization products. The results show that the extent of polymerization, the degree of heteropolymerization vs. homopolymerization, and the composition of the polymeric products all vary among the different nucleotides and depend upon which nucleotides and how many different nucleotides are present in the mixture.

  13. Kinetics and mechanism of aquation and formation reactions of carbonato complexes. XII. Deuterium solvent isotope effect on the rate of acid-catalyzed decarboxylation of the carbonatobis (ethylenediamine) cobalt(III) complex ion. A mechanistic reappraisal

    International Nuclear Information System (INIS)

    Harris, G.M.; Hyde, K.E.

    1978-01-01

    A recent study of the acid-catalyzed decarboxylation of the carbonatotetrakis(pyridine)cobalt(III) complex ion showed there to be rate acceleration in D 2 O solvent, consistent with a proton-preequilibration mechanism. This observation directly contradicts the results of a similar study made some years ago of the analogous ion, carbonatobis(ethylenediamine)cobalt(III), for which there appeared to be deceleration in D 2 O solvent. A reinvestigation of the latter reaction over a much wider acidity range has now shown the earlier work to be in error. The previously proposed generalized mechanism for aquation of chelated carbonato complex ions of the form CoN 4 CO 3 + (N 4 identical with various tetramine ligand groupings of uni-, bi-, or quadridentate type) has thus been revised to include a proton equilibration step. An unexpected complication arises in the interpretation of the data for the bis(ethylenediamine) complex ion in the acidity range 0.1 + ] + ] term, overtakes and exceeds the true first-order rate constant for CO 2 release. The interesting implications of this unusual first-order successive reaction system are fully explored in the context of the present study

  14. The Brønsted Acid-Catalyzed, Enantioselective Aza-Diels-Alder Reaction for the Direct Synthesis of Chiral Piperidones.

    Science.gov (United States)

    Weilbeer, Claudia; Sickert, Marcel; Naumov, Sergei; Schneider, Christoph

    2017-01-12

    We disclose herein the first enantioselective aza-Diels-Alder reaction of β-alkyl-substituted vinylketene silyl-O,O-acetals and imines furnishing a broad range of optically highly enriched 4-alkyl-substituted 2-piperidones. As a catalyst for this one-pot reaction we employed a chiral phosphoric acid which effects a vinylogous Mannich reaction directly followed by ring-closure to the lactam. Subsequent fully diastereoselective transformations including hydrogenation, enolate alkylation, and lactam alkylation/reduction processes converted the cycloadducts into various highly substituted piperidines of great utility for the synthesis of natural products and medicinally active compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. A computational study on Lewis acid-catalyzed diastereoselective acyclic radical allylation reactions with unusual selectivity dependence on temperature and epimer precursor.

    Science.gov (United States)

    Georgieva, Miglena K; Santos, A Gil

    2014-12-05

    In stereoselective radical reactions, it is accepted that the configuration of the radical precursor has no impact on the levels of stereoinduction, as a prochiral radical intermediate is planar, with two identical faces, independently of its origin. However, Sibi and Rheault (J. Am. Chem. Soc. 2000, 122, 8873-8879) remarkably obtained different selectivities in the trapping of radicals originated from two epimeric bromides, catalyzed by chelating Lewis acids. The selectivity rationalization was made on the basis of different conformational properties of each epimer. However, in this paper we show that the two epimers have similar conformational properties, which implies that the literature proposal is unable to explain the experimental results. We propose an alternative mechanism, in which the final selectivity is dependent on different reaction rates for radical formation from each epimer. By introducing a different perspective of the reaction mechanism, our model also allows the rationalization of different chemical yields obtained from each epimer, a result not rationalized by the previous model. Adaptation to other radical systems, under different reaction conditions, is also possible.

  16. Mechanism of Brønsted acid catalyzed conversion of carbohydrates

    NARCIS (Netherlands)

    Yang, G.; Pidko, E.A.; Hensen, E.J.M.

    2012-01-01

    A comprehensive DFT study of acid-catalyzed glucose and fructose reactions in water covering more than 100 potential reaction paths is performed with the aim to identify the main reaction channels for obtaining such desirable biorefinery platform products as 5-hydroxymethylfurfural (HMF) and

  17. Acid-catalyzed kinetics of indium tin oxide etching

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Jae-Hyeok; Kim, Seong-Oh; Hilton, Diana L. [School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798 (Singapore); Centre for Biomimetic Sensor Science, Nanyang Technological University, 50 Nanyang Drive, 637553 (Singapore); Cho, Nam-Joon, E-mail: njcho@ntu.edu.sg [School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, 639798 (Singapore); Centre for Biomimetic Sensor Science, Nanyang Technological University, 50 Nanyang Drive, 637553 (Singapore); School of Chemical and Biomedical Engineering, Nanyang Technological University, 62 Nanyang Drive, 637459 (Singapore)

    2014-08-28

    We report the kinetic characterization of indium tin oxide (ITO) film etching by chemical treatment in acidic and basic electrolytes. It was observed that film etching increased under more acidic conditions, whereas basic conditions led to minimal etching on the time scale of the experiments. Quartz crystal microbalance was employed in order to track the reaction kinetics as a function of the concentration of hydrochloric acid and accordingly solution pH. Contact angle measurements and atomic force microscopy experiments determined that acid treatment increases surface hydrophilicity and porosity. X-ray photoelectron spectroscopy experiments identified that film etching is primarily caused by dissolution of indium species. A kinetic model was developed to explain the acid-catalyzed dissolution of ITO surfaces, and showed a logarithmic relationship between the rate of dissolution and the concentration of undisassociated hydrochloric acid molecules. Taken together, the findings presented in this work verify the acid-catalyzed kinetics of ITO film dissolution by chemical treatment, and support that the corresponding chemical reactions should be accounted for in ITO film processing applications. - Highlights: • Acidic conditions promoted indium tin oxide (ITO) film etching via dissolution. • Logarithm of the dissolution rate depended linearly on the solution pH. • Acid treatment increased ITO surface hydrophilicity and porosity. • ITO film etching led to preferential dissolution of indium species over tin species.

  18. A kinetic mechanistic study of acid-catalyzed alkylation of isobutane with C4-olefins at low temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Doshi, B.M.

    1978-01-01

    A kinetic and mechanistic study of sulfuric acid-catalyzed alkylation of isobutane with C/sub 4/-Olefins at Low Temperatures(-20/sup 0/ to 0/sup 0/C) was based on a new two-step reaction sequence in which the desired first-step reactions are between acid and olefin to form sulfates and the desired second-step reactions are between sulfates and isobutane to form mostly trimethylpentanes. Linear butenes formed stable sulfates that formed alkylates of exceptionally high quality, up to 100 Research octane, whereas isobutylene and trimethylpentene mainly polymerized during the first step, and the alkylate produced had only 90 Research octane. Trimethylpentanes and dimethylhexanes, when contacted with concentrated sulfuric acid at -10/sup 0/ to +25/sup 0/C, degraded and isomerized to form C/sub 4/-C/sub 9/ and higher isoparaffins and acid-soluble hydrocarbons (conjunct polymers). For the two-step process and the degradation and isomerization reactions, kinetic models based on reaction at the interface were developed; but for isoolefins, a polymerization-cracking sequence (via C/sub 12/- and even C/sub 16/-olefins) is the preferred route. Commercial applications of the results are proposed.

  19. Solid Acid-Catalyzed Cellulose Hydrolysis Monitored by In Situ ATR-IR Spectroscopy

    NARCIS (Netherlands)

    Zakzeski, J.; Grisel, R.J.H.; Smit, A.T.; Weckhuysen, B.M.

    2012-01-01

    The solid acid-catalyzed hydrolysis of cellulose was studied under elevated temperatures and autogenous pressures using in situ ATR-IR spectroscopy. Standards of cellulose and pure reaction products, which include glucose, fructose, hydroxymethylfurfural (HMF), levulinic acid (LA), formic acid, and

  20. Competition Between Hydrotreating and Polymerization Reactions During Pyrolysis Oil Hydrodeoxygenation

    NARCIS (Netherlands)

    Mercader, F. De Miguel; Koehorst, P. J. J.; Heeres, H. J.; Kersten, S. R. A.; Hogendoorn, J. A.

    2011-01-01

    Hydrodeoxygenation (HDO) of pyrolysis oil is an upgrading step that allows further coprocessing of the oil product in (laboratory-scale) standard refinery units to produce advanced biofuels. During HDO, desired hydrotreating reactions are in competition with polymerization reactions that can lead to

  1. RADIOCHEMICAL YIELDS OF GRAFT POLYMERIZATION REACTIONS OF CELLULOSE

    Energy Technology Data Exchange (ETDEWEB)

    Arthur, Jr, J C; Blouin, F A

    1963-12-15

    The preparation of radioinduced graft polymers of cotton cellulose, while retaining the fibrous nature and high molecular weight of the cellulose, depended primarily on the radiochemical yields of cellulose reactions and of graft polymerization reactions. Yields of the initial major molecular changes in cellulosic polymer indicated that, in the case of scission of the molecule and carboxyl group formation, chain reactions were not initiated by radiation; however, in the case of carbonyl group formation chain reactions were initiated but quickly terminated. Generally, experimental procedures, used in graft polymerization reactions, were: simultaneous irradiation reactions, that is, application of monomers or solutions of monomers to cellulose or chemically modified celluloses, then irradiation; and post-irradiation reactions, that is, irradiation of cellulose or chemically modified celluloses, then after removal from the field of radiation, contacting the irradiated cellulose with monomer. Some of the most important factors influencing the radiochemical yields of graft polymerization reactions, of styrene and acrylonitrile onto cellulose were: concentration of monomer in treating solution; solvent; ratio of monomer solution to cellulose; prior chemical modification of cellulose; and absence of oxygen, particularly in post-irradiation reactions. Experimental data are presented, and the direct and indirect effects of Co/sup 60/ gamma radiation on these reactions are discussed. (auth)

  2. Estimation of the Polymerization Rate of Liquid Propylene Using Adiabatic Reaction Calorimetry and Reaction Dilatometry

    NARCIS (Netherlands)

    Al-haj Ali, Mohammad; Betlem, Ben; Roffel, Brian; Weickert, Günter

    2007-01-01

    The use of pressure-drop and constant-pressure dilatometry for obtaining rate data for liquid propylene polymerization in filled batch reactors was examined. The first method uses reaction temperature and pressure as well as the compressibility of the reactor contents to calculate the polymerization

  3. Comparison of techniques for the determination of conversion during suspension polymerization reactions

    Directory of Open Access Journals (Sweden)

    J. C. Santos

    2008-06-01

    Full Text Available The determination of conversion during suspension polymerization reactions is not an easy task due to the heterogeneity of the reaction medium and the tendency of particles to agglomerate rapidly when stirring is stopped. Usually, bulk polymerization in ampoules is employed to study the kinetics of suspension polymerization reactions. In this work, a comparison of different techniques for the determination of conversion during suspension polymerization reactions is presented. Results showed a good agreement between the conversion obtained by gravimetry during styrene suspension polymerization and on-line conversion monitoring data using fiber-optic based Raman Spectroscopy. Nevertheless, the polymerization rate of styrene bulk polymerization carried out in ampoules was higher than the real reaction rate of styrene suspension polymerization due to slightly higher reaction temperatures. Simulation results using the experimental temperature data in a mathematical model confirmed these results.

  4. Vinyl Chloride Emulsion Polymerization Reaction: Effect of Various Formulations

    Directory of Open Access Journals (Sweden)

    Seyed Mehrdad Jalilian

    2013-01-01

    Full Text Available A mixture  of  sodium  lauryl  sulfate  (SLS  as  ionic  emulsifer  and  stearyl alcohol as non-ionic emulsifer was employed in a vinyl chloride emulsion polymerization  reaction  to  study  the  infuence  of  various  interactive parameters involved in the reaction system. It was found that the particle size was dependent on the amount and type of emulsifer. The average particle size of polyvinyl chloride was dropped by higher amount of emulsifying agents.  At the gel point, more heat was generated by higher amount of vinyl chloride fed into the reaction system. The molecular weight of the polymer was decreased by increases in reaction temperature while,  it  increased by augmenting  the amount of emulsifer. According to the 13C NMR and FTIR spectroscopic data no defect was detected in the chain structure of synthetic polyvinylchloride product. An optimization of polymerization reaction condition was reached based on ultimate particle size desired for its favorable distribution in plastisols.

  5. Studies on the runaway reaction of ABS polymerization process

    International Nuclear Information System (INIS)

    Hu, K.-H.; Kao, C.-S.; Duh, Y.-S.

    2008-01-01

    Taiwan has the largest acrylonitrile-butadiene-styrene (ABS) copolymer production in the world. Preventing on unexpected exothermic reactions and related emergency relief hazard is essential in the safety control of ABS emulsion polymerization. A VSP2 (Vent Sizing Package 2) apparatus is capable of studying both normal and abnormal conditions (e.g., cooling failure, mischarge, etc.) of industrial process. In this study, the scenarios were verified from the following abnormal conditions: loss of cooling, double charge of initiator, overcharge of monomer, without charge of solvent, and external fire. An external fire with constant heating will promote higher self-heat rate and this is recommended as the worst case scenario of emulsion polymerization on butadiene. Cooling failure coupled with bulk system of reactant was determined to be the credible worst case in ABS emulsion polymerization. Finally, the emergency vent sizing based on thermokinetics from VSP associated with DIERS methodology were used for evaluating the vent sizing and compared to that of the industrial plants

  6. Single Turnover at Molecular Polymerization Catalysts Reveals Spatiotemporally Resolved Reactions.

    Science.gov (United States)

    Easter, Quinn T; Blum, Suzanne A

    2017-10-23

    Multiple active individual molecular ruthenium catalysts have been pinpointed within growing polynorbornene, thereby revealing information on the reaction dynamics and location that is unavailable through traditional ensemble experiments. This is the first single-turnover imaging of a molecular catalyst by fluorescence microscopy and allows detection of individual monomer reactions at an industrially important molecular ruthenium ring-opening metathesis polymerization (ROMP) catalyst under synthetically relevant conditions (e.g. unmodified industrial catalyst, ambient pressure, condensed phase, ca. 0.03 m monomer). These results further establish the key fundamentals of this imaging technique for characterizing the reactivity and location of active molecular catalysts even when they are the minor components. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. The Nanoconfined Free Radical Polymerization: Reaction Kinetics and Thermodynamics

    Science.gov (United States)

    Zhao, Haoyu; Simon, Sindee

    The reaction kinetics and thermodynamics of nanoconfined free radical polymerizations are investigated for methyl methacrylate (MMA) and ethyl methacrylate (EMA) monomers using differential scanning calorimetry. Controlled pore glass is used as the confinement medium with pore diameters as small as 7.5 nm; the influence of both hydrophobic (silanized such that trimethylsilyl groups cover the surface) and hydrophilic (native silanol) surfaces is investigated. Propagation rates increase when monomers are reacted in the hydrophilic pores presumably due to the specific interactions between the carbonyl and silanol groups; however, the more flexible EMA monomer shows weaker effects. On the other hand, initial rates of polymerization in hydrophobic pores are unchanged from the bulk. In both pores, the onset of autoacceleration occurs earlier due to the reduced diffusivity of confined chains, which may be compensated at high temperatures. In addition to changes in kinetics, the reaction thermodynamics can be affected under nanoconfinement. Specifically, the ceiling temperature (Tc) is shifted to lower temperatures in nanopores, with pore surface chemistry showing no significant effects; the equilibrium conversion is also reduced at high temperatures below Tc. These observations are attributed to a larger negative change in entropy on propagation for the confined system, with the MMA system again showing greater effects. Funding from ACS PRF is gratefully acknowledged.

  8. Hydrogen-bonded intermediates and transition states during spontaneous and acid-catalyzed hydrolysis of the carcinogen (+)-anti-BPDE.

    Science.gov (United States)

    Palenik, Mark C; Rodriguez, Jorge H

    2014-07-07

    Understanding mechanisms of (+)-anti-BPDE detoxification is crucial for combating its mutagenic and potent carcinogenic action. However, energetic-structural correlations of reaction intermediates and transition states during detoxification via hydrolysis are poorly understood. To gain mechanistic insight we have computationally characterized intermediate and transition species associated with spontaneous and general-acid catalyzed hydrolysis of (+)-anti-BPDE. We studied the role of cacodylic acid as a proton donor in the rate limiting step. The computed activation energy (ΔG‡) is in agreement with the experimental value for hydrolysis in a sodium cacodylate buffer. Both types of, spontaneous and acid catalyzed, BPDE hydrolysis can proceed through low-entropy hydrogen bonded intermediates prior to formation of transition states whose energies determine reaction activation barriers and rates.

  9. Convenient synthesis of benzothiazoles and benzimidazoles through Brønsted acid catalyzed cyclization of 2-amino thiophenols/anilines with β-diketones.

    Science.gov (United States)

    Mayo, Muhammad Shareef; Yu, Xiaoqiang; Zhou, Xiaoyu; Feng, Xiujuan; Yamamoto, Yoshinori; Bao, Ming

    2014-02-07

    Brønsted acid catalyzed cyclization reactions of 2-amino thiophenols/anilines with β-diketones under oxidant-, metal-, and radiation-free conditions are described. Various 2-substituted benzothiazoles/benzimidazoles are obtained in satisfactory to excellent yields. Different groups such as methyl, chloro, nitro, and methoxy linked on benzene rings were tolerated under the optimized reaction conditions.

  10. Kinetic study on the acid-catalyzed hydrolysis of cellulose to levulinic acid

    NARCIS (Netherlands)

    Girisuta, B.; Janssen, L. P. B. M.; Heeres, H. J.

    2007-01-01

    A variety of interesting bulk chemicals is accessible by the acid-catalyzed hydrolysis of cellulose. An interesting example is levulinic acid, a versatile precursor for fuel additives, polymers, and resins. A detailed kinetic study on the acid-catalyzed hydrolysis of cellulose to levulinic acid is

  11. Numerical Analysis Of Hooke Jeeves-Runge Kutta To Determine Reaction Rate Equation In Pyrrole Polymerization

    International Nuclear Information System (INIS)

    Gunawan, Indra; Sulistyo, Harry; Rochmad

    2001-01-01

    The numerical analysis of Hooke Jeeves Methods combined with Runge Kutta Methods is used to determine the exact model of reaction rate equation of pyrrole polymerization. Chemical polymerization of pyrrole was conducted with FeCI 3 / pyrrole solution at concentration ratio of 1.62 mole / mole and 2.18 mole / mole with varrying temperature of 28, 40, 50, and 60 o C. FeCl 3 acts as an oxidation agent to form pyrrole cation that will polymerize. The numerical analysis was done to examine the exact model of reaction rate equation which is derived from reaction equation of initiation, propagation, and termination. From its numerical analysis, it is found that the pyrrole polymerization follows third order of pyrrole cation concentration

  12. Application of acid-catalyzed hydrolysis of dispersed organic solvent in developing new microencapsulation process technology.

    Science.gov (United States)

    Lee, Honghwa; Lee, Sunhwa; Bhattacharjee, Himanshu; Sah, Hongkee

    2012-01-01

    The aim of this study was to evaluate a new microencapsulation technology employing an acid-catalyzed solvent extraction method in conjunction to an emulsion-based microencapsulation process. Its process consisted of emulsifying a dispersed phase of poly(D,L-lactide-co-glycolide) and isopropyl formate in an aqueous phase. This step was followed by adding hydrochloric acid to the resulting oil-in-water emulsion, in order to initiate the hydrolysis of isopropyl formate dissolved in the aqueous phase. Its hydrolysis caused the liberation of water-soluble species, that is, isopropanol and formic acid. This event triggered continual solvent leaching out of emulsion droplets, thereby initiating microsphere solidification. This new processing worked well for encapsulation of progesterone and ketoprofen that were chosen as a nonionizable model drug and a weakly acidic one, respectively. Furthermore, the structural integrity of poly(D,L-lactide-co-glycolide) was retained during microencapsulation. The new microencapsulation technology, being conceptually different from previous approaches, might be useful in preparing various polymeric particles.

  13. A two-step acid-catalyzed process for the production of biodiesel from rice bran oil

    Energy Technology Data Exchange (ETDEWEB)

    Zullaikah, S.; Lai, Chao Chin; Vali, S.R.; Ju, Yi Hsu [National Taiwan Univ. of Science and Technology, Taipei (China). Dept. of Chemical Engineering

    2005-11-15

    A study was undertaken to examine the effect of temperature, moisture and storage time on the accumulation of free fatty acid in the rice bran. Rice bran stored at room temperature showed that most triacylglyceride was hydrolyzed and free fatty acid (FFA) content was raised up to 76% in six months. A two-step acid-catalyzed methanolysis process was employed for the efficient conversion of rice bran oil into fatty acid methyl ester (FAME). The first step was carried out at 60 {sup o}C. Depending on the initial FFA content of oil, 55-90% FAME content in the reaction product was obtained. More than 98% FFA and less than 35% of TG were reacted in 2 h. The organic phase of the first step reaction product was used as the substrate for a second acid-catalyzed methanolysis at 100 {sup o}C. By this two-step methanolysis reaction, more than 98% FAME in the product can be obtained in less than 8 h. Distillation of reaction product gave 99.8% FAME (biodiesel) with recovery of more than 96%. The residue contains enriched nutraceuticals such as {gamma}-oryzanol (16-18%), mixture of phytosterol, tocol and steryl ester (19-21%). (author)

  14. Ultra-sensitive EUV resists based on acid-catalyzed polymer backbone breaking

    Science.gov (United States)

    Manouras, Theodoros; Kazazis, Dimitrios; Koufakis, Eleftherios; Ekinci, Yasin; Vamvakaki, Maria; Argitis, Panagiotis

    2018-03-01

    The main target of the current work was to develop new sensitive polymeric materials for lithographic applications, focusing in particular to EUV lithography, the main chain of which is cleaved under the influence of photogenerated acid. Resist materials based on the cleavage of polymer main chain are in principle capable to create very small structures, to the dimensions of the monomers that they consist of. Nevertheless, in the case of the commonly used nonchemically amplified materials of this type issues like sensitivity and poor etch resistance limit their areas of application, whereas inadequate etch resistance and non- satisfactory process reliability are the usual problems encountered in acid catalysed materials based on main chain scission. In our material design the acid catalyzed chain cleavable polymers contain very sensitive moieties in their backbone while they remain intact in alkaline ambient. These newly synthesized polymers bear in addition suitable functional groups for the achievement of desirable lithographic characteristics (thermal stability, acceptable glass transition temperature, etch resistance, proper dissolution behavior, adhesion to the substrate). Our approach for achieving acceptable etch resistance, a main drawback in other main chain cleavable resists, is based on the introduction of polyaromatic hydrocarbons in the polymeric backbone, whereas the incorporation of an inorganic component further enhances the etch resistance. Single component systems can also be designed following the proposed approach by the incorporation of suitable PAGs and base quencher molecules in the main chain. Resist formulations based on a random copolymer designed according to the described rules evaluated in EUV exhibit ultrahigh sensitivity, capability for high resolution patterning and overall processing characteristics that make them strong candidates for industrial use upon further optimization.

  15. Oligonucleotides as probes for studying polymerization reactions in dilute aqueous solution

    Science.gov (United States)

    Kolb, V.; Orgel, L. E.; Miller, S. L. (Principal Investigator)

    1994-01-01

    We have prepared a [32P]-labled oligonucleotide probe carrying a free primary amine at its 3'-terminus. This probe is used to initiate polymerization of aziridine (ethyleneimine) in aqueous solution. The nature of the oligomeric products and the kinetics of their formation are then monitored by gel electrophoresis. Our results are generally consistent with those obtained using conventional techniques. We have also investigated the effect of polyanionic templates on the rate of oligomerization of aziridine. We find that water-soluble polyanions generally accelerate the polymerization. The sodium salt of polymethacrylic acid is the most effective of the templates that we studied. The methods introduced in this paper should be applicable to a variety of polymerization reactions in aqueous solution. They should greatly simplify the screening of potentially prebiotic polymerization reactions.

  16. Production of Biodiesel from High Acid Value Waste Cooking Oil Using an Optimized Lipase Enzyme/Acid-Catalyzed Hybrid Process

    Directory of Open Access Journals (Sweden)

    N. Saifuddin

    2009-01-01

    Full Text Available The present study is aimed at developing an enzymatic/acid-catalyzed hybrid process for biodiesel production using waste cooking oil with high acid value (poor quality as feedstock. Tuned enzyme was prepared using a rapid drying technique of microwave dehydration (time required around 15 minutes. Further enhancement was achieved by three phase partitioning (TPP method. The results on the lipase enzyme which was subjected to pH tuning and TPP, indicated remarkable increase in the initial rate of transesterification by 3.8 times. Microwave irradiation was found to increase the initial reaction rates by further 1.6 times, hence giving a combined increase in activity of about 5.4 times. The optimized enzyme was used for hydrolysis and 88% of the oil taken initially was hydrolyzed by the lipase. The hydrolysate was further used in acid-catalyzed esterification for biodiesel production. By using a feedstock to methanol molar ratio of 1:15 and a sulphuric acid concentration of 2.5%, a biodiesel conversion of 88% was obtained at 50 °C for an hour reaction time. This hybrid process may open a way for biodiesel production using unrefined and used oil with high acid value as feedstock.

  17. Role of keto–enol tautomerization in a chiral phosphoric acid catalyzed asymmetric thiocarboxylysis of meso-epoxide: a DFT study

    KAUST Repository

    Ajitha, Manjaly John; Huang, Kuo-Wei

    2015-01-01

    The mechanism of a chiral phosphoric acid catalyzed thiocarboxylysis of meso-epoxide was investigated by density functional theory (DFT) calculations (M06-2X). The nucleophilic ring opening of epoxide by thiobenzoic acid was found to proceed via a concerted termolecular transition state with a simultaneous dual proton transfer to yield the β-hydroxy thioester product. Electrostatic interactions together with the steric environment inside the chiral catalyst play an important role in determining the enantioselectivity of the reaction.

  18. Role of keto–enol tautomerization in a chiral phosphoric acid catalyzed asymmetric thiocarboxylysis of meso-epoxide: a DFT study

    KAUST Repository

    Ajitha, Manjaly John

    2015-09-15

    The mechanism of a chiral phosphoric acid catalyzed thiocarboxylysis of meso-epoxide was investigated by density functional theory (DFT) calculations (M06-2X). The nucleophilic ring opening of epoxide by thiobenzoic acid was found to proceed via a concerted termolecular transition state with a simultaneous dual proton transfer to yield the β-hydroxy thioester product. Electrostatic interactions together with the steric environment inside the chiral catalyst play an important role in determining the enantioselectivity of the reaction.

  19. Molecular extinction coefficients of lead sulfide and polymerized diaminobenzidine as final reaction products of histochemical phosphatase reactions

    NARCIS (Netherlands)

    van Noorden, C. J.; Jonges, G. N.

    1992-01-01

    Molar extinction coefficients of precipitated lead sulfide (PbS) and polymerized diaminobenzidine (polyDAB) have been determined at wavelengths of 450 nm and 480 nm, respectively, for quantitative histochemical analysis of phosphatase reactions. These values are essential for the conversion of

  20. Reaction of Acetylenedicarboxylic Acid Made Easy: High-Pressure Route for Polymerization

    DEFF Research Database (Denmark)

    Delori, Amit; Hutchison, Ian B.; Bull, Craig L.

    2018-01-01

    A breakthrough has been achieved in improving the efficiency of solid-state polymerization of acetylenedicarboxylic acid (ADCA). Traditional solid-state polymerization of ADCA is marked by long exposure times of γ-radiation (>10 days) and very low yields (around 5.5%). We have been able to perform...... a reaction to an n = 8 oligomer, as confirmed by matrix-assisted laser desorption/ionization-time of flight, in less than 2 min by employing ∼6 GPa of pressure. We have determined the crystal structure of ADCA on increasing pressure to (5.2 GPa) to provide insight into the process of polymerization...... with Pixel calculations supporting our evaluation of the polymerization process....

  1. Characteristics of plastic scintillators fabricated by a polymerization reaction

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Cheol Ho; Son, Jaebum; Kim, Tae Hoon; Kim, Yong Kyun [Dept. of Nuclear Engineering, Hanyang University, Seoul (Korea, Republic of)

    2017-04-15

    Three plastic scintillators of 4.5 cm diameter and 2.5-cm length were fabricated for comparison with commercial plastic scintillators using polymerization of the styrene monomer 2.5-diphenyloxazole (PPO) and 1,4-bis benzene (POPOP). Their maximum emission wavelengths were determined at 426.06 nm, 426.06 nm, and 425.00 nm with a standard error of 0.2% using a Varian spectrophotometer (Agilent, Santa Clara, CA, USA). Compton edge spectra were measured using three gamma ray sources [i.e., cesium 137 ({sup 137}Cs), sodium 22 ({sup 22}Na), and cobalt 60 ({sup 60}Co)]. Energy was calibrated by analyzing the Compton edge spectra. The fabricated scintillators possessed more than 99.7% energy linearity. Light output was comparable to that of the BC-408 scintillator (Saint-Gobain, Paris, France). The fabricated scintillators showed a light output of approximately 59–64% of that of the BC-408 scintillator.

  2. Effects of different reaction mediums on ring opening polymerization ...

    African Journals Online (AJOL)

    This work examined the effects of reaction conditions on ring opening ... of this study was to observe molecular weight distribution, conversion rates, and thermal ... M monomer and 0.56 M solvent), 10 mg lipase were used in the experiments.

  3. Behaviors of glucose decomposition during acid-catalyzed hydrothermal hydrolysis of pretreated Gelidium amansii.

    Science.gov (United States)

    Jeong, Tae Su; Choi, Chang Ho; Lee, Ji Ye; Oh, Kyeong Keun

    2012-07-01

    Acid-catalyzed hydrothermal hydrolysis is one path to cellulosic glucose and subsequently to its dehydration end products such as hydroxymethyl furfural (HMF), formic acid and levulinic acid. The effect of sugar decomposition not only lowers the yield of fermentable sugars but also forms decomposition products that inhibit subsequent fermentation. The present experiments were conducted with four different acid catalysts (H(2)SO(4), HNO(3), HCl, and H(3)PO(4)) at various acid normalities (0.5-2.1N) in batch reactors at 180-210 °C. From the results, H(2)SO(4) was the most suitable catalyst for glucose production, but glucose decomposition occurred during the hydrolysis. The glucose production was maximized at 160.7 °C, 2.0% (w/v) H(2)SO(4), and 40 min, but resulted in a low glucan yield of 33.05% due to the decomposition reactions, which generated formic acid and levulinic acid. The highest concentration of levulinic acid, 7.82 g/L, was obtained at 181.2 °C, 2.0% (w/v) H(2)SO(4), and 40 min. Copyright © 2012 Elsevier Ltd. All rights reserved.

  4. Visible lights induced polymerization reactions: interactions between rose bengal and iron aren complex

    International Nuclear Information System (INIS)

    Burget, D.; Grotzinger, C.; Jacques, P.; Fouassier, J.P.

    1999-01-01

    The present paper is devoted to an investigation of the interactions between Rose Bengal (RB) and an Iron aren (Irg(+)) complex that are usable in visible light induced polymerization reactions. Steady state and flash photolysis experiments were performed in order to elucidate the nature of the intermediates formed after light excitation. A complete scheme of evolution of the excited states is discussed

  5. Condensed tannins. Base-catalysed reactions of polymeric procyanidins with phloroglucinol: Intramolecular rearrangements

    Science.gov (United States)

    Peter E. Laks; Richard W. Hemingway; Anthony H. Conner

    1987-01-01

    Reactions of polymeric procyanidins with phloroglucinol at pH 12.0 and temperatures of 23 or 50°C gave epicatechin-(4β)-phloroglucinol (7), by cleavage of the interflavanoid bond between procyanidin units with subsequent addition of phloroglucinol, and (+)-catechin from the terminal unit. The phloroglucinol adduct (7) rearranged to an enolic form of 8-(3,4-...

  6. Gas phase polymerization of propylene. Reaction kinetics and molecular weight distribution

    NARCIS (Netherlands)

    Meier, G.B.; Weickert, G.; van Swaaij, Willibrordus Petrus Maria

    2001-01-01

    Gas-phase polymerizations have been executed at different temperatures, pressures, and hydrogen concentrations using Me2Si[Ind]2ZrCl2 / methylaluminoxane / SiO2(Pennsylvania Quarts) as a catalyst. The reaction rate curves have been described by a kinetic model, which takes into account the initially

  7. Vapor phase reactions in polymerization plasma for divinylsiloxane-bis-benzocyclobutene film deposition

    International Nuclear Information System (INIS)

    Kinoshita, Keizo; Nakano, Akinori; Kawahara, Jun; Kunimi, Nobutaka; Hayashi, Yoshihiro; Kiso, Osamu; Saito, Naoaki; Nakamura, Keiji; Kikkawa, Takamaro

    2006-01-01

    Vapor phase reactions in plasma polymerization of divinylsiloxane-bis-benzocyclobutene (DVS-BCB) low-k film depositions on 300 mm wafers were studied using mass spectrometry, in situ Fourier transform infrared, and a surface wave probe. Polymerization via Diels-Alder cycloaddition reaction was identified by the detection of the benzocyclohexene group. Hydrogen addition and methyl group desorption were also detected in DVS-BCB monomer and related large molecules. The dielectric constant k of plasma polymerized DVS-BCB with a plasma source power range up to 250 W was close to ∼2.7 of thermally polymerized DVS-BCB, and increased gradually over 250 W. The electron density at 250 W was about 1.5x10 10 cm -3 . The increase of the k value at higher power was explained by the decrease of both large molecular species via multistep dissociation and incorporation of silica components into the polymer. It was found that the reduction of electron density as well as precursor residence time is important for the plasma polymerization process to prevent the excess dissociation of the precursor

  8. Study of aniline polymerization reactions through the particle size formation in acidic and neutral medium

    Science.gov (United States)

    Aribowo, Slamet; Hafizah, Mas Ayu Elita; Manaf, Azwar; Andreas

    2018-04-01

    In the present paper, we reported particle size kinetic studies on the conducting polyaniline (PANI) which synthesized through a chemical oxidative polymerization technique from aniline monomer. PANI was prepared using ammonium persulfate (APS) as oxidizing agent which carried out in acidic and neutral medium at various batch temperatures of respectively 20, 30 and 50 °C. From the studies, it was noticed that the complete polymerization reaction progressed within 480 minutes duration time. The pH of the solution during reaction kinetic reached values 0.8 - to 1.2 in acidic media, while in the neutral media the pH value reached values 3.8 - 4.9. The batch temperature controlled the polymerization reaction in which the reaction progressing, which followed by the temperature rise of solution above the batch temperature before settled down to the initial temperature. An increment in the batch temperature gave highest rise in the solution temperature for the two media which cannot be more than 50 °C. The final product of polymerization reaction was PANI confirmed by Fourier Transform Infra-Red (FTIR) spectrophotometer for molecule structure identification. The averages particle size of PANI which carried out in the two different media is evidently similar in the range 30 - 40 μm and insensitive to the batch temperature. However, the particle size of PANI which obtained from the polymerization reaction at a batch temperature of 50 °C under acidic condition reached ˜53.1 μm at the tip of the propagation stage which started in the first 5 minutes. The size is obviously being the largest among the batch temperatures. Whereas, under neutral condition the particle size is much larger which reached the size 135 μm at the batch temperature of 20 °C. It is concluded that the particle size formation during the polymerization reaction being one of the important parameter to determine particle growing of polymer which indicated the reaction kinetics mechanism of synthesize

  9. Reaction kinetics and modeling of photoinitiated cationic polymerization of an alicyclic based diglycidyl ether

    International Nuclear Information System (INIS)

    Harikrishna, R.; Ponrathnam, S.; Tambe, S.S.

    2014-01-01

    Highlights: • Photocationic polymerization of alicyclic based diglycidyl ether was carried out. • Kinetic parameters were influenced by gelation and diffusional restrictions. • Applicability of autocatalytic model was established by nonlinear regression. • System showed higher activation energy than cycloaliphatic and aromatic diepoxides. -- Abstract: Photoinitiated cationic polymerization of cycloaliphatic diepoxides had received tremendous attention, while studies with lesser polymerizable diglycidyl ethers are comparatively less reported. The present work deals with the photoinitiated cationic polymerization of cyclohexane dimethanol diglycidyl ether followed by estimation of kinetic parameters. The effects of concentration of photoinitiator and temperature on curing performance were studied using photo differential scanning calorimeter or photo DSC with polychromatic radiation. It was observed that the rate of polymerization as well as ultimate conversion increased with increasing concentration of photoinitiator and temperature. The influences of gelation as well as diffusional restrictions have remarkable effect on cure performance. The kinetic parameters as per autocatalytic kinetic model were studied by Levenberg–Marquardt nonlinear regression method instead of conventional linear method for obtaining more accurate values of apparent rate constant. It was observed that the model fits with data from initial stages to almost towards the end of the reaction. The activation energy was found to be higher than the values reported for more reactive cycloaliphatic diepoxides. The value of pre-exponential factor increased with increase in activation energy showing influence of gelation at early stages of reaction

  10. Ruthenium Hydride/Brønsted Acid-Catalyzed Tandem Isomerization/N-Acyliminium Cyclization Sequence for the Synthesis of Tetrahydro-β-carbolines

    DEFF Research Database (Denmark)

    Hansen, Casper Lykke; Clausen, Janie Regitse Waël; Ohm, Ragnhild Gaard

    2013-01-01

    This paper describes an efficient tandem sequence for the synthesis of 1,2,3,4-tetrahydro-β-carbolines (THBCs) relying on a ruthenium hydride/Brønsted acid- catalyzed isomerization of allylic amides to N-acyliminium ion intermediates which are trapped by a tethered indolenucleophile. The methodol...... the Suzuki cross-coupling reaction to the isomerization/N-acyliminium cyclization sequence. Finally, diastereo- and enantioselective versions of the title reaction have been examined using substrate control (with dr >15: 1) and asymmetric catalysis (ee up to 57%), respectively...

  11. Continuous enzyme reactions with immobilized enzyme tubes prepared by radiation cast-polymerization

    International Nuclear Information System (INIS)

    Kumakura, Minoru; Kaetsu, Isao

    1986-01-01

    Immobilized glucose oxidase tubes were prepared by radiation cast-polymerization of 2-hydroxyethyl methacrylate and tetraethyleneglycol diacrylate monomer at low temperatures. The immobilized enzyme tubes which were spirally set in a water bath were used as reactor, in which the enzyme activity varied with tube size and flow rate of the substrate. The conversion yield of the substrate in continuous enzyme reaction was about 80%. (author)

  12. Boric Acid Catalyzed Convenient Synthesis of Benzimidazoles in Aqueous Media

    OpenAIRE

    Poor Heravi, Mohammad Reza; Ashori, Marjan

    2013-01-01

    Synthesis of benzimidazoles has been developed by the o-phenylenediamine with aldehydes using boric acid an efficient catalyst under mild reaction conditions in aqueous media. The product is applicable to aryl and heteroaryl aldehydes. This reaction led to the formation of benzimidazoles new derivatives in good yields. The FT-IR, 19F-NMR, 1H-NMR, 13C-NMR spectra and elemental analysis confirm the structure of compounds.

  13. Boric Acid Catalyzed Convenient Synthesis of Benzimidazoles in Aqueous Media

    Directory of Open Access Journals (Sweden)

    Mohammad Reza Poor Heravi

    2013-01-01

    Full Text Available Synthesis of benzimidazoles has been developed by the o-phenylenediamine with aldehydes using boric acid an efficient catalyst under mild reaction conditions in aqueous media. The product is applicable to aryl and heteroaryl aldehydes. This reaction led to the formation of benzimidazoles new derivatives in good yields. The FT-IR, 19F-NMR, 1H-NMR, 13C-NMR spectra and elemental analysis confirm the structure of compounds.

  14. Acid-Catalyzed Preparation of Biodiesel from Waste Vegetable Oil: An Experiment for the Undergraduate Organic Chemistry Laboratory

    Science.gov (United States)

    Bladt, Don; Murray, Steve; Gitch, Brittany; Trout, Haylee; Liberko, Charles

    2011-01-01

    This undergraduate organic laboratory exercise involves the sulfuric acid-catalyzed conversion of waste vegetable oil into biodiesel. The acid-catalyzed method, although inherently slower than the base-catalyzed methods, does not suffer from the loss of product or the creation of emulsion producing soap that plagues the base-catalyzed methods when…

  15. CONCERNING CHAIN GROWTH SPECIFIC REACTION RATE AS A PART OF THE PROCESS OF METHYL METHACRYLATE MASS RADICAL POLYMERIZATION

    Directory of Open Access Journals (Sweden)

    A. A. Sultanova

    2017-02-01

    Full Text Available It is the chain growth specific reaction rate that was determined for the process of methyl methacrylate mass radical polymerization within the temperature range of 40–900 С in quasi-steady approximation by means of Monte Carlo method. The theoretical model of radical polymerization was developed taking the gel effect into account. Computer software was developed that enables to imitate radical polymerization process taking gel effect into account within the minimum run time. The programme was tested on asymptotic examples as well as was applied for methyl methacrylate mass radical polymerization. The programme makes it possible to calculate monomer conversion, molecular mass variation, molecular-mass distribution, etc.

  16. Coarse-grained molecular dynamics simulations of polymerization with forward and backward reactions.

    Science.gov (United States)

    Krajniak, Jakub; Zhang, Zidan; Pandiyan, Sudharsan; Nies, Eric; Samaey, Giovanni

    2018-06-11

    We develop novel parallel algorithms that allow molecular dynamics simulations in which byproduct molecules are created and removed because of the chemical reactions during the molecular dynamics simulation. To prevent large increases in the potential energy, we introduce the byproduct molecules smoothly by changing the non-bonded interactions gradually. To simulate complete equilibrium reactions, we allow the byproduct molecules attack and destroy created bonds. Modeling of such reactions are, for instance, important to study the pore formation due to the presence of e.g. water molecules or development of polymer morphology during the process of splitting off byproduct molecules. Another concept that could be studied is the degradation of polymeric materials, a very important topic in a recycling of polymer waste. We illustrate the method by simulating the polymerization of polyethylene terephthalate (PET) at the coarse-grained level as an example of a polycondensation reaction with water as a byproduct. The algorithms are implemented in a publicly available software package and are easily accessible using a domain-specific language that describes chemical reactions in an input configuration file. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

  17. Furfural production from fruit shells by acid-catalyzed hydrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Demirbas, A. [Selcuk Univ., Konya (Turkey). Dept. of Chemical Engineering

    2006-01-21

    Pentosans are hydrolyzed to pentoses by dilute mineral acid hydrolysis. The main source of pentosans is hemicelluloses. Furfural can be produced by the acid hydrolysis of pentosan from fruit shells such as hazelnut, sunflower, walnut, and almond of agricultural wastes. Further dehydration reactions of the pentoses yield furfural. The hydrolysis of each shell sample was carried out in dilute sulfuric acid (0.05 to 0.200 mol/l), at high temperature (450-525 K), and short reaction times (from 30 to 600 s). (author)

  18. Acid-catalyzed rearrangements of flavans to novelbenzofuran derivatives

    Science.gov (United States)

    Richard W. Hemingway; Weiling Peng; Anthony H. Conner; Petrus J. Steynberg; Jan P. Steynberg

    1998-01-01

    The objective of this work was to define reactions that occur when proanthocyanidins and their derivatives are reacted in the presence of acid catalysts. Pure compounds (either as the free phenols, the methyl ether, or the methyl ether-acetate derivatives) were isolated by a variety of chromatographic methods. Proof of their structure was based mainly on 2D-NMR, as...

  19. Diffusion-controlled reaction. V. Effect of concentration-dependent diffusion coefficient on reaction rate in graft polymerization

    International Nuclear Information System (INIS)

    Imre, K.; Odian, G.

    1979-01-01

    The effect of diffusion on radiation-initiated graft polymerization has been studied with emphasis on the single- and two-penetrant cases. When the physical properties of the penetrants are similar, the two-penetrant problems can be reduced to the single-penetrant problem by redefining the characteristic parameters of the system. The diffusion-free graft polymerization rate is assumed to be proportional to the upsilon power of the monomer concentration respectively, and, in which the proportionality constant a = k/sub p/R/sub i//sup w//k/sub t//sup z/, where k/sub p/ and k/sub t/ are the propagation and termination rate constants, respectively, and R/sub i/ is the initiation rate. The values of upsilon, w, and z depend on the particular reaction system. The results of earlier work were generalized by allowing a non-Fickian diffusion rate which predicts an essentially exponential dependence on the monomer concentration of the diffusion coefficient, D = D 0 [exp(deltaC/M)], where M is the saturation concentration. A reaction system is characterized by the three dimensionless parameters, upsilon, delta, and A = (L/2)[aM/sup (upsilon--1)//D 0 ]/sup 1/2/, where L is the polymer film thickness. Graft polymerization tends to become diffusion controlled as A increases. Larger values of delta and ν cause a reaction system to behave closer to the diffusion-free regime. Transition from diffusion-free to diffusion-controlled reaction involves changes in the dependence of the reaction rate on film thickness, initiation rate, and monomer concentration. Although the diffusion-free rate is w order in initiation rate, upsilon order in monomer, and independent of film thickness, the diffusion-controlled rate is w/2 order in initiator rate and inverse first-order in film thickness. Dependence of the diffusion-controlled rate on monomer is dependent in a complex manner on the diffusional characteristics of the reaction system. 11 figures, 4 tables

  20. Ozonation of clofibric acid catalyzed by titanium dioxide.

    Science.gov (United States)

    Rosal, Roberto; Gonzalo, María S; Rodríguez, Antonio; García-Calvo, Eloy

    2009-09-30

    The removal of clofibric acid from aqueous solution has been investigated in catalytic and non-catalytic semicontinuous ozonation runs. Kinetic data were analyzed using second order expressions for the reaction between organics and ozone or hydroxyl radicals. Catalytic runs used a commercial titanium dioxide catalyst consisting of fumed colloidal particles. The kinetic constant of the non-catalytic ozonation of clofibric acid at pH 3 was 8.16 x 10(-3)+/-3.4 x 10(-4)L mmol(-1)s(-1). The extent of mineralization during non-catalytic runs ranged from 50% at pH 7 to 20% at pH 3 in a reaction that essentially took place during the first 10-20 min. The catalyst increased the total extent of mineralization, its effect being more important during the first part of the reaction. The pseudo-homogeneous catalytic rate constant was 2.17 x 10(-2) L mmol(-1)s(-1) at pH 3 and 6.80 x 10(-1)L mmol(-1)s(-1) at pH 5, with up to a threefold increase with respect to non-catalytic constants using catalyst load of 1g/L. A set of stopped-flow experiments were designed to elucidate the role of catalyst, whose effect was probably due to the adsorption of organics on catalytic sites rather than to the promotion of ozone decomposition.

  1. A Highly Stereocontrolled, One-Pot Approach toward Pyrrolobenzoxazinones and Pyrroloquinazolinones through a Lewis Acid-Catalyzed [3 + 2]-Cycloannulation Process.

    Science.gov (United States)

    Boomhoff, Michael; Ukis, Rostyslav; Schneider, Christoph

    2015-08-21

    We report herein a stereocontrolled [3 + 2]-cycloheteroannulation of bis-silyl dienediolate 1 with 2-aminobenzoic acid- and 2-aminobenzamide-derived imines to furnish highly substituted pyrrolo[1,2-a]benzoxazinones 3 and pyrrolo[1,2-a]quinazolinones 4, respectively, in good overall yields. This one-pot process rapidly generates molecular complexity and comprises a Lewis acid-catalyzed, vinylogous Mannich reaction of 1 followed by an intramolecular N,O-acetal- and N,N-aminal formation, respectively, which proceeds with good to excellent stereocontrol.

  2. Lewis acid catalyzed transformations of Z-ligustilide

    Energy Technology Data Exchange (ETDEWEB)

    Rios, Maria Yolanda [Universidad Autonoma del Estado de Morelos, Cuernavaca, Morelos (Mexico); Delgado, Guillermo [Universidad Nacional Autonoma de Mexico, Mexico, D.F. (Mexico)

    1999-08-01

    Some Lewis acid mediated reactions of Z-ligustilide (1), a bioactive constituent of the medicinal species Ligusticum porteri, were investigated. These reactions provided varying mixtures of Z-butylidenephthalide (7), E-butylidenephthalide (8), n-butyphthalide (13), and novel linear dimeric phthalides (9-12) as the main products. The formation of the dimers occurred in low yields and with regio and situ-selectivity. Initial competitive O- and C- complexation of the Lewis acid with Z-ligustilide promoted the formation of the dimers occurred in low yields and with regio and situ- selectivity. Initial competitive O- and C- complexation of the Lewis acid with Z-ligustilide promoted the formation of carbocations at C(8), C(6) and C(7), which were stabilized by the addition of the C(6')-C(7') olefin of a second unit of the starting material, to provide cations at C(6') and C(7'). Subsequent isomerizations and elimination of the catalyst afforded the dimeric products 9-12. The yields and structure of the products are quite dependent on variations of the reaction conditions and the catalyst employed. [Spanish] Se investigaron algunas reacciones de Z-ligustilidas (1), un constituyente bioactivo de la planta medicinal Ligusticum porteri, catalizadas por acidos de Lewis. Estas reacciones produjeron mezclas variables de Z-butilidenftalida (7), E-butilidenftalida (8), n-butilftalida (13), y ftalidos dimetricos lineales novedosos (9-12) como productos principales. La formacion de los dimeros procedio en rendimientos bajos y con regio- y situ-selectividad. La O- y C- complejacion competitiva inicial del acido de Lewis con Z-lingustilida promueve la formacion de cationes en C(8), C(6) y C(7), los cuales son estabilizados por la adicion de la olefina C(6')-C(7') de una segunda unidad de la materia prima para generar los cationes en C(6')-C(7'). Isomerizaciones subsecuentes y la eliminacion del catalizador conducen a los productos dimericos 9

  3. Decomposition of peracetic acid catalyzed by vanadium complexes

    International Nuclear Information System (INIS)

    Makarov, A.P.; Gekhman, A.E.; Moiseev, I.I.; Polotryuk, O.Y.

    1986-01-01

    This paper studies the decomposition of peracetic acid (AcOOH) in acetic acid (AcOH) catalyzed by vanadium complexes. It is shown that peractic acid in acetic acid solutions of ammonium anadate decomposes with the predominant formation of 0 2 and small amounts of CO 2 , the yield of which increases with increasing temperature and peracetic acid concentration. Both reactions proceed without the formation of free radicals in amounts detectable by ESR spectroscopy. The rate of oxygen release under conditions in which the formation of CO 2 is insignificant obeys a kinetic equation indicating the intermediate formation of a complex between V 5+ ions and peracetic acid and the slow conversion of this complex into the observed products

  4. Stochastic simulation of biological reactions, and its applications for studying actin polymerization.

    Science.gov (United States)

    Ichikawa, Kazuhisa; Suzuki, Takashi; Murata, Noboru

    2010-11-30

    Molecular events in biological cells occur in local subregions, where the molecules tend to be small in number. The cytoskeleton, which is important for both the structural changes of cells and their functions, is also a countable entity because of its long fibrous shape. To simulate the local environment using a computer, stochastic simulations should be run. We herein report a new method of stochastic simulation based on random walk and reaction by the collision of all molecules. The microscopic reaction rate P(r) is calculated from the macroscopic rate constant k. The formula involves only local parameters embedded for each molecule. The results of the stochastic simulations of simple second-order, polymerization, Michaelis-Menten-type and other reactions agreed quite well with those of deterministic simulations when the number of molecules was sufficiently large. An analysis of the theory indicated a relationship between variance and the number of molecules in the system, and results of multiple stochastic simulation runs confirmed this relationship. We simulated Ca²(+) dynamics in a cell by inward flow from a point on the cell surface and the polymerization of G-actin forming F-actin. Our results showed that this theory and method can be used to simulate spatially inhomogeneous events.

  5. Stochastic simulation of biological reactions, and its applications for studying actin polymerization

    International Nuclear Information System (INIS)

    Ichikawa, Kazuhisa; Suzuki, Takashi; Murata, Noboru

    2010-01-01

    Molecular events in biological cells occur in local subregions, where the molecules tend to be small in number. The cytoskeleton, which is important for both the structural changes of cells and their functions, is also a countable entity because of its long fibrous shape. To simulate the local environment using a computer, stochastic simulations should be run. We herein report a new method of stochastic simulation based on random walk and reaction by the collision of all molecules. The microscopic reaction rate P r is calculated from the macroscopic rate constant k. The formula involves only local parameters embedded for each molecule. The results of the stochastic simulations of simple second-order, polymerization, Michaelis–Menten-type and other reactions agreed quite well with those of deterministic simulations when the number of molecules was sufficiently large. An analysis of the theory indicated a relationship between variance and the number of molecules in the system, and results of multiple stochastic simulation runs confirmed this relationship. We simulated Ca 2+ dynamics in a cell by inward flow from a point on the cell surface and the polymerization of G-actin forming F-actin. Our results showed that this theory and method can be used to simulate spatially inhomogeneous events

  6. Lactic Acid Yield Using Different Bacterial Strains, Its Purification, and Polymerization through Ring-Opening Reactions

    Directory of Open Access Journals (Sweden)

    F. G. Orozco

    2014-01-01

    Full Text Available Laboratory-scale anaerobic fermentation was performed to obtain lactic acid from lactose, using five lactic acid bacteria: Lactococcus lactis, Lactobacillus bulgaricus, L. delbrueckii, L. plantarum, and L. delbrueckii lactis. A yield of 0.99 g lactic acid/g lactose was obtained with L. delbrueckii, from which a final concentration of 80.95 g/L aqueous solution was obtained through microfiltration, nanofiltration, and inverse osmosis membranes. The lactic acid was polymerized by means of ring-opening reactions (ROP to obtain poly-DL-lactic acid (PDLLA, with a viscosity average molecular weight (Mv of 19,264 g/mol.

  7. Heteropoly acid catalyzed hydrolysis of glycogen to glucose

    International Nuclear Information System (INIS)

    Klein, Miri; Pulidindi, Indra Neel; Perkas, Nina; Gedanken, Aharon

    2015-01-01

    Complete conversion of glycogen to glucose is achieved by using H 3 PW 12 O 40 ·nH 2 O (HPW) and H 4 SiW 12 O 40 ·nH 2 O (HSiW) as catalysts for the hydrolysis under optimized hydrothermal conditions (mass fraction of catalyst 2.4%, 373 K and 2 h reaction time). The reusability of the catalyst (HPW) was demonstrated. In addition to carrying out the glycogen hydrolysis in an autoclave, other novel methods such as microwave irradiation and sonication have also been investigated. At higher mass fraction of the heteropoly acids (10.5%), glycogen could be completely converted to glucose under microwave irradiation. Sonication of an aqueous solution of glycogen in the presence of HPW and HSiW also yielded glucose. Thus, heteropoly acids are efficient, environmentally friendly and reusable catalysts for the conversion of glycogen to glucose. - Highlights: • Hydrothermal, microwave and sonication based methods of hydrolysis. • Heteropoly acids are green catalysts for glycogen hydrolysis. • Glycogen from cyanobacteria is demonstrated as a potential feedstock for glucose

  8. A green non-acid-catalyzed process for direct N=N-C group formation: comprehensive study, modeling, and optimization.

    Science.gov (United States)

    Khakyzadeh, Vahid; Zolfigol, Mohammad Ali; Derakhshan-Panah, Fatemeh; Jafarian, Majid; Miri, Mir Vahid; Gilandoust, Maryam

    2018-01-04

    The aim of this work is to introduce, model, and optimize a new non-acid-catalyzed system for a direct N[Formula: see text]N-C bond formation. By reacting naphthols or phenol with anilines in the presence of the sodium nitrite as nitrosonium ([Formula: see text] source and triethylammonium acetate (TEAA), a N[Formula: see text]N-C group can be formed in non-acid media. Modeling and optimization of the reaction conditions were investigated by response surface method. Sodium nitrite, TEAA, and water were chosen as variables, and reaction yield was also monitored. Analysis of variance indicates that a second-order polynomial model with F value of 35.7, a P value of 0.0001, and regression coefficient of 0.93 is able to predict the response. Based on the model, the optimum process conditions were introduced as 2.2 mmol sodium nitrite, 2.2 mL of TEAA, and 0.5 mL [Formula: see text] at room temperature. A quadratic (second-order) polynomial model, by analysis of variance, was able to predict the response for a direct N=N-C group formation. Predicted response values were in good agreement with the experimental values. Electrochemistry studies were done to introduce new Michael acceptor moieties. Broad scope, high yields, short reaction time, and mild conditions are some advantages of the presented method.

  9. β-Secondary and solvent deuterium kinetic isotope effects and the mechanisms of base- and acid-catalyzed hydrolysis of penicillanic acid

    International Nuclear Information System (INIS)

    Deraniyagala, S.A.; Adediran, S.A.; Pratt, R.F.

    1995-01-01

    β-Secondary and solvent deuterium kinetic isotope effects have been determined at 25 degrees C for the alkaline and acid-catalyzed hydrolysis of penicillanic acid. In order to determine the former isotope effect, [6,6- 2 H 2 ]dideuteriopenicillanic acid has been synthesized. In alkaline solution, the former isotope effect was found to be 0.95 ± 0.01. These values support the B AC 2 mechanism of hydrolysis with rate-determining formation of the tetrahedral intermediate that has been proposed for other β-lactams. The measured β-secondary kinetic isotope for the acid-catalyzed reaction was 1.00 ± 0.01. The data indicates that a likely pathway of acid-catalyzed hydrolysis would be that of an A AC 1 mechanism with an intermediate acylium ion. If this were so, the calculated β-secondary isotope effect per hydrogen coplanar with the breaking C-N bond and corrected for the inductive effect of deuterium would be 1.06 ± 0.01. This suggests an early A AC 1 transition state, which would be reasonable in this case because of destabilization of the N-protonated amide with respect to the acylium ion because of ring strain. The absence of specific participation by solvent in the transition state, as would be expected of an A AC 1 but not an associative mechanism, is supported by the strongly inverse solvent deuterium kinetic isotope effect of 0.25 ± 0.00 in 1 M HCl and 0.22 ± 0.01 in 33.3 wt % H 2 SO 4 . 1 fig., 3 tabs

  10. Modification of Clays by Sol-Gel Reaction and Their Use in the Ethylene In Situ Polymerization for Obtaining Nanocomposites

    Directory of Open Access Journals (Sweden)

    E. Moncada

    2012-01-01

    Full Text Available The nanocomposites formation by in situ polymerization used a metallocene catalyst (butyl-2-cyclopentadienyl zirconium 2-chlorines and a hectorite synthetic clay type which is discussed. This research was carried out in two phases. The first phase consisted of mixing the components of the metallocenic polymerization reaction (metallocene-methylaluminoxane-ethylene with clay in a reactor. In the second phase, the metallocenic catalytic system was supported by clay particles and then a polymerization reaction was made. In this second phase, the clay particles were modified using a sol-gel reaction with different pH values: pH = 3, pH = 8, and pH = 12. The results were compared in terms of the catalytic activity in the different systems (phase 1 and phase 2 and the nanoparticle morphology of nanocomposites generated in this study.

  11. Initiation of the microgene polymerization reaction with non-repetitive homo-duplexes

    International Nuclear Information System (INIS)

    Itsko, Mark; Zaritsky, Arieh; Rabinovitch, Avinoam; Ben-Dov, Eitan

    2008-01-01

    Microgene Polymerization Reaction (MPR) is used as an experimental system to artificially simulate evolution of short, non-repetitive homo-duplex DNA into multiply-repetitive products that can code for functional proteins. Blunt-end ligation by DNA polymerase is crucial in expansion of homo-duplexes (HDs) into head-to-tail multiple repeats in MPR. The propagation mechanism is known, but formation of the initial doublet (ID) by juxtaposing two HDs and polymerization through the gap has been ambiguous. Initiation events with pairs of HDs using Real-Time PCR were more frequent at higher HD concentrations and slightly below the melting temperature. A process molecularity of about 3.1, calculated from the amplification efficiency and the difference in PCR cycles at which propagation was detected at varying HD concentrations, led to a simple mechanism for ID formation: the gap between two HDs is bridged by a third. Considering thermodynamic aspects of the presumed intermediate 'nucleation complex' can predict relative propensity for the process with other HDs

  12. Ring-Expansion/Contraction Radical Crossover Reactions of Cyclic Alkoxyamines: A Mechanism for Ring Expansion-Controlled Radical Polymerization

    Directory of Open Access Journals (Sweden)

    Atsushi Narumi

    2018-06-01

    Full Text Available Macrocyclic polymers present an important class of macromolecules, displaying the reduced radius of gyration or impossibility to entangle. A rare approach for their synthesis is the ring expansion-controlled radical “vinyl” polymerization, starting from a cyclic alkoxyamine. We here describe ring-expansion radical crossover reactions of cyclic alkoxyamines which run in parallel to chain-propagation reactions in the polymerization system. The radical crossover reactions extensively occurred at 105–125 °C, eventually producing high molecular weight polymers with multiple inherent dynamic covalent bonds (NOC bonds. A subsequent ring-contraction radical crossover reaction and the second ring-expansion radical crossover reaction are also described. The major products for the respective three stages were shown to possess cyclic morphologies by the molecular weight profiles and the residual ratios for the NOC bonds (φ in %. In particular, the high φ values ranging from ca. 80% to 98% were achieved for this cyclic alkoxyamine system. This result verifies the high availability of this system as a tool demonstrating the ring-expansion “vinyl” polymerization that allows them to produce macrocyclic polymers via a one-step vinyl polymerization.

  13. System Identification for Experimental Study for Polymerization Catalyst Reaction in Fluidized Bed

    Directory of Open Access Journals (Sweden)

    Ahmmed Saadi Ibrehem

    2011-11-01

    Full Text Available In this work, system identification method is used to capture the reactor characteristics of production rate of polyethylene (PE based on published experimental data. The identification method is used to measure the percentage effect on the production rate of PE by measuring the effect of input factors of temperature of reaction, hydrogen concentration, and [Al]/[Ti] molar catalyst ratio. Temperature of reaction has big effects equal 52.4 % on the output of the system and 47.6 % on interaction of the system's parameters compare to other two factors. Also, hydrogen concentration has big effect equal 45.66 % on the output of the system and 14.7 % on interaction of the system's parameters. [Al]/[Ti] molar catalyst ratio has big effect on interaction of the system equal 28.6 and 1.94 % on the output of the system but less than the reaction temperature and hydrogen concentration. All these results depend on experiment results and these results are very important in industrial plants. ©2011 BCREC UNDIP. All rights reserved(Received: 13rd May 2011; Revised: 27th July 2011; Accepted: 22th September 2011[How to Cite: Ahmmed S. Ibrehem. (2011. System Identification for Experimental Study for Polymerization Catalyst Reaction in Fluidized Bed. Bulletin of Chemical Reaction Engineering & Catalysis, 6 (2: 137-146. doi:10.9767/bcrec.6.2.874.137-146][How to Link / DOI: http://dx,doi.org/10.9767/bcrec.6.2.874.137-146 || or local:  http://ejournal.undip.ac.id/index.php/bcrec/article/view/874 ] | View in 

  14. On the Brønsted acid-catalyzed homogeneous hydrolysis of furans.

    Science.gov (United States)

    Nikbin, Nima; Caratzoulas, Stavros; Vlachos, Dionisios G

    2013-11-01

    Furan affairs: Electronic structure calculations of the homogeneous Brønsted acid-catalyzed hydrolysis of 2,5-dimethylfuran show that proton transfer to the β-position is rate-limiting and provides support that the hydrolysis follows general acid catalysis. By means of projected Fukui indices, we show this to be the case for unsubstituted, 2-, and 2,5-substituted furans with electron-donating groups. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Polymerization of Acetonitrile via a Hydrogen Transfer Reaction from CH3 to CN under Extreme Conditions.

    Science.gov (United States)

    Zheng, Haiyan; Li, Kuo; Cody, George D; Tulk, Christopher A; Dong, Xiao; Gao, Guoying; Molaison, Jamie J; Liu, Zhenxian; Feygenson, Mikhail; Yang, Wenge; Ivanov, Ilia N; Basile, Leonardo; Idrobo, Juan-Carlos; Guthrie, Malcolm; Mao, Ho-Kwang

    2016-09-19

    Acetonitrile (CH3 CN) is the simplest and one of the most stable nitriles. Reactions usually occur on the C≡N triple bond, while the C-H bond is very inert and can only be activated by a very strong base or a metal catalyst. It is demonstrated that C-H bonds can be activated by the cyano group under high pressure, but at room temperature. The hydrogen atom transfers from the CH3 to CN along the CH⋅⋅⋅N hydrogen bond, which produces an amino group and initiates polymerization to form a dimer, 1D chain, and 2D nanoribbon with mixed sp(2) and sp(3) bonded carbon. Finally, it transforms into a graphitic polymer by eliminating ammonia. This study shows that applying pressure can induce a distinctive reaction which is guided by the structure of the molecular crystal. It highlights the fact that very inert C-H can be activated by high pressure, even at room temperature and without a catalyst. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. MALDI MS-based Composition Analysis of the Polymerization Reaction of Toluene Diisocyanate (TDI) and Ethylene Glycol (EG).

    Science.gov (United States)

    Ahn, Yeong Hee; Lee, Yeon Jung; Kim, Sung Ho

    2015-01-01

    This study describes an MS-based analysis method for monitoring changes in polymer composition during the polyaddition polymerization reaction of toluene diisocyanate (TDI) and ethylene glycol (EG). The polymerization was monitored as a function of reaction time using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI TOF MS). The resulting series of polymer adducts terminated with various end-functional groups were precisely identified and the relative compositions of those series were estimated. A new MALDI MS data interpretation method was developed, consisting of a peak-resolving algorithm for overlapping peaks in MALDI MS spectra, a retrosynthetic analysis for the generation of reduced unit mass peaks, and a Gaussian fit-based selection of the most prominent polymer series among the reconstructed unit mass peaks. This method of data interpretation avoids errors originating from side reactions due to the presence of trace water in the reaction mixture or MALDI analysis. Quantitative changes in the relative compositions of the resulting polymer products were monitored as a function of reaction time. These results demonstrate that the mass data interpretation method described herein can be a powerful tool for estimating quantitative changes in the compositions of polymer products arising during a polymerization reaction.

  17. Integrated Production of Xylonic Acid and Bioethanol from Acid-Catalyzed Steam-Exploded Corn Stover.

    Science.gov (United States)

    Zhu, Junjun; Rong, Yayun; Yang, Jinlong; Zhou, Xin; Xu, Yong; Zhang, Lingling; Chen, Jiahui; Yong, Qiang; Yu, Shiyuan

    2015-07-01

    High-efficiency xylose utilization is one of the restrictive factors of bioethanol industrialization. However, xylonic acid (XA) as a new bio-based platform chemical can be produced by oxidation of xylose with microbial. So, an applicable technology of XA bioconversion was integrated into the process of bioethanol production. After corn stover was pretreated with acid-catalyzed steam-explosion, solid and liquid fractions were obtained. The liquid fraction, also named as acid-catalyzed steam-exploded corn stover (ASC) prehydrolyzate (mainly containing xylose), was catalyzed with Gluconobacter oxydans NL71 to prepare XA. After 72 h of bioconversion of concentrated ASC prehydrolyzate (containing 55.0 g/L of xylose), the XA concentration reached a peak value of 54.97 g/L, the sugar utilization ratio and XA yield were 94.08 and 95.45 %, respectively. The solid fraction was hydrolyzed to produce glucose with cellulase and then fermented with Saccharomyces cerevisiae NL22 to produce ethanol. After 18 h of fermentation of concentrated enzymatic hydrolyzate (containing 86.22 g/L of glucose), the ethanol concentration reached its highest value of 41.48 g/L, the sugar utilization ratio and ethanol yield were 98.72 and 95.25 %, respectively. The mass balance showed that 1 t ethanol and 1.3 t XA were produced from 7.8 t oven dry corn stover.

  18. Decay Time Measurement for Different Energy Depositions of Plastic Scintillator Fabricated by High Temperature Polymerization Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Cheol Ho; Son, Jaebum; Lee, Sangmin; Kim, Tae Hoon; Kim, Yong-Kyun [Hanyang University, Seoul (Korea, Republic of)

    2016-10-15

    Plastic scintillators are based on organic fluorite. They have many advantages such as fast rise and decay time, high optical transmission, ease of manufacturing, low cost, and large available size. For these reasons they are widely used for particle identification. Also, protection of people against a variety of threats (such as nuclear, radiological, and explosive) represents a true challenge along with the continuing development of science and technology. The plastic scintillator is widely used in various devise, which serves for nuclear, photonics, quantum, and high-energy physics. The plastic scintillator is probably the most widely used organic detector, and polystyrene is one of the most widely used materials in the making of the plastic scintillator detector. Thus, a styrene monomer as a solvent was used to fabricate the plastic scintillator by using high temperature polymerization reaction, and then the emission wavelength and the decay times for different energy depositions were measured by using the fabricated plastic scintillator. A plastic scintillator was fabricated to measure decay time for different energy depositions using the high temperature polymerization. Emission wavelength was measured of 426.05 nm to confirm a scintillator property using the spectrophotometer. Four gamma-ray sources (Cs-137, Co-60, Na-22, and Ba-133) were used to evaluate effect for decay time of different energy depositions. The average decay time of the fabricated plastic scintillator was measured to approximately 4.72 ns slightly higher more than commercial plastic scintillator. In future, light output and linearity will be measured to evaluate other property compared with the commercial scintillator.

  19. Decay Time Measurement for Different Energy Depositions of Plastic Scintillator Fabricated by High Temperature Polymerization Reaction

    International Nuclear Information System (INIS)

    Lee, Cheol Ho; Son, Jaebum; Lee, Sangmin; Kim, Tae Hoon; Kim, Yong-Kyun

    2016-01-01

    Plastic scintillators are based on organic fluorite. They have many advantages such as fast rise and decay time, high optical transmission, ease of manufacturing, low cost, and large available size. For these reasons they are widely used for particle identification. Also, protection of people against a variety of threats (such as nuclear, radiological, and explosive) represents a true challenge along with the continuing development of science and technology. The plastic scintillator is widely used in various devise, which serves for nuclear, photonics, quantum, and high-energy physics. The plastic scintillator is probably the most widely used organic detector, and polystyrene is one of the most widely used materials in the making of the plastic scintillator detector. Thus, a styrene monomer as a solvent was used to fabricate the plastic scintillator by using high temperature polymerization reaction, and then the emission wavelength and the decay times for different energy depositions were measured by using the fabricated plastic scintillator. A plastic scintillator was fabricated to measure decay time for different energy depositions using the high temperature polymerization. Emission wavelength was measured of 426.05 nm to confirm a scintillator property using the spectrophotometer. Four gamma-ray sources (Cs-137, Co-60, Na-22, and Ba-133) were used to evaluate effect for decay time of different energy depositions. The average decay time of the fabricated plastic scintillator was measured to approximately 4.72 ns slightly higher more than commercial plastic scintillator. In future, light output and linearity will be measured to evaluate other property compared with the commercial scintillator

  20. Upgrading of bio-oil via acid-catalyzed reactions in alcohols : a mini review

    NARCIS (Netherlands)

    Hu, X.; Gunawan, R.; Mourant, D.; Mahmudul Hasan, M.D.; Wu, L.; Song, Y.; Lievens, C.; Li, C.Z.

    2017-01-01

    Bio-oil is a condensable liquid produced from the pyrolysis of biomass, which can be upgraded to biofuels. Bio-oil is corrosive as it contains significant amounts of carboxylic acids, creating difficulties in handling of bio-oil and applications of bio-oil. Acid-treatment of bio-oil in alcohols is

  1. Enhancement of Activity and Selectivity in Acid-Catalyzed Reactions by Dealuminated Hierarchical Zeolites

    Czech Academy of Sciences Publication Activity Database

    Sazama, Petr; Sobalík, Zdeněk; Dědeček, Jiří; Jakubec, Ivo; Parvulescu, V. I.; Bastl, Zdeněk; Rathouský, Jiří; Jirglová, Hana

    2013-01-01

    Roč. 52, č. 7 (2013), s. 2038-2041 ISSN 1433-7851 R&D Projects: GA ČR GAP106/11/0624; GA MPO FR-TI3/316 Institutional support: RVO:61388955 ; RVO:61388980 Keywords : alkylation * cracking * dealumination Subject RIV: CF - Physical ; Theoretical Chemistry; CA - Inorganic Chemistry (UACH-T) Impact factor: 11.336, year: 2013

  2. On reactions of polymerization of p-element hydroxides in aqueous solutions

    International Nuclear Information System (INIS)

    Tikavyj, V.F.; Lesnikovich, A.I.

    1978-01-01

    The tendency of p-element hydroxides towards polymerization in aqueous solutions has been considered with respect to their location in the Periodic Table. Stable hydroxides of d-elements are practically all polymerized; among s-elements only berillium and magnesium hydroxides polymerize as the least dissociated ones. Hydroxides of the elements located to the right of the 4 Group and above the 5-th Period do not polymerize in aqueous solutions. The structure and tendency towards polymerization of In, Te, and I compounds have been studied. The tendency to polymerization of all hydroxides of p-elements located below the 4-th Period is explained from the standpoint of electron structure and the simplest thermodynamic analysis (entropy, enthalpy)

  3. Primary and secondary kinetic isotope effects in the acid-catalyzed dehydration of 1,1'-diadamantylmethylcarbinol in aqueous acetic acid

    International Nuclear Information System (INIS)

    Lomas, J.S.

    1981-01-01

    The sulfuric acid catalyzed dehydration of 1,1'-diadamantyl-methylcarbinol in anhydrous acetic acid proceeds exclusively to 1,1'-bis(1-adamantyl)ethylene. The secondary deuterium isotope effect of 1.32 found for this reaction shows that carbonium ion formation from the protonated alcohol is rate determining. In the presence of water, however, capture of the carbonium ion competes with deprotonation, introducing a primary isotope effect. Consequently, the overall KIE rises, reaching 3.18 for 80% aqueous acetic acid. Analysis of the KIE for 80 to 100% aqueous acetic acid is consistent with a simple classical mechanism involving reversible formation of the intermediate carbonium ion. The primary isotope effect upon deprotonation is at the most 2.98, indicative of an asymmetric transition state close to the carbonium ion

  4. Molecular weight control in emulsion polymerization by catalytic chain transfer : a reaction engineering approach

    NARCIS (Netherlands)

    Smeets, N.M.B.; Meda, U.S.; Heuts, J.P.A.; Keurentjes, J.T.F.; Herk, van A.M.; Meuldijk, J.

    2007-01-01

    For the application of catalytic chain transfer in (mini)emulsion polymerization, catalyst partitioning and deactivation are key parameters that govern the actual catalyst concentration at the locus of polymerization and consequently the final molecular weight distribution. A global model, based on

  5. Metal nanoparticles/ionic liquid/cellulose: polymeric membrane for hydrogenation reactions

    Directory of Open Access Journals (Sweden)

    Marcos Alexandre Gelesky

    2014-01-01

    Full Text Available Rhodium and platinum nanoparticles were supported in polymeric membranes with 10, 20 and 40 µm thickness. The polymeric membranes were prepared combining cellulose acetate and the ionic liquid (IL 1-n-butyl-3-methylimidazolium bis(trifluoromethane sulfonylimide (BMI.(NTf2. The presence of metal nanoparticles induced an increase in the polymeric membrane surface areas. The increase of the IL content resulted in an improvement of elasticity and decrease in tenacity and toughness, whereas the stress at break was not affected. The presence of IL probably causes an increase in the separation between the cellulose molecules that result in a higher flexibility and processability of the polymeric membrane. The CA/IL/M(0 combinations exhibit an excellent synergistic effect that enhances the activity and durability of the catalyst for the hydrogenation of cyclohexene. The CA/IL/M(0 polymeric membrane displays higher catalytic activity (up to 7.353 h-1 for the 20 mm of CA/IL/Pt(0 and stability than the nanoparticles dispersed only in the IL.

  6. Recovery of arabinan in acetic acid-catalyzed hydrothermal pretreatment on corn stover

    DEFF Research Database (Denmark)

    Xu, Jian; Hedegaard, Mette Christina; Thomsen, Anne Belinda

    2009-01-01

    Acetic acid-catalyzed hydrothermal pretreatment was done on corn stover under 195 °C, 15 min with the acetic acid ranging from 5 × 10−3 to 0.2 g g−1 corn stover. After pretreatment, the water-insoluble solids (WISs) and liquors were collected respectively. Arabinan recoveries from both WIS...... and liquors were investigated. The results indicate that there was no detectable arabinan left in the WIS when the acetic acid of 0.1 and 0.2 g g−1 corn stover were used in the pretreatment. The arabinan contents in the other WISs were not more than 10%. However, the arabinan found in the liquors...... was not covering the amount of arabinan released from the raw corn stover. For the arabinan recovery from liquor fractions, the highest of 43.57% was obtained by the pretreatment of acetic acid of 0.01 g g−1 of corn stover and the lowest was only 26.77% when the acetic acid of 0.2 g g−1 corn stover was used...

  7. Secondary deuterium isotope effects for acid-catalyzed hydrolysis of inosine and adenosine

    International Nuclear Information System (INIS)

    Romero, R.; Stein, R.; Bull, H.G.; Cordes, E.H.

    1978-01-01

    Kinetic α deuterium isotope effects have been measured for acid-catalyzed hydrolysis of inosine and adenosine. For inosine hydrolysis, values of k/sub H/k/sub D/ follow: in 1.0 M HCl, 1.21 and 1.20 at 25 and 50 0 C, respectively; in 0.1 M HCl, 1.19 and 1.18 at 25 and 50 0 C, respectively. For adenosine hydrolysis, k/sub H/k/sub D/ is 1.23 in 0.1 M HCl at 25 0 C. The values require that the transition states for hydrolysis of both the monocation and dication of inosine and the dication of adenosine have marked oxocarbonium ion character. Detailed mechanisms which accord with this and other experimental observations include (1) a classical Al mechanism in which the C--N bond is largely cleaved in the transition state; (2) a mechanism involving some form of nucleophilic participation by solvent in which bond cleavage is advanced relative to bond formation in the transition state; or (3) complete C--N bond cleavage with rate-determining diffusion apart of oxocarbonium ion and purine base. 53 references, 1 figure, 2 tables

  8. Effect of degree of polymerization and of temperature on the reactivity of poly(vinyl alcohol) by applying T-for-H exchange reaction

    International Nuclear Information System (INIS)

    Imaizumi, Hiroshi; Imai, Kazunari

    1999-01-01

    In order to reveal the effect of the degree of polymerization and of temperature on the reactivity of functional polymers, the hydrogen-isotope exchange reaction between poly(vinyl alcohol) (PVA) having each degree of polymerization and tritiated water vapor (HTO vapor) was dynamically observed at 35-80 deg C in a gas-solid system. The reason of the observation at 35 deg C is to clarify the possibility of the T-for-H exchange reaction at a temperature near the environment. The degree of polymerization of PVA used in this work was 500, 1000, 2000, 2800, or 3500. Applying the A''-McKay plot method to the data obtained in each observation, the rate constant (k) for each PVA in the reaction was calculated. Moreover, the Arrhenius plot for each PVA was made by using the k values. Comparing the k values and the results obtained previously, the following six matters have been clarified. In the temperature range of 35-80 deg C, the T-for-H exchange reaction between HTO vapor and each PVA occurred, and in this case, the atoms participating in the reaction are the H atoms in the OH groups in PVA and T atoms in HTO vapor. The reactivity of each PVA increases with rising temperature, and decreases with increasing the degree of polymerization. The rate of the decreasing of k with increasing the degree of polymerization changes at near the degree of polymerization of 1000, and the rate is fairly large under the degree of 1000. Under the degree of polymerization of 1000, the reactivity of PVA is more affected by the effect of the degree of polymerization than by the effect of temperature, and the reactivity is large when the degree of polymerization is small. Over the degree of polymerization of 1000, the reactivity of PVA is affected by both the degree of polymerization and temperature, and the reactivity is large when temperature is high. For the T-for-H exchange reaction in a gas-solid system, the reaction form is unchanged in the range of 35-80 deg C, and the reactivity at 35

  9. Effect of the exothermal polymerization reaction on polymer gel dosimetric measurements

    International Nuclear Information System (INIS)

    Sedaghat, Mahbod; Bujold, Rachel; Lepage, Martin

    2010-01-01

    Discrepancies in polymer gel dosimetric measurements have been observed between containers of different sizes receiving the same radiation dose. We hypothesized that these deviations are caused by a change in the rate of polymerization due to internal heat increase in the gel containers resulting from the exothermic polymerization of monomers. Here, we test this hypothesis in a polyacrylamide gel dosimeter by recording the temperature in glass phantoms of different sizes during and after irradiation. The dose response of the samples was determined with magnetic resonance imaging. The difference of R 2 values along the depth of the containers was below ±1%. We discuss that this small difference can be attributed to variations in the rate of gelatin cooling during manufacture rather than to the measured heat increase during irradiation.

  10. Chain-growth cycloaddition polymerization via a catalytic alkyne [2 + 2 + 2] cyclotrimerization reaction and its application to one-shot spontaneous block copolymerization.

    Science.gov (United States)

    Sugiyama, Yu-ki; Kato, Rei; Sakurada, Tetsuya; Okamoto, Sentaro

    2011-06-29

    A cobalt-catalyzed alkyne [2 + 2 + 2] cycloaddition reaction has been applied to polymerizations yielding linear polymers via selective cross-cyclotrimerization of yne-diyne monomers, which occurs in a chain-growth manner. Additionally, through control of the alkyne reactivity of the two monomers, this method was efficiently applied to the spontaneous block copolymerization of their mixture. Here we present the proposed mechanism of the catalyst transfer process of this cycloaddition polymerization.

  11. Is it true that polymerization of vegetable oil occurs through Diels-Alder reaction?

    Science.gov (United States)

    Diels-Alder reaction mechanism is known to be one of the major reaction mechanisms to produce dimers and polymers during heating process of vegetable oil. However, our NMR study showed no evidence for Diels-Alder products. Soybean oil oxidized at 180 °C for 24 hrs with 1.45 surface area-to-volume ...

  12. The first experimental confirmation of the fractional kinetics containing the complex-power-law exponents: Dielectric measurements of polymerization reactions

    Science.gov (United States)

    Nigmatullin, R. R.; Arbuzov, A. A.; Salehli, F.; Giz, A.; Bayrak, I.; Catalgil-Giz, H.

    2007-01-01

    For the first time we achieved incontestable evidence that the real process of dielectric relaxation during the polymerization reaction of polyvinylpyrrolidone (PVP) is described in terms of the fractional kinetic equations containing complex-power-law exponents. The possibility of the existence of the fractional kinetics containing non-integer complex-power-law exponents follows from the general theory of dielectric relaxation that has been suggested recently by one of the authors (R.R.N). Based on the physical/geometrical meaning of the fractional integral with complex exponents there is a possibility to develop a general theory of dielectric relaxation based on the self-similar (fractal) character of the reduced (averaged) microprocesses that take place in the mesoscale region. This theory contains some essential predictions related to existence of the non-integer power-law kinetics and the results of this paper can be considered as the first confirmation of existence of the kinetic phenomena that are described by fractional derivatives with complex-power-law exponents. We want to stress here that with the help of a new complex fitting function for the complex permittivity it becomes possible to describe the whole process for real and imaginary parts simultaneously throughout the admissible frequency range (30 Hz-13 MHz). The fitting parameters obtained for the complex permittivity function for three temperatures (70, 90 and 110 °C) confirm in general the picture of reaction that was known qualitatively before. They also reveal some new features, which improve the interpretation of the whole polymerization process. We hope that these first results obtained in the paper will serve as a good stimulus for other researches to find the traces of the existence of new fractional kinetics in other relaxation processes unrelated to the dielectric relaxation. These results should lead to the reconsideration and generalization of irreversibility and kinetic phenomena that

  13. LC-MS/MS analysis of uncommon paracetamol metabolites derived through in vitro polymerization and nitration reactions in liquid nitrogen.

    Science.gov (United States)

    Trettin, Arne; Jordan, Jens; Tsikas, Dimitrios

    2014-09-01

    Paracetamol (acetaminophen, APAP) is a commonly used analgesic drug. Known paracetamol metabolites include the glucuronide, sulfate and mercapturate. N-Acetyl-benzoquinonimine (NAPQI) is considered the toxic intermediate metabolite of paracetamol. In vitro and in vivo studies indicate that paracetamol is also metabolized to additional poorly characterized metabolites. For example, metabolomic studies in urine samples of APAP-treated mice revealed metabolites such as APAP-sulfate-APAP and APAP-S-S-APAP in addition to the classical phase II metabolites. Here, we report on the development and application of LC-MS and LC-MS/MS approaches to study reactions of unlabelled and (2)H-labelled APAP with unlabelled and (15)N-labelled nitrite in aqueous phosphate buffers (pH 7.4) upon their immersion into liquid nitrogen (-196°C). In mechanistic studies, these reactions were also studied in aqueous buffer prepared in (18)O-labelled water. LC-MS and LC-MS/MS analyses were performed on a reverse-phase material (C18) using gradient elution (2mM ammonium acetate/acetonitrile), in positive and negative electrospray mode. We identified a series of APAP metabolites including di-, tri- and tetra-APAP, mono- and di-nitro-APAP and nitric ester of di-APAP. Our study indicates that nitrite induces oxidation, i.e., polymerization and nitration of APAP, when buffered APAP/nitrite solutions are immersed into liquid nitrogen. These reactions are specific for nitrite with respect to nitrate and do not proceed via intermediate formation of NAPQI. Potassium ions and physiological saline but not thiols inhibit nitrite- and shock-freeze-induced reactions of paracetamol. The underlying mechanism likely involves in situ formation of NO2 radicals from nitrite secondary to profound pH reduction (down to pH 1) and disproportionation. Polymeric paracetamol species can be analyzed as pentafluorobenzyl derivatives by LC-MS but not by GC-MS. Copyright © 2013 Elsevier B.V. All rights reserved.

  14. Reaction calorimetry for the development of ultrasound-induced polymerization processes in CO2-expanded fluids

    NARCIS (Netherlands)

    Kemmere, M.F.; Kuijpers, M.W.A.; Keurentjes, J.T.F.

    2007-01-01

    A strong viscosity increase upon polymn. hinders radical formation during an ultrasound-induced bulk polymn. Since CO2 acts as a strong anti-solvent for most polymers, it can be used to reduce the viscosity of the reaction mixt. In this work, a process for the ultrasound-induced polymn. in

  15. Radical-Mediated Enzymatic Polymerizations

    Science.gov (United States)

    Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

    2016-01-01

    Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

  16. Condensed tannins: Base-catalysed reactions of polymeric procyanidins with toluene-α-thiol, liability of the interflavanoid bond and pyran ring

    Science.gov (United States)

    Peter E. Laks; Richard W. Hemingway

    1987-01-01

    Reaction of polymeric procyanidins (condensed tannins) with toluene-α-thiol at pH 12.0 and 23°C gave predominantly one stereoisomer of 1.3-bisbenzylthio-1-(3,4-dihydroxyphenyl)-3-(2,4,6-trihydroxyphenyl) propan-2-ol (10) by stereoselective reaction at C-4 and C-2 of the Quinone methide derived from the upper 2,3-cis procyanidin units....

  17. Polymeric reaction of polymer-monomer system for pressure sensitive adhesives by low energy electron beam

    International Nuclear Information System (INIS)

    Takiguchi, R.; Uryu, T.

    1985-01-01

    Application of low-energy electron beam to non-solvent type pressure sensitive adhesives is investigated. The adhesive properties such as peel strength and holding time (dead-load strength) were closely related to the reaction of acrylate polymer-monomer systems. The reaction behavior is elucidated by combining the measurement of gel fraction, infrared spectrum of gel, and the molecular weight distribution detected by gel permeation chromatography. It was important for the production of pressure sensitive adhesives by electron beam that the adhesive with high peel strength and long holding time is composed of a proper combination of three factors, that is, about 35% gel fraction, 25% monomer units in gel, and 15% graft efficiency by irradiating the polymer-monomer system containing low molecular weight poly (butyl acrylate). (author)

  18. Computational study of chain transfer to monomer reactions in high-temperature polymerization of alkyl acrylates.

    Science.gov (United States)

    Moghadam, Nazanin; Liu, Shi; Srinivasan, Sriraj; Grady, Michael C; Soroush, Masoud; Rappe, Andrew M

    2013-03-28

    This article presents a computational study of chain transfer to monomer (CTM) reactions in self-initiated high-temperature homopolymerization of alkyl acrylates (methyl, ethyl, and n-butyl acrylate). Several mechanisms of CTM are studied. The effects of the length of live polymer chains and the type of monoradical that initiated the live polymer chains on the energy barriers and rate constants of the involved reaction steps are investigated theoretically. All calculations are carried out using density functional theory. Three types of hybrid functionals (B3LYP, X3LYP, and M06-2X) and four basis sets (6-31G(d), 6-31G(d,p), 6-311G(d), and 6-311G(d,p)) are applied to predict the molecular geometries of the reactants, products and transition sates, and energy barriers. Transition state theory is used to estimate rate constants. The results indicate that abstraction of a hydrogen atom (by live polymer chains) from the methyl group in methyl acrylate, the methylene group in ethyl acrylate, and methylene groups in n-butyl acrylate are the most likely mechanisms of CTM. Also, the rate constants of CTM reactions calculated using M06-2X are in good agreement with those estimated from polymer sample measurements using macroscopic mechanistic models. The rate constant values do not change significantly with the length of live polymer chains. Abstraction of a hydrogen atom by a tertiary radical has a higher energy barrier than abstraction by a secondary radical, which agrees with experimental findings. The calculated and experimental NMR spectra of dead polymer chains produced by CTM reactions are comparable. This theoretical/computational study reveals that CTM occurs most likely via hydrogen abstraction by live polymer chains from the methyl group of methyl acrylate and methylene group(s) of ethyl (n-butyl) acrylate.

  19. KSF-supported heteropoly acids catalyzed one-pot synthesis of α-aminonitriles

    Directory of Open Access Journals (Sweden)

    Ezzat Rafiee

    2010-08-01

    Full Text Available In the presence of KSF-supported heteropoly acid as a heterogeneous, reusable and inexpensive catalyst, three-component reactions between aldehydes or ketones, amines, and trimethylsilyl cyanide preceded to afford α-aminonitriles in excellent yields, very short reaction times, and low loading of catalyst. This catalyst was highly selective and other functional groups including carbon-carbon double bond, and heterocyclic moieties did not affect the reaction.

  20. KSF-supported heteropoly acids catalyzed one-pot synthesis of α ...

    African Journals Online (AJOL)

    In the presence of KSF-supported heteropoly acid as a heterogeneous, reusable and inexpensive catalyst, three-component reactions between aldehydes or ketones, amines, and trimethylsilyl cyanide preceded to afford α-aminonitriles in excellent yields, very short reaction times, and low loading of catalyst. This catalyst ...

  1. Tannic acid Catalyzed an Efficient Synthesis of 2,4,5-Triaryl-1H-Imidazole

    Directory of Open Access Journals (Sweden)

    Shitole Nana Vikram

    2013-05-01

    Full Text Available Tannic acid (C76H52O46 has been found to be an efficient catalyst for one-pot synthesis of 2,4,5-triaryl substituted imidazoles by the reaction of an arylaldehyde, benzyl/benzoin and an ammonium acetate. The short reaction time and excellent yields making this protocol practical and economically attractive.

  2. Synthesis of imine bond containing insoluble polymeric ligand and its transition metal complexes, structural characterization and catalytic activity on esterification reaction.

    Science.gov (United States)

    Gönül, İlyas; Ay, Burak; Karaca, Serkan; Saribiyik, Oguz Yunus; Yildiz, Emel; Serin, Selahattin

    2017-01-01

    In this study, synthesis of insoluble polymeric ligand (L) and its transition metal complexes [Cu(L)Cl 2 ]·2H 2 O (1) , [Co(L)Cl 2 (H 2 O) 2 ] (2) and [Ni(L)Cl 2 (H 2 O) 2 ] (3) , having the azomethine groups, were synthesized by the condensation reactions of the diamines and dialdehydes. The structural properties were characterized by the analytical and spectroscopic methods using by elemental analysis, Fourier Transform Infrared, Thermo Gravimetric Analysis, Powder X-ray Diffraction, magnetic susceptibility and Inductively Coupled Plasma. The solubilities of the synthesized polymeric materials were also investigated and found as insoluble some organic and inorganic solvents. Additionally, their catalytic performance was carried out for the esterification reaction of acetic acid and butyl acetate. The highest conversion rate is 75.75% by using catalyst 1 . The esterification of butanol gave butyl acetate with 100% selectivity.

  3. Acid-catalyzed Synthesis of Mono and Diakyl Benzenes over Zeolites. Active Sites, Zeolite Topology, and Reaction Mechanisms

    Czech Academy of Sciences Publication Activity Database

    Čejka, Jiří; Wichterlová, Blanka

    2002-01-01

    Roč. 44, - (2002), s. 375-422 ISSN 0161-4940 R&D Projects: GA AV ČR IAA4040001; GA AV ČR IAA4040707 Institutional research plan: CEZ:AV0Z4040901 Keywords : alkyl aromatic * zeolites * molecular sieves Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 6.455, year: 2002

  4. Polymeric reaction between aldehyde group in furfural and phenolic derivatives from liquefaction of oil palm empty fruit bunch fiber as phenol-furfural resin

    Science.gov (United States)

    Masli, M. Z.; Zakaria, S.; Chia, C. H.; Roslan, R.

    2016-11-01

    Resinification of liquefied empty fruit bunch with furfural (LEFB-Fu) was performed. During the resinification process, the samples were taken every hour up to 4 hours. FTIR analysis of the samples was conducted to understand the progress of the reaction. It showed that the bands of 1512 cm-1 and 1692 cm-1 evolving and diminishing respectively, indicating the consumption of furfural. The postulation of polymerization was also proven as the increasing extent of substitution of aromatic ring observed.

  5. Effect of Graphene Oxide on the Reaction Kinetics of Methyl Methacrylate In Situ Radical Polymerization via the Bulk or Solution Technique

    Directory of Open Access Journals (Sweden)

    Ioannis S. Tsagkalias

    2017-09-01

    Full Text Available The synthesis of nanocomposite materials based on poly(methyl methacrylate and graphene oxide (GO is presented using the in situ polymerization technique, starting from methyl methacrylate, graphite oxide, and an initiator, and carried out either with (solution or without (bulk in the presence of a suitable solvent. Reaction kinetics was followed gravimetrically and the appropriate characterization of the products took place using several experimental techniques. X-ray diffraction (XRD data showed that graphite oxide had been transformed to graphene oxide during polymerization, whereas FTIR spectra revealed no significant interactions between the polymer matrix and GO. It appears that during polymerization, the initiator efficiency was reduced by the presence of GO, resulting in a reduction of the reaction rate and a slight increase in the average molecular weight of the polymer formed, measured by gel permeation chromatography (GPC, along with an increase in the glass transition temperature obtained from differential scanning calorimetry (DSC. The presence of the solvent results in the suppression of the gel-effect in the reaction rate curves, the synthesis of polymers with lower average molecular weights and polydispersities of the Molecular Weight Distribution, and lower glass transition temperatures. Finally, from thermogravimetric analysis (TG, it was verified that the presence of GO slightly enhances the thermal stability of the nano-hybrids formed.

  6. Lewis-acid catalyzed depolymerization of Protobind lignin in supercritical water and ethanol

    NARCIS (Netherlands)

    Güvenatam, B.; Heeres, E.H.J.; Pidko, E.A.; Hensen, E.J.M.

    2014-01-01

    The use of metal acetates, metal chlorides and metal triflates as Lewis acid catalysts for the depolymerization of soda lignin under supercritical conditions was investigated. The reactions were carried out at 400°C in water and ethanol. Lignin conversion in supercritical water led to formation of

  7. Lewis-acid catalyzed depolymerization of Protobind lignin in supercritical water and ethanol

    NARCIS (Netherlands)

    Guvenatam, Burcu; Heeres, Erik H.J.; Pidko, Evgeny A.; Hensen, Ernie J. M.

    2016-01-01

    The use of metal acetates, metal chlorides and metal triflates as Lewis acid catalysts for the depolymerization of soda lignin under supercritical conditions was investigated. The reactions were carried out at 400 degrees C in water and ethanol. Lignin conversion in supercritical water led to

  8. Novel Routes to Ethylene Glycol Synthesis via Acid-Catalyzed Carbonylation of Formaldehyde and Dimethoxymethane

    OpenAIRE

    Celik, Fuat Emin

    2010-01-01

    Carbon-carbon bond forming carbonylation reactions were investigated as candidates to replace ethene epoxidation as the major source of ethylene glycol production. This work was motivated by the potentially lower cost of carbon derived from synthesis gas as compared to ethylene. Synthesis gas can be produced from relatively abundant and cheap natural gas, coal, and biomass resources whereas ethylene is derived from increasingly scarce and expensive crude oil. From synthesis gas, a range of...

  9. Synthesis of Isotactic-block-Syndiotactic Poly(methyl Methacrylate via Stereospecific Living Anionic Polymerizations in Combination with Metal-Halogen Exchange, Halogenation, and Click Reactions

    Directory of Open Access Journals (Sweden)

    Naoya Usuki

    2017-12-01

    Full Text Available Isotactic (it- and syndiotactic (st- poly(methyl methacrylates (PMMAs form unique crystalline stereocomplexes, which are attractive from both fundamental and application viewpoints. This study is directed at the efficient synthesis of it- and st-stereoblock (it-b-st- PMMAs via stereospecific living anionic polymerizations in combination with metal-halogen exchange, halogenation, and click reactions. The azide-capped it-PMMA was prepared by living anionic polymerization of MMA, which was initiated with t-BuMgBr in toluene at –78 °C, and was followed by termination using CCl4 as the halogenating agent in the presence of a strong Lewis base and subsequent azidation with NaN3. The alkyne-capped st-PMMA was obtained by living anionic polymerization of MMA, which was initiated via an in situ metal-halogen exchange reaction between 1,1-diphenylhexyl lithium and an α-bromoester bearing a pendent silyl-protected alkyne group. Finally, copper-catalyzed alkyne-azide cycloaddition (CuAAC between these complimentary pairs of polymers resulted in a high yield of it-b-st-PMMAs, with controlled molecular weights and narrow molecular weight distributions. The stereocomplexation was evaluated in CH3CN and was affected by the block lengths and ratios.

  10. The Effects of Reaction Variables on Solution Polymerization of Vinyl Acetate and Molecular Weight of Poly(vinyl alcohol Using Taguchi Experimental Design

    Directory of Open Access Journals (Sweden)

    M.H. Navarchian

    2009-12-01

    Full Text Available Poly(vinyl acetate is synthesized via solution polymerization, and then it is converted to poly(vinyl alcohol by alkaline alcoholysis. The aim of the work study was to investigate statistically the  influence of reaction variables in vinyl acetate polymerization, the conversion of this monomer to polymer, degree of branching of acetyl group in poly(vinyl acetate, as well as the molecular weight of poly(vinyl alcohol, using Taguchi experimental design approach. The reaction variables were polymerization time, molar ratio of initiator to monomer, and volume ratio of monomer to solvent. The statistical analysis of variance of the results revealed that all factors have significantly influenced the conversion and degree of branching. Volume ratio of monomer to solvent is the only factor affecting the molecular weight of poly(vinyl alcohol, and has the greatest influence on all responses. By increasing this ratio, the conversion, degree of branching of acetyl group in poly(vinyl acetate, and molecular weight of poly(vinyl alcohol were increased.

  11. Unraveling the role of entropy in tuning unimolecular vs . bimolecular reaction rates: The case of olefin polymerization catalyzed by transition metals

    KAUST Repository

    Falivene, Laura

    2018-04-24

    Olefin polymerization catalyzed by Group 4 transition metals is studied here as test case to reveal the entropy effects when bimolecular and unimolecular reactions are computed for processes occurring in solution. Catalytic systems characterized by different ligand frameworks, metal, and growing polymeric chain for which experimental data are available have been selected in order to validate the main approaches to entropy calculation. Applying the “standard” protocol results in a strong disagreement with the experimental results and the methods introducing a direct correction of the translational entropy term based on a single experimental parameter emerge as the most reliable. The general and powerful computational tool achieved in this study can represent a further step towards the “catalyst design” to control and predict the molecular mass of the resulting polymers.

  12. Acid-catalyzed reductive amination of aldoses with 8-aminopyrene-1,3,6-trisulfonate.

    Science.gov (United States)

    Evangelista, R A; Guttman, A; Chen, F T

    1996-02-01

    The reductive amination of monosaccharides with 8-aminopyrene-1,3,6-trisulfonate (APTS) in seven different organic acids including the commonly used acetic acid was investigated by capillary electrophoresis (CE) with laser-induced fluorescence (LIF) detection. The correlation between the yields of the saccharide-APTS adducts and pKa of the organic acid catalyst is consistent with general acid catalysis of the rate-determining step of the reductive amination reaction. Derivatization in the presence of organic acids of higher strength than acetic acid produced substantially higher yields of APTS-sugar adducts, an effect which is more pronounced for N-acetylamino sugars. Optimum yields were obtained using citric acid as a catalyst. Conversion of a few nanomoles of neutral saccharides to the APTS derivatives is achieved at 75 degrees C in less than 60 min.

  13. Synthesis of 5-hydroxymethylfurfural (HMF) by acid catalyzed dehydration of glucose-fructose mixtures

    DEFF Research Database (Denmark)

    Pedersen, Asbjørn Toftgaard; Ringborg, Rolf Hoffmeyer; Grotkjær, Thomas

    2015-01-01

    allowing the use of the cheapest available source of fructose: high fructose corn syrup. The dehydration was catalyzed by hydrochloric acid and conducted in acetone-water mixtures, which ensured good selectivity towards HMF and eliminated precipitation of polymer by-products (insoluble humins). Through......Synthesis of 5-hydroxymethylfurfural (HMF) from hexoses has been studied extensively in the scientific literature. However, a process has yet to be implemented at industrial scale. In this paper the simultaneous dehydration of glucose and fructose was investigated, in order to develop a process......-products: soluble humins, glucose dimers, anhydroglucose, and formic acid. The reaction conditions in four different reactor configurations were optimized and compared using the kinetic model. It was found that a recirculating reactor setup is preferable, where the equilibrium controlled by-products (anhydroglucose...

  14. Convenient enzymatic resolution of (R,S)-2-methylbutyric acid catalyzed by immobilized lipases.

    Science.gov (United States)

    Mittersteiner, Mateus; Linshalm, Bruna Luiza; Vieira, Ana Paula Furlan; Brondani, Patrícia Bulegon; Scharf, Dilamara Riva; de Jesus, Paulo Cesar

    2018-01-01

    The application of several immobilized lipases has been explored in the enantioselective esterification of (R,S)-2-methylbutyric acid, an insect pheromone precursor. With the use of Candida antarctica B, using hexane as solvent, (R)-pentyl 2-methylbutyrate was prepared in 2 h with c 40%, ee p 90%, and E = 35, while Thermomyces lanuginosus leads to c 18%, ee p 91%, and E = 26. The (S)-enantiomer was obtained by the use of Candida rugosa or Rhizopus oryzae (2-h reaction, c 34% and 35%, ee p 75 and 49%, and E = 10 and 4, respectively). Under optimal conditions, the effect of the solvent, the molar ratio, and the nucleophile were evaluated. © 2017 Wiley Periodicals, Inc.

  15. Theoretical Kinetic Study of the Formic Acid Catalyzed Criegee Intermediate Isomerization: Multistructural Anharmonicity and Atmospheric Implications

    KAUST Repository

    Monge Palacios, Manuel

    2018-01-29

    We performed a theoretical study on the double hydrogen shift isomerization reaction of a six carbon atom Criegee intermediate (C6-CI), catalyzed by formic acid (HCOOH), to produce vinylhydroperoxide (VHP), C6-CI+HCOOH→VHP+HCOOH. This Criegee intermediate can serve as a surrogate for larger CIs derived from important volatile organic compounds like monoterpenes, whose reactivity is not well understood and are difficult to handle computationally. The reactant HCOOH exerts a pronounced catalytic effect on the studied reaction by lowering the barrier height, but the kinetic enhancement is hindered by the multistructural anharmonicity. First, the rigid ring-structure adopted by the saddle point to facilitate simultaneous transfer of two atoms does not allow formation of as many conformers as those formed by the reactant C6-CI. And second, the flexible carbon chain of C6-CI facilitates the formation of stabilizing intramolecular C–H···O hydrogen bonds; this stabilizing effect is less pronounced in the saddle point structure due to its tightness and steric effects. Thus, the contribution of the reactant C6-CI conformers to the multistructural partition function is larger than that of the saddle point conformers. The resulting low multistructural anharmonicity factor partially cancels out the catalytic effect of the carboxylic acid, yielding in a moderately large rate coefficient, k(298 K) = 4.9·10-13 cm3 molecule-1 s-1. We show that carboxylic acids may promote the conversion of stabilized Criegee intermediates into vinylhydroperoxides in the atmosphere, which generates OH radicals and leads to secondary organic aerosol, thereby affecting the oxidative capacity of the atmosphere and ultimately the climate.

  16. Metathesis Polymerization Reactions Induced by the Bimetallic Complex (Ph4P2[W2(μ-Br3Br6

    Directory of Open Access Journals (Sweden)

    Despoina Chriti

    2015-12-01

    Full Text Available The reactivity of the bimetallic complex (Ph4P2[W2(μ-Br3Br6] ({W 2.5 W}7+, a′2e3 towards ring opening metathesis polymerization (ROMP of norbornene (NBE and some of its derivatives, as well as the mechanistically related metathesis polymerization of phenylacetylene (PA, is presented. Our results show that addition of a silver salt (AgBF4 is necessary for the activation of the ditungsten complex. Polymerization of PA proceeds smoothly in tetrahydrofuran (THF producing polyphenylacetylene (PPA in high yields. On the other hand, the ROMP of NBE and its derivatives is more efficient in CH2Cl2, providing high yields of polymers. 13C Cross Polarization Magic Angle Spinning (CPMAS spectra of insoluble polynorbornadiene (PNBD and polydicyclopentadiene (PDCPD revealed the operation of two mechanisms (metathetic and radical for cross-linking, with the metathesis pathway prevailing.

  17. Cellulose pretreatment with 1-n-butyl-3-methylimidazolium chloride for solid acid-catalyzed hydrolysis.

    Science.gov (United States)

    Kim, Soo-Jin; Dwiatmoko, Adid Adep; Choi, Jae Wook; Suh, Young-Woong; Suh, Dong Jin; Oh, Moonhyun

    2010-11-01

    This study has been focused on developing a cellulose pretreatment process using 1-n-butyl-3-methylimidazolium chloride ([bmim]Cl) for subsequent hydrolysis over Nafion(R) NR50. Thus, several pretreatment variables such as the pretreatment period and temperature, and the [bmim]Cl amount were varied. Additionally, the [bmim]Cl-treated cellulose samples were characterized by X-ray diffraction analysis, and their crystallinity index values including CI(XD), CI(XD-CI) and CI(XD-CII) were then calculated. When correlated with these values, the concentrations of total reducing sugars (TRS) obtained by the pretreatment of native cellulose (NC) and glucose produced by the hydrolysis reaction were found to show a distinct relationship with the [CI(NC)-CI(XD)] and CI(XD-CII) values, respectively. Consequently, the cellulose pretreatment step with [bmim]Cl is to loosen a crystalline cellulose through partial transformation of cellulose I to cellulose II and, furthermore, the TRS release, while the subsequent hydrolysis of [bmim]Cl-treated cellulose over Nafion(R) NR50 is effective to convert cellulose II to glucose. Copyright 2010 Elsevier Ltd. All rights reserved.

  18. Mannich reactions of alkynes: the role of sub-stoichiometric amounts of stable polymeric alkynylcopper (I) compounds in the catalytic cycle (abstract)

    International Nuclear Information System (INIS)

    Khan, A.N.; Buckley, B.R.; Heaney, H.

    2011-01-01

    The rapid development of the use of organocopper reagents and catalysts in organic synthesis since the middle of the last century has been comprehensively documented. The advantages of using heterogeneous catalysts include ease of work-up and purification, reduction in waste disposal, and the ability to recycle catalysts. Reactions of terminal alkynes that involve copper(I) catalysts have been widely studied, in particular as a result of the search for atom efficiency. Ligand associated alkynylcopper(I) derivatives have been reported many times, for example in copper(I) catalysed alkyne-azide cycloaddition (CuAAC) reactions. Our interest in Mannich reactions, and also in alkynylcopper(I) pre-catalysts, prompted this study of reactions of alkynes with secondary amines with aldehydes. Early studies of Mannich reactions involving alkynes almost always involved formaldehyde, exceptions included imines and derivatives of glyoxylic esters. An efficient one-pot three-component coupling of an aldehyde, alkyne, and amine to generate propargyl amines has been effected by microwave heating in water using a polymeric alkynylcopper(I) complex as catalyst (Scheme 1). This reaction utilizes water as a solvent which provides a green-approach for such reactions. This method has proved to be applicable to a wide range of substrates. (author)

  19. Optimization of Two-Step Acid-Catalyzed Hydrolysis of Oil Palm Empty Fruit Bunch for High Sugar Concentration in Hydrolysate

    Directory of Open Access Journals (Sweden)

    Dongxu Zhang

    2014-01-01

    Full Text Available Getting high sugar concentrations in lignocellulosic biomass hydrolysate with reasonable yields of sugars is commercially attractive but very challenging. Two-step acid-catalyzed hydrolysis of oil palm empty fruit bunch (EFB was conducted to get high sugar concentrations in the hydrolysate. The biphasic kinetic model was used to guide the optimization of the first step dilute acid-catalyzed hydrolysis of EFB. A total sugar concentration of 83.0 g/L with a xylose concentration of 69.5 g/L and a xylose yield of 84.0% was experimentally achieved, which is in well agreement with the model predictions under optimal conditions (3% H2SO4 and 1.2% H3PO4, w/v, liquid to solid ratio 3 mL/g, 130°C, and 36 min. To further increase total sugar and xylose concentrations in hydrolysate, a second step hydrolysis was performed by adding fresh EFB to the hydrolysate at 130°C for 30 min, giving a total sugar concentration of 114.4 g/L with a xylose concentration of 93.5 g/L and a xylose yield of 56.5%. To the best of our knowledge, the total sugar and xylose concentrations are the highest among those ever reported for acid-catalyzed hydrolysis of lignocellulose.

  20. Aza‐Michael addition reaction: Post‐polymerization modification and preparation of PEI/PEG‐based polyester hydrogels from enzymatically synthesized reactive polymers

    DEFF Research Database (Denmark)

    Hoffmann, Christian; Stuparu, Mihaiela C.; Daugaard, Anders Egede

    2015-01-01

    The utility of aza‐Michael addition chemistry for post‐polymerization functionalization of enzymatically prepared polyesters is established. For this, itaconate ester and oligoethylene glycol are selected as monomers. A Candida Antarctica lipase B catalyzed polycondensation reaction between the two...... monomers provides the polyesters, which carry an activated carbon‐carbon double bond in the polymer backbone. These electron deficient alkenes represent suitable aza‐Michael acceptors and can be engaged in a nucleophilic addition reaction with small molecular mono‐amines (aza‐Michael donors) to yield...... functionalized linear polyesters. Employing a poly‐amine as the aza‐Michael donor, on the other hand, results in the formation of hydrophilic polymer networks....

  1. A Near-Infrared Photothermal Effect-Responsive Drug Delivery System Based on Indocyanine Green and Doxorubicin-Loaded Polymeric Micelles Mediated by Reversible Diels-Alder Reaction.

    Science.gov (United States)

    Li, Hui; Li, Junjie; Ke, Wendong; Ge, Zhishen

    2015-10-01

    Near-infrared light (NIR) possesses great advantages for light-responsive controllable drug release, such as deep tissue penetration and low damage to healthy tissues. Herein, a NIR-responsive drug delivery system is developed based on a NIR dye, indocyanine green (ICG), and anticancer drug, doxorubicin (DOX)-loaded thermoresponsive block copolymer micelles, in which the drug release can be controlled via NIR irradiation. First, block copolymers, poly(oligo(ethylene glycol) methacrylate)-block-poly(furfuryl methacrylate) (POEGMA-b-PFMA), are synthesized by sequential reversible addition-fragmentation chain-transfer (RAFT) polymerization, followed by modification with N-octyl maleimide through Diels-Alder (DA) reaction to produce POEGMA-b-POMFMA. The self-assembly of POEGMA-b-POMFMA by nano-precipitation in aqueous solution affords the polymeric micelles which are used to simultaneously encapsulate ICG and DOX. Upon irradiation by NIR light (805 nm), the loaded DOX is released rapidly from the micelles due to partial retro DA reaction and local temperature increase-induced faster drug diffusion by the photothermal effect. Cytotoxicity evaluation and intracellular distribution observation demonstrate significant synergistic effects of NIR-triggered drug release, photothermal, and chemotherapy toward cancer cells under NIR irradiation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Polymeric-silica-based sols for membrane modification applications: sol-gel synthesis and characterization with SAXS

    NARCIS (Netherlands)

    de Lange, Rob; de Lange, R.S.A.; Hekkink, J.H.A.; Hekkink, J.H.A.; Keizer, Klaas; Burggraaf, Anthonie; Burggraaf, A.J.

    1995-01-01

    Polymeric SiO2 and binary SiO2/TiO2, SiO2/ZrO2 and SiO2/Al2O3 sols, for ceramic membrane modification applications, have been prepared by acid-catalyzed hydrolysis and condensation of alkoxides in alcohol. The sols were characterized with small angle X-ray scattering, using synchrotron radiation.

  3. Synthesis, Chemosensory Properties, and Self-Assembly of Terpyridine-Containing Conjugated Polycarbazole through RAFT Polymerization and Heck Coupling Reaction

    Directory of Open Access Journals (Sweden)

    Po-Chih Yang

    2017-09-01

    Full Text Available We report the responsive fluorescence chemosensory phenomena of a carbazole-functionalized crosslinked polymer (PCaT with pendent terpyridine (tpy groups as receptors of metal ions. The polymer was synthesized using Heck polymerization between 3,6-dibromide groups in a carbazole-based polymer (PC2Br and divinyl tpy monomer. The effects of the polymeric structure on the optical and chemosensory properties of the PCaT were compared with those of a carbazole-tpy alternating conjugated polymer (PCT. Photoluminescence titrations demonstrated that the PCaT and PCT had the high sensing ability toward Fe3+ ions, with Stern–Volmer constants of 8.10 × 104 and 6.68 × 104 M−1, respectively. The limit of detection (LOD toward Fe3+ of the PCaT and PCT was estimated to be 1.31 × 10−6 and 1.81 × 10−6 M, respectively, and the superior LOD of the PCaT was ascribed to its lowly crosslinked structure. The fluorescence of the solutions of these polymers that were quenched by Fe3+ ions recovered when trace CN− anions were added because of the high stability constant of the CN−–Fe3+ complex. Micellar aggregates with a mean diameter of approximately 239.5 nm were formed by dissolving the PCaT in tetrahydrofuran (THF solution. Our results suggest that the PCaT is a promising material for chemosensory applications.

  4. Development and Implementation of an Automatic Continuous Online Monitoring and Control Platform for Polymerization Reactions to Sharply Boost Energy and Resource Efficiency in Polymer Manufacturing

    Energy Technology Data Exchange (ETDEWEB)

    Reed, Wayne [Tulane Univ., New Orleans, LA (United States); Drenski, Michael [Tulane Univ., New Orleans, LA (United States); Romagnoli, Jose [Tulane Univ., New Orleans, LA (United States)

    2017-10-16

    The project goal was to create an energy saving paradigm shift in how polymers are manufactured in the 21st century. It used Automatic Continuous Online Monitoring of Polymerization reactions (ACOMP) integrated for the first time with automatic active control to create the innovative ‘ACOMP/Control Interface’, or ‘ACOMP/CI’. ACOMP/CI will begin the transformation from old, inefficient processes into highly evolved, energy and resource efficient ones. The ACOMP platform is broadly applicable to many types of reactions and processes throughout the vast polymer industry. The industry provides materials for sectors such as automotive, aerospace, oil recovery, agriculture, paints, resins, adhesives, pharmaceuticals and therapeutic proteins, optics, electronics, lightweight building materials, and many more. The U.S. chemical industry is one of the last major sectors in which the U.S. has top global stature. It consumes 24% of all U.S. manufacturing energy, produces over $800B of product annually, supports 25% of the U.S. GDP and employs over 6 million people. It is also a major source of GHG emissions. Polymers make up approximately 30% of this sector. It is estimated that annually 60 TBtu of energy could be saved and 3 million tons less of GHG emissions produced by optimizing production in the polyolefin manufacturing sector alone. The project scope included first time design and prototyping of an ACOMP/CI, creation of active reaction controllers, and demonstration of control capabilities on ideal, low concentration polymerization reactions. All these elements of the scope were met, including advances and findings not originally anticipated. Extensions to more complex reactions, beyond the reactor capabilities of the current project ACOMP/CI, such as polyolefins and other high pressure/high temperature reactions, are being proposed in Fall 2017 to CESMII, a DoE based NNMI. The initial proposal was for a three year funded project, but this was reduced to a two

  5. [Are there pseudophototropic reactions in biology? Part 4: On the reversibility of biologic/synthetic polymere systems (author's transl)].

    Science.gov (United States)

    Patschorke, J

    1979-01-01

    In further research on pseudophototropic behaviour in cellular membranes of halobacteria the reversibility of vinylmethylethermaleic anhydride-copolymeres with biological liquids is tested and the basic principles of different colour generating reactions are studied.

  6. Reporter-free potentiometric sensing of boronic acids and their reactions by using quaternary ammonium salt-functionalized polymeric liquid membranes.

    Science.gov (United States)

    Wang, Xuewei; Yue, Dengfeng; Lv, Enguang; Wu, Lei; Qin, Wei

    2014-02-18

    The tremendous applications of boronic acids (BAs) in chemical sensing, medical chemistry, molecular assembly, and organic synthesis lead to an urgent demand for developing effective sensing methods for BAs. This paper reports a facile and sensitive potentiometric sensor scheme for heterogeneous detection of BAs based on their unexpected potential responses on quaternary ammonium salt-doped polymeric liquid membranes. (11)B NMR data reveal that a quaternary ammonium chloride can trigger the hydrolysis of an electrically neutral BA in an aprotic solvent. Using the quaternary ammonium salt as the receptor, the BA molecules can be extracted from the sample solution into the polymeric membrane phase and undergo the concomitant hydrolysis. Such salt-triggered hydrolysis generates H(+) ions, which can be coejected into the aqueous phase with the counterions (e.g., Cl(-)) owing to their high hydrophilicities. The perturbation on the ionic partition at the sample-membrane interface changes the phase boundary potential and thus enables the potentiometric sensing of BAs. In contrast to other transduction methods for BAs, for which labeled or separate reporters are exclusively required, the present heterogeneous sensing scheme allows the direct detection of BAs without using any reporter molecules. This technique shows superior detection limits for BAs (e.g., 1.0 × 10(-6) M for phenylboronic acid) as compared to previously reported methods based on colorimetry, fluorimetry, and mass spectrometry. The proposed sensing strategy has also been successfully applied to potentiometric indication of the BA reactions with hydrogen peroxide and saccharides, which allows indirect and sensitive detection of these important species.

  7. Mechanocatalytic polymerization and cross-linking in a polymeric matrix

    NARCIS (Netherlands)

    Jakobs, R.T.M.; Ma, Shuang; Sijbesma, R.P.

    2013-01-01

    A latent olefin metathesis catalyst, bearing two polymeric NHC ligands, was embedded in a semicrystalline polymer matrix containing cyclic olefins. The catalyst was activated by straining the solid material under compression, resulting in polymerization and cross-linking reactions of the monomers in

  8. Heterogeneous acid-catalyzed biodiesel production from crude tall oil: a low-grade and less expensive feedstock

    CSIR Research Space (South Africa)

    Mkhize, NM

    2015-06-01

    Full Text Available was selected and WO3 activity was best at a loading mass fraction of 5% to ZrO2 support and activation at 500 C for five hours under air at atmospheric pressure. Optimal reaction conditions were reaction temperature at 250 C; methanol to CTO molar ratio at 10...

  9. First catalytic hetero-Diels-Alder reaction of imidazole-2-thiones and in silico biological evaluation of the cycloadducts

    NARCIS (Netherlands)

    Eleftheriadis, Nikolaos; Samatidou, Evanthia; Neochoritis, Constantinos G.

    The Lewis acid-catalyzed Diels-Alder reactions of suitably substituted imidazole-2-thiones with dienes were studied. It was found that the electron density of the imidazole core influenced the reaction, since electron withdrawing groups led to the novel spiro-derivatives 2 whereas electron donating

  10. Synthesis of 1,1-Diphenylethylene (DPE): The Marriage of a Grignard Reaction and a Column Chromatography Experiment

    Science.gov (United States)

    Alty, Lisa T.; France, Marcia B.; Alty, Isaac G.; Saber, Christine A.; Smith, Donna M.

    2016-01-01

    The synthesis of 1,1-diphenylethylene (DPE) via a Grignard reaction, followed by an acid-catalyzed dehydration reaction, yields a mixture of compounds. DPE is a high boiling liquid that cannot be purified using simple distillation. However, it is easily separated from the more polar starting material and intermediate alcohol using both thin layer…

  11. Visual detection of glial cell line-derived neurotrophic factor based on a molecular translator and isothermal strand-displacement polymerization reaction.

    Science.gov (United States)

    Zhang, Li-Yong; Xing, Tao; Du, Li-Xin; Li, Qing-Min; Liu, Wei-Dong; Wang, Ji-Yue; Cai, Jing

    2015-01-01

    Glial cell line-derived neurotrophic factor (GDNF) is a small protein that potently promotes the survival of many types of neurons. Detection of GDNF is vital to monitoring the survival of sympathetic and sensory neurons. However, the specific method for GDNF detection is also un-discovered. The purpose of this study is to explore the method for protein detection of GDNF. A novel visual detection method based on a molecular translator and isothermal strand-displacement polymerization reaction (ISDPR) has been proposed for the detection of GDNF. In this study, a molecular translator was employed to convert the input protein to output deoxyribonucleic acid signal, which was further amplified by ISDPR. The product of ISDPR was detected by a lateral flow biosensor within 30 minutes. This novel visual detection method based on a molecular translator and ISDPR has very high sensitivity and selectivity, with a dynamic response ranging from 1 pg/mL to 10 ng/mL, and the detection limit was 1 pg/mL of GDNF. This novel visual detection method exhibits high sensitivity and selectivity, which is very simple and universal for GDNF detection to help disease therapy in clinical practice.

  12. Detection of human papilloma virus (HPV and human immunodeficiency virus (HIV in oral squamous cell carcinoma: A polymerized chain reaction (PCR study

    Directory of Open Access Journals (Sweden)

    Suresh Dirasantchu

    2015-01-01

    Full Text Available Aims and Objectives: Certain strains of human papillomavirus (HPV have been shown to be etiologically related to the development of uterine, cervical, and other genital cancers, but their role in the development of malignancies at other sites is less well established. Previous studies have shown HPV in tumors of the head and neck, but its prevalence has varied depending on the detection methods and the types of tumor and/or tissue examined. This study was undertaken for the detection of high-risk HPV types 16 and 18 and human immunodeficiency virus (HIV in oral squamous cell carcinoma. Materials and Methods: Twenty-five patients histologically diagnosed with oral squamous cell carcinoma and 10 apparently normal persons as controls were selected for the present study. Two biopsy specimens were removed surgically by incision biopsy for histopathological examination and polymerized chain reaction (PCR study. Results: Out of 25 oral squamous cell carcinoma subjects, 8 were found to be HPV positive in PCR. Out of these eight subjects, four had HPV 16 and the other four had other genotypes, and one subject was HIV positive. Conclusion: The conclusion drawn from the present study was that well-defined risk factors like HPV may play a prominent role in the development of oral squamous cell carcinomas, in addition to other risk factors. Further studies with a larger sample size are necessary to arrive at conclusions and to explore the relationship of HPV and HIV in oral squamous cell carcinoma.

  13. The Formation of Pyrroline and Tetrahydropyridine Rings in Amino Acids Catalyzed by Pyrrolysine Synthase (PylD)

    KAUST Repository

    Quitterer, Felix; Beck, Philipp; Bacher, Adelbert; Groll, Michael

    2014-01-01

    various isopeptides to novel amino acids by combining chemical synthesis with enzyme kinetics and X-ray crystallography. The data enable a detailed description of the PylD reaction trajectory for the biosynthesis of pyrroline and tetrahydropyridine rings

  14. Hydrogen generation from formic acid catalyzed by a metal complex under amine-free and aqueous conditions

    KAUST Repository

    Huang, Kuo-Wei; Guan, Chao; Pan, Yupeng; Hu, Jinsong; Li, Huaifeng

    2018-01-01

    invention provides catalysts used to produce hydrogen that has a satisfactory and sufficient lifespan (measured by turnover number (TON)), that has stability in the presence of moisture, air, acid, or impurities, promote a rapid reaction rate, and remain

  15. Acid-catalyzed rearrangements of flavan-4-phloroglucinol derivatives to novel 6-hydroxyphenyl-6a,llb-dihydro-6H-[1]benzofuro[2,3-c]-chromenes and hydroxyphenyl-3,2'-spirobi[dihydro[l]benzofurans

    Science.gov (United States)

    Petrus J. Steynberg; Jan P. Steynberg; Richard W. Hemingway; Daneel Ferreira; G. Wayne McGraw

    1997-01-01

    Acetic acid-catalyzed cleavage of proanthocyanidins in the presence of phloroglucinol gives a series of 2R procyanidin- and prodelphinidin-phloroglucinol adducts together with a novel 2S all-cis derivative implicating cleavage of the pyran ring and subsequent inversion of stereochernistry at C-2c. These flavan-4-phloroglucinol adducts also suffer dehydration to...

  16. Radiation chemistry of polymeric system

    International Nuclear Information System (INIS)

    Machi, Sueo; Ishigaki, Isao

    1978-01-01

    Among wide application of radiation in the field of polymer chemistry, practices of polymerization, graft polymerization, bridging, etc. are introduced hereinafter. As for the radiation sources of radiation polymerization, in addition to the 60 Co-γ ray with long permeation distance which has been usually applied, electron beam accelerators with high energy, large current and high reliability have come to be produced, and the liquid phase polymerization by electron beam has attracted attention industrially. Concerning polymerizing reactions, explanations were given to electron beam polymerization under high dose rate, the polymerization in supercooling state or under high pressure, and emulsifying polymerization. As for radiation bridging, radiation is applied for the bridging of hydrogel, acceleration of bridging and improvement of radiation resistance. It is also utilized for reforming membranes by graft polymerization, and synthesis of polymers for medical use. Application of fixed enzymes in the medical field has been investigated by fixing various enzymes by low temperature γ-ray polymerization with glassy monomers such as HEMA. (Kobatake, H.)

  17. Experimental and Theoretical Studies of the Acid-Catalyzed Conversion of Furfuryl Alcohol to Levulinic Acid in Aqueous Solution

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez Maldonado, Gretchen M.; Assary, Rajeev S.; Dumesic, James A.; Curtiss, Larry A.

    2012-02-14

    The conversion of furfuryl alcohol (FAL) to levulinic acid over Amberlyst TM 15 in aqueous media was investigated using a combination of liquid chromatography-mass spectrometry (LC-MS) measurements, isotopic labeling studies, nuclear magnetic resonance (NMR) spectroscopy, and ab initio quantum chemical calculations using the G4MP2 method. The results of these combined studies showed that one of the major reaction pathways takes place via a geminal diol species (4,5,5- trihydroxypentan-2-one, denoted as intermediate A), formed by the addition of two water molecules to FAL, where two of the oxygen atoms from FAL are retained. This geminal diol species can also be produced from another intermediate found to be a dimer-like species, denoted as intermediate B. This dimer-like species is formed at the early stages of reaction, and it can also be converted to intermediate A, indicating that intermediate B is the product of the reaction of FAL with another early intermediate. Quantum chemical calculations suggested this to be a protonated acyclic species. Reaction of this early intermediate with water produces intermediate A, while reaction with FAL produces intermediate B.

  18. Experimental and Theoretical Studies of the Acid-Catalyzed Conversion of Furfuryl Alcohol to Levulinic Acid in Aqueous Solution

    Energy Technology Data Exchange (ETDEWEB)

    Gonzalez Maldonado, Gretchen; Assary, Rajeev S.; Dumesic, James A; Curtiss, Larry A

    2012-01-01

    The conversion of furfuryl alcohol (FAL) to levulinic acid over AmberlystTM 15 in aqueous media was investigated using a combination of liquid chromatography-mass spectrometry (LC-MS) measurements, isotopic labeling studies, nuclear magnetic resonance (NMR) spectroscopy, and ab initio quantum chemical calculations using the G4MP2 method. The results of these combined studies showed that one of the major reaction pathways takes place via a geminal diol species (4,5,5-trihydroxypentan-2-one, denoted as intermediate A), formed by the addition of two water molecules to FAL, where two of the oxygen atoms from FAL are retained. This geminal diol species can also be produced from another intermediate found to be a dimer-like species, denoted as intermediate B. This dimer-like species is formed at the early stages of reaction, and it can also be converted to intermediate A, indicating that intermediate B is the product of the reaction of FAL with another early intermediate. Quantum chemical calculations suggested this to be a protonated acyclic species. Reaction of this early intermediate with water produces intermediate A, while reaction with FAL produces intermediate B.

  19. An efficient synthesis of isocoumarins via a CuI catalyzed cascade reaction process

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    3-Alkyl isocoumarins are provided by CuI/amino acid-catalyzed Sonogashira coupling reaction of o-bromo benzoic acids and terminal alkynes and the subsequent additive cyclization. This cascade process allows synthesis of diverse isocoumarins by varying both coupling partners bearing a wide range of functional groups.

  20. Lewis Acid Catalyzed Conversion of 5-Hydroxymethylfurfural to 1,2,4-Benzenetriol, an Overlooked Biobased Compound.

    Science.gov (United States)

    Kumalaputri, Angela J; Randolph, Caelan; Otten, Edwin; Heeres, Hero J; Deuss, Peter J

    2018-03-05

    5-Hydroxymethylfurfural (HMF) is a platform chemical that can be produced from renewable carbohydrate sources. HMF can be converted to 1,2,4-benzenetriol (BTO) which after catalytic hydrodeoxygenation provides a route to cyclohexanone and cyclohexanol. This mixture, known as KA oil, is an important feedstock for polymeric products such as nylons which use benzene as feedstock that is obtained from the BTX fraction produced in oil refineries. Therefore, the conversion of HMF to BTO provides a renewable, alternative route toward products such as nylons. However, BTO is usually considered an undesired byproduct in HMF synthesis and is only obtained in small amounts. Here, we show that Lewis acid catalysts can be utilized for the selective conversion of HMF to BTO in subsuper critical water. Overall, up to 54 mol % yield of BTO was achieved at 89% HMF conversion using ZnCl 2 . ZnCl 2 and similarly effective Zn(OTf) 2 and Fe(OTf) 2 are known as relatively soft Lewis acids. Other Lewis acid like Hf(OTf) 4 and Sc(OTf) 3 gave increased selectivity toward levulinic acid (up to 33 mol %) instead of BTO, a well-known HMF derivative typically obtained by acid catalysis. Catalytic hydrodeoxygenation of BTO toward cyclohexanone in water was achieved in up to 45% yield using 5 wt % Pd on Al 2 O 3 combined with AlCl 3 or Al(OTf) 3 as catalysts. Additionally, a mild selective oxygen induced dimerization pathway of BTO to 2,2',4,4',5,5'-hexahydroxybiphenyl (5,5'-BTO dimer) was identified.

  1. Hydrogen generation from formic acid catalyzed by a metal complex under amine-free and aqueous conditions

    KAUST Repository

    Huang, Kuo-Wei

    2018-01-04

    The present invention provides a class of catalyst compounds that can safely and effectively release hydrogen gas from a chemical substrate without producing either noxious byproducts or byproducts that will deactivate the catalyst. The present invention provides catalysts used to produce hydrogen that has a satisfactory and sufficient lifespan (measured by turnover number (TON)), that has stability in the presence of moisture, air, acid, or impurities, promote a rapid reaction rate, and remain stable under the reaction conditions required for an effective hydrogen production system. Described herein are compounds for use as catalysts, as well as methods for producing hydrogen from formic acid and/or a formate using the disclosed catalysts. The methods include contacting formic acid and/or a formate with a catalyst as described herein, as well as methods of producing formic acid and/or a formate using the disclosed catalyst and methods for generating electricity using the catalysts described herein.

  2. Methanol oxidation reaction on Ti/RuO{sub 2(x)}Pt{sub (1-x)} electrodes prepared by the polymeric precursor method

    Energy Technology Data Exchange (ETDEWEB)

    Freitas, R.G.; Marchesi, L.F.; Mattos-Costa, F.I.; Pereira, E.C. [Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Centro Multidisciplinar para o Desenvolvimento de Materiais Ceramicos, Departamento de Quimica, Universidade Federal de Sao Carlos, Caixa Postal 676, 13560-905 Sao Carlos, SP (Brazil); Oliveira, R.T.S. [Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Centro Multidisciplinar para o Desenvolvimento de Materiais Ceramicos, Departamento de Quimica, Universidade Federal de Sao Carlos, Caixa Postal 676, 13560-905 Sao Carlos, SP (Brazil); Grupo de Materiais Eletroquimicos e Metodos Eletroanaliticos, Instituto de Quimica de Sao Carlos, Universidade de Sao Paulo, Caixa Postal 780, 13566-590 Sao Carlos, SP (Brazil); LEMN, Laboratorio de Eletroquimica e Materiais Nanoestruturados, CCNH-Centro de Ciencias Naturais e Humanas, UFABC-Universidade Federal do ABC, CEP 09.210-170, Rua Santa Adelia 166, Bairro Bangu, Santo Andre, SP (Brazil); Bulhoes, L.O.S. [Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Centro Multidisciplinar para o Desenvolvimento de Materiais Ceramicos, Departamento de Quimica, Universidade Federal de Sao Carlos, Caixa Postal 676, 13560-905 Sao Carlos, SP (Brazil); CENIP, Centro Universitario Central Paulista, UNICEP, Rua Miguel Petroni, 5111, CEP 13563-470, Sao Carlos, SP (Brazil); Santos, M.C. [Laboratorio Interdisciplinar de Eletroquimica e Ceramica, Centro Multidisciplinar para o Desenvolvimento de Materiais Ceramicos, Departamento de Quimica, Universidade Federal de Sao Carlos, Caixa Postal 676, 13560-905 Sao Carlos, SP (Brazil); LEMN, Laboratorio de Eletroquimica e Materiais Nanoestruturados, CCNH-Centro de Ciencias Naturais e Humanas, UFABC-Universidade Federal do ABC, CEP 09.210-170, Rua Santa Adelia 166, Bairro Bangu, Santo Andre, SP (Brazil)

    2007-09-27

    In this work, ruthenium oxide films containing platinum nanoparticles were prepared using the polymeric precursor method on Ti substrates with several molar ratios. This paper aims at presenting the characterization of the Pt content effect in the methanol electrochemical oxidation reaction. The films were physically characterized using X-ray diffraction and both Pt and RuO{sub 2} (rutile) phases were observed. The mean crystallite sizes were 6 nm for Pt and 25 nm for RuO{sub 2}. The X-ray photoelectronic results indicated that on the electrodes surfaces, depending on the substrate, there was RuO{sub 2}, Ru metal and Pt metal. Besides, it was not observed the formation of PtRu alloys. The atomic force microscopy images of the films showed highly rough surfaces. A decrease in the roughness mean square values is observed as the Pt content increases. These last results are similar to electroactive surface area values calculated by redox-couple (K{sub 4}FeCN{sub 6}/K{sub 3}FeCN{sub 6}). There was an increase in the globular size observed on the electrode surface and lower particle dispersion as the Pt content is increased from 12.5 to 75 mol%. Regarding the eletrode electrocatalytical behavior for methanol oxidation, it was observed that the onset oxidation overpotential is displaced towards more negative values as Pt content is decreased. Besides, an increase has been shown in the current density for methanol oxidation of 600% using a Ti/RuO{sub 2}-Pt (87.5:12.5) electrode compared to polycrystalline Pt. (author)

  3. One-Pot Synthesis of N-(α-Peroxy)Indole/Carbazole via Chemoselective Three-Component Condensation Reaction in Open Atmosphere

    KAUST Repository

    Wang, Xinbo; Pan, Yupeng; Huang, Kuo-Wei; Lai, Zhiping

    2015-01-01

    A facile one-pot synthesis of N-(α-peroxy)indole and N-(α-peroxy)carbazole has been developed using metal-free, organo-acid-catalyzed three-component condensation reactions of indole/carbazole, aldehyde, and peroxide. Based on the reaction

  4. Unraveling the role of entropy in tuning unimolecular vs . bimolecular reaction rates: The case of olefin polymerization catalyzed by transition metals

    KAUST Repository

    Falivene, Laura; Barone, Vincenzo; Talarico, Giovanni

    2018-01-01

    by different ligand frameworks, metal, and growing polymeric chain for which experimental data are available have been selected in order to validate the main approaches to entropy calculation. Applying the “standard” protocol results in a strong disagreement

  5. Elektroaktive polymerer

    DEFF Research Database (Denmark)

    West, K.

    Traditionelt tænker vi på polymerer (plastik) som elektrisk isolerende materialer - det som er udenpå ledningerne. I dag kender vi imidlertid også polymerer med intrinsisk elektrisk ledningsevne, og plast er på vej ind i anvendelser, der tidligereudelukkende var baseret på metaller og uorganiske...... halvledere. Hertil kommer, at en del af de ledende polymerer kan stimuleres til at skifte mellem en ledende og en halvledende tilstand, hvorved de ændret både form og farve. I foredraget gives der enrække eksempler på anvendelse af polymerer som elektriske komponenter - rækkende fra polymer elektronik over...

  6. Lewis acid catalyzed [3 + 2] annulation of ketenimines with donor-acceptor cyclopropanes: an approach to 2-alkylidenepyrrolidine derivatives.

    Science.gov (United States)

    Alajarin, Mateo; Egea, Adrian; Orenes, Raul-Angel; Vidal, Angel

    2016-11-02

    The [3 + 2] annulation reaction of C,C,N-trisubstituted ketenimines with donor-acceptor cyclopropanes bearing aryl, styryl and vinyl substituents at the C2 position, triggered by the Lewis acid Sc(OTf) 3 , supplies highly substituted pyrrolidines. Activated cyclopropanes fused to naphthalene and [1]benzopyrane nuclei are also suitable substrates in similar transformations, yielding partially saturated benz[g]indoles and [1]benzopyran[4,3-b]pyrroles. An intramolecular version of this ketenimine/cyclopropane [3 + 2] annulation has also been developed leading to the pyrrolo[2,1-a]isoindole framework.

  7. The Formation of Pyrroline and Tetrahydropyridine Rings in Amino Acids Catalyzed by Pyrrolysine Synthase (PylD)

    KAUST Repository

    Quitterer, Felix

    2014-06-10

    The dehydrogenase PylD catalyzes the ultimate step of the pyrrolysine pathway by converting the isopeptide L-lysine-Nε-3R-methyl-D-ornithine to the 22nd proteinogenic amino acid. In this study, we demonstrate how PylD can be harnessed to oxidize various isopeptides to novel amino acids by combining chemical synthesis with enzyme kinetics and X-ray crystallography. The data enable a detailed description of the PylD reaction trajectory for the biosynthesis of pyrroline and tetrahydropyridine rings as constituents of pyrrolysine analogues. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Twin screw extruders as polymerization reactors for a free radical homo polymerization

    NARCIS (Netherlands)

    Ganzeveld, K.J.; Janssen, L.P.B.M.

    The bulk polymerization of n-butylmethacrylate was investigated in a counter-rotating twin screw extruder. It appeared that the gel effect, occurring with bulk polymerizations, affected the polymerization progress very strongly. Due to this effect the conversion of the reaction is independent of the

  9. Catalytic Conversion of Bio-Oil to Oxygen-Containing Fuels by Acid-Catalyzed Reaction with Olefins and Alcohols over Silica Sulfuric Acid

    Directory of Open Access Journals (Sweden)

    Qingwen Wang

    2013-09-01

    Full Text Available Crude bio-oil from pine chip fast pyrolysis was upgraded with olefins (1-octene, cyclohexene, 1,7-octadiene, and 2,4,4-trimethylpentene plus 1-butanol (iso-butanol, t-butanol and ethanol at 120 °C using a silica sulfuric acid (SSA catalyst that possesses a good catalytic activity and stability. Gas chromatography-mass spectrometry (GC-MS, Fourier transform infrared spectroscopy (FT-IR and proton nuclear magnetic resonance (1H-NMR analysis showed that upgrading sharply increased ester content and decreased the amounts of levoglucosan, phenols, polyhydric alcohols and carboxylic acids. Upgrading lowered acidity (pH value rose from 2.5 to >3.5, removed the unpleasant odor and increased hydrocarbon solubility. Water content dramatically decreased from 37.2% to about 7.0% and the heating value increased from 12.6 MJ·kg−1 to about 31.9 MJ·kg−1. This work has proved that bio-oil upgrading with a primary olefin plus 1-butanol is a feasible route where all the original heating value of the bio-oil plus the added olefin and alcohol are present in the resulting fuel.

  10. Synthesis of nanocrystalline LaF3 doped silica glasses by hydrofluoric acid catalyzed sol–gel process

    International Nuclear Information System (INIS)

    Nagayama, Shuhei; Kajihara, Koichi; Kanamura, Kiyoshi

    2012-01-01

    Highlights: ► Silica glasses doped by LaF 3 nanocrystals are obtained by HF-catalyzed sol–gel method. ► The processing time (∼1 week) is much shorter than that of previous studies. ► The uptake of SiF groups in the glass matrix greatly reduces the SiOH concentration. ► Effects of sintering conditions and properties of Er 3+ -doped samples are presented. - Abstract: Silica glasses doped with LaF 3 nanocrystals were prepared by HF-catalyzed sol–gel method. HF was used both as fluorine source and as catalyst of the sol–gel reaction, making it possible to shorten the processing time with reducing the concentration of SiOH groups to ∼10 18 cm −3 . The resultant glasses are transparent at visible spectral range, and the optical loss at the ultraviolet absorption edge is dominated by the Rayleigh scattering from LaF 3 crystallites. The size of LaF 3 crystallites increases with an increase in the sintering temperature and time, and is smaller than ∼40 nm in samples showing good visible transparency. Green upconversion photoluminescence is observed in an Er 3+ -doped sample under excitation at 980 nm.

  11. Advanced Model Compounds for Understanding Acid-Catalyzed Lignin Depolymerization: Identification of Renewable Aromatics and a Lignin-Derived Solvent.

    Science.gov (United States)

    Lahive, Ciaran W; Deuss, Peter J; Lancefield, Christopher S; Sun, Zhuohua; Cordes, David B; Young, Claire M; Tran, Fanny; Slawin, Alexandra M Z; de Vries, Johannes G; Kamer, Paul C J; Westwood, Nicholas J; Barta, Katalin

    2016-07-20

    The development of fundamentally new approaches for lignin depolymerization is challenged by the complexity of this aromatic biopolymer. While overly simplified model compounds often lack relevance to the chemistry of lignin, the direct use of lignin streams poses significant analytical challenges to methodology development. Ideally, new methods should be tested on model compounds that are complex enough to mirror the structural diversity in lignin but still of sufficiently low molecular weight to enable facile analysis. In this contribution, we present a new class of advanced (β-O-4)-(β-5) dilinkage models that are highly realistic representations of a lignin fragment. Together with selected β-O-4, β-5, and β-β structures, these compounds provide a detailed understanding of the reactivity of various types of lignin linkages in acid catalysis in conjunction with stabilization of reactive intermediates using ethylene glycol. The use of these new models has allowed for identification of novel reaction pathways and intermediates and led to the characterization of new dimeric products in subsequent lignin depolymerization studies. The excellent correlation between model and lignin experiments highlights the relevance of this new class of model compounds for broader use in catalysis studies. Only by understanding the reactivity of the linkages in lignin at this level of detail can fully optimized lignin depolymerization strategies be developed.

  12. Radiation polymerization of tetrafluoroethylene

    International Nuclear Information System (INIS)

    Kadoi, H.; Lugao, A.B.; Oikawa, H.

    1984-01-01

    Tetrafluoroethylene (TFE) monomer was obtained by means of the pyrolysis of chlorodifluoromethane (R-22). The experiments were carried out in quartz tube with temperature between 700 0 and 800 0 C. The principal reaction of the pyrolysis is considered to be: 2CHClF2 ----> C 2 F 4 +2HCl. However, by-products such as HF, C 3 F 6 , C 2 HClF 4 , C 4 F 8 etc are also produced in the pyrolysis process. The conversions of R-22 varied from 30 to 50%, depending upon the temperature, pressure and flow rate of R-22 in the furnace. Finally the TFE monomer of purity higher than 99.98% was obtained by fractional distillation in low temperatures ranging from -10 0 to -30 0 C. The bulk polymerization of this monomer induced by γ-rays from 3000Ci cobalt-60 source was studied at various temperatures (room temperature, 0 0 , -23 0 and -78 0 C). The monomers were introduced into stainless steel vessels of 15 and 60 ml volume under vacuum. The control of polymerization reaction was rather hard at temperatures higher than -23 0 C due to the difficulty of removing the heat of reaction. However, the polymerization at -78 0 C was very easy to control. The white polymer particles were obtained in agglomerated state. The IR spectra of the polymers were consistent with those of commercial products. The melting points of samples were between 326 0 and 331 0 C. (Author) [pt

  13. Reaction

    African Journals Online (AJOL)

    abp

    19 oct. 2017 ... Reaction to Mohamed Said Nakhli et al. concerning the article: "When the axillary block remains the only alternative in a 5 year old child". .... Bertini L1, Savoia G, De Nicola A, Ivani G, Gravino E, Albani A et al ... 2010;7(2):101-.

  14. The Formation of Polymeric Products in Reactions of Polyvalent Recoil Atoms; Formation de Polymeres lors de Reactions Provoquees par des Atomes de Recul Polyvalents; Obrazovanie polimernykh produktov pri reaktsiyakh polivalentnykh atomov otdachi; Formacion de Polimeros en las Reacciones de Atomos de Retroceso Polivalentes

    Energy Technology Data Exchange (ETDEWEB)

    Dzantiev, B. G.; Stukan, R. A.; Shvedchikov, A. P.; Shishkov, A. V. [Institut Himicheskoj Fiziki AN SSSR, Moskva, SSSR (Russian Federation)

    1965-04-15

    One of the features of the hot-atom reactions obtained as a result of nuclear transformations is that labelled polymeric products can be formed. This tendency is very marked in the case of polyvalent recoil atoms, where the polymer yield can, in certain cases, reach an amount of about 90% of the total activity. The aim of the present research is a study of the behaviour of recoil atoms of sulphur-35 and carbon-14, obtained in the nuclear reactions Cl{sup 35}(n, p)S{sup 35} and N{sup 14}(n, p) C{sup 14} in gas and liquid phases. It can be assumed that in the stabilization process hot carbon atoms form methylene biradicals, whose behaviour, by reason of their reaction capacity, greatly resembles that of atomic sulphur. The investigations were conducted like those for paraffins (CH{sub 4}, C{sub 2}H{sub 6} ), and for cyclic hydrocarbons (cyclohexane, cyclohexene, benzene). The binary systems comprising hydrocarbons on the one hand and S{sup 35} and C{sup 14} hot-atom donors on the other were subjected to irradiation. Compounds of CCI{sub 4}, HCl and ammonia were used as the donors. Irradiation was carried out on a reactor of type IRT-1000 with a thermal neutron flux of 10{sup 11}-10{sup 12} n/cm{sup 2}. s. It is shown that for various compounds in the liquid phase, up to 60-90% of the sulphur-35 becomes stabilized in the form of a polymer, the yield of which is highly dependent on the composition, passing through the maximum at a nearly equimolecular ratio of components. In the gas phase the polymer yield amounts to 30-40% of the total activity. By means of paper radiochromatography it was established that labelled polymer products have a complex structure and are, at the least, a mixture of compounds of two qualitatively different types whose yield changes in various ways depending upon the ratio of the components. An increase in irradiation time leads to an increase in the labelled polymer yield. In the case of the liquid phase system C{sub 6}H{sub 12}-CCl{sub 4

  15. Synthesis of Precursors of the Agalacto (Exo) Fragment of the Quartromicins via an Auxiliary-Controlled Exo-Selective Diels-Alder Reaction

    Science.gov (United States)

    Qi, Jun; Roush, William R.

    2008-01-01

    A direct synthesis of the α-hydroxyaldehyde exo-5, a precursor of the exo-spirotetronate subunit o f the quartromicins, was achieved through an exo-selective Lewis acid-catalyzed Diels-Alder reaction of dienophile 12a and diene 1. PMID:16774259

  16. Bioethanol production from paperboard mill sludge using acid-catalyzed bio-derived choline acetate ionic liquid pretreatment followed by fermentation process

    International Nuclear Information System (INIS)

    Farghaly, Ahmed; Elsamadony, Mohamed; Ookawara, Shinichi; Tawfik, Ahmed

    2017-01-01

    Highlights: • Total reducing sugar concentration depends on [ChO][OAc] ionic liquid to biomass ratio. • Acid-catalyzed ionic liquid significantly enhance pretreatment process. • Prolonged pretreatment duration degraded sugars into furans compounds. • Maximum net energy of 5.36 ± 0.30 kJ/g PMS obtained by using acid catalyst IL. - Abstract: Paperboard mill sludge (PMS) composed of cellulose, hemicellulose, lignin and ash contents of 36.72 ± 2.81, 32.91 ± 1.75, 22.89 ± 0.56, and 7.48 ± 0.39%, respectively. Enzymatic hydrolysis process followed by fermentation of native PMS provided an ethanol yield of 0.36 ± 0.01 g/L which equivalent to net gain energy of −0.84 ± 0.03 kJ/g PMS . Choline acetate ionic liquid [Cho][OAc] IL was extensively used as a solvent for PMS to upgrade the performance. Pretreatment with [Cho][OAc] IL/PMS ratio of 10% (w/w) for 1.0 h, at a temperature of 120 °C exhibited hemicellulose and lignin removal efficiency of 5.05 ± 0.52 and 14.71 ± 1.22%, respectively with 89.19 ± 5.62% cellulose recovery. This corresponded to net gain energy of 0.60 ± 0.04 kJ/g PMS based on ethanol yield from enzymatic saccharification process which was quite low due to a limited hemicellulose removal and glucose yield of 24.1 ± 1.4 g/L. [Cho][OAc] IL/PMS ratio of 10% (w/w) supplemented with 1% (v/v) HCl substantially improved the removal efficiency of hemicellulose (36.38 ± 4.51%), lignin (17.42 ± 1.19%) and cellulose (82.17 ± 4.28%) which provided the maximum net energy of 5.36 ± 0.30 kJ/g PMS .

  17. High Vacuum Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar

    2015-09-01

    Anionic polymerization high vacuum techniques (HVTs) are the most suitable for the preparation of polymer samples with well-defined complex macromolecular architectures. Though HVTs require glassblowing skill for designing and making polymerization reactor, it is the best way to avoid any termination of living polymers during the number of steps for the synthesis of polymers with complex structure. In this chapter, we describe the different polymerization reactors and HVTs for the purification of monomers, solvents, and other reagents for anionic polymerization as well as few model reactions for the synthesis of polymers with simple to complex structure.

  18. Novel polymeric materials from triglycerides

    Science.gov (United States)

    Triglycerides are good platforms for new polymeric products that can substitute for petroleum-based materials. As part of our research emphasis in sustainability and green polymer chemistry, we have explored a number of reactions in efforts to produce a wide range of value-added products. In this ...

  19. Facile synthesis of hollow Sn–Co@PMMA nanospheres as high performance anodes for lithium-ion batteries via galvanic replacement reaction and in situ polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Yu, Xiaohui; Jiang, Anni; Yang, Hongyan; Meng, Haowen; Dou, Peng; Ma, Daqian [School of Materials Science and Engineering, Tianjin University, Tianjin 300072 (China); Xu, Xinhua, E-mail: xhxutju@gmail.com [School of Materials Science and Engineering, Tianjin University, Tianjin 300072 (China); Tianjin Key Laboratory of Composite and Functional Materials, Tianjin 300072 (China)

    2015-08-30

    Highlights: • Hollow Sn–Co nanospheres were synthesized via a facile galvanic replacement method. • PMMA layers were uniform coated on the surface of Sn–Co composites via in situ emulsion polymerization. • The coating layers are beneficial to suppress the aggregation and stabilize the SEI formation on the surface. • Excellent cycling stability and rate capability were obtained by coating PMMA protective layers on the surface of hollow Sn–Co nanospheres. - Abstract: Polymethyl methacrylate (PMMA)-coated hollow Sn–Co nanospheres (Sn–Co@PMMA) with superior electrochemical performance had been synthesized via a facile galvanic replacement method followed by an in situ emulsion polymerization route. The properties were investigated in detail and results show that the hollow Sn–Co nanospheres were evenly coated with PMMA. Benefiting from the protection of the PMMA layers, the hollow Sn–Co@PMMA nanocomposite is capable of retaining a high capacity of 590 mAh g{sup −1} after 100 cycles with a coulomb efficiency above 98%, revealing better electrochemical properties compared with hollow Sn–Co anodes. The PMMA coating could help accommodate the mechanical strain caused by volume expansion and stabilize the solid electrolyte interphase (SEI) film formed on the electrode. Such a facile process could be further extended to other anode materials for lithium-ion batteries.

  20. Facile synthesis of hollow Sn–Co@PMMA nanospheres as high performance anodes for lithium-ion batteries via galvanic replacement reaction and in situ polymerization

    International Nuclear Information System (INIS)

    Yu, Xiaohui; Jiang, Anni; Yang, Hongyan; Meng, Haowen; Dou, Peng; Ma, Daqian; Xu, Xinhua

    2015-01-01

    Highlights: • Hollow Sn–Co nanospheres were synthesized via a facile galvanic replacement method. • PMMA layers were uniform coated on the surface of Sn–Co composites via in situ emulsion polymerization. • The coating layers are beneficial to suppress the aggregation and stabilize the SEI formation on the surface. • Excellent cycling stability and rate capability were obtained by coating PMMA protective layers on the surface of hollow Sn–Co nanospheres. - Abstract: Polymethyl methacrylate (PMMA)-coated hollow Sn–Co nanospheres (Sn–Co@PMMA) with superior electrochemical performance had been synthesized via a facile galvanic replacement method followed by an in situ emulsion polymerization route. The properties were investigated in detail and results show that the hollow Sn–Co nanospheres were evenly coated with PMMA. Benefiting from the protection of the PMMA layers, the hollow Sn–Co@PMMA nanocomposite is capable of retaining a high capacity of 590 mAh g −1 after 100 cycles with a coulomb efficiency above 98%, revealing better electrochemical properties compared with hollow Sn–Co anodes. The PMMA coating could help accommodate the mechanical strain caused by volume expansion and stabilize the solid electrolyte interphase (SEI) film formed on the electrode. Such a facile process could be further extended to other anode materials for lithium-ion batteries

  1. Nanoparticles from a controlled polymerization process

    International Nuclear Information System (INIS)

    Tirumala, V.R.; Caneba, G.T.; Dar, Y.; Wang, H.-H.; Mancini, D.C.

    2003-01-01

    Free-radical retrograde precipitation polymerization process in the past has shown excellent control characteristics over reaction rate, molecular weight, and in the entrapment of live radicals for the generation of block copolymers. The same principle has now been extended to study the reaction confinement to a nanoscale region. Nanosized polymer particles have been reported to form from block copolymers, conventional precipitation polymerization methods, or through emulsion polymerization approaches. In this work, we present a new method of generating nanosized polymer particles by polymerizing the monomer in an environment that precipitates the polymer above the lower critical solution temperature. The nanoparticles have been characterized by both tapping-mode atomic force microscopy observations and in situ synchrotron time-resolved small-angle X-ray scattering analysis. The results from both the techniques showed the formation of nanoparticles in the size range of 15-30 nm, directly from the polymerization process.

  2. Chelating polymeric membranes

    KAUST Repository

    Peinemann, Klaus-Viktor; Villalobos Vazquez de la Parra, Luis Francisco; Hilke, Roland

    2015-01-01

    microporous chelating polymeric membrane. Embodiments include, but are not limited to, microporous chelating polymeric membranes, device comprising the membranes, and methods of using and making the same.

  3. Facile synthesis of hollow Sn-Co@PMMA nanospheres as high performance anodes for lithium-ion batteries via galvanic replacement reaction and in situ polymerization

    Science.gov (United States)

    Yu, Xiaohui; Jiang, Anni; Yang, Hongyan; Meng, Haowen; Dou, Peng; Ma, Daqian; Xu, Xinhua

    2015-08-01

    Polymethyl methacrylate (PMMA)-coated hollow Sn-Co nanospheres (Sn-Co@PMMA) with superior electrochemical performance had been synthesized via a facile galvanic replacement method followed by an in situ emulsion polymerization route. The properties were investigated in detail and results show that the hollow Sn-Co nanospheres were evenly coated with PMMA. Benefiting from the protection of the PMMA layers, the hollow Sn-Co@PMMA nanocomposite is capable of retaining a high capacity of 590 mAh g-1 after 100 cycles with a coulomb efficiency above 98%, revealing better electrochemical properties compared with hollow Sn-Co anodes. The PMMA coating could help accommodate the mechanical strain caused by volume expansion and stabilize the solid electrolyte interphase (SEI) film formed on the electrode. Such a facile process could be further extended to other anode materials for lithium-ion batteries.

  4. On-demand photoinitiated polymerization

    Science.gov (United States)

    Boydston, Andrew J; Grubbs, Robert H; Daeffler, Chris; Momcilovic, Nebojsa

    2013-12-10

    Compositions and methods for adjustable lenses are provided. In some embodiments, the lenses contain a lens matrix material, a masking compound, and a prepolymer. The lens matrix material provides structure to the lens. The masking compound is capable of blocking polymerization or crosslinking of the prepolymer, until photoisomerization of the compound is triggered, and the compound is converted from a first isomer to a second isomer having a different absorption profile. The prepolymer is a composition that can undergo a polymerization or crosslinking reaction upon photoinitiation to alter one or more of the properties of the lenses.

  5. Radiation Induced Polymerization of Pyrrole

    International Nuclear Information System (INIS)

    Sarada Idris; Ratnam, C.T.; Ahmad Ashrif Abu Bakar

    2016-01-01

    We demonstrate the polymerization of pyrrole by gamma irradiation. The pyrrole films were exposed to gamma ray from cobalt 60 source at doses ranging from 0 to 150 kGy. The films were subjected to structural and morphological analyses by using FTIR, SEM and AFM techniques. Similar studies were also made on pristine pyrrole film which serve as control. Results revealed that pyrrole has been successfully polymerized through irradiation induced reactions. The SEM images depicted the formation of cauliflower shape upon gamma irradiation. The structural changes of pyrrole also evidenced by FTIR spectra. Surface topography and roughness of pyrrole before and after gamma irradiation found to show significant differences. (author)

  6. Olefin metathesis and metathesis polymerization

    CERN Document Server

    Ivin, K J

    1997-01-01

    This book is a follow-up to Ivins Olefin Metathesis, (Academic Press, 1983). Bringing the standard text in the field up to date, this Second Edition is a result of rapid growth in the field, sparked by the discovery of numerous well-defined metal carbene complexes that can act as very efficient initiators of all types of olefin metathesis reaction, including ring-closing metathesis of acyclic dienes, enynes, and dienynes; ring-opening metathesis polymerizationof cycloalkenes, acyclic diene metathesis polymerization; and polymerization of alkynes, as well as simple olefin metathesis. Olefin Metathesis and Metathesis Polymerization provides a broad, up-to-date account of the subject from its beginnings in 1957 to the latest applications in organic synthesis. The book follows the same format as the original, making it useful toteachers and to researchers, and will be of particular interest to those working in the fields of organic chemistry, polymer chemistry, organometallic chemistry, catalysis, materials scien...

  7. Polymerization Simulator for Introductory Polymer and Material Science Courses

    Science.gov (United States)

    Chirdon, William M.

    2010-01-01

    This work describes how molecular simulation of polymerization reactions can be used to enrich introductory polymer or material science courses to give students a deeper understanding of free-radical chain and stepwise growth polymerization reactions. These simulations have proven to be effective media for instruction that do not require material…

  8. Regio-, Diastereo-, and Enantioselective Nitroso-Diels-Alder Reaction of 1,3-Diene-1-carbamates Catalyzed by Chiral Phosphoric Acids.

    Science.gov (United States)

    Pous, Jonathan; Courant, Thibaut; Bernadat, Guillaume; Iorga, Bogdan I; Blanchard, Florent; Masson, Géraldine

    2015-09-23

    Chiral phosphoric acid-catalyzed asymmetric nitroso-Diels-Alder reaction of nitrosoarenes with carbamate-dienes afforded cis-3,6-disubstituted dihydro-1,2-oxazines in high yields with excellent regio-, diastereo-, and enantioselectivities. Interestingly, we observed that the catalyst is able not only to control the enantioselectivity but also to reverse the regioselectivity of the noncatalyzed nitroso-Diels-Alder reaction. The regiochemistry reversal and asynchronous concerted mechanism were confirmed by DFT calculations.

  9. AZIDE-ALKYNE CLICK POLYMERIZATION: AN UPDATE

    Institute of Scientific and Technical Information of China (English)

    Hong-kun Li; Jing-zhi Sun; An-jun Qin; Ben Zhong Tang

    2012-01-01

    The great achievements of click chemistry have encouraged polymer scientists to use this reaction in their field.This review assembles an update of the advances of using azide-alkyne click polymerization to prepare functional polytriazoles (PTAs) with linear and hyperbranched structures.The Cu(Ⅰ)-mediated click polymerization furnishes 1,4-regioregular PTAs,whereas,the metal-free click polymerization of propiolates and azides produces PTAs with 1,4-regioisomer contents up to 90%.The PTAs display advanced functions,such as aggregation-induced emission,thermal stability,biocompatibility and optical nonlinearity.

  10. Online observation of emulsion polymerization by fluorescence technique

    CERN Document Server

    Rudschuck, S; Fuhrmann, J

    1999-01-01

    An online observation of local polarity via fluorescence spectroscopy was used to study the formation and growth of polymer particles during an emulsifier-free heterogeneous polymerization. The reaction mixture consisted of styrene dispersed in water and the polymerization was initiated by a macro-initiator (hydrolyzed propene-maleic acid copolymer with t-butyl perester groups). Pyrenyl probes were attached to the backbone of the initiator to analyze the heterogeneous reaction. The experimental results allow a clear distinction of different time regions during the heterogeneous polymerization. Information about the heating period, the latex formation, the particle growth and the final stage of the polymerization process (gel point) were obtained. (11 refs).

  11. Survey and research on precision polymerization polymeric materials; Seimitsu jugo kobunshi zairyo ni kansuru chosa kenkyu

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1996-03-01

    Survey and research on the precision control of primary structure of polymeric materials and the precision evaluation technology have been conducted to develop advanced polymeric materials. It is proposed that the three basic processes of polymer synthesis, i.e., addition, condensation, and biomimesis, in forming the precision polymerization skeleton are to be covered through a centralized joint research effort with participation of industry, academia, and the government institute and under the leadership of researchers from academic institutions as the team leaders. For the study of technology trends, international conferences held in UK, Germany, and Hawaii are introduced, and domestic meetings, i.e., Annual Polymer Congress and Polymer Conference, are summarized. In addition, Precision Polymerization Forum and International Workshop on Precision Polymerization were held. The basic studies include a quantum-chemical elucidation of the elementary process in polymerization reaction, time-resolved analysis of polymerization process and polymer properties, synthesis of polymers with controlled microstructures by coordination polymerization using metal complexes, synthesis of polymer with controlled microstructures by precision polycondensation, molecular recognition in catalyst-reaction site, and synthesis of imprinting polymers. 246 refs., 117 figs., 14 tabs.

  12. Kinetics of phosphotungstic acid catalyzed oxidation of propan-1,3-diol and butan-1,4-diol by N-chlorosaccharin

    Directory of Open Access Journals (Sweden)

    Sanjay Kumar Singh

    2011-09-01

    Full Text Available The kinetic studies of N-chlorosaccharin (NCSA oxidation of propan-1,3-diol and butan-1,4-diol have been reported in presence of phophotungstic acid and in aqueous acetic acid medium. The reactions follow first-order in NCSA and one to zero order with respect to substrate and phosphotungstic acid. Increase in the concentration of added perchloric acid increases the rate of oxidation. A negative effect on the oxidation rate is observed for solvent whereas the ionic strength does not influence the rate of reaction. Addition of the reaction product, saccharin, exhibited retarding effect. Various activation parameters have been evaluated. The products of the reactions were identified as the corresponding aldehydes. A suitable scheme of mechanism consistent with the experimental results has been proposed.

  13. Catalytic Asymmetric Piancatelli Rearrangement: Brønsted Acid Catalyzed 4π Electrocyclization for the Synthesis of Multisubstituted Cyclopentenones

    KAUST Repository

    Cai, Yunfei; Tang, Yurong; Atodiresei, Iuliana; Rueping, Magnus

    2016-01-01

    The first catalytic asymmetric Piancatelli reaction is reported. Catalyzed by a chiral Brønsted acid, the rearrangement of a wide range of furylcarbinols with a series of aniline derivatives provides valuable aminocyclopentenones in high yields

  14. "Click" i polymerer 2

    DEFF Research Database (Denmark)

    Hvilsted, Søren

    2012-01-01

    "Click"-reaktioner til fremstilling af ledende polymerer med funktionelle håndtag og bipolymermaterialer......"Click"-reaktioner til fremstilling af ledende polymerer med funktionelle håndtag og bipolymermaterialer...

  15. Conducting Polymeric Materials

    DEFF Research Database (Denmark)

    Hvilsted, Søren

    2016-01-01

    The overall objective of this collection is to provide the most recent developments within the various areas of conducting polymeric materials. The conductivity of polymeric materials is caused by electrically charged particles, ions, protons and electrons. Materials in which electrons...

  16. Preparation of a poly(3'-azido-3'-deoxythymidine-co-propargyl methacrylate-co-pentaerythritol triacrylate) monolithic column by in situ polymerization and a click reaction for capillary liquid chromatography of small molecules and proteins.

    Science.gov (United States)

    Lin, Zian; Yu, Ruifang; Hu, Wenli; Zheng, Jiangnan; Tong, Ping; Zhao, Hongzhi; Cai, Zongwei

    2015-07-07

    Combining free radical polymerization with click chemistry via a copper-mediated azide/alkyne cycloaddition (CuAAC) reaction in a "one-pot" process, a facile approach was developed for the preparation of a poly(3'-azido-3'-deoxythymidine-co-propargyl methacrylate-co-pentaerythritol triacrylate) (AZT-co-PMA-co-PETA) monolithic column. The resulting poly(AZT-co-PMA-co-PETA) monolith showed a relatively homogeneous monolithic structure, good permeability and mechanical stability. Different ratios of monomers and porogens were used for optimizing the properties of a monolithic column. A series of alkylbenzenes, amides, anilines, and benzoic acids were used to evaluate the chromatographic properties of the polymer monolith in terms of hydrophobic, hydrophilic and cation-exchange interactions, and the results showed that the poly(AZT-co-PMA-co-PETA) monolith exhibited more flexible adjustment in chromatographic selectivity than that of the parent poly(PMA-co-PETA) and AZT-modified poly(PMA-co-PETA) monoliths. Column efficiencies for toluene, DMF, and formamide with 35,000-48,000 theoretical plates per m could be obtained at a linear velocity of 0.17 mm s(-1). The run-to-run, column-to-column, and batch-to-batch repeatabilities of the retention factors were less than 4.2%. In addition, the proposed monolith was also applied to efficient separation of sulfonamides, nucleobases and nucleosides, anesthetics and proteins for demonstrating its potential.

  17. Polymeric reagents

    International Nuclear Information System (INIS)

    Bozkurt, C.

    1979-01-01

    The system polymer-bound triphenyl phosphine/carbon tetrachloride was used for preparation of 14 C-labelled organic compounds. 7- 14 C-benzyl chloride, 7- 14 C-benzoyl chloride and 7- 14 C-N-butyl benzamide have been prepared in this way. The reaction conditions were optimized using inactive compounds. Using the results of this optimization, radiochemical yields of 90% could be obtained for the first time for the preparation of 14 C-labelled alkyl chlorides and carboxylic acid chlorides from the corresponding alcohols and acids on the carrier. Polymer-bound triphenylphosphine was further studied as a catalyst for Beckmann rearrangement on the example of the rearrangement of cyclohexanoneoxime into epsilon-caprolactam. Yields exceeding 90% could be obtained with polymer-bound triphenylphosphine. However, regeneration of the catalyst could only be achieved by the already known method using trichlorosilane, in part also with methyldichlorosilane. Other reducing agents were unsuccessful in regenerating the catalyst. (G.G.)

  18. Polypropylene/graphite nanocomposites by in situ polymerization

    International Nuclear Information System (INIS)

    Milani, Marceo A.; Galland, Giselda B.; Quijada, Raul

    2011-01-01

    This work presents the synthesis of nanocomposites of polypropylene/graphite by in situ polymerization using metallocene catalyst and graphene nanosheets. Initially was analyzed which of the metallocene catalysts rac-Et(Ind) 2 ZrCl 2 or rac-Me 2 Si(Ind) 2 ZrCl 2 produces polypropylene with mechanical properties more relevant. Then it were performed the in situ polymerization reactions to obtain the nanocomposites. The polymeric materials were characterized by XRD, DSC, GPC and DMTA. (author)

  19. Asymmetric Brønsted Acid Catalyzed Substitution of Diaryl Methanols with Thiols and Alcohols for the Synthesis of Chiral Thioethers and Ethers

    KAUST Repository

    Chatupheeraphat, Adisak; Liao, Hsuan-Hung; Mader, Steffen; Sako, Makoto; Sasai, Hiroaki; Atodiresei, Iuliana; Rueping, Magnus

    2016-01-01

    An enantioselective addition of thiols and alcohols to aza-ortho-quinone methides, starting from diaryl methanols, was developed. The asymmetric additions occur under mild reaction conditions in the presence of chiral phosphoric acids and furnish the corresponding adducts with excellent yields and enantioselectivities.

  20. Asymmetric Brønsted Acid Catalyzed Substitution of Diaryl Methanols with Thiols and Alcohols for the Synthesis of Chiral Thioethers and Ethers

    KAUST Repository

    Chatupheeraphat, Adisak

    2016-03-08

    An enantioselective addition of thiols and alcohols to aza-ortho-quinone methides, starting from diaryl methanols, was developed. The asymmetric additions occur under mild reaction conditions in the presence of chiral phosphoric acids and furnish the corresponding adducts with excellent yields and enantioselectivities.

  1. Synthesis of bio-based methacrylic acid by decarboxylation of itaconic acid and citric acid catalyzed by solid transition-metal catalysts

    NARCIS (Netherlands)

    Notre, le J.E.L.; Witte-van Dijk, S.C.M.; Haveren, van J.; Scott, E.L.; Sanders, J.P.M.

    2014-01-01

    Methacrylic acid, an important monomer for the plastics industry, was obtained in high selectivity (up to 84%) by the decarboxylation of itaconic acid using heterogeneous catalysts based on Pd, Pt and Ru. The reaction takes place in water at 200–2508C without any external added pressure, conditions

  2. Amino acid-catalyzed conversion of citral : cis-trans isomerization and its conversion into 6-methyl-5-hepten-2-one and acetaldehyde

    NARCIS (Netherlands)

    Wolken, W.A.M.; Have, R. ten; Werf, M.J. van der

    2000-01-01

    Under alkaline conditions, amino acids or proteins catalyze the deacetylation of citral, a major aroma component, resulting in methylheptenone and acetaldehyde formation. 3-Hydroxycitronellal is an intermediate in this reaction. Amino acids also catalyze the cis-trans isomerization of the pure

  3. A model of frontal polymerization using complex initiation

    Directory of Open Access Journals (Sweden)

    P. M. Goldfeder

    1999-01-01

    Full Text Available Frontal polymerization is a process in which a spatially localized reaction zone propagates into a monomer, converting it into a polymer. In the simplest case of free-radical polymerization, a mixture of monomer and initiator is placed in a test tube. A reaction is then initiated at one end of the tube. Over time, a self-sustained thermal wave, in which chemical conversion occurs, is produced. This phenomenon is possible because of the highly exothermic nature of the polymerization reactions.

  4. Studies on the polymerization of acrolein oxime, 6

    International Nuclear Information System (INIS)

    Masuda, Seizo; Tamai, Harumi; Ota, Tadatoshi; Torii, Munetomo; Tanaka, Masami.

    1979-01-01

    Radiation-induced polymerization and copolymerization of acrolein oxime are investigated in different solvents and at a wide range of temperature for obtaining information on the reaction mechanism. Acrolein oxime is polymerized ionically, irrespective of dryness of the sample. Arrhenius plots for the polymerization rate, which do not yield a linear relation, can be adequately approximated by two straight lines. An anionic mechanism is operative above the room temperature, while a cationic mechanism predominates below -23 0 C. The reaction in the intermediate temperature range proceeds by a competitive mechanism, and the rate of the anionic and cationic polymerizations becomes equal at the temperature near -5 0 C. The reaction rate is proportional to the square root of dose rate at room temperature and -23 0 C. On the basis of these data, it is proposed that the polymerization of acrolein oxime by γ-irradiation proceeds by free-ionic mechanisms. (author)

  5. Synthesis of bio-based methacrylic acid by decarboxylation of itaconic acid and citric acid catalyzed by solid transition-metal catalysts.

    Science.gov (United States)

    Le Nôtre, Jérôme; Witte-van Dijk, Susan C M; van Haveren, Jacco; Scott, Elinor L; Sanders, Johan P M

    2014-09-01

    Methacrylic acid, an important monomer for the plastics industry, was obtained in high selectivity (up to 84%) by the decarboxylation of itaconic acid using heterogeneous catalysts based on Pd, Pt and Ru. The reaction takes place in water at 200-250 °C without any external added pressure, conditions significantly milder than those described previously for the same conversion with better yield and selectivity. A comprehensive study of the reaction parameters has been performed, and the isolation of methacrylic acid was achieved in 50% yield. The decarboxylation procedure is also applicable to citric acid, a more widely available bio-based feedstock, and leads to the production of methacrylic acid in one pot in 41% selectivity. Aconitic acid, the intermediate compound in the pathway from citric acid to itaconic acid was also used successfully as a substrate. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. The synthesis of mono- and diacetyl-9H-fluorenes. Reactivity and selectivity in the Lewis acid catalyzed Friedel-Crafts acetylation of 9H-fluorene

    DEFF Research Database (Denmark)

    Titinchi, Salam J. J.; Kamounah, Fadhil S.; Abbo, Hanna S.

    2008-01-01

    Friedel-Crafts acetylation of 9H-fluorene is an effective route for the preparation of mono- and diacetyl-9H-fluorenes. Using acetylchloride as the reagent and aluminum chloride as the Lewis acid catalyst the effect of the solvent polarity, the temperature, the reaction time and the mode of addit......Friedel-Crafts acetylation of 9H-fluorene is an effective route for the preparation of mono- and diacetyl-9H-fluorenes. Using acetylchloride as the reagent and aluminum chloride as the Lewis acid catalyst the effect of the solvent polarity, the temperature, the reaction time and the mode......,7-diacetyl-9H-fluorene was obtained in 5-11 % yield when carbon disulfide was used as the solvent. Acetylation of 9H-fluorene in dichloroethane and carbon disulfide, using an excess of acetyl chloride and aluminum chloride at reflux temperature, gives 2,7-diacetyl-9H-fluorene exclusively in high yields (> 97...

  7. Catalytic Asymmetric Piancatelli Rearrangement: Brønsted Acid Catalyzed 4π Electrocyclization for the Synthesis of Multisubstituted Cyclopentenones

    KAUST Repository

    Cai, Yunfei

    2016-10-13

    The first catalytic asymmetric Piancatelli reaction is reported. Catalyzed by a chiral Brønsted acid, the rearrangement of a wide range of furylcarbinols with a series of aniline derivatives provides valuable aminocyclopentenones in high yields as well as excellent enantioselectivities and diastereoselectivities. The high value of the aza-Piancatelli rearrangement was demonstrated by the synthesis of a cyclopentane-based hNK1 antagonist analogue.

  8. electrocatalytic reduction of oxygen at vapor phase polymerized poly ...

    African Journals Online (AJOL)

    Preferred Customer

    ABSTRACT. We successfully polymerized poly(3,4-ethylenedioxidethiophene) by vapor phase polymerization technique on rotating glassy carbon disk electrode. The catalytic activity of this electrode towards oxygen reduction reaction was investigated and showed remarkable activity. Rotating disk voltammetry was used to ...

  9. Electrocatalytic reduction of oxygen at vapor phase polymerized ...

    African Journals Online (AJOL)

    We successfully polymerized poly(3,4-ethylenedioxidethiophene) by vapor phase polymerization technique on rotating glassy carbon disk electrode. The catalytic activity of this electrode towards oxygen reduction reaction was investigated and showed remarkable activity. Rotating disk voltammetry was used to study the ...

  10. Polymerization of methyl methacrylate by diphenylamido bis (methylcyclopentadienyl) ytterbium complex

    Institute of Scientific and Technical Information of China (English)

    WANG, Yao-Rong(王耀荣); SHEN, Qi(沈琪); MA, Jia-Le(马家乐); ZHAO, Qun(赵群)

    2000-01-01

    Methyl methacrylate (MMA) was effectively polymerized by diphenylamido bis(methyicyclopentadienyl) ytterbium complex (MeCp)2YbNPh2(THF). Tne reaction can be carried out over a range of polymerization temperature from - 40℃ to 40℃ and gives the polyMMA with high molecular weights.The initiation mechanism was demonstrated by diphenylamidoterminated methyl methacrylate oligomer.

  11. Chain chemical reactions during matrix devitrification

    International Nuclear Information System (INIS)

    Barkalov, I.M.

    1980-01-01

    Investigation results of chain reaction mechanisms, proceeding at devitrification of glass-like matrices under the effect of γ-irradiation are summarized. Peculiarities of kinetics and mechanism of chain reactions proceeding at devitrification are considered: hydrocarbon chlorination, polymerization of vinyl monomers, copolymerization and graft polymerization. Possible application aspects of the chain reaction conducting during matrix devitrification are also considered

  12. Biocompatible Polymeric Materials Intended for Drug Delivery and Therapeutic Applications

    DEFF Research Database (Denmark)

    Hvilsted, Søren; Javakhishvili, Irakli; Bednarek, Melania

    2007-01-01

    of polymer blocks by “click chemistry”. An all polymerization strategy would imply preparing polymers by living/controlled techniques in such a manner that one block after polymerization can be converted to a macroinitiator enabling the second block to polymerize. The coupling strategy invariably inserts...... a linking unit, 1,4-triazol, resulting from the catalyzed, irreversible 1,3-dipolar cycloaddition reaction between an alkyne and an azide. Thus, this strategy necessitates the proper end functionalization of the polymeric building blocks. Fortunately the 1,4-triazol unit is FDA approved already existing...

  13. Polymerization Using Phosphazene Bases

    KAUST Repository

    Zhao, Junpeng

    2015-09-01

    In the recent rise of metal-free polymerization techniques, organic phosphazene superbases have shown their remarkable strength as promoter/catalyst for the anionic polymerization of various types of monomers. Generally, the complexation of phosphazene base with the counterion (proton or lithium cation) significantly improves the nucleophilicity of the initiator/chain end resulting in highly enhanced polymerization rates, as compared with conventional metalbased initiating systems. In this chapter, the general features of phosphazenepromoted/catalyzed polymerizations and the applications in macromolecular engineering (synthesis of functionalized polymers, block copolymers, and macromolecular architectures) are discussed with challenges and perspectives being pointed out.

  14. Polymerization of epoxidized triglycerides with fluorosulfonic acid

    Science.gov (United States)

    The use of triglycerides as agri-based renewable raw materials for the development of new products is highly desirable in view of uncertain future petroleum prices. A new method of polymerizing epoxidized soybean oil has been devised with the use of fluorosulfonic acid. Depending on the reaction con...

  15. Pressure-induced polymerization of phenoxyethyl acrylate

    Energy Technology Data Exchange (ETDEWEB)

    Kaminski, K; Wrzalik, R; Paluch, M; Ziolo, J [Institute of Physics, Silesian University, Uniwersytecka 4, 40-007 Katowice (Poland); Roland, C M [Naval Research Laboratory, Chemistry Division, Code 6120, Washington, DC 20375-5342 (United States)

    2008-06-18

    Polymerization of phenoxyethyl acrylate was induced without catalyst or initiators by the application of hydrostatic pressure at elevated temperature. Broadband dielectric and infrared spectroscopy were employed to follow the course of the reaction, which reached a degree of conversion of 60%. The structure of the obtained polymer was determined from density functional theory calculations.

  16. Anionic PPV polymerization from the sulfinyl precursor route : Block copolymer formation from sequential addition of monomers

    NARCIS (Netherlands)

    Cosemans, Inge; Vandenbergh, Joke; Voet, Vincent S. D.; Loos, Katja; Lutsen, Laurence; Vanderzande, Dirk; Junkers, Thomas

    2013-01-01

    The sulfinyl precursor route for the synthesis of poly(p-phenylene vinylene) (PPV) materials via an anionic polymerization procedure employing dedicated initiators is evaluated in depth. Reaction kinetics are investigated to gain more control over the polymerization, since polymerization proceeds to

  17. Chemo-enzymatic synthesis of furfuralcohol from chestnut shell hydrolysate by a sequential acid-catalyzed dehydration under microwave and Escherichia coli CCZU-Y10 whole-cells conversion.

    Science.gov (United States)

    Di, Junhua; Ma, Cuiluan; Qian, Jianghao; Liao, Xiaolong; Peng, Bo; He, Yucai

    2018-08-01

    In this study, chemo-enzymatic synthesis of furfuralcohol from biomass-derived xylose was successfully demonstrated by a sequential acid-catalyzed dehydration under microwave and whole-cells reduction. After dry dewaxed chestnut shells (CNS, 75 g/L) was acid-hydrolyzed with dilute oxalic acid (0.5 wt%) at 140 °C for 40 min, the obtained CNS-derived xylose (17.9 g/L xylose) could be converted to furfural at 78.8% yield with solid acid SO 4 2- /SnO 2 -Attapulgite (2.0 wt% catalyst loading) in the dibutyl phthalate-water (1:1, v:v) under microwave (600 W) at 180 °C for 10 min. In the dibutyl phthalate-water (1:1, v/v) media at 30 °C and pH 6.5, the furfural liquor (47.0 mM furfural) was biologically converted to furfuralcohol by recombinant Escherichia coli CCZU-Y10 whole-cells harboring an NADH-dependent reductase (PgCR) without extra addition of NAD + and glucose, and furfural was completely converted to furfuralcohol after 2.5 h. Clearly, this one-pot synthesis strategy can be effectively used for furfuralcohol production. Copyright © 2018 Elsevier Ltd. All rights reserved.

  18. Catalytic Asymmetric Total Synthesis of (+)- and (-)-Paeoveitol via a Hetero-Diels-Alder Reaction.

    Science.gov (United States)

    Li, Tian-Ze; Geng, Chang-An; Yin, Xiu-Juan; Yang, Tong-Hua; Chen, Xing-Long; Huang, Xiao-Yan; Ma, Yun-Bao; Zhang, Xue-Mei; Chen, Ji-Jun

    2017-02-03

    The first catalytic asymmetric total synthesis of (+)- and (-)-paeoveitol has been accomplished in 42% overall yield via a biomimetic hetero-Diels-Alder reaction. The chiral phosphoric acid catalyzed hetero-Diels-Alder reaction showed excellent diastereo- and enantioselectivity (>99:1 dr and 90% ee); two rings and three stereocenters were constructed in a single step to produce (-)-paeoveitol on a scale of 452 mg. This strategy enabled us to selectively synthesize both paeoveitol enantiomers from the same substrates by simply changing the enantiomer of the catalyst.

  19. Highly enantioselective access to cannabinoid-type tricyles by organocatalytic Diels–Alder reactions

    Directory of Open Access Journals (Sweden)

    Stefan Bräse

    2012-08-01

    Full Text Available After prosperous domino reactions towards benzopyrans, the products were used as the starting material in Lewis acid catalyzed and organocatalytic Diels–Alder reactions to build up a tricyclic system. Herein, an asymmetric induction up to 96% enantiomeric excess was obtained by the use of imidazolidinone catalysts. This approach can be utilized to construct the tricyclic system in numerous natural products, in particular the scaffold of tetrahydrocannabinol (THC being the most representative one. Compared with other published methods, condensation with a preexisting cyclohexane moiety in the precursor is needed to gain the heterogenic tricycle systems, whereas we present a novel strategy towards cannabinoid derivatives based on a flexible modular synthesis.

  20. Polymerization of N-(fluoro phenyl) maleimides

    International Nuclear Information System (INIS)

    Barrales-Rienda, J.M.; Ramos, J.G.; Chaves, M.S.

    1979-01-01

    Poly(N-aryl maleimide)s of characteristic structures have been synthesized and some of their physical properties studied. The polymerization of N-(fluoro phenyl) maleimides by free-radical initiation in bulk or in solution and by anionic catalyst have been studied to compare the characteristics of polymerization by γ-ray irradiation with that by free-radical initiation. The polymers were characterized by elemental analysis, intrinsic viscosity, spectroscopy (IR and NMR), programmed thermogravimetric analysis, and x-ray diffraction. Spectra of polymers prepared by radiation and anionic polymerization were nearly identical with those of polymers prepared by free-radical polymerization initiated by azobisisobutyronitrile in bulk or in solution and by the self-initiated thermal polymerization. A variety of reaction conditions were tried, but all attempts to change the molecular structure of the polymers were unsuccessful. Rates of thermal degradation for poly[N-(fluoro phenyl) maleimide]s have been analyzed by using a multiple-heating-rate procedure. Overall activation energy, order of reaction, and frequency factor have been evaluated. 6 figures, 8 tables

  1. Application of Carbohydrate-Templated Asymmetric Diels-Alder Reaction to the Syntheses of ent-Penicillones A and B.

    Science.gov (United States)

    Weng, Chia-Hao; Hsu, Day-Shin; Liao, Chun-Chen

    2016-11-18

    Total syntheses of ent-penicillones A (ent-1) and B (ent-2) from 3,5-dimethylcatechol (3) were accomplished in 10 and 9 synthetic steps, respectively. A carbohydrate-templated asymmetric intramolecular Diels-Alder reaction of a masked o-benzoquinone (MOB) 9 and an aqueous acid-catalyzed intramolecular aldol reaction are the key synthetic steps. In addition, the absolute configurations of the bicyclo[2.2.2]oct-5-en-2-one core obtained from the per-O-benzylated α-d-glucopyranosyl as a carbohydrate template in the intramolecular Diels-Alder reaction of MOBs were revised.

  2. Developing thin-film-composite forward osmosis membranes on the PES/SPSf substrate through interfacial polymerization

    KAUST Repository

    Wang, Kaiyu; Chung, Tai Shung Neal; Amy, Gary L.

    2011-01-01

    A new scheme has been developed to fabricate high-performance forward osmosis (FO) membranes through the interfacial polymerization reaction on porous polymeric supports. p-Phenylenediamine and 1,3,5-trimesoylchloride were adopted as the monomers

  3. NATO Advanced Study Institute on Ring-opening Metathesis Polymerization of Olefins and Polymerization of Alkynes

    CERN Document Server

    1998-01-01

    The first NATO Advanced Study Institute on Olefin Metathesis and Polymerization Catalysts was held on September 10-22, 1989 in Akcay, Turkey. Based on the fundamental research of RRSchrock, RGrubbs and K.B.Wagener in the field of ring opening metathesis polymerization (ROMP), acyclic diene metathesis (ADMET) and alkyne polymerization, these areas gained growing interest within the last years. Therefore the second NATO-ASI held on metathesis reactions was on Ring Opening Metathesis Po­ lymerization of Olefins and Polymerization of Alkynes on September 3-16, 1995 in Akcay, Turkey. The course joined inorganic, organic and polymer chemists to exchange their knowledge in this field. This volume contains the main and short lectures held in Akcay. To include ADMET reactions better into the title of this volume we changed it into: Metathesis Polymerization of Olefins and Alkyne Polymerization. This volume is addressed to research scientists, but also to those who start to work in the area of olefin metathesis and al...

  4. Applied bioactive polymeric materials

    CERN Document Server

    Carraher, Charles; Foster, Van

    1988-01-01

    The biological and biomedical applications of polymeric materials have increased greatly in the past few years. This book will detail some, but not all, of these recent developments. There would not be enough space in this book to cover, even lightly, all of the major advances that have occurred. Some earlier books and summaries are available by two of this book's Editors (Gebelein & Carraher) and these should be consul ted for additional information. The books are: "Bioactive Polymeric Systems" (Plenum, 1985); "Polymeric Materials In Medication" (Plenum, 1985); "Biological Acti vi ties of Polymers" (American Chemical Society, 1982). Of these three, "Bioacti ve Polymeric Systems" should be the most useful to a person who is new to this field because it only contains review articles written at an introductory level. The present book primarily consists of recent research results and applications, with only a few review or summary articles. Bioactive polymeric materials have existed from the creation of life...

  5. Carboxyl-Functionalized Polymeric Microspheres Prepared by One-Stage Photoinitiated RAFT Dispersion Polymerization

    Directory of Open Access Journals (Sweden)

    Jianbo Tan

    2017-12-01

    Full Text Available Herein, we report a photoinitiated reversible addition-fragmentation chain transfer (RAFT dispersion copolymerization of methyl methacrylate (MMA and methyl methacrylic (MAA for the preparation of highly monodisperse carboxyl-functionalized polymeric microspheres. High rates of polymerization were observed, with more than 90% particle yields being achieved within 3 h of UV irradiation. Effects of reaction parameters (e.g., MAA concentration, RAFT agent concentration, photoinitiator concentration, and solvent composition were studied in detail, and highly monodisperse polymeric microspheres were obtained in most cases. Finally, silver (Ag composite microspheres were prepared by in situ reduction of AgNO3 using the carboxyl-functionalized polymeric microspheres as the template. The obtained Ag composite microspheres were able to catalyze the reduction of methylene blue (MB with NaBH4 as a reductant.

  6. Experimental study of living free radical polymerization using trifunctional initiator and polymerization mediated by nitroxide

    International Nuclear Information System (INIS)

    Galhardo, Eduardo; Lona, Liliane M.F.

    2009-01-01

    Controlled free radical polymerization or living free radical polymerization has received increasing attention as a technique for the production of polymers with microstructure highly controlled. In particular, narrow molecular weight distributions are obtained with polydispersity very close to one. In this research it was investigate the controlled polymerization mediated by nitroxide, using a cyclic trifunctional peroxide. As long as we know, there are only publications in literature dealing with NMRP using mono- and bi-functional initiators. It was believed that the trifunctional peroxide can increase the rate of polymerization, since more free radicals are generated, if compared with initiators with lower functionality. Furthermore, the fact of the initiator be cyclic means that branches are not generated in the chains, which theoretically prevents an increase in polydispersity of the polymer. The effect of the dissociation constant of the trifunctional initiator in the velocity of the reaction was analyzed. (author)

  7. Introduction to chemical reaction engineering

    International Nuclear Information System (INIS)

    Kim, Yeong Geol

    1990-10-01

    This deals with chemical reaction engineering with thirteen chapters. The contents of this book are introduction on reaction engineering, chemical kinetics, thermodynamics and chemical reaction, abnormal reactor, non-isothermal reactor, nonideal reactor, catalysis in nonuniform system, diffusion and reaction in porosity catalyst, design catalyst heterogeneous reactor in solid bed, a high molecule polymerization, bio reaction engineering, reaction engineering in material process, control multi-variable reactor process using digital computer.

  8. Studies on radiation-induced graft polymerization

    International Nuclear Information System (INIS)

    Omichi, Hideki

    1978-09-01

    Radiation-induced graft polymerization is used extensively to improve physical properties of polymers, but few processes are now commercialized. The reason for this is partly inadequate basic research on the reaction and partly the difficulty in developing the grafting process with large radiation source. Firstly, new techniques are proposed of studying kinetics of the graft polymerization in heterogeneous system. Based on the grafting yield, the molecular weight of graft chains, and the amount of radicals given by ESR and activation analysis, kinetic parameters are obtained and the reaction mechanism of grafting process is discussed. Secondly, the development of grafting process of poly (vinyl chloride)-butadiene is described. By study of the reaction, process design, construction and operation of the pilot plant, and economic analysis of the process, this process with 60 Co gamma ray sources is shown to be industrially promising. (author)

  9. Polymeric bicontinuous microemulsions

    DEFF Research Database (Denmark)

    Bates, F.S.; Maurer, W.W.; Lipic, P.M.

    1997-01-01

    High molecular weight block copolymers can be viewed as macromolecular surfactants when blended with thermodynamically incompatible homopolymers. This Letter describes the formation of polymeric bicontinuous microemulsions in nurtures containing a model diblock copolymer and two homopolymers. Alt...

  10. Polymerization Using Phosphazene Bases

    KAUST Repository

    Zhao, Junpeng; Hadjichristidis, Nikolaos; Schlaad, Helmut

    2015-01-01

    . In this chapter, the general features of phosphazenepromoted/catalyzed polymerizations and the applications in macromolecular engineering (synthesis of functionalized polymers, block copolymers, and macromolecular architectures) are discussed with challenges

  11. Chelating polymeric membranes

    KAUST Repository

    Peinemann, Klaus-Viktor

    2015-01-22

    The present application offers a solution to the current problems associated with recovery and recycling of precious metals from scrap material, discard articles, and other items comprising one or more precious metals. The solution is premised on a microporous chelating polymeric membrane. Embodiments include, but are not limited to, microporous chelating polymeric membranes, device comprising the membranes, and methods of using and making the same.

  12. Reaction kinetics of polybutylene terephthalate polycondensation reaction

    NARCIS (Netherlands)

    Darda, P. J.; Hogendoorn, J. A.; Versteeg, G. F.; Souren, F.

    2005-01-01

    The kinetics of the forward polycondensation reaction of polybutylene terephthalate (PBT) has been investigated using thermogravimetric analysis (TGA). PBT - prepolymer with an initial degree of polymerization of 5.5 was used as starting material. The PBT prepolymer was prepared from dimethyl

  13. Iptycene synthesis: A new method for attaching a 2,3-anthracene moiety to the 9,10-positions of another anthracene moiety - Exceptional conditions for a Lewis acid catalyzed Diels-Alder reaction

    Science.gov (United States)

    Chen, Yong-Shing; Hart, Harold

    1989-01-01

    An efficient three-step method for appending a 2,3-anthracene moiety to the 9,10-positions of an existing anthracene moiety is described. The first step uses excess 1,4-anthraquinone (3 equiv) and aluminum chloride (6 equiv) to obtain the anthracene-quinone cycloadduct (omission of the AlCl3 resulted in no adduct). The resulting diketone was reduced to the corresponding diol (excess LiAlH4), which was dehydrated to the arene with phosphorus oxychloride and pyridine. Specific examples include the preparation of heptipycene 8 from pentiptycene 6 (66 percent overall yield) and a similar conversion of 8 to the noniptycene 13 (75 percent overall yield). The methodology led to a markedly improved synthesis of tritriptycene 9 and the first synthesis of undecaiptycene 14.

  14. Radiation induced emulsion polymerization

    International Nuclear Information System (INIS)

    Stannett, V.T.; Stahel, E.P.

    1990-01-01

    High energy radiation is particularly favored for the initiation of emulsion polymerization. The yield of free radicals, for example, from the radiolysis of the aqueous phase, is high; G(radical) values of 5-7. In addition, the rather special kinetics associated with emulsion polymerization lead, in general, to very large kinetic chain lengths, even with 'non-ideal' monomers such as vinyl acetate. Together, high polymerization rates at low doses become possible. There are some important advantages of radiation polymerization compared with chemical initiators, such as potassium persulfate. Perhaps the most important among them is the temperature independence of the initiation step. This makes low temperature polymerization very accessible. With monomers such as vinyl acetate, where chain termination to monomer is predominant, low temperatures lead to often highly desirable higher molecular weights. With styrene, the classical ideally behaved monomer, there are the advantages such as, for example, the feasibility of using cationic monomers. These and some attendant disadvantages are discussed in detail, including pilot plant studies

  15. Biodiesel forming reactions using heterogeneous catalysis

    Science.gov (United States)

    Liu, Yijun

    other comparisons between the catalytic behaviors of liquid and solid acids suggests a common mode of operation of their Bronsted acid sites in carrying out esterification of a carboxylic acid with alcohol. The hypothesized Eley-Rideal type heterogeneous reaction mechanism involving a nucleophilic attack between adsorbed carboxylic acid and unadsorbed alcohol as the rate-limiting step was found to fit well the experimental observations and successfully predict the esterification rate obtained with SAC-13 as reaction progresses. The SAC-13 catalysis assay was also extended to carboxylic acids of higher molecular weights. A set of carboxylic acids with various alkyl chain lengths was used to investigate the structural effect of reacting carboxylic acids on heterogeneous catalyzed esterification. It was found that the reactivity of carboxylic acids was controlled by steric factors as the alkyl chain linearly lengthened. Despite their increased hydrophobicity, large carboxylic acids hardly impacted the deactivating effect of water on Bronsted acid sites. However, catalyst reusability and regeneration showed significant dependency on the size of the carboxylic acid used. With the use of larger reacting carboxylic acids, SAC-13 underwent more significant activity loss in consecutive reaction cycles due to stronger adsorption of the larger organics in the polymeric domains of the Nafion resin. In parallel to the research activity on acid catalyzed esterification, the use of strong solid bases with organic functionality (quarternary ammonium, QN+) was investigated from a fundamental perspective. Using triacetin as a model compound for TG molecules, the effectiveness of this Bronsted base functionality in transesterification was demonstrated even at mild reaction conditions. But its catalytic behavior including catalyst selectivity and deactivation was significantly affected by the nature of the adopted support. A purposive design of the immobilizing matrix is expected to

  16. Radiation-induced polymerization and radiation effect on polymers

    International Nuclear Information System (INIS)

    Seguchi, Tadao

    1977-12-01

    The processes of radiation-induced polymerization of monomers and also radiation effects on polymers have been studied by instrumental analyses of electron spin resonance (ESR), nuclear magnetic resonance (NMR) and electron microscopy. In radiation-induced polymerization, graft-copolymerization and absorbed state polymerization were taken up. For graft-copolymerization, monomers such as methylmethacrylate and butadiene were made to react with irradiated polyethylene, and behaviors of the initiating radicals and propagating radicals were followed under the reaction by ESR. For absorbed state polymerization, acrylonitrile/zeolite and methylmethacrylate/zeolite were chosen. Absorbed monomers were irradiated at 77 0 K and polymerized at room temperature. Active species and the concentrations were measured by ESR and the yields of polymer were observed by NMR. In radiation effect on polymers, polyvinylfluoride, polyvinylidenfluoride and polytetrafluoroethylene were taken up. Active species trapped in the polymer matrixes were identified and decay and reactivity of the species were also studied. On the basis of information from the electron microscopy and x-ray analysis, radiation effects on these polymers are described. In polytetrafluoroethylene produced by radiation polymerization, the relation between morphology and polymerization conditions and also the process of crystallization during polymerization were studied. (auth.)

  17. Allylthioketone Mediated Free Radical Polymerization of Methacrylates

    Directory of Open Access Journals (Sweden)

    Feng Zhong

    2017-11-01

    Full Text Available By combination of high trapping free radical efficiency of the thioketone and resonance of the allylic radical, a new type of mediating agent, 1,3,3-triphenylprop-2-ene-1-thione (TPPT has been successfully synthesized, and then is used to study controlled free radical polymerization of methacrylates. Very stable TPPT radicals at the end of poly(methyl methacrylate (PMMA are detected in the polymerization of MMA using TPPT and AIBN as the control agent and initiator. The MALDI-TOF MS spectra are used to identify terminal groups of the resultant poly(glycidyl methacrylate (PGMA, and major component of the obtained polymer has the structure, (CH32(CNC-PGMA-C7H9O3. Chain extension reaction tests ascertain formation of the dead polymers during the polymer storage and purification process of the polymers. Owing to very slow fragmentation reaction of the TPPT-terminated polymethacrylate radical and addition reaction of this radical with a primary radical, the growing chain radicals are difficult to be regenerated, leading to an unobvious change of the molecular weight with monomer conversion. The molecular weights of polymers can be controlled by the ratios of monomer/initiator and TPPT/initiator. However, the first order kinetics of the polymerization and the polymers with narrow polydispersity are obtained, and these phenomena are discussed. This study provides useful information on how to design a better controlling agent.

  18. Plasma polymerization by Softplasma

    DEFF Research Database (Denmark)

    Jiang, J.; Wu, Zhenning; Benter, Maike

    2008-01-01

    , external electrode, and electrodeless microwave or high frequency reactors. [3] Softplasma™ is an internal electrode plasma setup powered by low frequenc~ gower supply. It was developed in late 90s for surface treatment of silicone rubber. [ ]- 5] It is a low pressure, low electron density, 3D homogenous......In the late 19th century, the first depositions - known today as plasma polymers, were reported. In the last century, more and more research has been put into plasma polymers. Many different deposition systems have been developed. [1, 2] Shi F. F. broadly classified them into internal electrode...... plasma. In this study, we are presenting the surface modification"pf polymers by plasma polymerization using Softplasma™. Softplasma™ can be used for two major types of polymerization: polymerization of vinyl monomers, where plasma acts as initiator; chemical vapour deposition, where plasma acts...

  19. Recent progress of atomic layer deposition on polymeric materials

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Hong Chen; Ye, Enyi [Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), 2 Fusionopolis Way, Innovis, #08-03, Singapore 138634 (Singapore); Li, Zibiao, E-mail: lizb@imre.a-star.edu.sg [Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), 2 Fusionopolis Way, Innovis, #08-03, Singapore 138634 (Singapore); Han, Ming-Yong [Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), 2 Fusionopolis Way, Innovis, #08-03, Singapore 138634 (Singapore); Loh, Xian Jun, E-mail: lohxj@imre.a-star.edu.sg [Institute of Materials Research and Engineering, A*STAR (Agency for Science, Technology and Research), 2 Fusionopolis Way, Innovis, #08-03, Singapore 138634 (Singapore); Department of Materials Science and Engineering, National University of Singapore, Singapore 117574 (Singapore); Singapore Eye Research Institute, 20 College Road, Singapore 169856 (Singapore)

    2017-01-01

    As a very promising surface coating technology, atomic layer deposition (ALD) can be used to modify the surfaces of polymeric materials for improving their functions and expanding their application areas. Polymeric materials vary in surface functional groups (number and type), surface morphology and internal structure, and thus ALD deposition conditions that typically work on a normal solid surface, usually do not work on a polymeric material surface. To date, a large variety of research has been carried out to investigate ALD deposition on various polymeric materials. This paper aims to provide an in-depth review of ALD deposition on polymeric materials and its applications. Through this review, we will provide a better understanding of surface chemistry and reaction mechanism for controlled surface modification of polymeric materials by ALD. The integrated knowledge can aid in devising an improved way in the reaction between reactant precursors and polymer functional groups/polymer backbones, which will in turn open new opportunities in processing ALD materials for better inorganic/organic film integration and potential applications. - Highlights: • ALD deposition on different natural and synthetic polymer materials • Reaction mechanism based on the surface functional groups of polymers • Application of ALD-modified polymers in different fields.

  20. Formation and reactions of radical cations of substituted benzenes in aqueous media

    International Nuclear Information System (INIS)

    Holcman, J.

    1977-08-01

    Radical cations of anisole, methylated benzenes, ethylbenzene, isopropylbenzene, tert-butylbenzene and N,N-dimethylaniline were studied in aqueous media by pulse radiolytic technique. Absorption spectra and reaction kinetics of the radical cations were recorded. The radical cations are formed from the corresponding OH adducts by the elimination of OH - , either by a simple dissociation or by an acid catalyzed reaction. The rate constants of the formation of the radical cations and their reactions with water, OH - and Fe 2+ , or the reaction of a proton loss, were measured. The rate constants for the reaction with water and OH - , together with the rate constants for the dissociation of the OH adducts, are correlated with the ionization potential of the parent compound. These correlations offer a possibility of predicting the acid-base properties of radical cations of substituted benzenes, or the estimation of their ionization potential. (author)

  1. Inflation of a Polymeric Menbrane

    DEFF Research Database (Denmark)

    Kristensen, Susanne B.; Larsen, Johannes R.; Hassager, Ole

    1998-01-01

    We consider an axisymmetric polymeric membrane inflated by a uniform pressure difference acting across the membrane.......We consider an axisymmetric polymeric membrane inflated by a uniform pressure difference acting across the membrane....

  2. Scale-up of microwave-assisted polymerizations in continuous-flow mode : cationic ring-opening polymerization of 2-ethyl-2-oxazoline

    NARCIS (Netherlands)

    Paulus, R.M.; Erdmenger, T.; Becer, C.R.; Hoogenboom, R.; Schubert, U.S.

    2007-01-01

    Microwave-assisted polymerizations is a growing field of interest because the use of microwave irradiation instead of thermal heating was demonstrated to result in faster, cleaner, and higher yielding reactions. To overcome the one-at-a-time nature of preparing polymerizations in single microwave

  3. Polymerized and functionalized triglycerides

    Science.gov (United States)

    Plant oils are useful sustainable raw materials for the development of new chemical products. As part of our research emphasis in sustainability and green polymer chemistry, we have explored a new method for polymerizing epoxidized triglycerides with the use of fluorosulfonic acid. Depending on the ...

  4. Polymerization by radiation. Application

    International Nuclear Information System (INIS)

    Romero, M.; Fernandez Miranda, J.

    1997-01-01

    Achieved results of the research work done in the field of radiation polymerization are summarized. Developing new chromatographic matrices, the radiation grafting of Glycidyl methacrylate on the surface of Low Density Polyethylene beads was studied. The dependence of both, the grafted degree and width of the grafted layer, with the radiation dose applied, is presented

  5. RAFT polymerization mediated bioconjugation strategies

    OpenAIRE

    Bulmuş, Volga

    2011-01-01

    This review aims to highlight the use of RAFT polymerization in the synthesis of polymer bioconjugates. It covers two main bioconjugation strategies using the RAFT process: (i) post-polymerization bioconjugations using pre-synthesized reactive polymers, and (ii) bioconjugations via in situ polymerization using biomolecule-modified monomers or chain transfer agents. © 2011 The Royal Society of Chemistry.

  6. Metal-catalyzed living radical polymerization and radical polyaddition for precision polymer synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Mizutani, M; Satoh, K [Department of Applied Chemistry, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603 (Japan); Kamigaito, M, E-mail: kamigait@apchem.nagoya-u.ac.j

    2009-08-01

    The metal-catalyzed radical addition reaction can be evolved into two different polymerization mechanisms, i.e.; chain- and step-growth polymerizations, while both the polymerizations are based on the same metal-catalyzed radical formation reaction. The former is a widely employed metal-catalyzed living radical polymerization or atom transfer radical polymerization of common vinyl monomers, and the latter is a novel metal-catalyzed radical polyaddition of designed monomer with an unconjugated C=C double bond and a reactive C-Cl bond in one molecule. The simultaneous ruthenium-catalyzed living radical polymerization of methyl acrylate and radical polyaddition of 3-butenyl 2-chloropropionate was achieved with Ru(Cp*)Cl(PPh{sub 3}){sub 2} to afford the controlled polymers, in which the homopolymer segments with the controlled chain length were connected by the ester linkage.

  7. One-Pot Synthesis of N-(α-Peroxy)Indole/Carbazole via Chemoselective Three-Component Condensation Reaction in Open Atmosphere

    KAUST Repository

    Wang, Xinbo

    2015-11-06

    A facile one-pot synthesis of N-(α-peroxy)indole and N-(α-peroxy)carbazole has been developed using metal-free, organo-acid-catalyzed three-component condensation reactions of indole/carbazole, aldehyde, and peroxide. Based on the reaction discovered, a new synthetic proposal for Fumitremorgin A and Verruculogen is introduced. Such a protocol could be easily handled and scaled up in an open atmosphere with a wide substrate scope, enabling the construction of a new molecule library.

  8. Radiation polymerization of tetrafluoroethylene in freon-22

    International Nuclear Information System (INIS)

    Schnautz, N.G.; Thompson, J.C.

    1979-02-01

    The radiation-induced solution-polymerization of tetrafluoroethylene in Freon-22 has been investigated over a temperature range of - 62 degrees celcius to 0 degrees celcius. The rate of polymerization for the in-source process was found to be directly propertional to monomer concentration and an activation energy of only 7,66 kj/mole was calculated. The number-average molecular mass of the product PTFE ranged from 2X10 4 to 6X10 4 and was relatively independent of the usual reaction parameters. The rate of postpolymerization was also found to be directly proportional to monomer concentration. The postpolyerization process did not result in any enchancement of the initial PTFE molecular mass [af

  9. Radiation-induced polymerization of hydrogen cyanide

    International Nuclear Information System (INIS)

    Mozhaev, P.S.; Kichigina, G.A.; Kiryukhin, D.P.

    1995-01-01

    The chain reaction of HCN polymerization in a γ-radiation field does not occur at 77 K. When irradiated HCN is warmed up to ambient temperature, a polymer is formed. The heat of polymerization of HCN is 44.0±6.0 kJ/mol and the polymer yield reaches 2.5% for a dose of 725 kGy. Amorphous polymer products (with yields increasing up to 33.5%) and needle crystals (presumably HCN tetramer) are formed upon storage of irradiated HCN at room temperature. The polymer is stable below 700 K, has a conductivity of 3x10 -5 Ω -1 cm -f1 , and displays an EPR spectrum typical of polyconjugated systems. A radical mechanism of the formation of conjugated chain -C=N-C=N- is suggested. The tetramer is produced by a combination of aminocyanocarbene biradicals

  10. RAFT polymerization and some of its applications.

    Science.gov (United States)

    Moad, Graeme; Rizzardo, Ezio; Thang, San H

    2013-08-01

    Reversible addition-fragmentation chain transfer (RAFT) is one of the most robust and versatile methods for controlling radical polymerization. With appropriate selection of the RAFT agent for the monomers and reaction conditions, it is applicable to the majority of monomers subject to radical polymerization. The process can be used in the synthesis of well-defined homo-, gradient, diblock, triblock, and star polymers and more complex architectures, which include microgels and polymer brushes. In this Focus Review we describe how the development of RAFT and RAFT application has been facilitated by the adoption of continuous flow techniques using tubular reactors and through the use of high-throughput methodology. Applications described include the use of RAFT in the preparation of polymers for optoelectronics, block copolymer therapeutics, and star polymer rheology control agents. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Reversible and Irreversible Binding of Nanoparticles to Polymeric Surfaces

    Directory of Open Access Journals (Sweden)

    Wolfgang H. Binder

    2009-01-01

    Full Text Available Reversible and irreversible binding of CdSe-nanoparticles and nanorods to polymeric surfaces via a strong, multiple hydrogen bond (= Hamilton-receptor/barbituric acid is described. Based on ROMP-copolymers, the supramolecular interaction on a thin polymer film is controlled by living polymerization methods, attaching the Hamilton-receptor in various architectures, and concentrations. Strong binding is observed with CdSe-nanoparticles and CdSe-nanorods, whose surfaces are equipped with matching barbituric acid-moieties. Addition of polar solvents, able to break the hydrogen bonds leads to the detachment of the nanoparticles from the polymeric film. Irreversible binding is observed if an azide/alkine-“click”-reaction is conducted after supramolecular recognition of the nanoparticles on the polymeric surface. Thus reversible or irreversible attachment of the nanosized objects can be achieved.

  12. 13C Kinetic isotopic effect of polymerization on monomers with multiple bond

    International Nuclear Information System (INIS)

    Berman, E.L.; Polyakov, V.B.; Makovetskij, K.L.; Golenko, T.G.; Galimov, Eh.M.; AN SSSR, Moscow. Inst. Organicheskoj Khimii; AN SSSR, Moscow. Inst. Geokhimii i Analiticheskoj Khimii)

    1988-01-01

    13 C kinetic isotopic effect (KIE) of anionic and radical polymerization and metathesis reaction of monomers with multiple bonds are studied and correlation between the found KIE values of polymerization and the structure of transition state is established. 13 C KIE of polymerization reactions are investigated using monomers with natural content of the isotope. Polymerization was carried out using high-vacuum equipment: radical polymerization of methyl acrylate (MA) and vinyl acetate in benzene solution under the effect of benzoyl peroxide (60 deg C); anionic polymerization of MA, initiated by potassium butyl cellosolvolate, was realized in mass at 25 deg C; cyclopentene metathesis reaction was conducted in benzene under the effect of initiating system WCl 6 - (C 3 H 5 ) 2 Si(CH 3 ) 2 at -30 deg C; phenylacetylene polymers were prepared by polymerization in benzene solution at 20 deg C under the effect of WCl 6 . It is ascertained that 13 C KIE of radical and anionic polymerization of olefins and cycloolefin metathesis constitutes 2.0 -2.4%. Polymerization of compound with ternary bond is accompanied by a lower value of 13 C KIE (<1%), which is explained by double bond of reacting bond in transition state

  13. Modeling of free radical polymerization up to high conversion. II. Development of a mathematical model.

    NARCIS (Netherlands)

    Tefera shibeshe, N.; Tefera, N.; Weickert, G.; Westerterp, K.R.

    1997-01-01

    In free radical polymerization diffusion-controlled processes take place simultaneously to the normal chemical reactions. Despite extensive efforts to model such processes a consistent model for the design of a polymerization reactor has not yet been established. In this article a semiempirical

  14. The effect of ethanol on the γ radiation induced polymerization of styrene

    International Nuclear Information System (INIS)

    Zhang Xujia; Ha Hongfei; Wu Jilan

    1990-01-01

    The γ radiation induced polymerization of styrene in the presence of ethanol was studied at dose rate of 5 x 10 17 eV/ml min. The result showed that the radiation induced polymerization of styrene was sensitized by ethanol. The experimental results were in agreement with the theoretical calculation of WAS equation. The mechanism of sensitization was proposed as proton transfer reaction

  15. Simulation of styrene polymerization reactors: kinetic and thermodynamic modeling

    Directory of Open Access Journals (Sweden)

    A. S. Almeida

    2008-06-01

    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.

  16. Packaging based on polymeric materials

    Directory of Open Access Journals (Sweden)

    Jovanović Slobodan M.

    2005-01-01

    Full Text Available In the past two years the consumption of common in the developed countries world wide (high tonnage polymers for packaging has approached a value of 50 wt.%. In the same period more than 50% of the packaging units on the world market were made of polymeric materials despite the fact that polymeric materials present 17 wt.% of all packaging materials. The basic properties of polymeric materials and their environmental and economical advantages, providing them such a position among packaging materials, are presented in this article. Recycling methods, as well as the development trends of polymeric packaging materials are also presented.

  17. Phosphazene-promoted anionic polymerization

    KAUST Repository

    Zhao, Junpeng

    2014-01-01

    In the recent surge of metal-free polymerization techniques, phosphazene bases have shown their remarkable potential as organic promoters/catalysts for the anionic polymerization of various types of monomers. By complexation with the counterion (e.g. proton or lithium cation), phosphazene base significantly improve the nucleophilicity of the initiator/chain-end resulting in rapid and usually controlled anionic/quasi-anionic polymerization. In this review, we will introduce the general mechanism, i.e. in situ activation (of initiating sites) and polymerization, and summarize the applications of such a mechanism on macromolecular engineering toward functionalized polymers, block copolymers and complex macromolecular architectures.

  18. Synthesis of magnetic polymeric microspheres

    Energy Technology Data Exchange (ETDEWEB)

    Gervald, A Yu; Gritskova, Inessa A; Prokopov, Nikolai I [M.V. Lomonosov Moscow State Academy of Fine Chemical Technology, Moscow (Russian Federation)

    2010-05-13

    The key types of magnetic polymeric microspheres are considered. Methods of synthesis of different types of magnetic nanoparticles and of preparation of stable magnetic fluids on their basis are outlined. The overview of the methods for the manufacture of magnetic polymeric microspheres is presented. The effect of the synthesis conditions on the characteristics of magnetic polymeric microspheres such as the diameter and the particle size distribution and the content of magnetic material is discussed by particular examples. The application fields of magnetic polymeric microspheres are briefly surveyed.

  19. Synthesis of magnetic polymeric microspheres

    International Nuclear Information System (INIS)

    Gervald, A Yu; Gritskova, Inessa A; Prokopov, Nikolai I

    2010-01-01

    The key types of magnetic polymeric microspheres are considered. Methods of synthesis of different types of magnetic nanoparticles and of preparation of stable magnetic fluids on their basis are outlined. The overview of the methods for the manufacture of magnetic polymeric microspheres is presented. The effect of the synthesis conditions on the characteristics of magnetic polymeric microspheres such as the diameter and the particle size distribution and the content of magnetic material is discussed by particular examples. The application fields of magnetic polymeric microspheres are briefly surveyed.

  20. Unlocking the Structure and Dynamics of Thin Polymeric Films

    Science.gov (United States)

    2016-11-13

    fundamental polymerization chemistry and the physical chemistry of reaction mixtures. 2) Surface properties of partly-fluorinated polymers Fluorine...13/2016 DISTRIBUTION A: Distribution approved for public release. AF Office Of Scientific Research (AFOSR)/ IOA Arlington, Virginia 22203 Air Force...adhesives, and in more advanced technologies such as functional microfluidic devices, batteries, displays and in the manufacture of integrated circuits

  1. Pressure induced graft-co-polymerization of acrylonitrile onto ...

    Indian Academy of Sciences (India)

    WINTEC

    The natural fibre (S. cilliare) (0⋅5 g) was masticated to create active sites onto the polymeric backbone and was then immersed in a known amount of distilled water for. 24 h. A known amount of initiator (FAS–KPS) and monomer (AN) were then added to the flask containing fibre at suitable pH and the reaction was carried ...

  2. Catalytic olefin polymerization with early transition metal compounds

    NARCIS (Netherlands)

    Eshuis, Johan Jan Willem

    1991-01-01

    The catalysis of organic reactions by soluble metal complexes has become a major tool in synthesis, both in the laboratory and in the chemical industry. Processes catalyzed by transition metal complexes include carbonylation, olefin polymerization, olefin addition, olefin oxidation and alkane and

  3. 21 CFR 175.300 - Resinous and polymeric coatings.

    Science.gov (United States)

    2010-04-01

    ... descriptions: (1) Coatings cured by oxidation. (2) Coatings cured by polymerization, condensation, and/or cross... condensation product formed by the reaction of hydrogenated castor oil with polyamide derived from...-oil emulsion, high- or low-fat. B. Oil-in-water emulsion, high- or low-fat. V. Low moisture fats and...

  4. Crosslinking polymerization of tetraethylene glycol dimethacrylate under high pressure

    Energy Technology Data Exchange (ETDEWEB)

    Kaminski, K; Paluch, M; Ziolo, J [Institute of Physics, Silesian University, Uniwersytecka 4, 40-007 Katowice (Poland); Bogoslovov, R; Roland, C M [Chemistry Division, Code 6120, Naval Research Laboratory, Washington DC 20375-5342 (United States)], E-mail: kaminski@us.edu.pl

    2008-07-15

    The polymerization reaction of tetraethylene glycol dimethacrylate was induced by application of high pressure. Broadband dielectric spectroscopy was employed to investigate dielectric properties of the produced polymers. Additionally swelling experiment was performed to determine the degree of crossliniking of the polymers.

  5. short communication synthesis and crystal structure of a polymeric

    African Journals Online (AJOL)

    Preferred Customer

    A new polymeric zinc(II) complex, [ZnL2(PDA)]n, has been prepared by the reaction of zinc sulfate ... complex has been characterized by single-crystal X-ray diffraction. .... Molecular structure of the complex at 30% probability displacement.

  6. Stimuli-Responsive Polymeric Nanoparticles.

    Science.gov (United States)

    Liu, Xiaolin; Yang, Ying; Urban, Marek W

    2017-07-01

    There is increasing evidence that stimuli-responsive nanomaterials have become significantly critical components of modern materials design and technological developments. Recent advances in synthesis and fabrication of stimuli-responsive polymeric nanoparticles with built-in stimuli-responsive components (Part A) and surface modifications of functional nanoparticles that facilitate responsiveness (Part B) are outlined here. The synthesis and construction of stimuli-responsive spherical, core-shell, concentric, hollow, Janus, gibbous/inverse gibbous, and cocklebur morphologies are discussed in Part A, with the focus on shape, color, or size changes resulting from external stimuli. Although inorganic/metallic nanoparticles exhibit many useful properties, including thermal or electrical conductivity, catalytic activity, or magnetic properties, their assemblies and formation of higher order constructs are often enhanced by surface modifications. Section B focuses on selected surface reactions that lead to responsiveness achieved by decorating nanoparticles with stimuli-responsive polymers. Although grafting-to and grafting-from dominate these synthetic efforts, there are opportunities for developing novel synthetic approaches facilitating controllable recognition, signaling, or sequential responses. Many nanotechnologies utilize a combination of organic and inorganic phases to produce ceramic or metallic nanoparticles. One can envision the development of new properties by combining inorganic (metals, metal oxides) and organic (polymer) phases into one nanoparticle designated as "ceramers" (inorganics) and "metamers" (metallic). © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Complex Macromolecular Architectures by Living Cationic Polymerization

    KAUST Repository

    Alghamdi, Reem D.

    2015-05-01

    Poly (vinyl ether)-based graft polymers have been synthesized by the combination of living cationic polymerization of vinyl ethers with other living or controlled/ living polymerization techniques (anionic and ATRP). The process involves the synthesis of well-defined homopolymers (PnBVE) and co/terpolymers [PnBVE-b-PCEVE-b-PSiDEGVE (ABC type) and PSiDEGVE-b-PnBVE-b-PSiDEGVE (CAC type)] by sequential living cationic polymerization of n-butyl vinyl ether (nBVE), 2-chloroethyl vinyl ether (CEVE) and tert-butyldimethylsilyl ethylene glycol vinyl ether (SiDEGVE), using mono-functional {[n-butoxyethyl acetate (nBEA)], [1-(2-chloroethoxy) ethyl acetate (CEEA)], [1-(2-(2-(t-butyldimethylsilyloxy)ethoxy) ethoxy) ethyl acetate (SiDEGEA)]} or di-functional [1,4-cyclohexanedimethanol di(1-ethyl acetate) (cHMDEA), (VEMOA)] initiators. The living cationic polymerizations of those monomers were conducted in hexane at -20 0C using Et3Al2Cl3 (catalyst) in the presence of 1 M AcOEt base.[1] The PCEVE segments of the synthesized block terpolymers were then used to react with living macroanions (PS-DPE-Li; poly styrene diphenyl ethylene lithium) to afford graft polymers. The quantitative desilylation of PSiDEGVE segments by n-Bu4N+F- in THF at 0 °C led to graft co- and terpolymers in which the polyalcohol is the outer block. These co-/terpolymers were subsequently subjected to “grafting-from” reactions by atom transfer radical polymerization (ATRP) of styrene to afford more complex macromolecular architectures. The base assisted living cationic polymerization of vinyl ethers were also used to synthesize well-defined α-hydroxyl polyvinylether (PnBVE-OH). The resulting polymers were then modified into an ATRP macro-initiator for the synthesis of well-defined block copolymers (PnBVE-b-PS). Bifunctional PnBVE with terminal malonate groups was also synthesized and used as a precursor for more complex architectures such as H-shaped block copolymer by “grafting-from” or

  8. Monte Carlo simulation on kinetics of batch and semi-batch free radical polymerization

    KAUST Repository

    Shao, Jing

    2015-10-27

    Based on Monte Carlo simulation technology, we proposed a hybrid routine which combines reaction mechanism together with coarse-grained molecular simulation to study the kinetics of free radical polymerization. By comparing with previous experimental and simulation studies, we showed the capability of our Monte Carlo scheme on representing polymerization kinetics in batch and semi-batch processes. Various kinetics information, such as instant monomer conversion, molecular weight, and polydispersity etc. are readily calculated from Monte Carlo simulation. The kinetic constants such as polymerization rate k p is determined in the simulation without of “steady-state” hypothesis. We explored the mechanism for the variation of polymerization kinetics those observed in previous studies, as well as polymerization-induced phase separation. Our Monte Carlo simulation scheme is versatile on studying polymerization kinetics in batch and semi-batch processes.

  9. Imidazoline and imidazolidine nitroxides as controlling agents in nitroxide-mediated pseudoliving radical polymerization

    Science.gov (United States)

    Edeleva, M. V.; Marque, S. R. A.; Bagryanskaya, E. G.

    2018-04-01

    Controlled, or pseudoliving, radical polymerization provides unique opportunities for the synthesis of structurally diverse polymers with a narrow molecular-weight distribution. These reactions occur under relatively mild conditions with broad tolerance to functional groups in the monomers. The nitroxide-mediated pseudoliving radical polymerization is of particular interest for the synthesis of polymers for biomedical applications. This review briefly describes one of the mechanisms of controlled radical polymerization. The studies dealing with the use of imidazoline and imidazolidine nitroxides as controlling agents for nitroxide-mediated pseudoliving radical polymerization of various monomers are summarized and analyzed. The publications addressing the key steps of the controlled radical polymerization in the presence of imidazoline and imidazolidine nitroxides and new approaches to nitroxide-mediated polymerization based on protonation of both nitroxides and monomers are considered. The bibliography includes 154 references.

  10. Neutral Polymeric Micelles for RNA Delivery

    Science.gov (United States)

    Lundy, Brittany B.; Convertine, Anthony; Miteva, Martina; Stayton, Patrick S.

    2013-01-01

    RNA interference (RNAi) drugs have significant therapeutic potential but delivery systems with appropriate efficacy and toxicity profiles are still needed. Here, we describe a neutral, ampholytic polymeric delivery system based on conjugatable diblock polymer micelles. The diblock copolymer contains a hydrophilic poly[N-(2-hydroxypropyl) methacrylamide-co-N-(2-(pyridin-2- yldisulfanyl)ethyl)methacrylamide) (poly[HPMA-co-PDSMA]) segment to promote aqueous stability and facilitate thiol-disulfide exchange reactions, and a second ampholytic block composed of propyl acrylic acid (PAA), dimethylaminoethyl methacrylate (DMAEMA), and butyl methacrylate (BMA). The poly[(HPMA-co-PDSMA)-b-(PAA-co-DMAEMA-co-BMA)] was synthesized using Reversible Addition-Fragmentation chain Transfer (RAFT) polymerization with an overall molecular weight of 22,000 g/mol and a PDI of 1.88. Dynamic light scattering and fluorescence measurements indicated that the diblock copolymers self-assemble under aqueous conditions to form polymeric micelles with a hydrodynamic radius and critical micelle concentration of 25 nm and 25 μg/mL respectively. Red blood cell hemolysis experiments show that the neutral hydrophilic micelles have potent membrane destabilizing activity at endosomal pH values. Thiolated siRNA targeting glyceraldehyde 3-phosphate dehydrogenase (GAPDH) was directly conjugated to the polymeric micelles via thiol exchange reactions with the pyridal disulfide groups present in the micelle corona. Maximum silencing activity in HeLa cells was observed at a 1:10 molar ratio of siRNA to polymer following a 48 h incubation period. Under these conditions 90 % mRNA knockdown and 65 % and protein knockdown of at 48 h was achieved with negligible toxicity. In contrast the polymeric micelles lacking a pH-responsive endosomalytic segment demonstrated negligible mRNA and protein knockdown under these conditions. The potent mRNA knockdown and excellent biocompatibility of the neutral siRNA conjugates

  11. Simultaneous measurement of polymerization stress and curing kinetics for photo-polymerized composites with high filler contents.

    Science.gov (United States)

    Wang, Zhengzhi; Landis, Forrest A; Giuseppetti, Anthony A M; Lin-Gibson, Sheng; Chiang, Martin Y M

    2014-12-01

    Photopolymerized composites are used in a broad range of applications with their performance largely directed by reaction kinetics and contraction accompanying polymerization. The present study was to demonstrate an instrument capable of simultaneously collecting multiple kinetics parameters for a wide range of photopolymerizable systems: degree of conversion (DC), reaction exotherm, and polymerization stress (PS). Our system consisted of a cantilever beam-based instrument (tensometer) that has been optimized to capture a large range of stress generated by lightly-filled to highly-filled composites. The sample configuration allows the tensometer to be coupled to a fast near infrared (NIR) spectrometer collecting spectra in transmission mode. Using our instrument design, simultaneous measurements of PS and DC are performed, for the first time, on a commercial composite with ≈80% (by mass) silica particle fillers. The in situ NIR spectrometer collects more than 10 spectra per second, allowing for thorough characterization of reaction kinetics. With increased instrument sensitivity coupled with the ability to collect real time reaction kinetics information, we show that the external constraint imposed by the cantilever beam during polymerization could affect the rate of cure and final degree of polymerization. The present simultaneous measurement technique is expected to provide new insights into kinetics and property relationships for photopolymerized composites with high filler content such as dental restorative composites. Published by Elsevier Ltd.

  12. Recent Syntheses of 1,2,3,4-Tetrahydroquinolines, 2,3-Dihydro-4(1H-quinolinones and 4(1H-Quinolinones using Domino Reactions

    Directory of Open Access Journals (Sweden)

    Baskar Nammalwar

    2013-12-01

    Full Text Available A review of the recent literature is given focusing on synthetic approaches to 1,2,3,4-tetrahydroquinolines, 2,3-dihydro-4(1H-quinolinones and 4(1H-quinolinones using domino reactions. These syntheses involve: (1 reduction or oxidation followed by cyclization; (2 SNAr-terminated sequences; (3 acid-catalyzed ring closures or rearrangements; (4 high temperature cyclizations and (5 metal-promoted processes as well as several less thoroughly studied reactions. Each domino method is presented with a brief discussion of mechanism, scope, yields, simplicity and potential utility.

  13. NATO Advanced Research Workshop on Frontiers in Polymerization Catalysis and Polymer Synthesis

    CERN Document Server

    Guyot, A

    1987-01-01

    Due to their specific properties, polymers with well-defined structures have been receiving increasing attention over the last several years. Owing to the wide variability of their properties, these specialty polymers have been used in various areas from biomedical engineering to electronics or energy applications. The synthesis of such polymers necessi­ tates the use of new methods of polymerization which derived from an insight into the mechanism of polymerization reactions. A NATO Advanced Research Workshop on "Frontiers in Polymerization Catalysis and Polymer Synthesis" was held in BANDOl (FRANCE) in February 1987. Its aim was to assess the new polymerization methods, as well as the latest advances in the mechanisms of conventional polymerization reactions together with their applications to the synthesis of new macromolecular structures. The financial support from the NATO Scientific Affairs Division which covered the "lecturers' accomodation and travel expenses as well as the organization charges of th...

  14. Kinetic advantages of using microwaves in the emulsion polymerization of MMA

    Energy Technology Data Exchange (ETDEWEB)

    Costa, C. [Departamento de Engenharia Quimica, Universidade Federal de Santa Catarina, Campus Universitario, CEP: 88040-900, Florianopolis, SC (Brazil); Santos, A.F.; Fortuny, M. [Programa de Mestrado em Engenharia de Processos, Universidade Tiradentes, Instituto de Tecnologia e Pesquisa, Av. Murilo Dantas, 300, CEP: 49032-490, Aracaju, SE (Brazil); Araujo, P.H.H. [Departamento de Engenharia Quimica, Universidade Federal de Santa Catarina, Campus Universitario, CEP: 88040-900, Florianopolis, SC (Brazil); Sayer, C. [Departamento de Engenharia Quimica, Universidade Federal de Santa Catarina, Campus Universitario, CEP: 88040-900, Florianopolis, SC (Brazil)], E-mail: csayer@enq.ufsc.br

    2009-03-01

    Microwave irradiation has been an interesting alternative for heating systems and several chemical reactions. In polymerization processes, microwaves can enhance reaction rates or improve specific characteristics of the formed polymer. In this work, the use of microwave irradiation in emulsion polymerization reactions has been studied, using a commercial microwave reactor, which is able to perform syntheses under controlled conditions of temperature and power. Methyl methacrylate emulsion polymerization reactions were faster, resulting in smaller polymer particles, in comparison to the conventional heating method (reactions in a jacketed reactor). Different effects were observed in the emulsion polymerization of butyl acrylate. To study the effect of high power microwave irradiation upon the emulsion polymerization, a pulsed irradiation strategy was developed, in which the samples were repeatedly heated within short intervals of time (about 27 s) at the maximum microwave power. A significant reduction of the total time of irradiation was observed in reactions carried out under the pulsed scheme, showing the kinetic advantages of using microwaves in emulsion polymerization processes.

  15. Kinetics of exchange reaction between neodymium(3) transcyclohexanediaminetetraacetate and europium(3)- and holmium(3) aquo-ions in the H2O and D2O solutions

    International Nuclear Information System (INIS)

    Nikitenko, S.I.; Martynenko, L.I.; Pechurova, N.I.; Spitsyn, V.I.

    1983-01-01

    The exchange reaction between central ions in the NdD - Ln' 3+ systems, where Ln' 3+ is a substituting cation (Eu 3+ and Ho 3+ , D 4 =cyclohexanediaminetetraacetate) is studied and the electrophilic suhstitution mechanism is considered. To study the kinetic isotope effects, the reagents have been solVed in heavy water containing 99.9% D 2 O. The electrophilic substitution in the indicated systems proceeds through the dissociative mechanism catalyzed by protons and via the spontaneous dissociation mechanism. The exchange via the acid-catalyzed mechanism is limited by the intermediate protonated complex decay. The associative mechanism of the electrophilic exchange in the studied systems is not realized

  16. Radiation-induced in-source polymerization of acrylonitrile in urea canal complex

    International Nuclear Information System (INIS)

    Yoshii, Fumio; Abe, Toshihiko; Kobayashi, Yasushi.

    1975-01-01

    Effect of reaction conditions on the radiation-induced in-source polymerization of acrylonitrile in urea canal complex and the properties of obtained polyacrylonitriles were investigated. The results were discussed in comparison with previously reported of the post-polymerization experiments. 1) Rate of polymerization and viscosity (eta sub(sp)/C) were the highest when the molar ratio of acrylonitrile to urea in canal complex was unity. Similar results were also obtained in the post-polymerization. However, eta sub(sp)/C exhibited different behavior on polymerization time in comparison with post-polymerization. 2) The initial rate (Rsub(p)) of polymerization is proportional to the dose rate (I) at low dose rate, but at high dose rates (above 2x10 5 r/hr) makes Rsub(p) proportional to Isup(0.5). 3) Molecular weight distribution become broader with increasing polymerization time and is broad as compared with those obtained by the post-polymerization. G-value of initiation of polymerization decreased with increasing polymerization time. These value was larger than the that obtained in the post-polymerization. 4) The stereoregularity of the polyacrylonitriles was independent of the molar ratio of acrylonitrile to urea in the canal complex and conversion. 5) The appearance of the polyacrylonitriles observed by the scanning electron microscope changed from curled string to extended one as the polymerization proceed. 6) Infrared spectrum revealed the ketenimine and cyclization structure in the polyacrylonitriles obtained below -100 0 C. The content of these abnormal structures increased with increasing conversion. (auth.)

  17. Studies on the polymerization of acrolein oxime, 13

    International Nuclear Information System (INIS)

    Ota, Tadatoshi; Mori, Yoshikazu; Tamai, Harumi; Masuda, Seizo; Tanaka, Masami.

    1980-01-01

    The radiation-induced polymerization of acrolein oxime was carried out at temperatures ranging from room temperature to -78 0 C, and the resulting low molecular products were analyzed by gas chromatography-mass spectrometry. Acetaldoxime, propionaldoxime, propenylhydroxylamines, dioximes etc. were obtained. Initial processes of the polymerization are discussed on the basis of these reaction products. The present work offers further corroborating evidence for the already-described postulation that an anionic mechanism is operative above room temperature, and a cationic mechanism is predominant below -23 0 C. (author)

  18. Collaborative Research: Polymeric Multiferroics

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Shenqiang [Temple Univ., Philadelphia, PA (United States). College of Engineering

    2017-04-20

    The goal of this project is to investigate room temperature magnetism and magnetoelectric coupling of polymeric multiferroics. A new family of molecular charge-transfer crystals has been emerged as a fascinating opportunity for the development of all-organic electrics and spintronics due to its weak hyperfine interaction and low spin-orbit coupling; nevertheless, direct observations of room temperature magnetic spin ordering have yet to be accomplished in organic charge-transfer solids. Furthermore, room temperature magnetoelectric coupling effect hitherto known multiferroics, is anticipated in organic donor-acceptor complexes because of magnetic field effects on charge-transfer dipoles, yet this is also unexplored. The PI seeks to fundamental understanding of the control of organic crystals to demonstrate and explore room temperature multiferroicity. The experimental results have been verified through the theoretical modeling.

  19. Polymerization with freezing

    International Nuclear Information System (INIS)

    Ben-Naim, E; Krapivsky, P L

    2005-01-01

    Irreversible aggregation processes involving reactive and frozen clusters are investigated using the rate equation approach. In aggregation events, two clusters join irreversibly to form a larger cluster; additionally, reactive clusters may spontaneously freeze. Frozen clusters do not participate in merger events. Generally, freezing controls the nature of the aggregation process, as demonstrated by the final distribution of frozen clusters. The cluster mass distribution has a power-law tail, F k ∼k -γ , when the freezing process is sufficiently slow. Different exponents, γ = 1 and 3, are found for the constant and the product aggregation rates, respectively. For the latter case, the standard polymerization model, either no gels, or a single gel, or even multiple gels, may be produced

  20. Biodegradable Polyelectrolyte Obtained by Radiation Polymerization

    International Nuclear Information System (INIS)

    Craciun, G.; Martin, D.; Manaila, E.; Nemtanu, M.; Brasoveanu, M.; Ighigeanu, D.

    2009-01-01

    Poly electrolytes are water-soluble polymers carrying ionic charge along the polymer chain. Depending upon the charge, these polymers are anionic or cationic. The inherent solid - liquid separating efficiency makes these poly electrolytes a unique class of polymers which find extensive application in potable water, industrial raw and process water, municipal sewage treatment, mineral processing and metallurgy, oil drilling and recovery, etc. Also, due to their ability to produce advanced induced coagulation, a considerable amount of bacteria and viruses are precipitated together with the suspended solids. Especially the acrylamide polymers are very efficacious for water treatment but acrylamide is a toxic monomer and therefore their use are governed by international standards that provide the residual acrylamide monomer content (RAMC) in them be less than 0.05%. Under these circumstances our attention was focused on the following research steps that are presented in this paper: 1) Preparation of a special class of poly electrolytes, named Pn, with very low RAMC values, based on electron beam (EB), microwave (MW) and EB + MW induced co-polymerization of aqueous solutions containing appropriate mixtures of acrylamide (AMD) and acrylic acid (AA) monomers (AMD - AA co-polymers). The Pn were obtained by radiation technology with very small RAMC (under 0.01%) as well as in a wide range of molecular weights and charge densities. Very low AMD monomer content of Pn is due to the major advantages of radiation induced polymerization in aqueous solution containing monomers. Due to water presence in the EB irradiated system, irradiated water radicals facilitate the polymerization process and increase rate and level of monomers conversion in co-polymers. Also, once again, by the presence of water, which absorbs MW energy very strongly, the MW polymerization reaction rate is much enhanced resulting in a reaction time about 50-100 times lowers than by conventional heating. Also

  1. Polymeric micelles for drug targeting.

    Science.gov (United States)

    Mahmud, Abdullah; Xiong, Xiao-Bing; Aliabadi, Hamidreza Montazeri; Lavasanifar, Afsaneh

    2007-11-01

    Polymeric micelles are nano-delivery systems formed through self-assembly of amphiphilic block copolymers in an aqueous environment. The nanoscopic dimension, stealth properties induced by the hydrophilic polymeric brush on the micellar surface, capacity for stabilized encapsulation of hydrophobic drugs offered by the hydrophobic and rigid micellar core, and finally a possibility for the chemical manipulation of the core/shell structure have made polymeric micelles one of the most promising carriers for drug targeting. To date, three generations of polymeric micellar delivery systems, i.e. polymeric micelles for passive, active and multifunctional drug targeting, have arisen from research efforts, with each subsequent generation displaying greater specificity for the diseased tissue and/or targeting efficiency. The present manuscript aims to review the research efforts made for the development of each generation and provide an assessment on the overall success of polymeric micellar delivery system in drug targeting. The emphasis is placed on the design and development of ligand modified, stimuli responsive and multifunctional polymeric micelles for drug targeting.

  2. Controlled radical polymerization of acrylates by {gamma}-irradiation in the presence of 1,1-diphenylethene

    Energy Technology Data Exchange (ETDEWEB)

    Wu Zongtao [Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, Anhui 230026 (China); Zhang Zhicheng [Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, Anhui 230026 (China)]. E-mail: zczhang@ustc.edu.cn

    2005-12-15

    Poly (butyl acrylate) and poly (methyl acrylate) were successfully prepared in the presence of 1,1-diphenylethene (DPE) by {gamma}-irradiation-induced polymerization in both bulk and solution. The influences of polymerization time, amounts of DPE in system on conversion, molecular weight (MW) and its distribution (M{sub w}/M{sub n}) were studied. The results indicate that the polymerization initiated by {gamma}-irradiation in the presence of DPE shows the character of living radical reaction.

  3. Facile graft polystyrene onto multi-walled carbon nanotubes via in situ thermo-induced radical polymerization

    International Nuclear Information System (INIS)

    Liu Peng

    2009-01-01

    A facile procedure was developed for the grafting of polystyrene onto the surfaces of multi-walled carbon nanotubes (MWNTs) via the in situ thermo-induced bulk radical polymerization of styrene at the different polymerizing temperatures, in the presence of MWNTs without any initiator added. The grafting products were validated by the dispersibility, TEM, TGA, FT-IR, and Raman analysis. The TGA results also showed the lower polymerizing temperature was propitious to the free radical addition reactions.

  4. Synthesis and Characterization of Polyethylene/Starch Nanocomposites: A Spherical Starch-Supported Catalyst and In Situ Ethylene Polymerization.

    Science.gov (United States)

    Zhanga, Hao; Xi, Shixia; Wang, Shuwei; Liu, Jingsheng; Yoon, Keun-Byoung; Lee, Dong-Ho; Zhang, Hexin; Zhang, Xuequan

    2017-01-01

    In the present article, a novel spherical starch-supported vanadium (V)-based Ziegler-Natta catalyst was synthesized. The active centers of the obtained catalyst well dispersed in the starch through the SEM-EDX analysis. The effects of reaction conditions on ethylene polymerization were studied. The synthesized catalyst exhibited high activity toward ethylene polymerization in the presence of ethylaluminium sesquichloride (EASC) cocatalyst. Interestingly, the fiber shape PE was obtained directly during the polymerization process.

  5. Measurement of in vitro microtubule polymerization by turbidity and fluorescence.

    Science.gov (United States)

    Mirigian, Matthew; Mukherjee, Kamalika; Bane, Susan L; Sackett, Dan L

    2013-01-01

    Tubulin polymerization may be conveniently monitored by the increase in turbidity (optical density, or OD) or by the increase in fluorescence intensity of diamidino-phenylindole. The resulting data can be a quantitative measure of microtubule (MT) assembly, but some care is needed in interpretation, especially of OD data. Buffer formulations used for the assembly reaction significantly influence the polymerization, both by altering the critical concentration for polymerization and by altering the exact polymer produced-for example, by increasing the production of sheet polymers in addition to MT. Both the turbidity and the fluorescence methods are useful for demonstrating the effect of MT-stabilizing or -destabilizing additives. 2013 Published by Elsevier Inc.

  6. Conductive cotton prepared by polyaniline in situ polymerization using laccase.

    Science.gov (United States)

    Zhang, Ya; Dong, Aixue; Wang, Qiang; Fan, Xuerong; Cavaco-Paulo, Artur; Zhang, Ying

    2014-09-01

    The high-redox-potential catalyst laccase, isolated from Aspergillus, was first used as a biocatalyst in the oxidative polymerization of water-soluble conductive polyaniline, and then conductive cotton was prepared by in situ polymerization under the same conditions. The polymerization of aniline was performed in a water dispersion of sodium dodecylbenzenesulfonate (SDBS) micellar solution with atmospheric oxygen serving as the oxidizing agent. This method is ecologically clean and permits a greater degree of control over the kinetics of the reaction. The conditions for polyaniline synthesis were optimized. Characterizations of the conducting polyaniline and cotton were carried out using Fourier transform infrared spectroscopy, UV-vis spectroscopy, cyclic voltammetry, the fabric induction electrostatic tester, and the far-field EMC shielding effectiveness test fixture.

  7. Recent advances on polymeric membranes for membrane reactors

    KAUST Repository

    Buonomenna, M. G.

    2012-06-24

    Membrane reactors are generally applied in high temperature reactions (>400 °C). In the field of fine chemical synthesis, however, much milder conditions are generally applicable and polymeric membranes were applied without their damage. The successful use of membranes in membrane reactors is primary the result of two developments concerning: (i) membrane materials and (ii) membrane structures. The selection of a suited material and preparation technique depends on the application the membrane is to be used in. In this chapter a review of up to date literature about polymers and configuration catalyst/ membranes used in some recent polymeric membrane reactors is given. The new emerging concept of polymeric microcapsules as catalytic microreactors has been proposed. © 2012 Bentham Science Publishers. All rights reserved.

  8. Organometallic Polymeric Conductors

    Science.gov (United States)

    Youngs, Wiley J.

    1997-01-01

    For aerospace applications, the use of polymers can result in tremendous weight savings over metals. Suitable polymeric materials for some applications like EMI shielding, spacecraft grounding, and charge dissipation must combine high electrical conductivity with long-term environmental stability, good processability, and good mechanical properties. Recently, other investigators have reported hybrid films made from an electrically conductive polymer combined with insulating polymers. In all of these instances, the films were prepared by infiltrating an insulating polymer with a precursor for a conductive polymer (either polypyrrole or polythiophene), and oxidatively polymerizing the precursor in situ. The resulting composite films have good electrical conductivity, while overcoming the brittleness inherent in most conductive polymers. Many aerospace applications require a combination of properties. Thus, hybrid films made from polyimides or other engineering resins are of primary interest, but only if conductivities on the same order as those obtained with a polystyrene base could be obtained. Hence, a series of experiments was performed to optimize the conductivity of polyimide-based composite films. The polyimide base chosen for this study was Kapton. 3-MethylThiophene (3MT) was used for the conductive phase. Three processing variables were identified for producing these composite films, namely time, temperature, and oxidant concentration for the in situ oxidation. Statistically designed experiments were used to examine the effects of these variables and synergistic/interactive effects among variables on the electrical conductivity and mechanical strength of the films. Multiple linear regression analysis of the tensile data revealed that temperature and time have the greatest effect on maximum stress. The response surface of maximum stress vs. temperature and time (for oxidant concentration at 1.2 M) is shown. Conductivity of the composite films was measured for

  9. Recent Developments of Versatile Photoinitiating Systems for Cationic Ring Opening Polymerization Operating at Any Wavelengths and under Low Light Intensity Sources

    Directory of Open Access Journals (Sweden)

    Jacques Lalevée

    2015-04-01

    Full Text Available Photoinitiators (PI or photoinitiating systems (PIS usable in light induced cationic polymerization (CP and free radical promoted cationic polymerization (FRPCP reactions (more specifically for cationic ring opening polymerization (ROP together with the involved mechanisms are briefly reviewed. The recent developments of novel two- and three-component PISs for CP and FRPCP upon exposure to low intensity blue to red lights is emphasized in details. Examples of such reactions under various experimental conditions are provided.

  10. Recent Developments of Versatile Photoinitiating Systems for Cationic Ring Opening Polymerization Operating at Any Wavelengths and under Low Light Intensity Sources.

    Science.gov (United States)

    Lalevée, Jacques; Mokbel, Haifaa; Fouassier, Jean-Pierre

    2015-04-20

    Photoinitiators (PI) or photoinitiating systems (PIS) usable in light induced cationic polymerization (CP) and free radical promoted cationic polymerization (FRPCP) reactions (more specifically for cationic ring opening polymerization (ROP)) together with the involved mechanisms are briefly reviewed. The recent developments of novel two- and three-component PISs for CP and FRPCP upon exposure to low intensity blue to red lights is emphasized in details. Examples of such reactions under various experimental conditions are provided.

  11. De fysica van polymere materialen

    NARCIS (Netherlands)

    Struik, L.C.E.

    1987-01-01

    Rede, uitgesproken ter gelegenheid van de aanvaarding van het ambt van buitengewoon hoogleraar in de fysica van polymere materialen aan de Universitelt Twente op donderdag 22 januarì 1987 door Dr.lr. L.C.E. Struik.

  12. Phosphazene-promoted anionic polymerization

    KAUST Repository

    Zhao, Junpeng; Hadjichristidis, Nikolaos; Gnanou, Yves

    2014-01-01

    .e. in situ activation (of initiating sites) and polymerization, and summarize the applications of such a mechanism on macromolecular engineering toward functionalized polymers, block copolymers and complex macromolecular architectures.

  13. Schlenk Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar; Zhao, Junpeng; Zhang, Hefeng; Hadjichristidis, Nikolaos; Mays, Jimmy

    2015-01-01

    Anionic polymerization-high vacuum techniques (HVTs) are doubtlessly the most prominent and reliable experimental tools to prepare polymer samples with well-defined and, in many cases, complex macromolecular architectures. Due to the high demands

  14. Pulsed-laser polymerization in compartmentalized liquids. 1. Polymerization in vesicles

    NARCIS (Netherlands)

    Jung, M.; Casteren, van I.A.; Monteiro, M.J.; Herk, van A.M.; German, A.L.

    2000-01-01

    Polymerization in vesicles is a novel type of polymerization in heterogeneous media, leading to parachute-like vesicle-polymer hybrid morphologies. To explore the kinetics of vesicle polymerizations and to learn more about the actual locus of polymerization we applied the pulsed-laser polymerization

  15. Smart polymeric materials in forms of fiber and film

    International Nuclear Information System (INIS)

    Sugo, Takanobu

    1998-01-01

    Chemical grafting: graft polymerization is a powerful technology to append novel functionality to base fibers, clothes, felts, films and others, while maintaining their original properties. As shown in Figure 1, while a gardener may use a pair of shears to cut the branch, to cut the molecular branch of a polymeric material, one can utilize the radiation energy. Effective utilization of the radiation energy can proceed to a novel reaction that is impossible for other conventional methods and develop a new material bearing outstanding functions. This technology is named radiation-induced graft polymerization (RIGP). In this article, the present research and development of novel functional polymeric materials by radiation-induced graft polymerization is described. The felt of intertwined fibers has been widely used as a filter to remove particles from air but not toxic gaseous compounds. However, by RIGP, one can transform the felt into a high functional filter that will absorb the toxic gaseous compounds while removing particles simultaneously. As a result, the RIGP technology, which is impossible by conventional technology, has enabled the development of a novel functional material that produce highly pure air. Commercialization of this filter for applications in a semiconductor manufacturing facility and as an air purifier is under process. Moreover, this filter can also be used to produce highly purified water by removing toxic heavy metals. Commercially available polyethylene films are also been transform into conductive separators by RIGP to increase the lifetime of a battery by more than five-fold. (J.P.N)

  16. Direct surface PEGylation of nanodiamond via RAFT polymerization

    International Nuclear Information System (INIS)

    Shi, Yingge; Liu, Meiying; Wang, Ke; Huang, Hongye; Wan, Qing; Tao, Lei; Fu, Lihua; Zhang, Xiaoyong; Wei, Yen

    2015-01-01

    Graphical abstract: In this paper, we describe an efficient, practical and novel method to modify ND via direct immobilization of chain transfer agent for RAFT polymerization. - Highlights: • Surface PEGylation of ND via RAFT polymerization. • ND with high water dispersibility and excellent biocompatibility. • Controlled living polymerization. - Abstract: Nanodiamond (ND) is a novel class of carbon nanomaterials, which has been extensively investigated for biomedical applications because of its small size, high surface area and excellent biocompatibility. However, the biomedical applications of unmodified ND are still largely restricted because of their poor dispersibility in both aqueous and organic medium. In this work, we reported a novel strategy for the surface modification of ND via reversible addition fragmentation chain transfer (RAFT) polymerization. For preparation of the PEGylated ND (pPEGMA-ND), chain transfer agent (CTA) was immobilized onto ND through reaction between the hydroxyl group of ND and the carboxyl group of CTA, which was used as the initiator for surface-initiated RAFT polymerization. The successful preparation of pPEGMA-ND was characterized by nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectra and thermal gravimetric analysis in detail. Results demonstrated that pPEGMA-ND exhibited enhanced water dispersibility and desirable biocompatibility, making it promising for biomedical applications.

  17. Direct surface PEGylation of nanodiamond via RAFT polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Yingge [Department of Chemistry and Jiangxi Provincial Key Laboratory of New Energy Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004 (China); Liu, Meiying [Department of Chemistry and Jiangxi Provincial Key Laboratory of New Energy Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wang, Ke [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing 100084 (China); Huang, Hongye; Wan, Qing [Department of Chemistry and Jiangxi Provincial Key Laboratory of New Energy Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Tao, Lei [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing 100084 (China); Fu, Lihua [School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry and Jiangxi Provincial Key Laboratory of New Energy Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wei, Yen, E-mail: weiyen@tsinghua.edu.cn [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing 100084 (China)

    2015-12-01

    Graphical abstract: In this paper, we describe an efficient, practical and novel method to modify ND via direct immobilization of chain transfer agent for RAFT polymerization. - Highlights: • Surface PEGylation of ND via RAFT polymerization. • ND with high water dispersibility and excellent biocompatibility. • Controlled living polymerization. - Abstract: Nanodiamond (ND) is a novel class of carbon nanomaterials, which has been extensively investigated for biomedical applications because of its small size, high surface area and excellent biocompatibility. However, the biomedical applications of unmodified ND are still largely restricted because of their poor dispersibility in both aqueous and organic medium. In this work, we reported a novel strategy for the surface modification of ND via reversible addition fragmentation chain transfer (RAFT) polymerization. For preparation of the PEGylated ND (pPEGMA-ND), chain transfer agent (CTA) was immobilized onto ND through reaction between the hydroxyl group of ND and the carboxyl group of CTA, which was used as the initiator for surface-initiated RAFT polymerization. The successful preparation of pPEGMA-ND was characterized by nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectra and thermal gravimetric analysis in detail. Results demonstrated that pPEGMA-ND exhibited enhanced water dispersibility and desirable biocompatibility, making it promising for biomedical applications.

  18. Polyolefin nanocomposites in situ polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Galland, Griselda Barrera; Fim, Fabiana de C.; Milani, Marceo A.; Silva, Silene P. da; Forest, Tadeu; Radaelli, Gislaine, E-mail: griselda.barrera@ufrgs.br [Universidade Federal do Rio Grande de Sul - UFRGS, Porto Alegre, RS (Brazil); Basso, Nara R.S. [Pontificia Universidade Catolica do Rio Grande do Sul, Porto Alegre, RS (Brazil); Quijada, Raul [Universidad de Chile, Santiago (Chile)

    2011-07-01

    Polyethylene and polypropylene nanocomposites using grapheme nanosheets and treated chrysotile have been synthesized by in situ polymerization using metallocene catalysts. The fillers have been submitted to acid, thermal and/ou ultrasound treatments before to introduce them into the polymerization reactor. A complete characterization of the fillers has been done. The nanocomposites have been characterized by SEM, TEM, DRX and AFM. The thermal, mechanic -dynamic, mechanical and electrical properties of the nanocomposites are discussed. (author)

  19. Polyolefin nanocomposites in situ polymerization

    International Nuclear Information System (INIS)

    Galland, Griselda Barrera; Fim, Fabiana de C.; Milani, Marceo A.; Silva, Silene P. da; Forest, Tadeu; Radaelli, Gislaine; Basso, Nara R.S.; Quijada, Raul

    2011-01-01

    Polyethylene and polypropylene nanocomposites using grapheme nanosheets and treated chrysotile have been synthesized by in situ polymerization using metallocene catalysts. The fillers have been submitted to acid, thermal and/ou ultrasound treatments before to introduce them into the polymerization reactor. A complete characterization of the fillers has been done. The nanocomposites have been characterized by SEM, TEM, DRX and AFM. The thermal, mechanic -dynamic, mechanical and electrical properties of the nanocomposites are discussed. (author)

  20. Electroactivity in Polymeric Materials

    CERN Document Server

    2012-01-01

    Electroactivity in Polymeric Materials provides an in-depth view of the theory of electroactivity and explores exactly how and why various electroactive phenomena occur. The book explains the theory behind electroactive bending (including ion-polymer-metal-composites –IPMCs), dielectric elastomers, electroactive contraction, and electroactive contraction-expansion cycles.  The book also balances theory with applications – how electroactivity can be used – drawing inspiration from the manmade mechanical world and the natural world around us.  This book captures: A complete introduction to electroactive materials including examples and recent developments The theory and applications of numerous topics like electroactive bending of dielectric elastomers and electroactive contraction and expansion New topics, such as biomimetic applications and energy harvesting This is a must-read within the electroactive community, particularly for professionals and graduate students who are interested in the ...

  1. Influência das condições reacionais nas características de copolímeros de metacrilato de metila e divinilbenzeno obtidos por polimerização em suspensão Influence from the reaction conditions on the characteristics of methyl methacrylate-divinylbenzene copolymers obtained by suspension polymerization

    Directory of Open Access Journals (Sweden)

    Anelise M. Cardoso

    2004-09-01

    Full Text Available Foram sintetizados copolímeros esféricos e porosos à base de metacrilato de metila e divinilbenzeno através de polimerização em suspensão aquosa utilizando metil-etil-cetona (MEK e ciclo-hexano (CH como diluentes. Diferentes estruturas morfológicas foram obtidas através da modificação dos parâmetros reacionais tais como teor de divinilbenzeno e razão MEK/CH. Os copolímeros foram caracterizados por porosimetria de mercúrio, análise de área específica, densidade aparente e microscopia ótica. Foram obtidas estruturas macroporosas com os teores mais altos do DVB e do diluente não-solvatante (CH.Spherical and porous copolymers based on methyl methacrylate and divinylbenzene were synthesized by aqueous suspension polymerization using methyl-ethyl-ketone (MEK and cyclohexane (CH as diluents. Different morphological structures were obtained by modifying the reaction parameters, such as divinylbenzene content and MEK/CH ratio. The copolymers were characterized by several techniques: mercury porosimetry, specific superficial area analyzer, apparent density and optical microcopy. Macroporous structures were obtained when using high content of DVB and of nonsolvatant diluent (CH.

  2. Pressure-induced polymerization in substituted acetylenes

    Energy Technology Data Exchange (ETDEWEB)

    Chellappa, Raja S.; Dattelbaum, Dana M.; Sheffield, Stephen; Robbins, David (LANL)

    2012-04-10

    A fundamental understanding of shock-induced chemical reactions in organics is still lacking and there are limited studies devoted to determining reaction mechanisms, evolution of bonding, and effect of functional group substitutions. The fast timescale of reactions occurring during shock compression create significant experimental challenges (diagnostics) to fully quantify the mechanisms involved. Static compression combined with temperature provides a complementary route to investigate the equilibrium phase space and metastable intermediates under extreme P-T conditions. In this study, we present our results from our ongoing high pressure in situ synchrotron x-ray diffraction experiments on substituted acetylenes: tert-butyl acetylene [TBA: (CH{sub 3}){sub 3}-C=CH] and ethynyl trimethylsilane [ETMS: (CH{sub 3}){sub 3}-SiC=CH]. We observed that the onset pressure of chemical reactions (at room temperature) in these compounds is higher under static compression (TBA: 12 GPa and ETMS: 17.6 GPa) when compared to shock input pressures (TBA: 6.1 GPa and ETMS: 6.6 GPa). At elevated temperatures, reactivity was observed to occur at pressures comparable to shock conditions. The products were polymeric in nature, recovered to ambient conditions with little degradation.

  3. Stereoselectivity in metallocene-catalyzed coordination polymerization of renewable methylene butyrolactones: From stereo-random to stereo-perfect polymers

    KAUST Repository

    Chen, Xia; Caporaso, Lucia; Cavallo, Luigi; Chen, Eugene You Xian

    2012-01-01

    Coordination polymerization of renewable α-methylene-γ-(methyl) butyrolactones by chiral C 2-symmetric zirconocene catalysts produces stereo-random, highly stereo-regular, or perfectly stereo-regular polymers, depending on the monomer and catalyst structures. Computational studies yield a fundamental understanding of the stereocontrol mechanism governing these new polymerization reactions mediated by chiral metallocenium catalysts. © 2012 American Chemical Society.

  4. Stereoselectivity in metallocene-catalyzed coordination polymerization of renewable methylene butyrolactones: From stereo-random to stereo-perfect polymers

    KAUST Repository

    Chen, Xia

    2012-05-02

    Coordination polymerization of renewable α-methylene-γ-(methyl) butyrolactones by chiral C 2-symmetric zirconocene catalysts produces stereo-random, highly stereo-regular, or perfectly stereo-regular polymers, depending on the monomer and catalyst structures. Computational studies yield a fundamental understanding of the stereocontrol mechanism governing these new polymerization reactions mediated by chiral metallocenium catalysts. © 2012 American Chemical Society.

  5. Tunable, Quantitative Fenton-RAFT Polymerization via Metered Reagent Addition.

    Science.gov (United States)

    Nothling, Mitchell D; McKenzie, Thomas G; Reyhani, Amin; Qiao, Greg G

    2018-05-10

    A continuous supply of radical species is a key requirement for activating chain growth and accessing quantitative monomer conversions in reversible addition-fragmentation chain transfer (RAFT) polymerization. In Fenton-RAFT, activation is provided by hydroxyl radicals, whose indiscriminate reactivity and short-lived nature poses a challenge to accessing extended polymerization times and quantitative monomer conversions. Here, an alternative Fenton-RAFT procedure is presented, whereby radical generation can be finely controlled via metered dosing of a component of the Fenton redox reaction (H 2 O 2 ) using an external pumping system. By limiting the instantaneous flux of radicals and ensuring sustained radical generation over tunable time periods, metered reagent addition reduces unwanted radical "wasting" reactions and provides access to consistent quantitative monomer conversions with high chain-end fidelity. Fine tuning of radical concentration during polymerization is achieved simply via adjustment of reagent dose rate, offering significant potential for automation. This modular strategy holds promise for extending traditional RAFT initiation toward more tightly regulated radical concentration profiles and affords excellent prospects for the automation of Fenton-RAFT polymerization. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Polymerization of Alkylsilanes on ZIF-8 to Hierarchical Siloxane Microspheres and Microflowers

    Directory of Open Access Journals (Sweden)

    Lin Yang

    2017-03-01

    Full Text Available The use of metal-organic frameworks (MOFs in the polymerization field remains comparatively rare up to now, let alone studies on the fabrication of polymer microstructures through a MOFs-catalyzed assembly process. Zeolitic imidazolate framework-8 (ZIF-8, a well-known MOF for its chemical and thermal stabilities, was used to induce a polymerization reaction of saturated alkylsilanes for the first time. The reaction temperature was found to be critical for morphology control of the polymerized ZIF-siloxane composites. The polymerization of alkylsilanes by ZIF-8 at room temperature resulted in siloxane microspheres while rose petal-like microstructures were obtained at higher temperature. The effects of the reaction time on the structures of the polymerization products were also investigated and the polymerization reaction process was proposed. This work expands the field of MOFs’ applications and develops a reasonable method for the multidimensional assembly of MOFs building blocks into required structures or platforms for designing new kinds of hierarchical morphologies, which to our knowledge has not been previously investigated.

  7. Highly efficient and selective pressure-assisted photon-induced polymerization of styrene

    Energy Technology Data Exchange (ETDEWEB)

    Guan, Jiwen [Department of Physics and Astronomy, University of Western Ontario, London, Ontario N6A 3K7 (Canada); Song, Yang, E-mail: yang.song@uwo.ca [Department of Physics and Astronomy, University of Western Ontario, London, Ontario N6A 3K7 (Canada); Department of Chemistry, University of Western Ontario, London, Ontario N6A 5B7 (Canada)

    2016-06-07

    The polymerization process of condensed styrene to produce polystyrene as an industrially important polymeric material was investigated using a novel approach by combining external compression with ultraviolet radiation. The reaction evolution was monitored as a function of time and the reaction products were characterized by in situ Fourier transform infrared spectroscopy. By optimizing the loading pressures, we observed highly efficient and selective production of polystyrene of different tacticities. Specifically, at relatively low loading pressures, infrared spectra suggest that styrene monomers transform to amorphous atactic polystyrene (APS) with minor crystalline isotactic polystyrene. In contrast, APS was found to be the sole product when polymerization occurs at relatively higher loading pressures. The time-dependent reaction profiles allow the examination of the polymerization kinetics by analyzing the rate constant and activation volume as a function of pressure. As a result, an optimized pressure condition, which allows a barrierless reaction to proceed, was identified and attributed to the very desirable reaction yield and kinetics. Finally, the photoinitiated reaction mechanism and the growth geometry of the polymer chains were investigated from the energy diagram of styrene and by the topology analysis of the crystal styrene. This study shows strong promise to produce functional polymeric materials in a highly efficient and controlled manner.

  8. GAMMA RADIATION INITIATED POLYMERIZATION OF FLUOROMONOMERS. II. COPOLYMER OF CHLOROTRIFLUOROETHYLENE AND ETHYLENE

    Energy Technology Data Exchange (ETDEWEB)

    Manno, P. J.

    1963-06-15

    The radioinduced copolymerization of chlorotrifluoro ethylene and ethylene was studied. The polymerization rate increased with time and radiation intensity, and the Gvalues after 50% polymerization varied from 13,000 at 10/sup 5/ rep/hr to 25,000 at 6 x 10/sup 3/ rep/hr. The polymerization rate is proportional to the 0.7 or 0.8th power of the radiation intensity. The polymerization reaction is highly exothermic, and the optimum conditions for the best polymer properties occurred in a stirred autoclave cooled to 0 deg C containing a monomer-- water mixture and irradiated at 10/sup 4/ rep/hr. Catalytic polymerization was also studied, and the economics of or the preparation of the copolymer by catalytic and radiation processes is discussed briefly. (D.L.C.)

  9. Synthesis of nanosized (polymerization in miniemulsion employing in situ surfactant formation.

    Science.gov (United States)

    Guo, Yi; Zetterlund, Per B

    2011-10-18

    A novel method for synthesis of ultrafine polymeric nanoparticles of diameters less than 20 nm has been developed. The method is based on miniemulsion polymerization exploiting combination of the in situ surfactant generation approach (whereby the surfactant is formed at the oil-water interface by reaction between an organic acid and a base) and ultrasonication. Conventional radical polymerization and nitroxide-mediated radical polymerization of styrene have been conducted in miniemulsion using oleic acid/potassium hydroxide, demonstrating that particles with diameters less than 20 nm can be obtained by this approach at surfactant contents much lower than traditionally required in microemulsion polymerizations. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Pre-irradiation induced emulsion graft polymerization of acrylonitrile onto polyethylene nonwoven fabric

    International Nuclear Information System (INIS)

    Liu Hanzhou; Yu Ming; Deng Bo; Li Linfan; Jiang Haiqing; Li Jingye

    2012-01-01

    Acrylonitrile has been widely used in the modification of polymers by graft polymerization. In the present work, pre-irradiation induced emulsion graft polymerization method is used to introduce acrylonitrile onto PE nonwoven fabric instead of the traditional reaction in organic solvents system. The degree of grafting (DG) is measured by gravimetric method and the kinetics of the graft polymerization is studied. The existence of the graft chains is proven by Fourier transform infrared spectroscopy (FT-IR) analysis. Thermal stability of the grafted polymer is measured by Thermogravimetric analysis (TGA). - Highlights: → Acrylonitrile is grafted onto pre-irradiated polyethylene (PE) nonwoven fabrics. → Emulsion system is applied, for the graft polymerization avoids organic solvent. → Kinetic of the pre-irradiation induced graft polymerization is studied. → Optimal condition is determined at the temperature below the b.p. of acrylonitrile.

  11. Fluorescent polymeric nanocomposite films generated by surface-mediated photoinitiation of polymerization

    International Nuclear Information System (INIS)

    Avens, Heather J.; Chang, Erin L.; May, Allison M.; Berron, Brad J.; Seedorf, Gregory J.; Balasubramaniam, Vivek; Bowman, Christopher N.

    2011-01-01

    Incorporation of nanoparticles (NPs) into polymer films represents a valuable strategy for achieving a variety of desirable physical, optical, mechanical, and electrical attributes. Here, we describe and characterize the creation of highly fluorescent polymer films by entrapment of fluorescent NPs into polymer matrices through surface-mediated eosin photoinitiation reactions. Performing surface-mediated polymerizations with NPs combines the benefits of a covalently anchored film with the unique material properties afforded by NPs. The effects of monomer type, crosslinker content, NP size, and NP surface chemistry were investigated to determine their impact on the relative amount of NPs entrapped in the surface-bound films. The density of entrapped NPs was increased up to 6-fold by decreasing the NP diameter. Increasing the crosslinking agent concentration enabled a greater than 2-fold increase in the amount of NPs entrapped. Additionally, the monomer chemistry played a significant role as poly(ethylene glycol) diacrylate (PEGDA)-based monomer formulations entrapped a 10-fold higher density of carboxy-functionalized NPs than did acrylamide/bisacrylamide formulations, though the latter formulations ultimately immobilized more fluorophores by generating thicker films. In the context of a polymerization-based microarray biodetection platform, these findings enabled tailoring of the monomer and NP selection to yield a 200-fold improvement in sensitivity from 31 (±1) to 0.16 (±0.01) biotinylated target molecules per square micron. Similarly, in polymerization-based cell staining applications, appropriate monomer and NP selection enabled facile visualization of microscale, sub-cellular features. Careful consideration of monomer and NP selection is critical to achieve the desired properties in applications that employ surface-mediated polymerization to entrap NPs.

  12. Self-Propagating Frontal Polymerization in Water at Ambient Pressure

    Science.gov (United States)

    Olten, Nesrin; Kraigsley, Alison; Ronney, Paul D.

    2003-01-01

    Advances in polymer chemistry have led to the development of monomers and initiation agents that enable propagating free-radical polymerization fronts to exist. These fronts are driven by the exothermicity of the polymerization reaction and the transport of heat from the polymerized product to the reactant monomer/solvent/initiator solution. The thermal energy transported to the reactant solution causes the initiator to decompose, yielding free radicals, which start the free radical polymerization process as discussed in recent reviews. The use of polymerization processes based on propagating fronts has numerous applications. Perhaps the most important of these is that it enables rapid curing of polymers without external heating since the polymerization process itself provides the high temperatures necessary to initiate and sustain polymerization. This process also enables more uniform curing of arbitrarily thick samples since it does not rely on heat transfer from an external source, which will necessarily cause the temperature history of the sample to vary with distance from the surface according to a diffusion-like process. Frontal polymerization also enables filling and sealing of structures having cavities of arbitrary shape without having to externally heat the structure. Water at atmospheric pressure is most convenient solvent to employ and the most important for practical applications (because of the cost and environmental issues associated with DMSO and other solvents). Nevertheless, to our knowledge, steady, self-propagating polymerization fronts have not been reported in water at atmospheric pressure. Currently, polymerization fronts require a high boiling point solvent (either water at high pressures or an alternative solvent such as dimethyl sulfoxide (DMSO) (boiling point 189 C at atmospheric pressure.) Early work on frontal polymerization, employed pressures up to 5000 atm in order to avoid boiling of the monomer/solvent/initiator solution. High

  13. Metallophilic interactions in polymeric group 11 thiols

    Science.gov (United States)

    Kolari, Kalle; Sahamies, Joona; Kalenius, Elina; Novikov, Alexander S.; Kukushkin, Vadim Yu.; Haukka, Matti

    2016-10-01

    Three polymeric group 11 transition metal polymers featuring metallophilic interactions were obtained directly via self-assembly of metal ions and 4-pyridinethiol ligands. In the cationic [Cu2(S-pyH)4]n2+ with [ZnCl4]n2- counterion (1) and in the neutral [Ag(S-py) (S-pyH)]n (2) 4-pyridinethiol (S-pyH) and its deprotonated form (S-py) are coordinated through the sulfur atom. Both ligands are acting as bridging ligands linking the metal centers together. In the solid state, the gold(I) polymer [Au(S-pyH)2]Cl (3) consists of the repeating cationic [Au(S-pyH)2]+ units held together by aurophilic interactions. Compound 1 is a zig-zag chain, whereas the metal chains in the structures of 2 and 3 are linear. The protonation level of the thiol ligand had an impact on the crystallization of polymers. Both nature of the metal center and reaction conditions affected the polymerization. QTAIM analysis confirmed direct metal-metal contacts only in polymers 1 and 3. In polymer 2, no theoretical evidence of argentophilic contacts was obtained even though the AgṡṡṡAg distance was found to be less than sum of the Bondi's van der Waals radius of silver.

  14. A pulse radiolysis study of emulsion polymerization

    International Nuclear Information System (INIS)

    McAskill, N.A.

    1976-01-01

    The emulsion polymerisation of slightly water soluble monomers such as styrene occurs initially in micelles of surfactant swollen with monomer and later in larger particles consisting of polymer swollen with monomer and stabilized with an outer layer of surfactant. There is considerable controversy on whether the reaction sites of polymerization are inside or on the surface of the particle or micelle. The relative amounts of micelle and particles present at various stages of the polymerization are also nuclear. In the present study the OH radical formed by pulse radiolysis has been used as a probe to investigate the site of solubilization of styrene in various surfactant micelles. Two products can be distinguished by UV spectrometry, a benzyl type radical formed by OH addition to the side chain of styrene and a cyclohexadienyl type radical formed by addition to the ring. Wide differences in the relative amounts of each product were observed suggesting that in some surfactants the styrene ring is buried inside the micelle whilst in other systems the styrene appears to be so solubilized at the interface leaving both the ring and the side chain open to attack by the OH radical. (author)

  15. Reactivity of polymeric proanthocyanidins toward salivary proteins and their contribution to young red wine astringency.

    Science.gov (United States)

    Sun, Baoshan; de Sá, Marta; Leandro, Conceição; Caldeira, Ilda; Duarte, Filomena L; Spranger, Isabel

    2013-01-30

    Recent studies have indicated the presence of significant amount of highly polymerized and soluble proanthocyanidins in red wine and such compounds interacted readily with proteins, suggesting that they might be particularly astringent. Thus, the objective of this work was to verify the astringency of polymeric proanthocyanidins and their contribution to red wine astringency. The precipitation reactions of the purified oligomeric procyanidins (degree of polymerization ranging from 2 to 12-15) and polymeric procyanidins (degree of polymerization ranging from 12-15 to 32-34) with human salivary proteins were studied; salivary proteins composition changes before and after the reaction was verified by SDS-PAGE and procyanidins composition changes by spectrometric, direct HPLC and thiolysis-HPLC methods. The astringency intensity of these two procyanidin fractions was evaluated by a sensory analysis panel. For verifying the correlation between polymeric proanthocyanidins and young red wine astringency, the levels of total oligomeric and total polymeric proanthocyanidins and other phenolic composition in various young red wines were quantified and the astringency intensities of these wines were evaluated by a sensory panel. The results showed that polymeric proanthocyanidins had much higher reactivity toward human salivary proteins and higher astringency intensity than the oligomeric ones. Furthermore, young red wine astringency intensities were highly correlated to levels of polymeric proanthocyanidins, particularly at low concentration range (correlation coefficient r = 0.9840) but not significant correlated to total polyphenols (r = 0.2343) or other individual phenolic compounds (generally r wine astringency and the levels of polymeric polyphenols in red wines may be used as an indicator for its astringency.

  16. Surface Initiated Polymerizations via e-ATRP in Pure Water

    Directory of Open Access Journals (Sweden)

    Seyed Schwan Hosseiny

    2013-10-01

    Full Text Available Here we describe the combined process of surface modification with electrochemical atom transfer radical polymerization (e-ATRP initiated from the surface of a modified gold-electrode in a pure aqueous solution without any additional supporting electrolyte. This approach allows for a very controlled growth of the polymer chains leading towards a steady increase in film thickness. Electrochemical quartz crystal microbalance displayed a highly regular increase in surface confined mass only after the addition of the pre-copper catalyst which is reduced in situ and transformed into the catalyst. Even after isolation and washing of the modified electrode surface, reinitiation was achieved with retention of the controlled electrochemical ATRP reaction. This reinitiation after isolation proves the livingness of the polymerization. This approach has interesting potential for smart thin film materials and offers also the possibility of post-modification via additional electrochemical induced reactions.

  17. Polyacrylamide grafting of modified graphene oxides by in situ free radical polymerization

    International Nuclear Information System (INIS)

    Tang, Mingyi; Xu, Xiaoyang; Wu, Tao; Zhang, Sai; Li, Xianxian; Li, Yi

    2014-01-01

    Highlights: • Graphene oxide (GO) was modified by chemical reactions to functionalized GO (FGO). • The FGOs and the GO were then subjected to in situ free radical polymerization. • Hydroxyl groups of GO were the most reactive grafting sites. - Abstract: Graphene oxide (GO) was modified using chemical reactions to obtain three types of functionalized GO sheets (FGO). The FGO sheets and the GO were then subjected to in situ free radical polymerization in order to study the grafting polymerization. The FGO and grafted-.FGO were analyzed with Fourier transform infrared spectroscopy, scanning electronic microscopy, thermo-gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The grafting percentages in the materials were calculated using the TGA and XPS results. The FGO sheets with different functional groups exhibited different grafting abilities, and hydroxyl groups were proven to be the most reactive grafting sites for the in situ free radical grafting polymerization of polyacrylamide

  18. Polyacrylamide grafting of modified graphene oxides by in situ free radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Tang, Mingyi [Department of Applied Chemistry, School of Science, Tianjin University of Commerce, Tianjin 300134 (China); Xu, Xiaoyang, E-mail: xiaoyangxu2012@163.com [School of Science, Tianjin University, Tianjin 30072 (China); Wu, Tao [School of Science, Tianjin University, Tianjin 30072 (China); Zhang, Sai; Li, Xianxian [Department of Applied Chemistry, School of Science, Tianjin University of Commerce, Tianjin 300134 (China); Li, Yi, E-mail: liyi@tju.edu.cn [School of Science, Tianjin University, Tianjin 30072 (China)

    2014-12-15

    Highlights: • Graphene oxide (GO) was modified by chemical reactions to functionalized GO (FGO). • The FGOs and the GO were then subjected to in situ free radical polymerization. • Hydroxyl groups of GO were the most reactive grafting sites. - Abstract: Graphene oxide (GO) was modified using chemical reactions to obtain three types of functionalized GO sheets (FGO). The FGO sheets and the GO were then subjected to in situ free radical polymerization in order to study the grafting polymerization. The FGO and grafted-.FGO were analyzed with Fourier transform infrared spectroscopy, scanning electronic microscopy, thermo-gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The grafting percentages in the materials were calculated using the TGA and XPS results. The FGO sheets with different functional groups exhibited different grafting abilities, and hydroxyl groups were proven to be the most reactive grafting sites for the in situ free radical grafting polymerization of polyacrylamide.

  19. Oxidative polymerization of lignins by laccase in water-acetone mixture.

    Science.gov (United States)

    Fiţigău, Ionița Firuța; Peter, Francisc; Boeriu, Carmen Gabriela

    2013-01-01

    The enzymatic oxidative polymerization of five technical lignins with different molecular properties, i.e. Soda Grass/Wheat straw Lignin, Organosolv Hardwood Lignin, Soda Wheat straw Lignin, Alkali pretreated Wheat straw Lignin, and Kraft Softwood was studied. All lignins were previously fractionated by acetone/water 50:50 (v/v) and the laccase-catalyzed polymerization of the low molecular weight fractions (Mw Reactivity of lignin substrates in laccase-catalyzed reactions was determined by monitoring the oxygen consumption. The oxidation reactions in 50% acetone in water mixture proceed with high rate for all tested lignins. Polymerization products were analyzed by size exclusion chromatography, FT-IR, and (31)P-NMR and evidence of important lignin modifications after incubation with laccase. Lignin polymers with higher molecular weight (Mw up to 17500 g/mol) were obtained. The obtained polymers have potential for applications in bioplastics, adhesives and as polymeric dispersants.

  20. Catalytic olefin polymerization with early transition metal compounds

    OpenAIRE

    Eshuis, Johan Jan Willem

    1991-01-01

    The catalysis of organic reactions by soluble metal complexes has become a major tool in synthesis, both in the laboratory and in the chemical industry. Processes catalyzed by transition metal complexes include carbonylation, olefin polymerization, olefin addition, olefin oxidation and alkane and arene oxidation. Traditionally, heterogeneous catalysts have been used for the production of large-scale commodity chemicals such as methanol and ammonia and in the production of high octane gasoline...

  1. Optimal control of batch emulsion polymerization of vinyl chloride

    Energy Technology Data Exchange (ETDEWEB)

    Damslora, Andre Johan

    1998-12-31

    The highly exothermic polymerization of vinyl chloride (VC) is carried out in large vessels where the heat removal represents a major limitation of the production rate. Many emulsion polymerization reactors are operated in such a way that a substantial part of the heat transfer capacity is left unused for a significant part of the total batch time. To increase the reaction rate so that it matches the heat removal capacity during the course of the reaction, this thesis proposes the use of a sufficiently flexible initiator system to obtain a reaction rate which is high throughout the reaction and real-time optimization to compute the addition policy for the initiator. This optimization based approach provides a basis for an interplay between design and control and between production and research. A simple model is developed for predicting the polymerization rate. The model is highly nonlinear and open-loop unstable and may serve as an interesting case for comparison of nonlinear control strategies. The model is fitted to data obtained in a laboratory scale reactor. Finally, the thesis discusses optimal control of the emulsion polymerization reactor. Reduction of the batch cycle time is of major economic importance, as long as the quality parameters are within their specifications. The control parameterization had a major influence on the performance. A differentiable spline parameterization was applied and the optimization is illustrated in a number of cases. The best performance is obtained when the reactor temperature is obtained when the optimization is combined with some form of closed-loop control of the reactor temperature. 112 refs., 48 figs., 4 tabs.

  2. Polymeric molecular sieve membranes for gas separation

    Science.gov (United States)

    Dai, Sheng; Qiao, Zhenan; Chai, Songhai

    2017-08-15

    A porous polymer membrane useful in gas separation, the porous polymer membrane comprising a polymeric structure having crosslinked aromatic groups and a hierarchical porosity in which micropores having a pore size less than 2 nm are present at least in an outer layer of the porous polymer membrane, and macropores having a pore size of over 50 nm are present at least in an inner layer of the porous polymer membrane. Also described are methods for producing the porous polymer membrane in which a non-porous polymer membrane containing aromatic rings is subjected to a Friedel-Crafts crosslinking reaction in which a crosslinking molecule crosslinks the aromatic rings in the presence of a Friedel-Crafts catalyst and organic solvent under sufficiently elevated temperature, as well as methods for using the porous polymer membranes for gas or liquid separation, filtration, or purification.

  3. Microwave-assisted Polymerization of D, L-Lactide with Stannous Octanoate as Catalyst

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    Poly (lactic acid) (PLA) was synthesized by microwave-assisted ring-opening poly- merization of D, L-lactide with stannous octanoate (SnOct2) as catalyst. Its weight-average molar mass (Mw) ranged from 39000 to 67000 and the polydispersity index from 1.3 to 1.7. The polymerization rate was much faster than that of the conventional thermal polymerization. A degradation of newly formed PLA in reaction mixture by microwave irradiation was observed.

  4. Magnetic Levitation To Characterize the Kinetics of Free-Radical Polymerization.

    Science.gov (United States)

    Ge, Shencheng; Semenov, Sergey N; Nagarkar, Amit A; Milette, Jonathan; Christodouleas, Dionysios C; Yuan, Li; Whitesides, George M

    2017-12-27

    This work describes the development of magnetic levitation (MagLev) to characterize the kinetics of free-radical polymerization of water-insoluble, low-molecular-weight monomers that show a large change in density upon polymerization. Maglev measures density, and certain classes of monomers show a large change in density when monomers covalently join in polymer chains. MagLev characterized both the thermal polymerization of methacrylate-based monomers and the photopolymerization of methyl methacrylate and made it possible to determine the orders of reaction and the Arrhenius activation energy of polymerization. MagLev also made it possible to monitor polymerization in the presence of solids (aramid fibers, and carbon fibers, and glass fibers). MagLev offers a new analytical technique to materials and polymer scientists that complements other methods (even those based on density, such as dilatometry), and will be useful in investigating polymerizations, evaluating inhibition of polymerizations, and studying polymerization in the presence of included solid materials (e.g., for composite materials).

  5. Polymeric media for tritium fixation

    International Nuclear Information System (INIS)

    Franz, J.A.; Burger, L.L.

    1975-01-01

    The synthesis and leach testing of several polymeric media for tritium fixation are presented. Tritiated bakelite, poly(acrylonitrile) and polystyrene successfully fixed tritium. Tritium leach rates at the tracer level appear to be negligible. Advantages and disadvantages of the processes are discussed, and further bench-scale investigations underway are reported. Rough cost estimates are presented for the different media and are compared with alternate approaches such as deep-well injection and long-term tank storage. Polymeric media costs are high compared to deep-well storage and are of the same order of magnitude per liter of water as for isotopic enrichment. With this limitation, polymeric media can be economically feasible only for highly concentrated tritiated wastes. It is recommended that the bakelite and polystyrene processes be examined on a larger scale to permit more accurate cost analysis and process design. (auth)

  6. Dynamic bioactive stimuli-responsive polymeric surfaces

    Science.gov (United States)

    Pearson, Heather Marie

    This dissertation focuses on the design, synthesis, and development of antimicrobial and anticoagulant surfaces of polyethylene (PE), polypropylene (PP), and poly(tetrafluoroethylene) (PTFE) polymers. Aliphatic polymeric surfaces of PE and PP polymers functionalized using click chemistry reactions by the attachment of --COOH groups via microwave plasma reactions followed by functionalization with alkyne moieties. Azide containing ampicillin (AMP) was synthesized and subsequently clicked into the alkyne prepared PE and PP surfaces. Compared to non-functionalized PP and PE surfaces, the AMP clicked surfaces exhibited substantially enhanced antimicrobial activity against Staphylococcus aureus bacteria. To expand the biocompatibility of polymeric surface anticoagulant attributes, PE and PTFE surfaces were functionalized with pH-responsive poly(2-vinyl pyridine) (P2VP) and poly(acrylic acid) (PAA) polyelectrolyte tethers terminated with NH2 and COOH groups. The goal of these studies was to develop switchable stimuli-responsive polymeric surfaces that interact with biological environments and display simultaneous antimicrobial and anticoagulant properties. Antimicrobial AMP was covalently attached to --COOH terminal ends of protected PAA, while anticoagulant heparin (HEP) was attached to terminal --NH2 groups of P2VP. When pH 5.5, they collapse while the PAA segments extend. Such surfaces, when exposed to Staphylococcus aureus, inhibit bacterial growth due to the presence of AMP, as well as are effective anticoagulants due to the presence of covalently attached HEP. Comparison of these "dynamic" pH responsive surfaces with "static" surfaces terminated with AMP entities show significant enhancement of longevity and surface activity against microbial film formation. The last portion of this dissertation focuses on the covalent attachment of living T1 and Φ11 bacteriophages (phages) on PE and PTFE surface. This was accomplished by carbodiimide coupling between --COOH

  7. Study of radiation-induced polymerization of vinyl monomers adsorbed on inorganic substances. VIII. Polymerization of styrene and methyl methacrylate adsorbed on aerosil

    International Nuclear Information System (INIS)

    Fukano, K.; Kageyama, E.

    1976-01-01

    Aerosol is silica having a purity which is very high compared with that of silica gel and having, unlike silica gel, no micropores. To investigate the effects of impurities and micropores on the radiation-induced polymerization of styrene and methyl methacrylate adsorbed on silica gel, the radiation-induced polymerization of styrene and methyl methacrylate adsorbed on Aerosil was carried out. The results of both the styrene--Aerosil 300 system and the methyl methacrylate--Aerosil 300 system were similar to those of the styrene-silica gel and methyl methacrylate-silica gel systems, respectively. This suggests that in the radiation-induced polymerization of both styrene--silica gel and methyl methacrylate--silica gel systems the impurities and the presence of micropores have almost no effect on the reaction mechanism. The effect of aluminum as an impurity was investigated on the styrene--Aerosil MOX 170 system. It was found that aluminum accelerated the cationic polymerization

  8. Monte Carlo simulation of non-linear free radical polymerization using a percolation kinetic gelation model (I): free radical homo polymerization

    International Nuclear Information System (INIS)

    Ghiass, M.; Dabir, B.; Nikazar, M.; Rey, A.D.; Mirzadeh, H.

    2001-01-01

    A kinetic gelation model that incorporates the kinetics of free radical homo polymerization is implemented to determine the effects of kinetics on polymerization statistics and microstructures. The simulation is performed on a simple cubic lattice that has 100 sites in each direction. A new algorithm for random selecting of the next step in a self-avoiding random walk and very efficient mechanisms of mobility of components are introduced to improve the generality of the predictions by removing commonly accruing deficiencies due to early trapping of radicals. A first order kinetics is considered for decomposition of initiator that enables us to consider the effect of temperature on polymerization reaction. Better understanding of microstructural evolution during polymerization and providing a framework to produce a realistic system of highly packed random chains within polymer network are among the benefits of model

  9. Modeling intraparticle transports during propylene polymerizations using supported metallocene and dual function metallocene as catalysts: Single particle model

    Directory of Open Access Journals (Sweden)

    Li Hua-Rong

    2014-01-01

    Full Text Available Two improved multigrain models (MGMs for preparing homopolypropylene and long chain branched polypropylene via propylene polymerization using silica-supported metallocene or dual function metallocene as catalysts are presented in this paper. The presented models are used to predict the intraparticle flow fields involved in the polymerizations. The simulation results show that the flow field distributions involve dare basically identical. The results also show that both the two polymerization processes have an initiation stage and the controlling step for them is reaction-diffusion-reaction with the polymerization proceeding. Furthermore, the simulation results show that the intra particle mass transfer resistance has significant effect on the polymerization but the heat transfer resistance can be ignored.

  10. Pentafluorosulfanyl Substituents in Polymerization Catalysis.

    Science.gov (United States)

    Kenyon, Philip; Mecking, Stefan

    2017-10-04

    Highly electron-withdrawing pentafluorosulfanyl groups were probed as substituents in an organometallic catalyst. In Ni(II) salicylaldiminato complexes as an example case, these highly electron-withdrawing substituents allow for polymerization of ethylene to higher molecular weights with reduced branching due to significant reductions in β-hydrogen elimination. Combined with the excellent functional group tolerance of neutral Ni(II) complexes, this suppression of β-hydrogen elimination allows for the direct polymerization of ethylene in water to nanocrystal dispersions of disentangled, ultrahigh-molecular-weight linear polyethylene.

  11. Esterification with ethanol to produce biodiesel from high acidity raw materials. Kinetic studies and analysis of secondary reactions

    Energy Technology Data Exchange (ETDEWEB)

    Pisarello, M.L.; Dalla Costa, B.; Mendow, G.; Querini, C.A. [Instituto de Investigaciones en Catalisis y Petroquimica (INCAPE)-(FIQ-UNL, CONICET), Santiago del Estero 2654-Santa Fe, S3000AOJ (Argentina)

    2010-09-15

    In this work, the esterification reaction of free fatty acids (FFA) in sunflower oil, coconut oil and concentrated FFA, with ethanol, methanol and ethanol 96%, using homogeneous acid catalysts to produce biodiesel is studied. Kinetic parameters are estimated with a simplified model, and then used to predict the reaction behavior. Reactions other than the reversible esterification are considered to explain the behavior that this system displays. Such reactions are the triglycerides conversion by acid catalyzed transesterification and hydrolysis. In addition, we include kinetic studies of the reaction that occur between the sulphuric acid and methanol (or ethanol), forming mono and dialkylsulphates. This reaction produces water and consumes methanol (or ethanol), and consequently has a direct impact in the esterification reaction rate and equilibrium conversion. The concentration of sulphuric acid decreases to less than 50% of the initial value due to the reaction with the alcohol. A minimum in the acidity due to the free fatty acids as a function of time was clearly observed during the reaction, which has not been reported earlier. This behavior is related to the consecutive reactions that take place during the esterification of FFA in the presence of triglycerides. The phase separation due to the presence of water, which is generated during the reaction, is also studied. (author)

  12. High-pressure synthesis of CuBa2Ca3Cu4O10+δ superconductor from precursors prepared by a polymerized complex method

    International Nuclear Information System (INIS)

    Aoba, Tomoya; Bizen, Takeshi; Suzuki, Tsuneo; Nakayama, Tadachika; Suematsu, Hisayuki; Niihara, Koichi; Katsumata, Tetsuhiro; Inaguma, Yoshiyuki

    2011-01-01

    Samples of a CuBa 2 Ca 3 Cu 4 O 10+ δ superconductor were synthesized under a high pressure of 5 GPa at 1100-1200degC for 30 min using precursors produced by solid-state reaction and polymerized complex methods. Compared with the precursors prepared by the solid-state reaction method, the precursors produced by the polymerized complex method have low grain sizes. The superconductive transition temperature of the samples prepared using precursors made by the polymerized complex method was found to be 113 K. The volume fractions of the superconducting phase in the samples prepared using precursors made by the solid-state reaction and polymerized complex methods were 49 and 36%, respectively. From these results, precursors made by the polymerized complex method can be used in the high-pressure synthesis of superconductors similarly to those made by the solid-state reaction method. (author)

  13. Functionalization and Polymerization on the CNT Surfaces

    KAUST Repository

    Albuerne, Julio

    2013-07-01

    In this review we focus on the current status of using carbon nanotube (CNT) as a filler for polymer nanocomposites. Starting with the historical background of CNT, its distinct properties and the surface functionalization of the nanotube, the three different surface polymerization techniques, namely grafting "from", "to" and "through/in between" were discussed. Wider focus has been given on "grafting from" surface initiated polymerizations, including atom transfer radical polymerization (ATRP), reversible addition fragmentation chain-transfer (RAFT) Polymerization, nitroxide mediated polymerization (NMP), ring opening polymerization (ROP) and other miscellaneous polymerization methods. The grafting "to" and "through / in between" also discussed and compared with grafting from polymerization. The merits and shortcomings of all three grafting methods were discussed and the bottleneck issue in grafting from method has been highlighted. Furthermore the current and potential future industrial applications were deliberated. Finally the toxicity issue of CNTs in the final product has been reviewed with the limited available literature knowledge. © 2013 Bentham Science Publishers.

  14. High Vacuum Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar; Hadjichristidis, Nikolaos; Mays, Jimmy

    2015-01-01

    Anionic polymerization high vacuum techniques (HVTs) are the most suitable for the preparation of polymer samples with well-defined complex macromolecular architectures. Though HVTs require glassblowing skill for designing and making polymerization

  15. The Research on Modeling and Simulation of TFE Polymerization Process

    Directory of Open Access Journals (Sweden)

    Jing Gao Sun

    2014-01-01

    Full Text Available PTFE (polytetrafluoroethylene is the fluorinated straight-chain polymer, made by the polymerization of tetrafluoroethylene monomer; it is used widely because of its excellent performance and can be obtained by the polymerization of body, solutions, suspensions, and emulsions. But only the last two are the main ways. This research paper makes simulation based on Polymer Plus. It uses the emulsion polymerization method at background to carry out a semibatch reactor system. Upon the actual production conditions, simulation process under the steady state conditions is used to analyze the effects of the changes on operating conditions; the corresponding dynamic model is created to analyze the impact of the changes of conditions on the entire system. Moreover, the amount of APS which plays an important part in this reaction is discussed for getting the most suitable amount of initiator. Because of less research work on this job, it is so difficult to find the related data from the literature. Therefore, this research will have a great significance for the process of the tetrafluoroethylene emulsion polymerization in the future.

  16. Polymerization of impregnated monomer in wood by microwave irradiation

    International Nuclear Information System (INIS)

    Kawase, Kaoru; Hayakawa, Kiyoshi

    1976-01-01

    The manufacturing of a wood-plastic combination (WPC) by irradiation of microwave (2,450 and 915 +- 50 MHz) or gamma-ray was carried out. After the impregnation of dry woods (Hinoki: Chamaecyparis obtusa Endl., Buna: Acer mono Maxim., and Kaede: Fagus crenata Blume) with the mixture of the vinyl monomers and chemical reagents, the monomer in wood was polymerized by irradiation. In case of polymerization with microwave (2,450 MHz) the effect of oxygen was not recognized, but in the case of gamma-ray the rate of polymerization remarkably decreased in the presence of oxygen. The polymerization of various monomers was carried out also in the air, and the conversions of styrene, methyl-, ethyl-, n-propyl-, and n-butyl-methacrylate were 51.8 -- 89.1%, but that of vinyl acetate was lower (4.3 -- 8.2%). The conversion of monomers with irradiation of 915 MHz microwave was very low (2.6 -- 33.5%). The conversion of monomers increased when toluylene diisocyanate was added in the monomers. The percentage of extraction with hot benzene of WPC (chip) decreased by the addition of toluylene diisocyanate. It was concluded from C.H.N. analyses that the reaction took place among the wood, toluylene diisocyanate and methyl methacrylate. (auth.)

  17. Polythiophene films obtained by polymerization under atmospheric pressure plasma conditions

    Energy Technology Data Exchange (ETDEWEB)

    Teslaru, T.; Topala, I., E-mail: ionut.topala@uaic.ro; Dobromir, M.; Pohoata, V.; Curecheriu, L.; Dumitrascu, N.

    2016-02-01

    The present work describes the experimental arrangement used to initiate polymerization reactions of thiophene monomer based on a dielectric barrier discharge with plane – parallel geometry, working at atmospheric pressure in argon, in turn to obtain conductive polymeric films for different applications. The resulting plasma polymerized polythiophene (pPTh) film was characterized by FT-IR, UV–Vis, XPS spectroscopy, AFM and contact angle measurements. Characterization of pPTh films showed a higher hydrophobic character and roughness, as compared with films obtained by chemical methods, and the thickness is depending on polymerization duration. Also it can conclude that our samples represent oxidised state of pPTh. As a possible application, it analysed in situ the iodine absorption phenomenon in the pPTh matrix and its time evolution by UV–Vis spectroscopy. The presence of iodine 3d{sub 5/2} and 3d{sub 3/2} peaks in the pPTh sample after absorption was identified by XPS spectroscopy. The hydrophobic pPTh film is transformed in a super hydrophilic film after absorption of iodine vapors. - Highlights: • We obtained polythiophene films (pPTh) by atmospheric pressure plasma technique. • The pPTh films showed a hydrophobic character and conducting properties. • The pPTh films were used as sensor for iodine vapors in biological environment.

  18. Effect of homopolymer in polymerization-induced microphase separation process

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jongmin; Saba, Stacey A.; Hillmyer, Marc A.; Kang, Dong-Chang; Seo, Myungeun (IBS-Korea); (KAIST); (UMMN)

    2017-09-01

    We report on the phase separation behaviors of polymerization mixtures containing a polylactide macro-chain transfer agent (PLA-CTA), styrene, divinylbenzene, hydroxyl-terminated PLA (PLA-OH), and a molecular chain transfer agent which enable the ability to tune the pore size of a cross-linked polymer monolith in a facile manner. Cross-linked monoliths were produced from the mixtures via reversible addition-fragmentation chain transfer (RAFT) polymerization and converted into cross-linked porous polymers by selective removal of PLA while retaining the parent morphology. We demonstrate that pore sizes are tunable over a wide range of length scales from the meso- to macroporous regimes by adjusting the ratio of PLA-CTA to PLA-OH in the reaction mixture which causes the phase separation mechanism to change from polymerization-induced microphase separation to polymerization-induced phase separation. The possibility of increasing porosity and inducing simultaneous micro- and macrophase separation was also realized by adjustments in the molar mass of PLA which enabled the synthesis of hierarchically meso- and macroporous polymers.

  19. Novel solid state polymeric batteries

    Energy Technology Data Exchange (ETDEWEB)

    Patrick, A.; Glasse, M.; Latham, R.; Linford, R.

    1986-01-01

    AC conductivity measurements have been performed on a number of polymeric electrolytes containing Mg, Ca, Sr and Zn perchlorates and Mg and Ca thiocyanates. The electrolytes were characterized using DSC. Results are reported of preliminary tests of cells incorporating anodes of the above metals. 11 refs.

  20. Reactive surfactants in heterophase polymerization

    NARCIS (Netherlands)

    Guyot, A.; Tauer, K.; Asua, J.M.; Es, van J.J.G.S.; Gauthier, C.; Hellgren, A.C.; Sherrington, D.C.; Montoya-Goni, A.; Sjöberg, M.; Sindt, O.; Vidal, F.F.M.; Unzue, M.; Schoonbrood, H.A.S.; Schipper, E.T.W.M.; Lacroix-Desmazes, P.

    1999-01-01

    This paper summarizes the work carried out during 3 years in a Network of the program "Human Capital and Mobility" of the European Union CHRX 93-0159 entitled "Reactive surfactants in heterophase polymerization for high performance polymers". A series of about 25 original papers will be published in

  1. Biodegradable polymeric prodrugs of naltrexone

    NARCIS (Netherlands)

    Bennet, D.B.; Li, X.; Adams, N.W.; Kim, S.W.; Hoes, C.J.T.; Hoes, C.J.T.; Feijen, Jan

    1991-01-01

    The development of a biodegradable polymeric drug delivery system for the narcotic antagonist naltrexone may improve patient compliance in the treatment of opiate addiction. Random copolymers consisting of the ¿-amino acids N5-(3-hydroxypropyl--glutamine and -leucine were synthesized with equimolar

  2. Preparations of spherical polymeric particles from Tanzanian ...

    African Journals Online (AJOL)

    Spherical Polymeric Particles (SPP) have been prepared from Tanzanian Cashew Nut Shell Liquid (CNSL) by suspension polymerization technique involving either step-growth or chain- growth polymerization mechanisms. The sizes of the SPP, which ranged from 0.1 to 2.0 mm were strongly influenced by the amounts of ...

  3. Novel Reaction of N,N'-Bisarylmethanediamines with Formaldehyde. Synthesis of Some New 1,3,5-Triaryl-1,3,5-hexahydrotriazines

    Directory of Open Access Journals (Sweden)

    Abolfazl Olyaei

    2006-07-01

    Full Text Available The acid-catalyzed cyclocondensation of N,N'-bisaryl (aryl = 2-pyrimidinyl, 2- pyrazinyl and 4-nitrophenyl methanediamines 5a-c with aqueous formaldehyde in refluxing acetonitrile leads to the formation of the corresponding 1,3,5-triaryl-1,3,5-hexa- hydrotriazines 6a-c. The stoichiometric reactions of 2-aminopyrimidine and 2-amino- pyrazine with aqueous formaldehyde in acetonitrile under reflux conditions also afforded 6a and 6b, respectively. Treatment of 2-aminopyrimidine with aqueous formaldehyde in a 3:2 ratio yielded N,N',N"-tris(2-pyrimidinyldimethylenetriamine (7a as a sole product, which upon subsequent reaction with formaldehyde also afforded 6a. The reaction of N,N'-biphenylmethanediamine with formaldehyde was also investigated.

  4. The Effect of the Chain Length on MMA Free Radicl Polymerization

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    In the polymerization process of methyl methacrylate (MMA), the Arrhenius parameters (activation energy and frequency factor) of propagating reaction monotonically decrease with increasing monomer conversion. At the beginning and middle stage of the propagating reaction, the increase of radical chain length is the main reason of above mentioned change. And at the end stage, the sharp decrease of kp indicates that the activation energy is approximately incline to zero and the propagating reaction is controlled by molecular diffusion motion.

  5. Glycine Polymerization on Oxide Minerals

    Science.gov (United States)

    Kitadai, Norio; Oonishi, Hiroyuki; Umemoto, Koichiro; Usui, Tomohiro; Fukushi, Keisuke; Nakashima, Satoru

    2017-06-01

    It has long been suggested that mineral surfaces played an important role in peptide bond formation on the primitive Earth. However, it remains unclear which mineral species was key to the prebiotic processes. This is because great discrepancies exist among the reported catalytic efficiencies of minerals for amino acid polymerizations, owing to mutually different experimental conditions. This study examined polymerization of glycine (Gly) on nine oxide minerals (amorphous silica, quartz, α-alumina and γ-alumina, anatase, rutile, hematite, magnetite, and forsterite) using identical preparation, heating, and analytical procedures. Results showed that a rutile surface is the most effective site for Gly polymerization in terms of both amounts and lengths of Gly polymers synthesized. The catalytic efficiency decreased as rutile > anatase > γ-alumina > forsterite > α- alumina > magnetite > hematite > quartz > amorphous silica. Based on reported molecular-level information for adsorption of Gly on these minerals, polymerization activation was inferred to have arisen from deprotonation of the NH3 + group of adsorbed Gly to the nucleophilic NH2 group, and from withdrawal of electron density from the carboxyl carbon to the surface metal ions. The orientation of adsorbed Gly on minerals is also a factor influencing the Gly reactivity. The examination of Gly-mineral interactions under identical experimental conditions has enabled the direct comparison of various minerals' catalytic efficiencies and has made discussion of polymerization mechanisms and their relative influences possible Further systematic investigations using the approach reported herein (which are expected to be fruitful) combined with future microscopic surface analyses will elucidate the role of minerals in the process of abiotic peptide bond formation.

  6. Glycine Polymerization on Oxide Minerals.

    Science.gov (United States)

    Kitadai, Norio; Oonishi, Hiroyuki; Umemoto, Koichiro; Usui, Tomohiro; Fukushi, Keisuke; Nakashima, Satoru

    2017-06-01

    It has long been suggested that mineral surfaces played an important role in peptide bond formation on the primitive Earth. However, it remains unclear which mineral species was key to the prebiotic processes. This is because great discrepancies exist among the reported catalytic efficiencies of minerals for amino acid polymerizations, owing to mutually different experimental conditions. This study examined polymerization of glycine (Gly) on nine oxide minerals (amorphous silica, quartz, α-alumina and γ-alumina, anatase, rutile, hematite, magnetite, and forsterite) using identical preparation, heating, and analytical procedures. Results showed that a rutile surface is the most effective site for Gly polymerization in terms of both amounts and lengths of Gly polymers synthesized. The catalytic efficiency decreased as rutile > anatase > γ-alumina > forsterite > α- alumina > magnetite > hematite > quartz > amorphous silica. Based on reported molecular-level information for adsorption of Gly on these minerals, polymerization activation was inferred to have arisen from deprotonation of the NH 3 + group of adsorbed Gly to the nucleophilic NH 2 group, and from withdrawal of electron density from the carboxyl carbon to the surface metal ions. The orientation of adsorbed Gly on minerals is also a factor influencing the Gly reactivity. The examination of Gly-mineral interactions under identical experimental conditions has enabled the direct comparison of various minerals' catalytic efficiencies and has made discussion of polymerization mechanisms and their relative influences possible Further systematic investigations using the approach reported herein (which are expected to be fruitful) combined with future microscopic surface analyses will elucidate the role of minerals in the process of abiotic peptide bond formation.

  7. Facile synthesis of polymeric fluorescent organic nanoparticles based on the self-polymerization of dopamine for biological imaging.

    Science.gov (United States)

    Shi, Yingge; Jiang, Ruming; Liu, Meiying; Fu, Lihua; Zeng, Guangjian; Wan, Qing; Mao, Liucheng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2017-08-01

    Polymeric fluorescent organic nanoparticles (polymer-FONs) have raised considerable research attention for biomedical applications owing to their advantages as compared with fluorescent inorganic nanoparticles and small organic molecules. In this study, we presented an efficient, facile and environment-friendly strategy to produce polymer-FONs, which relied on the self-polymerization of dopamine and polyethyleneimine (PEI) in rather mild conditions. To obtain the final polymer-FONs, aldehyde group-containing copolymers (named as poly(UA-co-PEGMA)) were synthesized by reversible addition-fragmentation chain-transfer polymerization using polyethylene glycol methyl ether methacrylate (PEGMA) and 1-undecen-10-al (UA) as monomers. The dopamine was conjugated onto poly(UA-co-PEGMA) through a multicomponent reaction between UA and dopamine to obtain poly(UA-co-PEGMA)-DA, which was further utilized for preparation of polymer-FONs through self-polymerization of dopamine and PEI. 1 H nuclear magnetic resonance, Fourier transform infrared spectroscopy, transmission electron microscopy and fluorescence spectroscopy were employed to characterize the structure, morphology, compositions and optical properties of these polymer-FONs. Cell viability and cell uptake behavior results suggested that these polymer-FONs possess good biocompatibility and can be potentially utilized for biomedical applications. More importantly, the method can be also applied to fabricate many other multifunctional polymer-FONs with great potential for biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Experimental conditions affecting the kinetics of aqueous HCN polymerization as revealed by UV-vis spectroscopy.

    Science.gov (United States)

    Marín-Yaseli, Margarita R; Moreno, Miguel; de la Fuente, José L; Briones, Carlos; Ruiz-Bermejo, Marta

    2018-02-15

    HCN polymerization is one of the most important and fascinating reactions in prebiotic chemistry, and interest in HCN polymers in the field of materials science is growing. However, little is known about the kinetics of the HCN polymerization process. In the present study, a first approach to the kinetics of two sets of aqueous HCN polymerizations, from NH 4 CN and NaCN, at middle temperatures between 4 and 38°C, has been carried out. For each series, the presence of air and salts in the reaction medium has been systematically explored. A previous kinetic analysis was conducted during the conversion of the insoluble black HCN polymers obtained as gel fractions in these precipitation polymerizations for a reaction of one month, where a limit conversion was achieved at the highest polymerization temperature. The kinetic description of the gravimetric data for this complex system shows a clear change in the linear dependence with the polymerization temperature for the reaction from NH 4 CN, besides a relevant catalytic effect of ammonium, in comparison with those data obtained from the NaCN series. These results also demonstrated the notable influence of air, oxygen, and the saline medium in HCN polymer formation. Similar conclusions were reached when the sol fractions were monitored by UV-vis spectroscopy, and a Hill type correlation was used to describe the polymerization profiles obtained. This technique was chosen because it provides an easy, prompt and fast method to follow the evolution of the liquid or continuous phase of the process under study. Copyright © 2017 Elsevier B.V. All rights reserved.

  9. Atom transfer radical polymerization of n-butyl acrylate catalyzed by atom transfer radical polymerization of n-butyl acrylate catalyzed by

    NARCIS (Netherlands)

    Zhang, H.; Linde, van der R.

    2002-01-01

    The homogeneous atom transfer radical polymerization (ATRP) of n-butyl acrylate with CuBr/N-(n-hexyl)-2-pyridylmethanimine as a catalyst and ethyl 2-bromoisobutyrate as an initiator was investigated. The kinetic plots of ln([M]0/[M]) versus the reaction time for the ATRP systems in different

  10. Reactions of alkylnitrosoureas in aqueous solution

    International Nuclear Information System (INIS)

    Snyder, J.K.; Stock, L.M.

    1980-01-01

    The acid- and base-catalyzed decompositions of N-methyl-,N,N'-dimethyl-, and N,N',N'-trimethyl-N-nitrosourea in aqueous solution have been studied. Below pH 2, the N-methyl compound undergoes both denitrosation and hydrolysis to yield methylurea, nitrous acid, methylamine, nitrogen, and carbon dioxide. The acid-catalyzed denitrosation and hydrolysis of the trimethylnitrosourea are somewhat more rapid than the corresponding reactions of N-methyl-N-nitrosourea. The solvent isotope effect, k/sub H 2 O//k/sub D 2 O/ = 1.3, and the absence of chloride ion catalysis suggest that the denitrosation reaction proceeds by a rate-determining proton transfer which is followed by the rapid loss of the nitroso group. The results for the hydrolysis reaction are compatible with a formulation in which a hydrate of the nitrosourea is protonated in a rate-determining step to form a tetrahedral intermediate which subsequently decomposes to yield methyldiazonium hydroxide and a carbamic acid derivative. The base-catalyzed reactions of the mono, di-, and trimethylnitrosoureas are first order in hydroxide ion over a broad pH range. The hydrolysis of N-methyl-N-nitrosourea yields methanol and derivatives of carbamic acid. Salt effects on the reaction rate are negligible except for the influence of lithium ion. The rate constants for the hydrolysis of the mono- and dimethyl compounds depend upon the buffer concentrationat pH 9.5. The rate constants for the hydrolysis of the trimethyl compound also depend upon the buffer concentration, but a limiting value is not achieved. The solvent isotope effect for the base-catalyzed reaction, the exchange reaction of water- 18 O with the carbonyl group of the urea, and the fact that N-methyl-N-nitrosourea is hydrolyzed about 2.2 x 10 4 times more rapidly than N,N',N'-trimethyl-N-nitrosourea suggest that the hydrolysis occurs by a mechanism in which a tetrahedral intermediate is formed

  11. Polymerization of Polar Monomers from a Theoretical Perspective

    KAUST Repository

    Alghamdi, Miasser

    2016-10-11

    Density functional theory calculations have been used to investigate catalytic mechanism of polymer formation containing polar groups, from the synthesis of the monomer to the synthesis of the macromolecule. In the spirit of a sustainable and green chemistry, we initially focused attention on the coupling of CO2 as economically convenient and recyclable C1 source with C2H4 to form acrylate and/or butirro-lactone, two important polar monomers. In this process formation of a mettallolactone via oxidative coupling of CO2 and C2H4 is an important intermediate. Given this background, we explored in detail (chapter-3) several Ni based catalysts for CO2 coupling with C2H4 to form acrylate. In this thesis we report on the competitive reaction mechanisms (inner vs outer sphere) for the oxidative coupling of CO2 and ethylene for a set of 11 Ni-based complexes containing bisphosphine ligands. In another effort, considering incorporation of a C=C bond into a metal-oxygen-Functional-Group moiety is a challenging step in several polymerization reactions, we explored the details of this reaction (chapter4) using two different catalysts that are capable to perform this reaction in the synthesis of heterocycles. Specifically, the [Rh]-catalyzed intramolecular alkoxyacylation ([Rh] = [RhI(dppp)+] (dppp, 1,3-Bis-diphenylphosphino-propane), and the [Pd]/BPh3 intramolecular alkoxyfunctionalizations. Rest of the thesis we worked on understanding the details of the polymerization of polar monomers using organocatalysts based on N-heterocyclic carbenes (NHC) or N-heterocyclic olefins (NHO). In particular (chapter-5) we studied the polymerization of N-methyl N-carboxy- anhydrides, towards cyclic poly(N-substituted glycine)s, promoted by NHC catalysts. In good agreement with the experimental findings, we demonstrated that NHC promoted ring opening polymerization of N-Me N-Carboxyanhydrides may proceed via two different catalytic pathways. In a similar effort we studied polymerization of

  12. Functional bio-based polyesters by enzymatic polymerization

    DEFF Research Database (Denmark)

    Daugaard, Anders Egede; Hoffmann, Christian; Andersen, Christian

    During recent years enzymatic polymerization has become increasingly popular as an alternative to classical polyesterification processes. The high regioselectivity observed for lipases permits preparation of novel polyesters with a high number of functional groups.1 This is particularly interesting...... polymerization was applied to prepare functional water soluble polyesters based on dimethyl itaconate and poly(ethyleneglycol).2 The monomer permits postfunctionalization using thiol-ene chemistry or aza-michael additions, which was used to illustrate the possibilites of preparing functional hydrogels. Hydrogels...... based on the polyesters were shown to be degradable and could be prepared either from the pure polyester or from prefunctionalized polyesters, though the thiol-ene reactions were found to be less effective. Since then a new monomer, trans-2,5-dihydroxy-3-pentenoic acid methyl ester (DPM) has been...

  13. Development and characterization of polymeric membranes for water desalination

    International Nuclear Information System (INIS)

    Bresciani, Danusa; Guimaraes, Danilo H.; Santos, Diego K.M.; Brioude, Michel M.; Jose, Nadia M.; Prado, Luis A.S.A.

    2009-01-01

    This work reports a development of polymeric membranes for water desalination by reverse osmosis. The polyester was synthesized by the reaction between glycerol, and dicarboxylic acids, and was coded PAF. Cellulose acetate/PAF blends containing 10% and 30% of polyester PAF blends were prepared using compression molding. The materials were characterized by DRX, DSC, TGA and SEM techniques. The results blends showed good thermal resistance and thermal events due to the individual components of the blends. The membranes exhibited a good performance in comparison to the neat cellulose acetate membrane. The addition of PAF in the polyester composition of the polymeric blends caused a significant increase of the salt retention of the studied samples. (author)

  14. FLUIDDYNAMIC ASPECTS OF GAS-PHASE ETHYLENE POLYMERIZATION REACTOR DESIGN

    Directory of Open Access Journals (Sweden)

    Guardani R.

    1998-01-01

    Full Text Available The relative importance of design variables affecting the fluiddynamic behavior of a fluidized bed reactor for the gas-phase ethylene polymerization is discussed, based on mathematical modeling. The three-phase bubbling fluidized bed model is based on axially distributed properties for the bubble, cloud and emulsion phases, combined with correlations for population balance and entrainment. Under the operating conditions adopted in most industrial processes, the reactor performance is affected mainly by the reaction rate and solids entrainment. Simulation results indicate that an adequate design of the freeboard and particle collecting equipment is of primary importance in order to produce polymeric particles with the desired size distribution, as well as to keep entrainment and catalyst feed rates at adequate levels.

  15. Micellar polymerization: Computer simulations by dissipative particle dynamics.

    Science.gov (United States)

    Shupanov, Ruslan; Chertovich, Alexander; Kos, Pavel

    2018-07-15

    Nowadays, micellar polymerization is widely used in different fields of industry and research, including modern living polymerization technique. However, this process has many variables and there is no comprehensive model to describe all features. This research presents simulation methodology which describes key properties of such reactions to take a guide through a variety of their modifications. Dissipative particle dynamics is used in addition to Monte Carlo scheme to simulate initiation, propagation, and termination events. Influence of initiation probability and different termination processes on final conversion and molecular-weight distribution are presented. We demonstrate that prolonged initiation leads to increasing in polymer average molecular weight, and surface termination events play major role in conversion limitation, in comparison with recombination. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.

  16. Polymerization reactivity of sulfomethylated alkali lignin modified with horseradish peroxidase.

    Science.gov (United States)

    Yang, Dongjie; Wu, Xiaolei; Qiu, Xueqing; Chang, Yaqi; Lou, Hongming

    2014-03-01

    Alkali lignin (AL) was employed as raw materials in the present study. Sulfomethylation was conducted to improve the solubility of AL, while sulfomethylated alkali lignin (SAL) was further polymerized by horseradish peroxidase (HRP). HRP modification caused a significant increase in molecular weight of SAL which was over 20 times. It was also found to increase the amount of sulfonic and carboxyl groups while decrease the amount of phenolic and methoxyl groups in SAL. The adsorption quantity of self-assembled SAL film was improved after HRP modification. Sulfonation and HRP modification were mutually promoted. The polymerization reactivity of SAL in HRP modification was increased with its sulfonation degree. Meanwhile, HRP modification facilitated SAL's radical-sulfonation reaction. Copyright © 2014. Published by Elsevier Ltd.

  17. Click polymerization for the synthesis of reduction-responsive polymeric prodrug

    Science.gov (United States)

    Zhang, Xiaojin; Wang, Hongquan; Dai, Yu

    2018-05-01

    Click polymerization is a powerful polymerization technique for the construction of new macromolecules with well-defined structures and multifaceted functionalities. Here, we synthesize reduction-responsive polymeric prodrug PEG- b-(PSS- g-MTX)- b-PEG containing disulfide bonds and pendant methotrexate (MTX) via two-step click polymerization followed by conjugating MTX to pendant hydroxyl. MTX content in polymeric prodrug is 13.5%. Polymeric prodrug is able to form polymeric micelles by self-assembly in aqueous solution. Polymeric micelles are spherical nanoparticles with tens of nanometers in size. Of note, polymeric micelles are reduction-responsive due to disulfide bonds in the backbone of PEG- b-(PSS- g-MTX)- b-PEG and could release pendant drugs in the presence of the reducing agents such as dl-dithiothreitol (DTT).

  18. Highly Defined Multiblock Copolypeptoids: Pushing the Limits of Living Nucleophilic Ring-Opening Polymerization

    KAUST Repository

    Fetsch, Corinna

    2012-06-05

    Advanced macromolecular engineering requires excellent control over the polymerization reaction. Living polymerization methods are notoriously sensitive to impurities, which makes a practical realization of such control very challenging. Reversible-deactivation radical polymerization methods are typically more robust, but have other limitations. Here, we demonstrate by repeated (ge;10 times) chain extension the extraordinary robustness of the living nucleophilic ring-opening polymerization of N-substituted glycine N-carboxyanhydrides, which yields polypeptoids. We observe essentially quantitative end-group fidelity under experimental conditions that are comparatively easily managed. This is employed to synthesize a pentablock quinquiespolymer with high definition. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Radiation polymerization of butyl acrylate for using as organic compounds recovery system from waste water

    International Nuclear Information System (INIS)

    Kattan, M.; Al-Kassiri, H.

    2008-02-01

    In this work, radiation polymerization of butyl acrylate using 60 Co gamma rays was studied. The effects of different parameters, such as the irradiation dose, dose rate and the temperature of irradiation on the polymerization were investigated. The relationship between polymerization yield with the dose rate and the temperature found to be linear. The kinetic of irradiation polymerization at 10 kGy/h was studied. The activation energy of reaction was calculated and it was E=9.27 j/mol. The thermal properties and the effect of irradiation dose on the glass transition were investigated. The application of this polymer in the field of environment treatment such as extraction of organics compounds dissolved in water was studied. The swelling in several organic compounds was studied, the weight percentages of both the swelling and the liberation were calculated. (author)

  20. Modular in situ-Functionalization Strategy: Multicomponent Polymerization via Palladium/Norbornene Cooperative Catalysis.

    Science.gov (United States)

    Yoon, Ki-Young; Dong, Guangbin

    2018-05-23

    Herein, we report the palladium/norbornene cooperatively catalyzed polymerization, which simplifies synthesis of functional aromatic polymers, including conjugated polymers. Specifically, an A2B2C-type multicomponent polymerization is developed using ortho-amination/ipso-alkynylation reaction for preparing various amine-functionalized arylacetylene-containing polymers. Within a single catalytic cycle, the amine side-chains are site-selectively installed in situ via C-H activation during the polymerization process, which represents a major difference from conventional cross-coupling polymerizations. This in situ-functionalization strategy enables modular incorporation of functional side-chains from simple monomers, thereby conveniently affording a diverse range of functional polymers. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Kinetics of Vinyl Polymerization of Methyl Methacrylate Initiated by Ce(IV-Vanillin Redox System

    Directory of Open Access Journals (Sweden)

    M. Palanivelu

    2012-01-01

    Full Text Available The kinetics of polymerization of methyl methacrylate initiated by Ce(IV-Vanillin redox system was studied in aqueous solution of sulfuric acid at 40°C. The rate of polymerization (Rp and the reaction orders with respect to monomer, initiator and ligand have been determined and found to be 1.5, 0.5 and 0.5 respectively. The effect of concentration of sulfuric acid on the polymerization was also studied. The rate of polymerization was found to increase with increasing temperature 30–60°C and decreases at higher temperature (>60°C. The overall activation energy (Ea was found to be 36.7 kJ/mol. A suitable kinetic scheme has been proposed.

  2. Highly Defined Multiblock Copolypeptoids: Pushing the Limits of Living Nucleophilic Ring-Opening Polymerization

    KAUST Repository

    Fetsch, Corinna; Luxenhofer, Robert

    2012-01-01

    Advanced macromolecular engineering requires excellent control over the polymerization reaction. Living polymerization methods are notoriously sensitive to impurities, which makes a practical realization of such control very challenging. Reversible-deactivation radical polymerization methods are typically more robust, but have other limitations. Here, we demonstrate by repeated (ge;10 times) chain extension the extraordinary robustness of the living nucleophilic ring-opening polymerization of N-substituted glycine N-carboxyanhydrides, which yields polypeptoids. We observe essentially quantitative end-group fidelity under experimental conditions that are comparatively easily managed. This is employed to synthesize a pentablock quinquiespolymer with high definition. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. SCATTERING FROM RAMIFIED POLYMERIC SYSTEMS

    Directory of Open Access Journals (Sweden)

    M.Benhamou

    2004-01-01

    Full Text Available Here, of great interest to us is a quantitative study of the scattering properties from ramified polymeric systems of arbitrary topology. We consider three types of systems, namely ramified polymers in solution, ramified polymer blends, or ternary mixtures made of two ramified polymers of different chemical nature immersed in a good solvent. To achieve the goal of the study, use is made of the Random Phase Approximation. First we determine the exact expression of the form factor of an ideal ramified polymer of any topology, from which we extract the exact expression of its gyration radius. Using the classical Zimm's formulae and the exact form factor, we determine all scattering properties of these three types of ramified polymeric systems. The main conclusion is that ramification of the chains induces drastic changes of the scattering properties.

  4. Polymeric nanoparticles for optical sensing.

    Science.gov (United States)

    Canfarotta, Francesco; Whitcombe, Michael J; Piletsky, Sergey A

    2013-12-01

    Nanotechnology is a powerful tool for use in diagnostic applications. For these purposes a variety of functional nanoparticles containing fluorescent labels, gold and quantum dots at their cores have been produced, with the aim of enhanced sensitivity and multiplexing capabilities. This work will review progress in the application of polymeric nanoparticles in optical diagnostics, both for in vitro and in vivo detection, together with a discussion of their biodistribution and biocompatibility. © 2013.

  5. Studies in reactive extrusion processing of biodegradable polymeric materials

    Science.gov (United States)

    Balakrishnan, Sunder

    Various reaction chemistries such as Polymerization, Polymer cross-linking and Reactive grafting were investigated in twin-screw extruders. Poly (1,4-dioxan-2-one) (PPDX) was manufactured in melt by the continuous polymerization of 1,4-dioxan-2-one (PDX) monomer in a twin-screw extruder using Aluminum tri-sec butoxide (ATSB) initiator. Good and accurate control over molecular weight was obtained by controlling the ratio of monomer to initiator. A screw configuration consisting of only conveying elements was used for the polymerization. The polymerization reaction was characterized by a monomer-polymer dynamic equilibrium, above the melting temperature of the polymer, limiting the equilibrium conversion to 78-percent. Near complete (˜100-percent) conversion was obtained on co-polymerizing PDX monomer with a few mol-percent (around 8-percent) Caprolactone (CL) monomer in a twin-screw extruder using ATSB initiator. The co-polymers exhibited improved thermal stability with reduction in glass transition temperature. The extruder was modeled as an Axial Dispersed Plug Flow Reactor for the polymerization of CL monomer using Residence Time Distribution (RTD) Analysis. The model provided a good fit to the experimental RTD and conversion data. Aliphatic and aliphatic-aromatic co-polyesters, namely Polycaprolactone (PCL) and Poly butylenes (adipate-co-terephthalate) (Ecoflex) were cross-linked in a twin-screw extruder using radical initiator to form micro-gel reinforced biodegradable polyesters. Cross-linked Ecoflex was further extrusion blended with talc to form blends suitable to be blown into films. A screw configuration consisting of conveying and kneading elements was found to be effective in dispersion of the talc particles (5--10 microns) in the polyester matrix. While the rates of crystallization increased for the talc filled polyester blends, overall crystallinity reduced. Mechanical, tear and puncture properties of films made using the talc filled polyester blends

  6. Polymeric Coatings for Combating Biocorrosion

    Science.gov (United States)

    Guo, Jing; Yuan, Shaojun; Jiang, Wei; Lv, Li; Liang, Bin; Pehkonen, Simo O.

    2018-03-01

    Biocorrosion has been considered as big trouble in many industries and marine environments due to causing great economic loss. The main disadvantages of present approaches to prevent corrosion include being limited by environmental factors, being expensive, inapplicable to field, and sometimes inefficient. Studies show that polymer coatings with anti-corrosion and anti-microbial properties have been widely accepted as a novel and effective approach to preventbiocorrosion. The main purpose of this review is to summarize up the progressive status of polymer coatings used for combating microbially-induced corrosion. Polymers used to synthesize protective coatings are generally divided into three categories: i) traditional polymers incorporated with biocides, ii) antibacterial polymers containing quaternary ammonium compounds, and iii) conductive polymers. The strategies to synthesize polymer coatings resort mainly to grafting anti-bacterial polymers from the metal substrate surface using novel surface-functionalization approaches, such as free radical polymerization, chemically oxidative polymerization and surface-initiated atom transfer radical polymerization, as opposed to the traditional approaches of dip coating or spin coating.

  7. Non-equilibrium supramolecular polymerization.

    Science.gov (United States)

    Sorrenti, Alessandro; Leira-Iglesias, Jorge; Markvoort, Albert J; de Greef, Tom F A; Hermans, Thomas M

    2017-09-18

    Supramolecular polymerization has been traditionally focused on the thermodynamic equilibrium state, where one-dimensional assemblies reside at the global minimum of the Gibbs free energy. The pathway and rate to reach the equilibrium state are irrelevant, and the resulting assemblies remain unchanged over time. In the past decade, the focus has shifted to kinetically trapped (non-dissipative non-equilibrium) structures that heavily depend on the method of preparation (i.e., pathway complexity), and where the assembly rates are of key importance. Kinetic models have greatly improved our understanding of competing pathways, and shown how to steer supramolecular polymerization in the desired direction (i.e., pathway selection). The most recent innovation in the field relies on energy or mass input that is dissipated to keep the system away from the thermodynamic equilibrium (or from other non-dissipative states). This tutorial review aims to provide the reader with a set of tools to identify different types of self-assembled states that have been explored so far. In particular, we aim to clarify the often unclear use of the term "non-equilibrium self-assembly" by subdividing systems into dissipative, and non-dissipative non-equilibrium states. Examples are given for each of the states, with a focus on non-dissipative non-equilibrium states found in one-dimensional supramolecular polymerization.

  8. In Situ Monitoring of RAFT Polymerization by Tetraphenylethylene-Containing Agents with Aggregation-Induced Emission Characteristics.

    Science.gov (United States)

    Liu, Shunjie; Cheng, Yanhua; Zhang, Haoke; Qiu, Zijie; Kwok, Ryan T K; Lam, Jacky W Y; Tang, Ben Zhong

    2018-05-22

    A facile and efficient approach is demonstrated to visualize the polymerization in situ. A group of tetraphenylethylene (TPE)-containing dithiocarbamates were synthesized and screened as agents for reversible addition fragmentation chain transfer (RAFT) polymerizations. The spatial-temporal control characteristics of photochemistry enabled the RAFT polymerizations to be ON and OFF on demand under alternating visible light irradiation. The emission of TPE is sensitive to the local viscosity change owing to its aggregation-induced emission characteristic. Quantitative information could be easily acquired by the naked eye without destroying the reaction system. Furthermore, the versatility of such a technique was well demonstrated by 12 different polymerization systems. The present approach thus demonstrated a powerful platform for understanding the controlled living radical polymerization process. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Grafting study of polysulfone polymeric membranes by gamma ray irradiation

    International Nuclear Information System (INIS)

    Furtado Filho, Acacio A.M.; Gomes, Ailton de S.

    2011-01-01

    Radiation-induced grafting of styrene poli sulfone films were investigated by simultaneous method in solution using gamma-ray from a radio nuclide 60 Co source. The gamma-ray energy of high intensity induced breaking of chemical bonds leading to free radical formation. The radical start a conventional polymerization sequence comparable with that obtained with a chemical catalyst acting as initiator. The effects of grafting conditions such as irradiation total dose, dose rate and addition of cross linking agent, were studied by means of morphology analysis, thermal degradation and crystallinity. After the grafting reaction, the membranes were submitted to an exhaustive extraction with solvent to remove the polystyrene homopolymer formed. The degree of grafting (DOG) was analyzed by percentage of weight increase. As a result, the reaction always follows the same pattern: DOG increases rapidly initially whilst propagation is the main reaction, then more slowly as termination becomes more frequent. (author)

  10. Multiwalled carbon nanotubes@octavinyl polyhedral oligomeric silsesquioxanes nanocomposite preparation via cross-linking reaction in acidic media

    Energy Technology Data Exchange (ETDEWEB)

    Somasekharan, Lakshmipriya; Thomas, Sabu [Mahatma Gandhi University, International and Interuniversity Centre for Nanoscience and Nanotechnology (India); Comoy, Corinne [Université de Lorraine, SRSMC, UMR 7565 (France); Sivasankarapillai, Anilkumar [NSS Hindu College (India); Kalarikkal, Nandakumar [Mahatma Gandhi University, International and Interuniversity Centre for Nanoscience and Nanotechnology (India); Lamouroux, Emmanuel, E-mail: Emmanuel.Lamouroux@univ-lorraine.fr [Université de Lorraine, SRSMC, UMR 7565 (France)

    2016-11-15

    Multiwalled carbon nanotubes have unique properties allowing their use in a wide range of applications—from microelectronics to biomedical and polymer fields. Nevertheless, a crucial aspect for their use resides in the ease of handling them during the process. Here, we report a facile route to prepare multiwalled carbon nanotubes@octavinyl polyhedral oligomeric silsesquioxanes (MWCNT@POSS) nanocomposite. The method involves the formation of a covalent bond between carboxylated MWCNTs and OV-POSS using acid-catalyzed electrophilic addition reaction. The resulting nanocomposite have been characterized by Fourier transform infrared spectroscopy (FTIR), powder X-Ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). The results confirmed that the formation of MWCNT@POSS nanocomposite did not deteriorate MWCNT structure or morphology. Here, we used a 1:1 ratio of carboxylated MWCNTs and OV-POSS and the POSS content in the nanocomposite was 39.5 wt%.

  11. Nanoporous Polymeric Grating-Based Biosensors

    KAUST Repository

    Gao, Tieyu

    2012-05-02

    We demonstrate the utilization of an interferometrically created nanoporous polymeric gratings as a platform for biosensing applications. Aminopropyltriethoxysilane (APTES)-functionalized nanoporous polymeric gratings was fabricated by combining holographic interference patterning and APTES-functionalization of pre-polymer syrup. The successful detection of multiple biomolecules indicates that the biofunctionalized nanoporous polymeric gratings can act as biosensing platforms which are label-free, inexpensive, and applicable as high-throughput assays. Copyright © 2010 by ASME.

  12. Nanoporous Polymeric Grating-Based Biosensors

    KAUST Repository

    Gao, Tieyu; Hsiao, Vincent; Zheng, Yue Bing; Huang, Tony Jun

    2012-01-01

    We demonstrate the utilization of an interferometrically created nanoporous polymeric gratings as a platform for biosensing applications. Aminopropyltriethoxysilane (APTES)-functionalized nanoporous polymeric gratings was fabricated by combining holographic interference patterning and APTES-functionalization of pre-polymer syrup. The successful detection of multiple biomolecules indicates that the biofunctionalized nanoporous polymeric gratings can act as biosensing platforms which are label-free, inexpensive, and applicable as high-throughput assays. Copyright © 2010 by ASME.

  13. Volumetric polymerization shrinkage of contemporary composite resins

    OpenAIRE

    Nagem Filho, Halim; Nagem, Haline Drumond; Francisconi, Paulo Afonso Silveira; Franco, Eduardo Batista; Mondelli, Rafael Francisco Lia; Coutinho, Kennedy Queiroz

    2007-01-01

    The polymerization shrinkage of composite resins may affect negatively the clinical outcome of the restoration. Extensive research has been carried out to develop new formulations of composite resins in order to provide good handling characteristics and some dimensional stability during polymerization. The purpose of this study was to analyze, in vitro, the magnitude of the volumetric polymerization shrinkage of 7 contemporary composite resins (Definite, Suprafill, SureFil, Filtek Z250, Fill ...

  14. Kinetics of vinyl acetate emulsion polymerization in a pulsed tubular reactor: comparison between experimental and simulation results

    Directory of Open Access Journals (Sweden)

    Sayer C.

    2002-01-01

    Full Text Available A new reactor, the pulsed sieve plate column (PSPC, was developed to perform continuous emulsion polymerization reactions. This reactor combines the enhanced flexibility of tubular reactors with the mixing behavior provided by sieved plates and by the introduction of pulses that is important to prevent emulsion destabilization. The main objective of this work is to study the kinetics of vinyl acetate (VA emulsion polymerization reactions performed in this PSPC. Therefore, both experimental studies and reaction simulations were performed. Results showed that it is possible to obtain high conversions with rather low residence times in the PSPC.

  15. Polymeric membrane materials for artificial organs.

    Science.gov (United States)

    Kawakami, Hiroyoshi

    2008-01-01

    Many polymeric materials have already been used in the field of artificial organs. However, the materials used in artificial organs are not necessarily created with the best material selectivity and materials design; therefore, the development of synthesized polymeric membrane materials for artificial organs based on well-defined designs is required. The approaches to the development of biocompatible polymeric materials fall into three categories: (1) control of physicochemical characteristics on material surfaces, (2) modification of material surfaces using biomolecules, and (3) construction of biomimetic membrane surfaces. This review will describe current issues regarding polymeric membrane materials for use in artificial organs.

  16. Role of β-h elimination in rhodium-mediated carbene insertion polymerization

    NARCIS (Netherlands)

    Finger, M.; Reek, J.N.H.; de Bruin, B.

    2011-01-01

    The importance of β-H elimination as a possible mechanism to induce chain termination/transfer and/or the formation of stereodefects in the Rh(diene)-mediated oligomerization and polymerization of carbenes has been studied by means of different approaches. As a remarkable feature, this reaction is

  17. Thermally Self-Healing Polymeric Materials : The Next Step to Recycling Thermoset Polymers?

    NARCIS (Netherlands)

    Zhang, Youchun; Broekhuis, Antonius A.; Picchioni, Francesco

    2009-01-01

    We developed thermally self-healing polymeric materials on the basis of furan-functionalized, alternating thermosetting polyketones (PK-furan) and bis-maleimide by using the Diels-Alder (DA) and Retro-Diels-Alder (RDA) reaction sequence. PK-furan can be easily obtained under mild conditions by the

  18. Modeling of branching density and branching distribution in low-density polyethylene polymerization

    NARCIS (Netherlands)

    Kim, D.M.; Iedema, P.D.

    2008-01-01

    Low-density polyethylene (ldPE) is a general purpose polymer with various applications. By this reason, many publications can be found on the ldPE polymerization modeling. However, scission reaction and branching distribution are only recently considered in the modeling studies due to difficulties

  19. Polymeric carbon nitride nanomesh as an efficient and durable metal-free catalyst for oxidative desulfurization.

    Science.gov (United States)

    Shen, Lijuan; Lei, Ganchang; Fang, Yuanxing; Cao, Yanning; Wang, Xinchen; Jiang, Lilong

    2018-03-06

    We report the first use of polymeric carbon nitride (CN) for the catalytic selective oxidation of H 2 S. The as-prepared CN with unique ultrathin "nanomeshes" structure exhibits excellent H 2 S conversion and high S selectivity. In particular, the CN nanomesh also displays better durability in the desulfurization reaction than traditional catalysts, such as carbon- and iron-based materials.

  20. Radical polymerization by a supramolecular catalyst: cyclodextrin with a RAFT reagent

    Directory of Open Access Journals (Sweden)

    Kohei Koyanagi

    2016-11-01

    Full Text Available Supramolecular catalysts have received a great deal of attention because they improve the selectivity and efficiency of reactions. Catalysts with host molecules exhibit specific reaction properties and recognize substrates via host–guest interactions. Here, we examined radical polymerization reactions with a chain transfer agent (CTA that has α-cyclodextrin (α-CD as a host molecule (α-CD-CTA. Prior to the polymerization of N,N-dimethylacrylamide (DMA, we investigated the complex formation of α-CD with DMA. Single X-ray analysis demonstrated that α-CD includes DMA inside its cavity. When DMA was polymerized in the presence of α-CD-CTA using 2,2'-azobis[2-(2-imidazolin-2-ylpropane dihydrochloride (VA-044 as an initiator in an aqueous solution, poly(DMA was obtained in good yield and with narrow molecular weight distribution. In contrast, the polymerization of DMA without α-CD-CTA produced more widely distributed polymers. In the presence of 1,6-hexanediol (C6 diol which works as a competitive molecule by being included in the α-CD cavity, the reaction yield was lower than that without C6 diol.

  1. Hydrolysis of 4-Acetoxystyrene Polymers Prepared by Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Chen, Xianyi; Jankova, Katja; Kops, Jørgen

    1999-01-01

    Hydrolysis of 4-acetoxystyrene polymers prepared by atom transfer radical polymerization was carried out under various reaction conditions. It was found that hydrazinolysis of 4-acetoxystyrene homopolymers, random and block copolymers with styrene in 1,4-dioxane, afforded the corresponding narrow...

  2. Stabilization of extracellular polymeric substances (Bacillus subtilis) by adsorption to and coprecipitation with Al forms

    NARCIS (Netherlands)

    Mikutta, R.; Zang, U.; Chorover, J.; Haumaier, L.; Kalbitz, K.

    2011-01-01

    Extracellular polymeric substances (EPS) are continuously produced by bacteria during their growth and metabolism. In soils, EPS are bound to cell surfaces, associated with biofilms, or released into solution where they can react with other solutes and soil particle surfaces. If such reaction

  3. Electrochemical supercapacitor application of electroless surface polymerization of polyaniline nanostructures

    International Nuclear Information System (INIS)

    Amarnath, Chellachamy A.; Chang, Jin Ho; Kim, Doyoung; Mane, Rajaram S.; Han, Sung-Hwan; Sohn, Daewon

    2009-01-01

    Electrochemical supercapacitive behaviour of polyaniline nanostructures, i.e., nanorods and nanospheres fabricated on aniline-primed conducting indium-tin oxide substrate via electroless surface polymerization using ammonium persulfate as initiator and selenious acid as efficient dopant is investigated. The self-assembled monolayer of urea derivative in presence of 3-(triethoxysilyl)-propyl isocyanate and aniline plays role of aniline-primed substrate. Polyaniline electrode composed of nanorods of excess surface area responsible for large redox reactions has shown 592 F g -1 specific capacitance which is significantly greater than closely compact polyaniline nanospheres, i.e., 214 F g -1

  4. Polymeric Biodegradable Stent Insertion in the Esophagus

    Directory of Open Access Journals (Sweden)

    Kai Yang

    2016-04-01

    Full Text Available Esophageal stent insertion has been used as a well-accepted and effective alternative to manage and improve the quality of life for patients diagnosed with esophageal diseases and disorders. Current stents are either permanent or temporary and are fabricated from either metal or plastic. The partially covered self-expanding metal stent (SEMS has a firm anchoring effect and prevent stent migration, however, the hyperplastic tissue reaction cause stent restenosis and make it difficult to remove. A fully covered SEMS and self-expanding plastic stent (SEPS reduced reactive hyperplasia but has a high migration rate. The main advantage that polymeric biodegradable stents (BDSs have over metal or plastic stents is that removal is not require and reduce the need for repeated stent insertion. But the slightly lower radial force of BDS may be its main shortcoming and a post-implant problem. Thus, strengthening support of BDS is a content of the research in the future. BDSs are often temporarily effective in esophageal stricture to relieve dysphagia. In the future, it can be expect that biodegradable drug-eluting stents (DES will be available to treat benign esophageal stricture, perforations or leaks with additional use as palliative modalities for treating malignant esophageal stricture, as the bridge to surgery or to maintain luminal patency during neoadjuvant chemoradiation.

  5. preparation of bicyclic lactones using lewis acids catalyzed ene

    African Journals Online (AJOL)

    Administrator

    The synthesis of the cis-fused bicyclic lactones relies extensively on the Lewis acid ... having an allylic hydrogen (an"ene") and a compound containing an electron .... observed that the lithium enolate obtained from 3-methyl-2(5H)- furanone ...

  6. LEWIS ACID CATALYZED FORMATION OF TETRAHYDROPYRANS IN IONIC LIQUID

    Science.gov (United States)

    Tetrahydropyrans are integral moieties in innumerable natural products and have inspired the development of a variety of different methodologies. A Prins-type cyclization involving the coupling of a homoallylic alcohol and an aldehyde in the presence of catalytic scandium triflat...

  7. Detoxification of acidic catalyzed hydrolysate of Kappaphycus alvarezii (cottonii).

    Science.gov (United States)

    Meinita, Maria Dyah Nur; Hong, Yong-Ki; Jeong, Gwi-Taek

    2012-01-01

    Red seaweed, Kappaphycus alvarezii, holds great promise for use in biofuel production due to its high carbohydrate content. In this study, we investigated the effect of fermentation inhibitors to the K. alvarezii hydrolysate on cell growth and ethanol fermentation. In addition, detoxification of fermentation inhibitors was performed to decrease the fermentation inhibitory effect. 5-Hydroxymethylfurfural and levulinic acid, which are liberated from acidic hydrolysis, was also observed in the hydrolysate of K. alvarezii. These compounds inhibited ethanol fermentation. In order to remove these inhibitors, activated charcoal and calcium hydroxide were introduced. The efficiency of activated charcoals was examined and over-liming was used to remove the inhibitors. Activated charcoal was found to be more effective than calcium hydroxide to remove the inhibitors. Detoxification by activated charcoal strongly improved the fermentability of dilute acid hydrolysate in the production of bioethanol from K. alvarezii with Saccharomyces cerevisiae. The optimal detoxifying conditions were found to be below an activated charcoal concentration of 5%.

  8. New method to access hyperbranched polymers with uniform structure via one-pot polymerization of inimer in microemulsion.

    Science.gov (United States)

    Min, Ke; Gao, Haifeng

    2012-09-26

    A facile approach is presented for successful synthesis of hyperbranched polymers with high molecular weight and uniform structure by a one-pot polymerization of an inimer in a microemulsion. The segregated space in the microemulsion confined the inimer polymerization and particularly the polymer-polymer reaction within discrete nanoparticles. At the end of polymerization, each nanoparticle contained one hyperbranched polymer that had thousands of inimer units and low polydispersity. The hyperbranched polymers were used as multifunctional macroinitiators for synthesis of "hyper-star" polymers. When a degradable inimer was applied, the hyper-stars showed fast degradation into linear polymer chains with low molecular weight.

  9. Wood-polymer composites from Philippine tree plantation species by radiation polymerization I. Uptake and irradiation parameters

    International Nuclear Information System (INIS)

    Dela Rosa, A.M.; Castaneda, S.S.; Real, M.P.N.; Sta Ana, L.P.; Mosteiro, A.P.; Bauza, E.; Carandang, J.P.

    1993-01-01

    Radiation catalyzed polymerization of methyl methacrylate (MMA) in various Philippine tree plantation species were investigated. Wood samples measuring 1x6cm were impregnated with monomer at reduced pressure and gamma irradiated for various doses at a dose rate of 0.53 kGy/h. The parameters used to assess the polymerization reaction were the uptake of monomer by the wood samples, monomer conversion, and polymer loading in the irradiated samples. The uptake and polymerization data indicate that coconut wood, rubber wood, bagras, and Moluccan sau could be potential raw materials for the production of wood-polymer composites (WPC). (author). 6 refs.; 2 figs.; 1 tab

  10. A novel headspace gas chromatographic method for in situ monitoring of monomer conversion during polymerization in an emulsion environment.

    Science.gov (United States)

    Chai, Xin-Sheng; Zhong, Jin-Feng; Hu, Hui-Chao

    2012-05-18

    This paper describes a novel multiple-headspace extraction/gas chromatographic (MHE-GC) technique for monitoring monomer conversion during a polymerization reaction in a water-based emulsion environment. The polymerization reaction of methyl methacrylate (MMA) in an aqueous emulsion is used as an example. The reaction was performed in a closed headspace sample vial (as a mini-reactor), with pentane as a tracer. In situ monitoring of the vapor concentration of the tracer, employing a multiple headspace extraction (sampling) scheme, coupled to a GC, makes it possible to quantitatively follow the conversion of MMA during the early stages of polymerization. Data on the integrated amount of the tracer vapor released from the monomer droplet phase during the polymerization is described by a mathematic equation from which the monomer conversion can be calculated. The present method is simple, automated and economical, and provides an efficient tool in the investigation of the reaction kinetics and effects of the reaction conditions on the early stage of polymerization. Copyright © 2012 Elsevier B.V. All rights reserved.

  11. Effect of tamoxifen in RAFT miniemulsion polymerization during the synthesis of polymer nanoparticles

    Directory of Open Access Journals (Sweden)

    Tailane Sant'Anna Moreira

    2014-01-01

    Full Text Available Tamoxifen (TXF is currently the only hormonal agent used for treatment of breast cancer. Although very effective, TXF presents low solubility in water, which affects its absorption and bioavailability. A common strategy to overcome this barrier is the formulation of a drug delivery system (DDS in order to increase the drug stability and improve the treatment effectiveness. Reversible addition-fragmentation chain transfer (RAFT polymerization is the most versatile method of controlled/living radical polymerization (CLRP, allowing for synthesis of well-defined polymers and being adapted to a wide range of polymerization systems. Miniemulsion polymerization is a dispersed system that is commonly used to prepare nanoparticles (NP with 50 to 500 nm of diameter. The aim of this work was to evaluate the effect of the in situ incorporation of TXF during miniemulsion conventional and RAFT polymerizations, using methyl methacrylate (MMA as monomer. Although the in situ addition of TXF promoted a slight reduction of the reaction rate, it did not affect the final particle size distribution of the latex or the molecular weight control exerted by the RAFT agent. The obtained results suggest that in situ incorporation of TXF during the synthesis of polymer NP via RAFT polymerization allows for production of a polymer DDS for different uses, such as the breast cancer treatment.

  12. Schlenk Techniques for Anionic Polymerization

    KAUST Repository

    Ratkanthwar, Kedar

    2015-09-01

    Anionic polymerization-high vacuum techniques (HVTs) are doubtlessly the most prominent and reliable experimental tools to prepare polymer samples with well-defined and, in many cases, complex macromolecular architectures. Due to the high demands for time and skilled technical personnel, HVTs are currently used in only a few research laboratories worldwide. Instead, most researchers in this filed are attracted to more facile Schlenk techniques. The basic principle of this technique followed in all laboratories is substantially the same, i.e. the use of alternate vacuum and inert gas atmosphere in glass apparatus for the purification/charging of monomer, solvents, additives, and for the manipulation of air-sensitive compounds such as alkyl metal initiators, organometallic or organic catalysts. However, it is executed quite differently in each research group in terms of the structure of Schlenk apparatus (manifolds, connections, purification/storage flasks, reactors, etc.), the use of small supplementary devices (soft tubing, cannulas, stopcocks, etc.) and experimental procedures. The operational methods are partly purpose-oriented while also featured by a high flexibility, which makes it impossible to describe in detail each specific one. In this chapter we will briefly exemplify the application of Schlenk techniques for anionic polymerization by describing the performance of a few experiments from our own work.

  13. Polymerization of 5-alkyl δ-lactones catalyzed by diphenyl phosphate and their sequential organocatalytic polymerization with monosubstituted epoxides

    KAUST Repository

    Zhao, Junpeng

    2015-02-04

    Organocatalytic ring-opening polymerization (ROP) reactions of three renewable 5-alkyl δ-lactones, namely δ-hexalactone (HL), δ-nonalactone (NL) and δ-decalactone (DL), using diphenyl phosphate (DPP) were investigated. Room temperature, together with a relatively high monomer concentration (≥3 M), was demonstrated to be suitable for achieving a living ROP behavior, a high conversion of the lactone, a controlled molecular weight and a low dispersity of the polyester. HL, containing a 5-methyl substituent, showed a much higher reactivity (polymerization rate) and a slightly higher equilibrium conversion than the compounds with longer alkyl substituents (NL and DL). The effectiveness of DPP-catalyzed ROP of 5-alkyl δ-lactones facilitated the one-pot performance following the t-BuP4-promoted ROP of monosubstituted epoxides. It has been shown in an earlier study that substituted polyethers acted as "slow initiators" for non-substituted lactones. However, efficient initiations were observed in the present study as substituted lactones were polymerized from the substituted polyethers. Therefore, this reinforces the previously developed "catalyst switch" strategy, making it a more versatile tool for the synthesis of well-defined polyether-polyester block copolymers from a large variety of epoxide and lactone monomers. © The Royal Society of Chemistry 2015.

  14. Highly efficient reversible addition-fragmentation chain-transfer polymerization in ethanol/water via flow chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Ye, Piaoran [Case Western Reserve Univ., Cleveland, OH (United States); Cao, Peng -Fei [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Su, Zhe [Case Western Reserve Univ., Cleveland, OH (United States); Advincula, Rigoberto [Case Western Reserve Univ., Cleveland, OH (United States)

    2017-03-23

    Here, utilization of a flow reactor under high pressure allows highly efficient polymer synthesis via reversible addition–fragmentation chain-transfer (RAFT) polymerization in an aqueous system. Compared with the batch reaction, the flow reactor allows the RAFT polymerization to be performed in a high-efficiency manner at the same temperature. The adjustable pressure of the system allows further elevation of the reaction temperature and hence faster polymerization. Other reaction parameters, such as flow rate and initiator concentration, were also well studied to tune the monomer conversion and the molar mass dispersity (Ð) of the obtained polymers. Gel permeation chromatography, nuclear magnetic resonance (NMR), and Fourier transform infrared spectroscopies (FTIR) were utilized to monitor the polymerization process. With the initiator concentration of 0.15 mmol L–1, polymerization of poly(ethylene glycol) methyl ethermethacrylate with monomer conversion of 52% at 100 °C under 73 bar can be achieved within 40 min with narrow molar mass dispersity (D) Ð (<1.25). The strategy developed here provides a method to produce well-defined polymers via RAFT polymerization with high efficiency in a continuous manner.

  15. Design and synthesis of structurally well-defined functional polypropylenes via transition metal-mediated olefin polymerization chemistry

    Institute of Scientific and Technical Information of China (English)

    Dong Jinyong

    2006-01-01

    Functionalization of polyolefins is an industrially important yet scientifically challenging research subject.This paper summarizes our recent effort to access structurally well-defined functional polypropylenes via transition metal-mediated olefin polymerization.In one approach,polypropylenes containing side chain functional groups of controlled concentrations were obtained by Ziegler-Natta-catalyzed copolymerization of propylene in combination with either living anionic or controlled radical polymerization of polar monomers.The copolymerization of propylene with 1,4-divinylbenzene using an isospecific MgC12-supported TIC14 catalyst yielded potypropylenes containing pendant styrene moieties.Both metalation reaction with n-butyllithium and hydrochlorination reaction with dry hydrogen chloride selectively and quantitatively occurred at the pendant reactive sites,generating polymeric benzyllithium and 1-chloroethylbenzene species.These species initiated living anionic polymerization of styrene(S)and atom transfer radical polymerization(in the presence of CuC1 and pentamethyldiethylenetriamine) of methyl methacrylate(MMA),respectively,resulting in functional polypropylene graft copolymers(PP-g-PS and PP-g-PMMA)with controllable graft lengths.In another approach,chain end-functionalized polypropylenes containing a terminal OH-group with controlled molecular weights were directly prepared by propylene polymerization with a metaUocene catalyst through a selective aluminum chain transfer reaction.Both approaches proved to be desirable polyolefin functionalization routes in terms of efficiency and polymer structure controllability.

  16. Unique effects of microwave heating on polymerization kinetics of poly(methyl methacrylate) composites

    Energy Technology Data Exchange (ETDEWEB)

    Spasojević, Pavle [Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11120 Belgrade (Serbia); Jovanović, Jelena, E-mail: jelenaj@ffh.bg.ac.rs [Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, 11001 Belgrade (Serbia); Adnadjevic, Borivoj [Faculty of Physical Chemistry, University of Belgrade, Studentski trg 12-16, 11001 Belgrade (Serbia)

    2013-09-16

    The effects of heating mode (conventional and microwave) on the kinetics of isothermal polymerization of MMA composite materials were investigated. Isothermal kinetics curves at temperature range from 343 K to 363 K for both conventional (CH) and microwave heating (MWH) were determined. It was found that the polymerization of MMA composite materials was kinetically elementary reaction for both CH and MWH. The kinetics of CH polymerization can be described by the model of phase-boundary controlled process (contracting volume), whereas the kinetics of MWH polymerization can be described by the model of first-order chemical reaction. The kinetics parameters (E{sub a} and ln A) of the polymerization under microwave heating are lower than for conventional heating. The established decreases in the activation energy and pre-exponential factor under the MWH compared to the CH is explained with the increase in the energy of ground vibrational level of the C–O valence vibrations (ν = 987 cm{sup −1}) in methyl methacrylate molecule and with the decrease in its anharmonicity factor which is caused with the selective resonant transfer of energy from the energetic reservoir to the oscillators in methyl methacrylate molecules. - Graphical abstract: Display Omitted - Highlights: • The MWH speeds the MMA material polymerization and changes the kinetics model. • A novel concept of MWH action based on activation complexes formation is presented. • The Selective Energy Transfer model is used to explain the effects of MWH. • The kinetics parameters under MWH are lower than for CH. • The activation energy for both MWH and CH polymerization is quantized.

  17. In situ polymerization of L-Lactide in the presence of fumed silica

    International Nuclear Information System (INIS)

    Prebe, A.; Alcouffe, P.; Cassagnau, Ph.; Gerard, J.F.

    2010-01-01

    Chemiorheology, i.e. rheological changes during the polymerization, of a biosourced monomer, i.e. L-Lactide, containing fumed silica have been studied. For that purpose, the reaction was proceeded in situ between the plates of a dynamic rheometer. The polymerization kinetics was followed from the variation of the complex shear modulus versus reaction time. Moreover, at temperatures lower than the crystallization temperature, it was possible to follow the crystallization process while the polymerization takes place. Adding fumed silica particles into the monomer leads to the formation of a physical (percolated) network from particle-particle interactions, i.e. silica, in the L-Lactide probably hydrophilic interactions. The gel-like structure was kept while the polymerization as long as the strain remains low indicating that the silica particle network remains weak. Furthermore, the mechanism of the break down of the gel structure under large deformation as well as the recovery was discussed. It seems that the non-linearity effect of the nanocomposites stems in the silica inter-particle interactions. It was found that silica particles do not have any effect on the temperature of crystallization - molar mass relation but could act as nucleating agent. In situ polymerization of L-Lactide in the presence of 5 wt.% of modified fumed silica was carried out in a reactor. It was found that fumed hydrophilic silica leaded to a microcomposite with highly dense agglomerates in the polymer matrix whereas with a less hydrophilic silica it was possible to decrease the size of the agglomerates increasing the dispersion. The finest dispersion state was achieved with the 'initiating' functionalized silica leading to a 'grafting from' polymerization of the L-Lactide. Such functionalized silica leads to a nanoscale dispersion in a one-step bulk polymerization with only a few small agglomerates.

  18. In situ polymerization of L-Lactide in the presence of fumed silica

    Energy Technology Data Exchange (ETDEWEB)

    Prebe, A. [Universite de Lyon, F-69361, Lyon (France); CNRS, UMR 5223, Ingenierie des Materiaux Polymeres, F-69622, Villeurbanne (France); Universite Claude Bernard Lyon 1, F-69622, Villeurbanne (France); INSA Lyon, F-69621, Villeurbanne (France); Alcouffe, P. [Universite de Lyon, F-69361, Lyon (France); CNRS, UMR 5223, Ingenierie des Materiaux Polymeres, F-69622, Villeurbanne (France); Universite Claude Bernard Lyon 1, F-69622, Villeurbanne (France); Cassagnau, Ph., E-mail: philippe.cassagnau@univ-lyon1.fr [Universite de Lyon, F-69361, Lyon (France); CNRS, UMR 5223, Ingenierie des Materiaux Polymeres, F-69622, Villeurbanne (France); Universite Claude Bernard Lyon 1, F-69622, Villeurbanne (France); Gerard, J.F. [Universite de Lyon, F-69361, Lyon (France); CNRS, UMR 5223, Ingenierie des Materiaux Polymeres, F-69622, Villeurbanne (France); INSA Lyon, F-69621, Villeurbanne (France)

    2010-11-01

    Chemiorheology, i.e. rheological changes during the polymerization, of a biosourced monomer, i.e. L-Lactide, containing fumed silica have been studied. For that purpose, the reaction was proceeded in situ between the plates of a dynamic rheometer. The polymerization kinetics was followed from the variation of the complex shear modulus versus reaction time. Moreover, at temperatures lower than the crystallization temperature, it was possible to follow the crystallization process while the polymerization takes place. Adding fumed silica particles into the monomer leads to the formation of a physical (percolated) network from particle-particle interactions, i.e. silica, in the L-Lactide probably hydrophilic interactions. The gel-like structure was kept while the polymerization as long as the strain remains low indicating that the silica particle network remains weak. Furthermore, the mechanism of the break down of the gel structure under large deformation as well as the recovery was discussed. It seems that the non-linearity effect of the nanocomposites stems in the silica inter-particle interactions. It was found that silica particles do not have any effect on the temperature of crystallization - molar mass relation but could act as nucleating agent. In situ polymerization of L-Lactide in the presence of 5 wt.% of modified fumed silica was carried out in a reactor. It was found that fumed hydrophilic silica leaded to a microcomposite with highly dense agglomerates in the polymer matrix whereas with a less hydrophilic silica it was possible to decrease the size of the agglomerates increasing the dispersion. The finest dispersion state was achieved with the 'initiating' functionalized silica leading to a 'grafting from' polymerization of the L-Lactide. Such functionalized silica leads to a nanoscale dispersion in a one-step bulk polymerization with only a few small agglomerates.

  19. Study on the effects of temperature, time and policy of pre polymerization on particle morphology in propylene slurry polymerization with heterogeneous ziegler-Natta catalysts

    International Nuclear Information System (INIS)

    Pircheraghi, G.; Pourmahdian, S.; Vatankhah, M.

    2008-01-01

    The effects of temperature, time and the strategy of pre polymerization were studied on the morphology of polypropylene particles. Propylene polymerization was carried out in slurry phase using fourth generation of Ziegler-Natta Catalyst, cyclohexylmethyl dimethoxysilane as external electron donor, and triethyl aluminum as co-catalyst. Pre polymerizations were carried out based on two strategies: isothermal and non-isothermal conditions. Particle imaging using SEM, bulk density, and particle size distribution was used to analyse the particle morphology. It was found that the variation of initial condition together with the change in the mechanism of particle fracture has a dominant effect on particle morphology. Each combination between the temperature and reaction time causes to have a special effect on the product particle morphology. It has become clear that in isothermal pre polymerization, spherical particles with identical properties were produced. In low temperature experiments particles with porous surface were observed. At increasing temperature, however, the pores disappeared. Non-isothermal pre polymerization produced different morphological types. In all experiments core shell structures were observed that seemed to be related to the structure of catalysts

  20. Synthesis of polystyrene with high melting temperature through BDE/CuCl catalyzed polymerization

    Institute of Scientific and Technical Information of China (English)

    WAN; Xiaolong

    2001-01-01

    [1]Ewen, J. A., Novel method for plastic production, Science (in Chinese), 1997, 9: 34.[2]Brintzinger, H. H., Fischer, D., Waymouth, R. M. et al., Stereospecific olefin polymerization with chiral metallocene catalysts, Angewandte Chemie International Edition in English, 1995, 34(11): 1143.[3]Matyjaszewski, K., Atom transfer radical polymerization, role of various components and reaction conditions, Polym. Prep., 1997, 38(2): 736.[4]Wang, J. S., Matyjaszewski, K., Controlled/"living" radical polymerization, atom transfer radical polymerization in the presence of transition-metal complex, J. Am. Soc., 1995, 117: 5614.[5]Wang, J. S., Matyjaszewski, K., Controlled/"living" radical polymerization, halogen atom transfer radical polymerization promoted by a Cu(I)/Cu(II) redox process, Macromolecules, 1995, 28: 7901.[6]Koto, M., Kamigaito, M., Sawamoto, M. et al., Polymerization of methyl methacrylate with the carbon tetrachloride/dichloro-tris(triphenyphosphine) ruthenium(II)/methylaluminum bis(2,6-di-tert-butylphenoxide) initiating system: possible of living radical polymerization, Macromolecules, 1995, 28: 1721.[7]Ando, T., Kato, M., Living radical polymerization of methyl methacrylate with Ruthenium complex: formation of polymers with controlled molecular weights and very narrow distributions, Macromolecules, 1996, 29: 1070.[8]Granel, C., Dubios, P., Jerome, R. et al., Controlled radical polymerization of methacrylic monomers in the presence of a bis(ortho-chelated) arylnickel(II) complex and different activated alkyl halides, Macromolecules, 1996, 29: 8576.[9]Granel, C., Moineau, G., Lecome, P. et al., (Meth)acrylates pseudo-living radical polymerization in the presence of transition metal complexes: the kharasch reaction revisited, Polym. Prep., 1997, 38(1): 450.[10]Ando, T., Kamigaito, M., Sawamoto, M., Iron(II) chloride complex for living radical polymerization of methyl methacrylate, Macromolecules, 1997, 30: 4507.[11

  1. Polymeric implant of methylprednisolone for spinal injury ...

    African Journals Online (AJOL)

    Polymeric implant of methylprednisolone for spinal injury: preparation and characterization. Bo Yin, Jian-Jun Ji, Ming Yang. Abstract. Purpose: To improve the effectiveness and reduce the systemic side effects of methylprednisolone in traumatic spinal injuries, its polymeric implants were prepared using chitosan and sodium ...

  2. Asymmetric Construction of Benzindoloquinolizidine: Application of An Organocatalytic Enantioselective Conjugate Addition-Cyclization Cascade Reaction

    International Nuclear Information System (INIS)

    Kim, Cheolwoong; Seo, Seung Woo; Lee, Yona; Kim, Sunggon

    2014-01-01

    We have developed the synthetic methodology of enantioenriched benzindoloquinolizidines based on the organocatalytic enantioselective conjugate addition-cyclization cascade reaction of o-N-(3-indoleacetyl)amino-cinnamaldehydes with malonates followed by an acid-catalyzed intramolecular Pictet-Spengler type cyclization. The asymmetric reaction using diphenylprolinol TMS ether as an organocatalyst produces the desired products with good to excellent yields and high enantioselectivities (up to 98% ee). The evaluation of the applications of this synthetic methodology for generating enantioenriched benzindolo-quinolizidines and studies on the biological activity of these compounds against human prostate cancer in particular are now in progress. Results of these studies will be presented in due course. Many new types of chemical reactions have been developed to facilitate easier synthesis of complex compounds. Among the strategies, domino reactions, which have been utilized for the efficient and stereoselective construction of complex molecules from simple precursors in a single process, are widely used due to their high synthetic efficiency by reducing both the number of synthetic operation required and the quantities of chemicals and solvents used

  3. Fluid Effects in Polymers and Polymeric Composites

    CERN Document Server

    Weitsman, Y Jack

    2012-01-01

    Fluid Effects in Polymers and Polymeric Composites, written by the late Dr. Y. Jack Weitsman, addresses the wide range of parameters that affect the interaction of fluids with polymers and polymeric composites. The book aims at broadening the scope of available data, mostly limited up to this time to weight-gain recordings of fluid ingress into polymers and composites, to the practical circumstances of fluctuating exposure. Various forms of experimental data are given, in conjunction with theoretical models derived from basic scientific principles, and correlated with severity of exposure conditions and interpreted by means of rationally based theoretical models. The practical implications of the effects of fluids are discussed. The issue of fluid effects on polymers and polymeric composites is of concern to engineers and scientists active in aerospace and naval structures, as an increasing portion of these structures are made of polymeric composites and employ polymeric adhesives as a joining device. While...

  4. Gold-Catalyzed Formal C-C Bond Insertion Reaction of 2-Aryl-2-diazoesters with 1,3-Diketones.

    Science.gov (United States)

    Ren, Yuan-Yuan; Chen, Mo; Li, Ke; Zhu, Shou-Fei

    2018-06-29

    The transition-metal-catalyzed formal C-C bond insertion reaction of diazo compounds with monocarbonyl compounds is well established, but the related reaction of 1,3-diketones instead gives C-H bond insertion products. Herein, we report a protocol for a gold-catalyzed formal C-C bond insertion reaction of 2-aryl-2-diazoesters with 1,3-diketones, which provides efficient access to polycarbonyl compounds with an all-carbon quaternary center. The aryl ester moiety plays a crucial role in the unusual chemoselectivity, and the addition of a Brønsted acid to the reaction mixture improves the yield of the C-C bond insertion product. A reaction mechanism involving cyclopropanation of a gold carbenoid with an enolate and ring-opening of the resulting donor-acceptor-type cyclopropane intermediate is proposed. This mechanism differs from that of the traditional Lewis-acid-catalyzed C-C bond insertion reaction of diazo compounds with monocarbonyl compounds, which involves a rearrangement of a zwitterion intermediate as a key step. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Modeling liquid crystal polymeric devices

    Science.gov (United States)

    Gimenez Pinto, Vianney Karina

    The main focus of this work is the theoretical and numerical study of materials that combine liquid crystal and polymer. Liquid crystal elastomers are polymeric materials that exhibit both the ordered properties of the liquid crystals and the elastic properties of rubbers. Changing the order of the liquid crystal molecules within the polymer network can induce shape change. These materials are very valuable for applications such as actuators, sensors, artificial muscles, haptic displays, etc. In this work we apply finite element elastodynamics simulations to study the temperature induced shape deformation in nematic elastomers with complex director microstructure. In another topic, we propose a novel numerical method to model the director dynamics and microstructural evolution of three dimensional nematic and cholesteric liquid crystals. Numerical studies presented in this work are in agreement with experimental observations and provide insight into the design of application devices.

  6. Polymerization of lanthanide acrylonitrile complexes.

    Science.gov (United States)

    el-Mossalamy, El-Sayed H; Khalil, Ahmed A

    2002-01-01

    The molecular complexes of some lanthanides scandium (Sc3+), yttrium (Y3+), lanthanum (La3+), gadolinium (Gd3+), cerium (Ce3+) and ytterbium (Yb3) have been studies in dimethyl formamide (DMF) spectrophtometrically equilibrium constants (K), molar extintion coefficient (epsilon), energy of transition (E) and free energy (delta G*) were calculated. The polymerization of acrylonitrile has been studied and investigated in the presence of Sc3+, Y3+, La3+, Gd3+, Ce3+, and Yb3+ ions. The IR spectra of the formed AN-M (III) Br3 polymer complexes show the absence of the C identical to N band and the presence of two new bands corresponding to NH2 and OH groups. Magnetic moment values and the thermal stabilities of homopolymer and the polymer complexes were studied by means of thermogravimetric analysis and the activation energies for degradation were calculated.

  7. SIMULTANEOUS MEASUREMENT OF FREE RADICAL DECAY IN POLYMERIZATION OF MMA INITIATED BY AIBN USING ESR AND ITS KINETIC MODEL

    Institute of Scientific and Technical Information of China (English)

    Ping Xia; Qing-song Hu; Xiao-lan Qian; Xul-in Jiang; De-yue Yan

    2001-01-01

    The kinetics of free radical decay in the polymerization of MMA initiated by AIBN was studied by means of ESR spectroscopy. It was found that the curves of radical decay are strongly associated with the reaction temperature, the initiator concentration and the solvent. In the case of the radical polymerization carried out at high temperature or in solution, the radical concentration first reached a maximum, then declined monotonously with reaction time. It was also found that the greater the amount of initiator or the higher the temperature, the more rapidly the radicals decay. When the bulk polymerization was implemented at a relatively low temperature, the curves of radical decay became more complicated, i.e.,the radical concentration rapidly rose to a maximum, then dropped to a minimum, finally increased again with reaction time.Taking into account the diffusion effect, a semi-empirical equation is suggested to describe the kinetics of propagating radical decay.

  8. Polymeric materials from renewable resources

    Energy Technology Data Exchange (ETDEWEB)

    Frollini, Elisabete; Rodrigues, Bruno V. M.; Silva, Cristina G. da; Castro, Daniele O.; Ramires, Elaine C.; Oliveira, Fernando de; Santos, Rachel P. O. [Macromolecular Materials and Lignocellulosic Fibers Group, Center for Research on Science and Technology of BioResources, Institute of Chemistry of São Carlos, University of São Paulo, CP 780, 13560-970 São Carlos, São Paulo (Brazil)

    2016-05-18

    The goals of our studies have been the use of renewable raw materials in the preparation of polymeric materials with diversified properties. In this context, lignosulfonate, which is produced in large scale around the world, but not widely used in the production of polymeric materials, was used to replace phenol and polyols in the preparation of phenolic- (Ligno-PH) and polyurethane-type (Ligno-PU) polymers, respectively. These polymers were used to prepare composites reinforced with sisal lignocellulosic fibers. The use of lignosulfonate in the formulation of both types of polymers was beneficial, because in general composites with improved properties, specially impact strength, were obtained. Composites were also prepared from the so called “biopolyethylene” (HDPE), curaua lignocellulosic fiber, and castor oil (CO). All composites HDBPE/CO/Fiber exhibited higher impact strength, when compared to those of the corresponding HDBPE/Fiber. These results, combined with others (eg SEM images of the fractured surfaces) indicated that, in addition to acting as a plasticizer, this oil may have acted as a compatibilizer of the hydrophilic fiber with the hydrophobic polymer. The set of results indicated that (i) mats with nano (diameter ≤ 100nm) and/or ultrafine (submicron scale) fibers were produced, (ii) hybrid fibers were produced (bio-based mats composites), (iii) cellulosic pulp (CP) and/or lignin (Lig) can be combined with PET matrices to control properties such as stiffness and hydrophilicity of the respective mats. Materials with diversified properties were prepared from high content of renewable raw materials, thus fulfilling the proposed targets.

  9. Polymeric materials from renewable resources

    Science.gov (United States)

    Frollini, Elisabete; Rodrigues, Bruno V. M.; da Silva, Cristina G.; Castro, Daniele O.; Ramires, Elaine C.; de Oliveira, Fernando; Santos, Rachel P. O.

    2016-05-01

    The goals of our studies have been the use of renewable raw materials in the preparation of polymeric materials with diversified properties. In this context, lignosulfonate, which is produced in large scale around the world, but not widely used in the production of polymeric materials, was used to replace phenol and polyols in the preparation of phenolic- (Ligno-PH) and polyurethane-type (Ligno-PU) polymers, respectively. These polymers were used to prepare composites reinforced with sisal lignocellulosic fibers. The use of lignosulfonate in the formulation of both types of polymers was beneficial, because in general composites with improved properties, specially impact strength, were obtained. Composites were also prepared from the so called "biopolyethylene" (HDPE), curaua lignocellulosic fiber, and castor oil (CO). All composites HDBPE/CO/Fiber exhibited higher impact strength, when compared to those of the corresponding HDBPE/Fiber. These results, combined with others (eg SEM images of the fractured surfaces) indicated that, in addition to acting as a plasticizer, this oil may have acted as a compatibilizer of the hydrophilic fiber with the hydrophobic polymer. The set of results indicated that (i) mats with nano (diameter ≤ 100nm) and/or ultrafine (submicron scale) fibers were produced, (ii) hybrid fibers were produced (bio-based mats composites), (iii) cellulosic pulp (CP) and/or lignin (Lig) can be combined with PET matrices to control properties such as stiffness and hydrophilicity of the respective mats. Materials with diversified properties were prepared from high content of renewable raw materials, thus fulfilling the proposed targets.

  10. In situ self-polymerization of unsaturated metal methacrylate and its dispersion mechanism in rubber-based composites

    Energy Technology Data Exchange (ETDEWEB)

    Wen, Shipeng; Zhou, Yao; Yao, Lu [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029 (China); Zhang, Liqun [State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029 (China); Chan, Tung W. [Department of Materials Science and Engineering, Virginia Polytechnic Institute and State University, VA 24061 (United States); Liang, Yongri [Beijing National Laboratory for Molecular Sciences, Joint Laboratory of Polymer Science and Materials, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190 (China); Liu, Li, E-mail: LiuL@mail.buct.edu.cn [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029 (China)

    2013-11-10

    Highlights: • In situ self-polymerization of unsaturated metal methacrylate was investigated mainly by the thermal effect. • UMM with low melting point can self-polymerize to a large extent. • The fine dispersion phase is composed of poly(UMM) nanoparticles formed by in situ self-polymerization in the rubber matrix. • The UMM crystals in the presence of peroxide and rubber undergo the processes of melting, diffusion, polymerization, and phase separation in this order. - Abstract: Unsaturated metal methacrylate (UMM) as one kind of functional filler has played an important role in reinforcing rubber materials. The in situ self-polymerization of UMM in UMM/rubber composite leads to the uniform dispersion of poly(UMM) in the rubber matrix, while the crosslinking of rubber and grafting between UMM and rubber chains occur simultaneously, making it difficult to clarify the effect of the in situ polymerization on the dispersion of poly(UMM) in the rubber matrix. In this work, we investigated the dispersion mechanism of UMM without rubber matrix for the first time using differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. Three types of UMMs including zinc methacrylate (Zn(MA){sub 2}), sodium methacrylate (Na(MA)) and samarium methacrylate (Sm(MA){sub 3}) were chosen to investigate the in situ self-polymerization of UMM. Based on DSC results, we conclude that the crystals with low melting point tend to self-polymerize first and generate a large amount of heat in the presence of peroxide. The high heat of reaction can melt the crystals with high melting point, and more UMM molecules are dissolved in the rubber matrix, thus increasing the extent of the in situ polymerization. Hence, the UMM with low melting point can self-polymerize to a large extent. Our findings provide in-depth understanding of the dispersion mechanism of UMM in rubber.

  11. In situ self-polymerization of unsaturated metal methacrylate and its dispersion mechanism in rubber-based composites

    International Nuclear Information System (INIS)

    Wen, Shipeng; Zhou, Yao; Yao, Lu; Zhang, Liqun; Chan, Tung W.; Liang, Yongri; Liu, Li

    2013-01-01

    Highlights: • In situ self-polymerization of unsaturated metal methacrylate was investigated mainly by the thermal effect. • UMM with low melting point can self-polymerize to a large extent. • The fine dispersion phase is composed of poly(UMM) nanoparticles formed by in situ self-polymerization in the rubber matrix. • The UMM crystals in the presence of peroxide and rubber undergo the processes of melting, diffusion, polymerization, and phase separation in this order. - Abstract: Unsaturated metal methacrylate (UMM) as one kind of functional filler has played an important role in reinforcing rubber materials. The in situ self-polymerization of UMM in UMM/rubber composite leads to the uniform dispersion of poly(UMM) in the rubber matrix, while the crosslinking of rubber and grafting between UMM and rubber chains occur simultaneously, making it difficult to clarify the effect of the in situ polymerization on the dispersion of poly(UMM) in the rubber matrix. In this work, we investigated the dispersion mechanism of UMM without rubber matrix for the first time using differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy. Three types of UMMs including zinc methacrylate (Zn(MA) 2 ), sodium methacrylate (Na(MA)) and samarium methacrylate (Sm(MA) 3 ) were chosen to investigate the in situ self-polymerization of UMM. Based on DSC results, we conclude that the crystals with low melting point tend to self-polymerize first and generate a large amount of heat in the presence of peroxide. The high heat of reaction can melt the crystals with high melting point, and more UMM molecules are dissolved in the rubber matrix, thus increasing the extent of the in situ polymerization. Hence, the UMM with low melting point can self-polymerize to a large extent. Our findings provide in-depth understanding of the dispersion mechanism of UMM in rubber

  12. Chemical Reactor Automation as a way to Optimize a Laboratory Scale Polymerization Process

    Science.gov (United States)

    Cruz-Campa, Jose L.; Saenz de Buruaga, Isabel; Lopez, Raymundo

    2004-10-01

    The automation of the registration and control of variables involved in a chemical reactor improves the reaction process by making it faster, optimized and without the influence of human error. The objective of this work is to register and control the involved variables (temperatures, reactive fluxes, weights, etc) in an emulsion polymerization reaction. The programs and control algorithms were developed in the language G in LabVIEW®. The designed software is able to send and receive RS232 codified data from the devices (pumps, temperature sensors, mixer, balances, and so on) to and from a personal Computer. The transduction from digital information to movement or measurement actions of the devices is done by electronic components included in the devices. Once the programs were done and proved, chemical reactions of emulsion polymerization were made to validate the system. Moreover, some advanced heat-estimation algorithms were implemented in order to know the heat caused by the reaction and the estimation and control of chemical variables in-line. All the information gotten from the reaction is stored in the PC. The information is then available and ready to use in any commercial data processor software. This work is now being used in a Research Center in order to make emulsion polymerizations under efficient and controlled conditions with reproducible results. The experiences obtained from this project may be used in the implementation of chemical estimation algorithms at pilot plant or industrial scale.

  13. EXPLORING THE POTENTIAL FORMATION OF ORGANIC SOLIDS IN CHONDRITES AND COMETS THROUGH POLYMERIZATION OF INTERSTELLAR FORMALDEHYDE

    International Nuclear Information System (INIS)

    Kebukawa, Yoko; Cody, George D.; David Kilcoyne, A. L.

    2013-01-01

    Polymerization of interstellar formaldehyde, first through the formose reaction and then through subsequent condensation reactions, provides a plausible explanation for how abundant and highly chemically complex organic solids may have come to exist in primitive solar system objects. In order to gain better insight on the reaction, a systematic study of the relationship of synthesis temperature with resultant molecular structure was performed. In addition, the effect of the presence of ammonia on the reaction rate and molecular structure of the product was studied. The synthesized formaldehyde polymer is directly compared to chondritic insoluble organic matter (IOM) isolated from primitive meteorites using solid-state 13 C nuclear magnetic resonance, Fourier transform infrared, and X-ray absorption near edge structure spectroscopy. The molecular structure of the formaldehyde polymer is shown to exhibit considerable similarity at the functional group level with primitive chondritic IOM. The addition of ammonia to the solution enhances the rate of polymerization reaction at lower temperatures and results in substantial incorporation of nitrogen into the polymer. Morphologically, the formaldehyde polymer exists as submicron to micron-sized spheroidal particles and spheroidal particle aggregates that bare considerable similarity to the organic nanoglobules commonly observed in chondritic IOM. These spectroscopic and morphological data support the hypothesis that IOM in chondrites and refractory organic carbon in comets may have formed through the polymerization of interstellar formaldehyde after planetesimal accretion, in the presence of liquid water, early in the history of the solar system.

  14. EXPLORING THE POTENTIAL FORMATION OF ORGANIC SOLIDS IN CHONDRITES AND COMETS THROUGH POLYMERIZATION OF INTERSTELLAR FORMALDEHYDE

    Energy Technology Data Exchange (ETDEWEB)

    Kebukawa, Yoko; Cody, George D. [Geophysical Laboratory, Carnegie Institution of Washington, 5251 Broad Branch Road NW, Washington, DC 20015 (United States); David Kilcoyne, A. L., E-mail: ykebukawa@ciw.edu, E-mail: yoko@ep.sci.hokudai.ac.jp [Advanced Light Source, Lawrence Berkeley National Laboratory, Mail Stop 7R0222, 1 Cyclotron Road, Berkeley, CA 94720 (United States)

    2013-07-01

    Polymerization of interstellar formaldehyde, first through the formose reaction and then through subsequent condensation reactions, provides a plausible explanation for how abundant and highly chemically complex organic solids may have come to exist in primitive solar system objects. In order to gain better insight on the reaction, a systematic study of the relationship of synthesis temperature with resultant molecular structure was performed. In addition, the effect of the presence of ammonia on the reaction rate and molecular structure of the product was studied. The synthesized formaldehyde polymer is directly compared to chondritic insoluble organic matter (IOM) isolated from primitive meteorites using solid-state {sup 13}C nuclear magnetic resonance, Fourier transform infrared, and X-ray absorption near edge structure spectroscopy. The molecular structure of the formaldehyde polymer is shown to exhibit considerable similarity at the functional group level with primitive chondritic IOM. The addition of ammonia to the solution enhances the rate of polymerization reaction at lower temperatures and results in substantial incorporation of nitrogen into the polymer. Morphologically, the formaldehyde polymer exists as submicron to micron-sized spheroidal particles and spheroidal particle aggregates that bare considerable similarity to the organic nanoglobules commonly observed in chondritic IOM. These spectroscopic and morphological data support the hypothesis that IOM in chondrites and refractory organic carbon in comets may have formed through the polymerization of interstellar formaldehyde after planetesimal accretion, in the presence of liquid water, early in the history of the solar system.

  15. Exploring the Potential Formation of Organic Solids in Chondrites and Comets through Polymerization of Interstellar Formaldehyde

    Science.gov (United States)

    Kebukawa, Yoko; Kilcoyne, A. L. David; Cody, George D.

    2013-07-01

    Polymerization of interstellar formaldehyde, first through the formose reaction and then through subsequent condensation reactions, provides a plausible explanation for how abundant and highly chemically complex organic solids may have come to exist in primitive solar system objects. In order to gain better insight on the reaction, a systematic study of the relationship of synthesis temperature with resultant molecular structure was performed. In addition, the effect of the presence of ammonia on the reaction rate and molecular structure of the product was studied. The synthesized formaldehyde polymer is directly compared to chondritic insoluble organic matter (IOM) isolated from primitive meteorites using solid-state 13C nuclear magnetic resonance, Fourier transform infrared, and X-ray absorption near edge structure spectroscopy. The molecular structure of the formaldehyde polymer is shown to exhibit considerable similarity at the functional group level with primitive chondritic IOM. The addition of ammonia to the solution enhances the rate of polymerization reaction at lower temperatures and results in substantial incorporation of nitrogen into the polymer. Morphologically, the formaldehyde polymer exists as submicron to micron-sized spheroidal particles and spheroidal particle aggregates that bare considerable similarity to the organic nanoglobules commonly observed in chondritic IOM. These spectroscopic and morphological data support the hypothesis that IOM in chondrites and refractory organic carbon in comets may have formed through the polymerization of interstellar formaldehyde after planetesimal accretion, in the presence of liquid water, early in the history of the solar system.

  16. Method for forming polymerized microfluidic devices

    Science.gov (United States)

    Sommer, Gregory J.; Hatch, Anson V.; Wang, Ying-Chih; Singh, Anup K.; Renzi, Ronald F.; Claudnic, Mark R.

    2013-03-12

    Methods for making a microfluidic device according to embodiments of the present invention include defining.about.cavity. Polymer precursor solution is positioned in the cavity, and exposed to light to begin the polymerization process and define a microchannel. In some embodiments, after the polymerization process is partially complete, a solvent rinse is performed, or fresh polymer precursor introduced into the microchannel. This may promote removal of unpolymerized material from the microchannel and enable smaller feature sizes. The polymer precursor solution may contain an iniferter. Polymerized features therefore may be capped with the iniferter, which is photoactive. The iniferter may aid later binding of a polyacrylamide gel to the microchannel surface.

  17. Nuclear reactions

    International Nuclear Information System (INIS)

    Lane, A.M.

    1980-01-01

    In reviewing work at Harwell over the past 25 years on nuclear reactions it is stated that a balance has to be struck in both experiment and theory between work on cross-sections of direct practical relevance to reactors and on those relevant to an overall understanding of reaction processes. The compound nucleus and direct process reactions are described. Having listed the contributions from AERE, Harwell to developments in nuclear reaction research in the period, work on the optical model, neutron capture theory, reactions at doorway states with fine structure, and sum-rules for spectroscopic factors are considered in more detail. (UK)

  18. Supported Catalysts Useful in Ring-Closing Metathesis, Cross Metathesis, and Ring-Opening Metathesis Polymerization

    Directory of Open Access Journals (Sweden)

    Jakkrit Suriboot

    2016-04-01

    Full Text Available Ruthenium and molybdenum catalysts are widely used in synthesis of both small molecules and macromolecules. While major developments have led to new increasingly active catalysts that have high functional group compatibility and stereoselectivity, catalyst/product separation, catalyst recycling, and/or catalyst residue/product separation remain an issue in some applications of these catalysts. This review highlights some of the history of efforts to address these problems, first discussing the problem in the context of reactions like ring-closing metathesis and cross metathesis catalysis used in the synthesis of low molecular weight compounds. It then discusses in more detail progress in dealing with these issues in ring opening metathesis polymerization chemistry. Such approaches depend on a biphasic solid/liquid or liquid separation and can use either always biphasic or sometimes biphasic systems and approaches to this problem using insoluble inorganic supports, insoluble crosslinked polymeric organic supports, soluble polymeric supports, ionic liquids and fluorous phases are discussed.

  19. Ionic polymerization of p-methoxystyrene and other styrene derivatives by radiation. [Gamma radiation

    Energy Technology Data Exchange (ETDEWEB)

    Hayashi, K; Pepper, D C [Trinity Coll., Dublin (Ireland)

    1976-01-01

    Polymerization of p-methoxystyrene by radiation was studied in bulk. Upon drying the monomer, the rate of polymerization, Rsub(p), became greater, changing its dose rate dependence from 0.5 to 1. The molecular weight distribution of the obtained polymers failed to give a bimodal curve; however, the peak molecular weight increased with higher Rsub(p). These kinetic features can be explained by a coexistence of radical and cationic mechanisms, as has been established in styrene, though there remain ambiguities about the effects of additives. Copolymerizations with styrene and 2-chloroethyl vinyl ether also showed a cationic nature for the reaction. A survey of possibilities of ionic polymerization by radiation was also carried out in ten ring-substituted styrene derivatives.

  20. Polymerization of Various Lignins via Immobilized Myceliophthora thermophila Laccase (MtL

    Directory of Open Access Journals (Sweden)

    Daniela Huber

    2016-08-01

    Full Text Available Enzymatic polymerization of lignin is an environmentally-friendly and sustainable method that is investigated for its potential in opening-up new applications of one of the most abundant biopolymers on our planet. In this work, the laccase from Myceliophthora thermophila was successfully immobilized onto Accurel MP1000 beads (67% of protein bound to the polymeric carrier and the biocatalyzed oxidation of Kraft lignin (KL and lignosulfonate (LS were carried out. Fluorescence intensity determination, phenol content analysis and size exclusion chromatography were performed in order to elucidate the extent of the polymerization reaction. The collected results show an 8.5-fold decrease of the LS samples’ fluorescence intensity after laccase-mediated oxidation and a 12-fold increase of the weight average molecular weight was obtained.

  1. Acrylate intercalation and in situ polymerization in iron-, cobalt-, or manganese-substituted nickel hydroxides.

    Science.gov (United States)

    Vaysse, C; Guerlou-Demourgues, L; Duguet, E; Delmas, C

    2003-07-28

    A chimie douce route based on successive redox and exchange reactions has allowed us to prepare new hybrid organic-inorganic materials, composed of polyacrylate macromolecules intercalated into layered double hydroxides (LDHs), deriving from Ni(OH)(2). Monomer intercalation and in situ polymerization mechanisms have appeared to be strongly dependent upon the nature of the substituting cation in the slabs. In the case of iron-based LDHs, a phase containing acrylate monomeric intercalates has been isolated and identified by X-ray diffraction and infrared spectroscopy. Second, interslab free-radical polymerization of acrylate anions has been successfully initiated using potassium persulfate. In cobalt- or manganese-based LDHs, one-step polymerization has been observed, leading directly to a material containing polyacrylate intercalate.

  2. Study of n-Butyl Acrylate Self-Initiation Reaction Experimentally and via Macroscopic Mechanistic Modeling

    Directory of Open Access Journals (Sweden)

    Ahmad Arabi Shamsabadi

    2016-04-01

    Full Text Available This paper presents an experimental study of the self-initiation reaction of n-butyl acrylate (n-BA in free-radical polymerization. For the first time, the frequency factor and activation energy of the monomer self-initiation reaction are estimated from measurements of n-BA conversion in free-radical homo-polymerization initiated only by the monomer. The estimation was carried out using a macroscopic mechanistic mathematical model of the reactor. In addition to already-known reactions that contribute to the polymerization, the model considers a n-BA self-initiation reaction mechanism that is based on our previous electronic-level first-principles theoretical study of the self-initiation reaction. Reaction rate equations are derived using the method of moments. The reaction-rate parameter estimates obtained from conversion measurements agree well with estimates obtained via our purely-theoretical quantum chemical calculations.

  3. Role of the reaction intermediates in determining PHIP (parahydrogen induced polarization) effect in the hydrogenation of acetylene dicarboxylic acid with the complex [Rh (dppb)]+ (dppb: 1,4-bis(diphenylphosphino)butane)

    International Nuclear Information System (INIS)

    Reineri, F.; Aime, S.; Gobetto, R.; Nervi, C.

    2014-01-01

    This study deals with the parahydrogenation of the symmetric substrate acetylene dicarboxylic acid catalyzed by a Rh(I) complex bearing the chelating diphosphine dppb (1,4-bis(diphenylphosphino)butane). The two magnetically equivalent protons of the product yield a hyperpolarized emission signal in the 1 H-NMR spectrum. Their polarization intensity varies upon changing the reaction solvent from methanol to acetone. A detailed analysis of the hydrogenation pathway is carried out by means of density functional theory calculations to assess the structure of hydrogenation intermediates and their stability in the two solvents. The observed polarization effects have been accounted on the basis of the obtained structures. Insights into the lifetime of a short-lived reaction intermediate are also obtained

  4. One-Pot Synthesis of Charged Amphiphilic Diblock and Triblock Copolymers Via High-Throughput Cu(0-Mediated Polymerization

    Directory of Open Access Journals (Sweden)

    Lenny Voorhaar

    2017-07-01

    Full Text Available Block copolymers containing functionalized monomers, for example those containing charged groups, can be used for many purposes, one of which is the design of polymeric supramolecular materials based on electrostatic interactions. In this paper the synthesis of diblock copolymers and ABA-triblock copolymers containing poly(n-butyl acrylate as a first or middle block and poly(2-(dimethylaminoethyl acrylate, poly(1-ethoxyethyl acrylate and poly(1-ethoxyethyl-2-carboxyethyl acrylate as second or outer blocks, resulting in block copolymers that can contain positive or negative charges, is reported. The polymerizations were performed and optimized via one-pot sequential monomer addition reactions via Cu(0-mediated polymerization using an automated parallel synthesizer. Different initiators, monomer concentrations and polymerization times were tested. While a bromide-containing initiator led to the best results for most monomers, when polymerizing 2-(dimethylaminoethyl acrylate the use of a chloride-containing initiator was necessary. Due to the slower polymerization using this initiator, a longer polymerization time was needed before addition of the second monomer. Using the optimized conditions, the diblock and triblock copolymers could be synthesized with good control over molecular weight and dispersities around 1.1 were obtained.

  5. Radiation-induced controlled polymerization of acrylic acid by RAFT and RAFT-MADIX methods in protic solvents

    Science.gov (United States)

    Sütekin, S. Duygu; Güven, Olgun

    2018-01-01

    The kinetic investigation of one-pot synthesis of poly(acrylic acid) (PAA) prepared via gamma radiation induced controlled polymerization was reported. PAA homopolymers were prepared by Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization in the presence of trithiocarbonate-based chain transfer agent (CTA) 2-(Dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT) and also by Reversible Addition-Fragmentation/Macromolecular Design by Inter-change of Xanthates (RAFT/MADIX) polymerization in the presence of a xanthate based CTA O-ethyl-S-(1-methoxycarbonyl) ethyl dithiocarbonate (RA1). The polymerizations were performed at room temperature by the virtue of ionizing radiation. Protic solvents were used for the RAFT polymerization of AA considering environmental profits. The linear first-order kinetic plot, close control of molecular weight by the monomer/CTA molar ratio supported that the polymerization proceeds in a living fashion. The linear increase in molecular weight with conversion monitored by Size Exclusion Chromatography (SEC) is another proof of controlling of polymerization. [Monomer]/[RAFT] ratio and conversion was controlled to obtain PAA in the molecular weight range of 6900-35,800 with narrow molecular weight distributions. Reaction kinetics and effect of the amount of RAFT agent were investigated in detail. Between two different types of CTA, trithiocarbonate based DDMAT was found to be more efficient in terms of low dispersity (Đ) and linear first-order kinetic behavior for the radiation induced controlled synthesis of PAA homopolymers.

  6. Synthesis and polymerization of vinyl triazolium ionic liquids

    Science.gov (United States)

    Luebke, David; Nulwala, Hunaid; Matyjaszewski, Krzysztof; Adzima, Brian

    2018-05-15

    Herein, we describe polymerized ionic liquids, demonstrate the synthesis of polymerized ionic liquids, and demonstrate the polymerization of triazolium monomers. One embodiment shows the polymeriazation of the triazolium monomers with bis(trifluoromethanesulfonyl)imide anions. In another embodiment we show the feasibility of copolymerizing with commodity monomers such as styrene using free radical polymerization techniques.

  7. Better flocculants by radiation induced polymerization

    International Nuclear Information System (INIS)

    Laizier, J.; Gaussens, G.

    1978-01-01

    The use of radiation induced polymerization should theoritically allow to prepare better flocculants. The testings of several products prepared by such a process shows that better properties are indeed obtained: better efficiencies, lower amounts needed, better overall properties [fr

  8. Compression Behavior of High Performance Polymeric Fibers

    National Research Council Canada - National Science Library

    Kumar, Satish

    2003-01-01

    Hydrogen bonding has proven to be effective in improving the compressive strength of rigid-rod polymeric fibers without resulting in a decrease in tensile strength while covalent crosslinking results in brittle fibers...

  9. Silicon dioxide obtained by Polymeric Precursor Method

    International Nuclear Information System (INIS)

    Oliveira, C.T.; Granado, S.R.; Lopes, S.A.; Cavalheiro, A.A.

    2011-01-01

    The Polymeric Precursor Method is able for obtaining several oxide material types with high surface area even obtained in particle form. Several MO 2 oxide types such as titanium, silicon and zirconium ones can be obtained by this methodology. In this work, the synthesis of silicon oxide was monitored by thermal analysis, XRD and surface area analysis in order to demonstrate the influence of the several synthesis and calcining parameters. Surface area values as higher as 370m2/g and increasing in the micropore volume nm were obtained when the material was synthesized by using ethylene glycol as polymerizing agent. XRD analysis showed that the material is amorphous when calcinated at 600°C in despite of the time of calcining, but the material morphology is strongly influenced by the polymeric resin composition. Using Glycerol as polymerizing agent, the pore size increase and the surface area goes down with the increasing in decomposition time, when compared to ethylene glycol. (author)

  10. Thermal polymerization of Moringa oleifera oil

    International Nuclear Information System (INIS)

    Melo, Tania M.S.; Novack, Katia M.; Leandro, Cristiano

    2011-01-01

    It is increasingly clear both for society and the scientific community, that is necessary to find alternatives to reduce the use of polymeric materials because of their damage to the environment. One way to minimize the environmental problems related to the use of polymers is try to make them quickly degradable. In this study it was obtained a material with polymeric appearance derived from heating of the vegetable oil extracted from seeds of Moringa oleifera. The resulting product is an interesting alternative to obtain polymeric materials that may have biodegradable characteristics, coming from a renewable source and low cost. Moringa oil can be used since it has a high content of unsaturated fatty acids, and its main constituent oleic acid. All samples were characterized by FTIR, NMR and GPC. It was obtained a polymeric material, malleable, high viscosity, with some elasticity, low crystallinity and no unpleasant odor. (author)

  11. Deformation and flow of polymeric materials

    CERN Document Server

    Münstedt, Helmut

    2014-01-01

    This book describes the properties of single polymer molecules and polymeric materials and the methods how to characterize them. Molar masses, molar mass distributions and branching structure are discussed in detail. These properties are decisive for a deeper understanding of structure/properties relationships of polymeric materials. This book therefore describes and discusses them in detail. The mechanical behavior as a function of time and temperature is a key subject of the book. The authors present it on the basis of many original results they have obtained in their long research careers. They present the temperature dependence of mechanical properties of various polymeric materials in a wide temperature range: from cryogenic temperatures to the melt. Besides an extensive data collection on the transitions of various different polymeric materials, they also carefully present the physical explanations of the observed phenomena. Glass transition and melting temperatures are discussed, particularly, with the...

  12. Polymerization of sodium methacrylate induced by irradiation

    International Nuclear Information System (INIS)

    Galvan S, A.

    1998-01-01

    This work has two objectives, first: it is pretended to localize the lines of carbon links in its IR spectra, and second: following the polymerization of sodium methacrylate according to that it is irradiated with gamma rays. (Author)

  13. Reverse-osmosis membranes by plasma polymerization

    Science.gov (United States)

    Hollahan, J. R.; Wydeven, T.

    1972-01-01

    Thin allyl amine polymer films were developed using plasma polymerization. Resulting dry composite membranes effectively reject sodium chloride during reverse osmosis. Films are 98% sodium chloride rejective, and 46% urea rejective.

  14. Bioadhesive polymeric platforms for transmucosal drug delivery ...

    African Journals Online (AJOL)

    Bioadhesive polymeric platforms for transmucosal drug delivery systems – a review. ... administration of certain classes of drugs, especially peptides and proteins. ... characteristics of desired bioadhesive polymers, this article then proceeds to ...

  15. Transformation kinetics of mixed polymeric substrates under ...

    African Journals Online (AJOL)

    bglucosidase and a-mannosidase were abundantly secreted in the growth medium. This research is the first report on mixed polymeric substrate biodegradation under sewer condition by A. niger, and could be considered as an open window on ...

  16. Deposition of a thin electro-polymerized organic film on iron surface

    International Nuclear Information System (INIS)

    Lecayon, Gerard

    1980-01-01

    We use an electrochemical method to prepare a polymerized thin film, obtained from acrylonitrile in a solution of acetonitrile and tetraethylammonium perchlorate. The films are deposited on oxidized iron electrodes, with a surface area varying from a few mm to several cm, their thickness ranges from ten A to thousand A. This result is obtained by controlling the evolution of reactions: duplication, hydrogenation, polymerization which occur during the electrochemical reduction of acrylonitrile. The choice of suitable experimental conditions enhances the polymerization and increases the adherence of the polymer on the electrode. The usual methods of surface studies: S.E.M., A.E.S., S.I.M.S., permit the characterization of the electrode surface and the chemical composition of the deposit films. The molecular structure of polymer, and its evolution under aging or heating was studied by infrared multi-reflection spectroscopy. Very good correlation exists between the electrochemical characteristic: I = f(t), the initial surface state of the electrodes, and the homogeneity of the electro-polymerized films. Diagrams corresponding to mechanisms of different stages of electro-polymerization are proposed. (author) [fr

  17. Supramolecular intermediates in the synthesis of polymeric carbon nitride from melamine cyanurate

    International Nuclear Information System (INIS)

    Dante, Roberto C.; Sánchez-Arévalo, Francisco M.; Chamorro-Posada, Pedro; Vázquez-Cabo, José; Huerta, Lazaro; Lartundo-Rojas, Luis; Santoyo-Salazar, Jaime

    2015-01-01

    The adduct of melamine and cyanuric acid (MCA) was used in past research to produce polymeric carbon nitride and precursors. The reaction yield was considerably incremented by the addition of sulfuric acid. The polymeric carbon nitride formation occurs around 450 °C at temperatures above the sublimation of the adduct components, which occurs around 400 °C. In this report the effect of sulfuric acid on MCA was investigated. It was found that the MCA rosette supramolecular channel structures behave as a solid solvent able to host small molecules, such as sulfuric acid, inside these channels and interact with them. Therefore, the sulfuric acid effect was found to be close to that of a solute that causes a temperature increment of the “solvent sublimation” enough to allowing the formation of polymeric carbon nitride to occur. Sulfate ions are presumably hosted in the rosette channels of MCA as shown by simulations. - Graphical abstract: The blend of melamine cyanurate and sulfuric acid behaves like a solution so that melamine cyanurate decomposition is shifted to temperatures high enough to react and form polymeric carbon nitride. - Highlights: • The adduct of melamine and cyanuric acid behaves as a solid solvent. • The blend of sulfuric acid and melamine cyanurate behaves like a solution. • Melamine cyanurate decomposition is shifted to higher temperatures by sulfuric acid. • The formation of polymeric carbon nitride occurs for these higher temperatures

  18. Emulsion Polymerization of Tung Oil-Based Latexes with Asolectin as a Biorenewable Surfactant

    Directory of Open Access Journals (Sweden)

    Ashley Johns

    2016-11-01

    Full Text Available Bio-based vesicles, with potential application in drug delivery and/or catalyst encapsulation, have been prepared by the free radical emulsion co-polymerization of tung oil, divinylbenzene (DVB, n-butyl methacrylate (BMA, and asolectin in a xylene/water mixture. The free radical polymerization was initiated by di-tert-butyl peroxide (DTBP at 100 °C in a convection oven. Molecular weights of approximately 11,000 Da were measured by Matrix-assisted Laser Desorption/Ionization-Time of Flight (Maldi-TOF for tung oil-asolectin copolymers, verifying that significant polymerization occurs under the cure conditions employed. The cure of the co-monomer mixture employed in this work was monitored by Dielectric Analysis (DEA, while changes in the Raman spectrum of all co-monomers before and after the cure, along with differential scanning calorimetry (DSC analysis, have been used to verify the need of a post-cure step and completion of the polymerization reaction. Scanning Transmission Electron Microscopy (STEM images of the emulsion after polymerization indicate that vesicles were formed, and vesicle size distribution of samples prepared with different amounts of tung oil were determined using a Zetasizer.

  19. Real time in situ spectroscopic characterization of radiation induced cationic polymerization of glycidyl ethers

    International Nuclear Information System (INIS)

    Mascioni, Matteo; Sands, James M.; Palmese, Giuseppe R.

    2003-01-01

    Radiation curable polymeric materials suffer from relatively poor mechanical properties. Moreover, the curing behavior of such systems (i.e. the exact relationship between chemical kinetics and key processing variables) is not fully understood. In order to design improved epoxy based electron beam (EB) curable systems, and in order to develop appropriate process models, a detailed knowledge of the kinetics of epoxy cationic polymerization induced by ultraviolet (UV) or EB irradiation is required. In this work, we present our development of a technique based on real time near infrared (RTIR) spectroscopy for performing in situ kinetic analysis of radiation induced cationic polymerization of epoxy systems. To our knowledge this is the first time such data have been collected and presented for high-energy EB (10 MeV) induced polymerization. A demonstration of the technique for deterministic evaluation of degree of cure is shown using model glycidyl ether (phenyl glycidyl ether and diglycidyl ether of bisphenol A) resins and isothermal curing conditions. The impact of initiation rate on polymerizations with UV and EB for the cationic initiator is directly evident by comparative analysis. The sensitivity of the RTIR method and ability to produce quantitative data evidence of reaction mechanisms is demonstrated. The type of data presented in this work forms the basis for cure models being developed

  20. Supramolecular intermediates in the synthesis of polymeric carbon nitride from melamine cyanurate

    Energy Technology Data Exchange (ETDEWEB)

    Dante, Roberto C., E-mail: rcdante@yahoo.com [Facultad de Mecánica, Escuela Politécnica Nacional (EPN), Ladrón de Guevara E11-253, Quito (Ecuador); Sánchez-Arévalo, Francisco M. [Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de Mexico, Apdo. Postal 70-360, Cd. Universitaria, Mexico D.F. 04510 (Mexico); Chamorro-Posada, Pedro [Dpto. de Teoría de la Señal y Comunicaciones e IT, Universidad de Valladolid, ETSI Telecomunicación, Paseo Belén 15, 47011 Valladolid (Spain); Vázquez-Cabo, José [Dpto. de Teoría de la Señal y Comunicaciones, Universidad de Vigo, ETSI Telecomunicación, Lagoas Marcosende s/n, Vigo (Spain); Huerta, Lazaro [Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de Mexico, Apdo. Postal 70-360, Cd. Universitaria, Mexico D.F. 04510 (Mexico); Lartundo-Rojas, Luis [Centro de Nanociencias y Micro y Nanotecnologías—IPN, Luis Enrique Erro s/n, U. Prof. Adolfo López Mateos, 07738 Ciudad de Mexico, Distrito Federal (Mexico); Santoyo-Salazar, Jaime [Departamento de Física, Centro de Investigación y de Estudios Avanzados del Instituto Politécnico Nacional, CINVESTAV-IPN, Apdo. Postal 14-740, Mexico D.F. 07360 (Mexico); and others

    2015-03-15

    The adduct of melamine and cyanuric acid (MCA) was used in past research to produce polymeric carbon nitride and precursors. The reaction yield was considerably incremented by the addition of sulfuric acid. The polymeric carbon nitride formation occurs around 450 °C at temperatures above the sublimation of the adduct components, which occurs around 400 °C. In this report the effect of sulfuric acid on MCA was investigated. It was found that the MCA rosette supramolecular channel structures behave as a solid solvent able to host small molecules, such as sulfuric acid, inside these channels and interact with them. Therefore, the sulfuric acid effect was found to be close to that of a solute that causes a temperature increment of the “solvent sublimation” enough to allowing the formation of polymeric carbon nitride to occur. Sulfate ions are presumably hosted in the rosette channels of MCA as shown by simulations. - Graphical abstract: The blend of melamine cyanurate and sulfuric acid behaves like a solution so that melamine cyanurate decomposition is shifted to temperatures high enough to react and form polymeric carbon nitride. - Highlights: • The adduct of melamine and cyanuric acid behaves as a solid solvent. • The blend of sulfuric acid and melamine cyanurate behaves like a solution. • Melamine cyanurate decomposition is shifted to higher temperatures by sulfuric acid. • The formation of polymeric carbon nitride occurs for these higher temperatures.

  1. Effect of reaction conditions on film morphology of polyaniline composite membranes for gas separation

    KAUST Repository

    Blinova, Natalia V.; Stejskal, Jaroslav; Frechet, Jean; Švec, František

    2012-01-01

    precipitation, dispersion, or emulsion polymerization of aniline with simultaneous deposition on top of the porous polypropylene support, which was immersed in the reaction mixture. Variables such as temperature, concentration of reagents, presence of steric

  2. Post polymerization cure shape memory polymers

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, Thomas S.; Hearon, II, Michael Keith; Bearinger, Jane P.

    2017-01-10

    This invention relates to chemical polymer compositions, methods of synthesis, and fabrication methods for devices regarding polymers capable of displaying shape memory behavior (SMPs) and which can first be polymerized to a linear or branched polymeric structure, having thermoplastic properties, subsequently processed into a device through processes typical of polymer melts, solutions, and dispersions and then crossed linked to a shape memory thermoset polymer retaining the processed shape.

  3. Polymeric Nanogels Obtained by Radiation Technique

    Energy Technology Data Exchange (ETDEWEB)

    Ulanski, P.; Kadłubowski, A. K.; Olejnik,; Rokita, B.; Wach, R.; Rosiak, J. M. [Institute of Applied Radiation Chemistry, Technical University of Lodz, Lodz (Poland)

    2009-07-01

    Soft nanomaterials - polymeric nanogels and microgels - have made a fast and brilliant career, from an unwanted by-product of polymerization processes to an important and fashionable topic of interdisciplinary research in the fields of polymer chemistry and physics, materials science, pharmacy and medicine. Together with their larger analogues - macroscopic gels, most known in the form of water-swellable hydrogels - they have a broad field of actual and potential applications ranging from filler materials in coating industry to modern biomaterials.

  4. Volumetric polymerization shrinkage of contemporary composite resins

    Directory of Open Access Journals (Sweden)

    Halim Nagem Filho

    2007-10-01

    Full Text Available The polymerization shrinkage of composite resins may affect negatively the clinical outcome of the restoration. Extensive research has been carried out to develop new formulations of composite resins in order to provide good handling characteristics and some dimensional stability during polymerization. The purpose of this study was to analyze, in vitro, the magnitude of the volumetric polymerization shrinkage of 7 contemporary composite resins (Definite, Suprafill, SureFil, Filtek Z250, Fill Magic, Alert, and Solitaire to determine whether there are differences among these materials. The tests were conducted with precision of 0.1 mg. The volumetric shrinkage was measured by hydrostatic weighing before and after polymerization and calculated by known mathematical equations. One-way ANOVA (a or = 0.05 was used to determine statistically significant differences in volumetric shrinkage among the tested composite resins. Suprafill (1.87±0.01 and Definite (1.89±0.01 shrank significantly less than the other composite resins. SureFil (2.01±0.06, Filtek Z250 (1.99±0.03, and Fill Magic (2.02±0.02 presented intermediate levels of polymerization shrinkage. Alert and Solitaire presented the highest degree of polymerization shrinkage. Knowing the polymerization shrinkage rates of the commercially available composite resins, the dentist would be able to choose between using composite resins with lower polymerization shrinkage rates or adopting technical or operational procedures to minimize the adverse effects deriving from resin contraction during light-activation.

  5. Post polymerization cure shape memory polymers

    Science.gov (United States)

    Wilson, Thomas S; Hearon, Michael Keith; Bearinger, Jane P

    2014-11-11

    This invention relates to chemical polymer compositions, methods of synthesis, and fabrication methods for devices regarding polymers capable of displaying shape memory behavior (SMPs) and which can first be polymerized to a linear or branched polymeric structure, having thermoplastic properties, subsequently processed into a device through processes typical of polymer melts, solutions, and dispersions and then crossed linked to a shape memory thermoset polymer retaining the processed shape.

  6. Polymeric Nanogels Obtained by Radiation Technique

    International Nuclear Information System (INIS)

    Ulanski, P.; Kadłubowski, A.K.; Olejnik; Rokita, B.; Wach, R.; Rosiak, J.M.

    2009-01-01

    Soft nanomaterials - polymeric nanogels and microgels - have made a fast and brilliant career, from an unwanted by-product of polymerization processes to an important and fashionable topic of interdisciplinary research in the fields of polymer chemistry and physics, materials science, pharmacy and medicine. Together with their larger analogues - macroscopic gels, most known in the form of water-swellable hydrogels - they have a broad field of actual and potential applications ranging from filler materials in coating industry to modern biomaterials

  7. Nonperturbative Renormalization Group Approach to Polymerized Membranes

    Science.gov (United States)

    Essafi, Karim; Kownacki, Jean-Philippe; Mouhanna, Dominique

    2014-03-01

    Membranes or membrane-like materials play an important role in many fields ranging from biology to physics. These systems form a very rich domain in statistical physics. The interplay between geometry and thermal fluctuations lead to exciting phases such flat, tubular and disordered flat phases. Roughly speaking, membranes can be divided into two group: fluid membranes in which the molecules are free to diffuse and thus no shear modulus. On the other hand, in polymerized membranes the connectivity is fixed which leads to elastic forces. This difference between fluid and polymerized membranes leads to a difference in their critical behaviour. For instance, fluid membranes are always crumpled, whereas polymerized membranes exhibit a phase transition between a crumpled phase and a flat phase. In this talk, I will focus only on polymerized phantom, i.e. non-self-avoiding, membranes. The critical behaviour of both isotropic and anisotropic polymerized membranes are studied using a nonperturbative renormalization group approach (NPRG). This allows for the investigation of the phase transitions and the low temperature flat phase in any internal dimension D and embedding d. Interestingly, graphene behaves just as a polymerized membrane in its flat phase.

  8. The tempered polymerization of human neuroserpin.

    Directory of Open Access Journals (Sweden)

    Rosina Noto

    Full Text Available Neuroserpin, a member of the serpin protein superfamily, is an inhibitor of proteolytic activity that is involved in pathologies such as ischemia, Alzheimer's disease, and Familial Encephalopathy with Neuroserpin Inclusion Bodies (FENIB. The latter belongs to a class of conformational diseases, known as serpinopathies, which are related to the aberrant polymerization of serpin mutants. Neuroserpin is known to polymerize, even in its wild type form, under thermal stress. Here, we study the mechanism of neuroserpin polymerization over a wide range of temperatures by different techniques. Our experiments show how the onset of polymerization is dependent on the formation of an intermediate monomeric conformer, which then associates with a native monomer to yield a dimeric species. After the formation of small polymers, the aggregation proceeds via monomer addition as well as polymer-polymer association. No further secondary mechanism takes place up to very high temperatures, thus resulting in the formation of neuroserpin linear polymeric chains. Most interesting, the overall aggregation is tuned by the co-occurrence of monomer inactivation (i.e. the formation of latent neuroserpin and by a mechanism of fragmentation. The polymerization kinetics exhibit a unique modulation of the average mass and size of polymers, which might suggest synchronization among the different processes involved. Thus, fragmentation would control and temper the aggregation process, instead of enhancing it, as typically observed (e.g. for amyloid fibrillation.

  9. Characterization behavior of some polymeric composite ion exchangers

    International Nuclear Information System (INIS)

    El-Zahhar, A.A; Ahdel-Aziz, H.M.; Siyam, T.

    2005-01-01

    Polymeric composite resins were prepared by template polymerization process in aqueous solution. Thermogravimetric analysis (TGA), differential thermal analysis (DTA) and The X-ray diffraction patterns (XRD) were performed to evaluate the physico chemical properties of the different polymeric composite resins. The TGA and DTA clarify high thermal stability of prepared polymeric composite resins. XRD of prepared polymeric composite shows that there is crystalline structure of some resins while other are amorphous one

  10. Ultrasound-induced radical polymerization

    NARCIS (Netherlands)

    Kuijpers, M.W.A.; Kemmere, M.F.; Keurentjes, J.T.F.

    2004-01-01

    Sonochemistry comprises all chemical effects that are induced by ultrasound. Most of these effects are caused by cavitations, ie, the collapse of microscopic bubbles in a liquid. The chemical effects of ultrasound include the formation of radicals and the enhancement of reaction rates at ambient

  11. Research and development of a technology to create original high-function materials in fiscal 1998 (development of precision structure controlling materials by improving petroleum refining). Report on achievements in research and development of precision catalytic polymerization; 1998 nendo dokusoteki kokino zairyo sosei gijutsu no kenkyu kaihatsu seika hokokusho. Sekiyu seisei kodoka seimitsu kozo seigyo zairyo kaihatsu (seimitsu shokubai jugo no kenkyu kaihatsu)

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1999-03-01

    Research and development on precision catalytic polymerization aims at developing polymerizing catalysts that can control arbitrarily the molecular weight and three-dimensional regularity by which rapid enhancement can be expected in performance of additional polymerization type polymers, and the primary structure of terminal groups. Works are being done on two sub-themes of ultimate additional polymerization and orientation catalyst polymerization. The research and development of the ultimate additional polymerization included structural control in polymerization reaction in vinyl chloride, vinylester and acrylic monomers, radical polymerization with precision orientation control, anionic polymerization with precision structural control, and precision polymerization utilizing asymmetric metal porphyrin complexes. In the research and development of the orientation catalyst polymerization, the orientation catalyst polymerization was researched and developed, elementary reaction of metallocene was elucidated, high-performance carrier catalysts were developed, advanced function polymers were synthesized at high precision based on metathesis, and improvement of functions of polyolefin was researched and developed. Surveys and studies were carried out on fundamental technologies common to the above two themes re-commissioned to five universities. (NEDO)

  12. Copolymer Synthesis and Characterization by Post-Polymerization Modification

    Science.gov (United States)

    Galvin, Casey James

    This PhD thesis examines the physical behavior of surface-grafted polymer assemblies (SGPAs) derived from post-polymerization modification (PPM) reactions in aqueous and vapor enriched environments, and offers an alternative method of creating SGPAs using a PPM approach. SGPAs comprise typically polymer chains grafted covalently to solid substrates. These assemblies show promise in a number of applications and technologies due to the stability imparted by the covalent graft and ability to modify interfacial properties and stability. SGPAs also offer a set of rich physics to explore in fundamental investigations as a result of confining macromolecules to a solid substrate. PPM reactions (also called polymer analogous reactions) apply small molecule organic chemistry reactions to the repeat units of polymer chains in order to generate new chemistries. By applying a PPM strategy to SGPAs, a wide variety of functional groups can be introduced into a small number of well-studied and well-behaved model polymer systems. This approach offers the advantage of holding constant other properties of the SGPA (e.g., molecular weight, MW, and grafting density, sigma) to isolate the effect of chemistry on physical behavior. Using a combination of PPM and fabrication methods that facilitate the formation of SPGAs with position-dependent gradual variation of sigma on flat impenetrable substrate, the influence of polymer chemistry and sigma is examined on the stability of weak polyelectrolyte brushes in aqueous environments at different pH levels. Degrafting of polymer chains in SGPAs exhibits a complex dependence on side chain chemistry, sigma, pH and the charge fraction (alpha) within the brush. Results of these experiments support a proposed mechanism of degrafting, wherein extension of the grafted chains away from the substrate generates tension along the polymer backbone, which activates the grafting chemistry for hydrolysis. The implications of these findings are important in

  13. Genotoxic evaluation of polymeric nanoparticles

    Directory of Open Access Journals (Sweden)

    Tamara Iglesias Alonso

    2015-06-01

    Full Text Available An important strategy for optimizing the therapeutic efficacy of many conventional drugs is the development of polymeric nanoparticles (NPs, as it may expand their activities, reduce their toxicity, increase their bioactivity and improve biodistribution. The main objective of this study was to evaluate the genotoxicity of 8 different poly (anhydride NPs designed for the oral administration of therapeutic compounds by using the comet assay in combination with the enzyme formamidopypiridine DNA-glycosylase (FPG. Furthermore, the mitogen capacity of the NPs was evaluated by the proliferation assay. All NPs were tested at four concentrations (0, 0.5, 1 and 2 mg/mL in Caco-2 cells after 3 hours of treatment while selected NPs were also tested after 24 h. The comet assay was performed immediately after the treatment and cell proliferation was assessed by counting the treated cells after their incubation at 37 °C for 48h. Cells treated with 1 µM of the photosensitizer Ro 19-8022 plus 5 min of light, as well as cells treated with 100 µM H2O2 were included as positive controls in all the experiments. All NPs studied did not result in any increase in the frequency of strand breaks or alkali-labile sites in Caco-2 cells but they induced a slight concentration-dependent increase in net FPG sensitive sites (oxidized and/or alkylated bases. Furthermore, treated cells did not show changes in levels of proliferation in comparison with the negative control.

  14. Transglycosylation reactions, a main mechanism of phenolics incorporation in coffee melanoidins: Inhibition by Maillard reaction.

    Science.gov (United States)

    Moreira, Ana S P; Nunes, Fernando M; Simões, Cristiana; Maciel, Elisabete; Domingues, Pedro; Domingues, M Rosário M; Coimbra, Manuel A

    2017-07-15

    Under roasting conditions, polysaccharides depolymerize and also are able to polymerize, forming new polymers through non-enzymatic transglycosylation reactions (TGRs). TGRs can also occur between carbohydrates and aglycones, such as the phenolic compounds present in daily consumed foods like coffee. In this study, glycosidically-linked phenolic compounds were quantified in coffee melanoidins, the polymeric nitrogenous brown-colored compounds formed during roasting, defined as end-products of Maillard reaction. One third of the phenolics present were in glycosidically-linked form. In addition, the roasting of solid-state mixtures mimicking coffee beans composition allowed the conclusion that proteins play a regulatory role in TGRs extension and, consequently, modulate melanoidins composition. Overall, the results obtained showed that TGRs are a main mechanism of phenolics incorporation in melanoidins and are inhibited by amino groups through Maillard reaction. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Mercuric iodide semiconductor detectors encapsulated in polymeric resin

    Energy Technology Data Exchange (ETDEWEB)

    Martins, Joao F. Trencher; Santos, Robinson A. dos; Ferraz, Caue de M.; Oliveira, Adriano S.; Velo, Alexandre F.; Mesquita, Carlos H. de; Hamada, Margarida M., E-mail: mmhamada@ipen.br [Instituto de Pesquisas Energeticas e Nucleares (IPEN/CNEN-SP), Sao Paulo, SP (Brazil); Disch, Christian; Fiederle, Michael [Albert-Ludwigs Universität Freiburg - UniFreibrug, Freiburg Materials Research Center - FMF, Freiburg (Germany)

    2015-07-01

    The development of new semiconductor radiation detectors always finds many setback factors, such as: high concentration of impurities in the start materials, poor long term stability, the surface oxidation and other difficulties discussed extensively in the literature, that limit their use. In this work was studied, the application of a coating resin on HgI2 detectors, in order to protect the semiconductor crystal reactions from atmospheric gases and to isolate electrically the surface of the crystals. Four polymeric resins were analyzed: Resin 1: 50% - 100%Heptane, 10% - 25% methylcyclohexane, <1% cyclohexane; Resin 2: 25% - 50% ethanol, 25% - 50% acetone, <2,5% ethylacetate; Resin 3: 50% - 100% methylacetate, 5% - 10% n-butylacetate; Resin 4: 50% - 100% ethyl-2-cyanacrylat. The influence of the polymeric resin type used on the spectroscopic performance of the HgI{sub 2} semiconductor detector is, clearly, demonstrated. The better result was found for the detector encapsulated with Resin 3. An increase of up to 26 times at the stability time was observed for the detectors encapsulated compared to that non-encapsulated detector. (author)

  16. Immobilization of biomolecules to plasma polymerized pentafluorophenyl methacrylate.

    Science.gov (United States)

    Duque, Luis; Menges, Bernhard; Borros, Salvador; Förch, Renate

    2010-10-11

    Thin films of plasma polymerized pentafluorophenyl methacrylate (pp-PFM) offer highly reactive ester groups throughout the structure of the film that allow for subsequent reactions with different aminated reagents and biological molecules. The present paper follows on from previous work on the plasma deposition of pentafluorophenyl methacrylate (PFM) for optimum functional group retention (Francesch, L.; Borros, S.; Knoll, W.; Foerch, R. Langmuir 2007, 23, 3927) and reactivity in aqueous solution (Duque, L.; Queralto, N.; Francesch, L.; Bumbu, G. G.; Borros, S.; Berger, R.; Förch, R. Plasma Process. Polym. 2010, accepted for publication) to investigate the binding of a biologically active peptide known to induce cellular adhesion (IKVAV) and of biochemically active proteins such as BSA and fibrinogen. Analyses of the films and of the immobilization of the biomolecules were carried out using infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). The attachment of the biomolecules on pulsed plasma polymerized pentafluorophenyl methacrylate was monitored using surface plasmon resonance spectroscopy (SPR). SPR analysis confirmed the presence of immobilized biomolecules on the plasma polymer and was used to determine the mass coverage of the peptide and proteins adsorbed onto the films. The combined analysis of the surfaces suggests the covalent binding of the peptide and proteins to the surface of the pp-PFM.

  17. In situ polymerization process of polypyrrole ultrathin films

    International Nuclear Information System (INIS)

    Onoda, Mitsuyoshi; Tada, Kazuya; Shinkuma, Akira

    2006-01-01

    A novel thin film processing technique has been developed for the fabrication of ultrathin films of conducting polymers with molecular-level control over thickness and multilayer architecture. This new self-assembly process opens up vast possibilities in applications which require large area, ultrathin films of conducting polymers and more importantly in applications that can take advantage of the unique interactions achievable in the complex, supermolecular architectures of multilayer films. In in situ polymerized polypyrrole (PPy), the deposition process strongly depends on the nature of the substrate surface. That is, for a surface that is negatively charged, there is a linear correspondence between dipping time and the amount of PPy deposited on the substrate. However, in the case of a positively charged surface, there is an apparent rest period of approximately 10-20 min, during which no PPy is deposited. From optical absorption spectroscopy and photoelectron emission studies etc., it became clear that oligomers of pyrrole were adsorbed on the positively charged surface during the rest period, as a result the polymerization reaction of PPy could proceed

  18. Synthesis and characterization of hydrophobically modified polymeric betaines

    Directory of Open Access Journals (Sweden)

    Alexey Shakhvorostov

    2015-09-01

    Full Text Available Polymeric betaines containing long alkyl chains C12H25, C14H29, C16H33 and C18H37 were synthesized by Michael addition reaction of alkylaminocrotonates and methacrylic acid (MAA. They were characterized by FTIR, 13C NMR, DSC, DLS, GPC, cryo-TEM, viscometry and zeta-potential measurements. The polymers were fully soluble in DMF, THF and DMSO, partially dissolved in aromatic hydrocarbons (benzene, toluene, o-xylene and formed colloid solutions in aqueous KOH. In aqueous KOH and DMSO solutions, hydrophobically modified polymeric betaines behaved as polyelectrolytes. The average hydrodynamic size and zeta potential of diluted aqueous solutions of hydrophobic polybetainess containing dodecyl-, tetradecyl-, hexadecyl-, and octadecyl groups were studied as a function of pH. Anomalous low values of the isoelectric point (IEP of amphoteric macromolecules were found to be in the range of pH 2.7-3.4. According to DLS data, the average size of macromolecules tends to decrease with dilution. Zeta-potential of amphoteric macromolecules in aqueous solution is much higher than that in DMSO. The cryo-TEM results revealed that in both aqueous KOH and DMSO media, the micron- and nanosized vesicles existed. The structural organization of vesicles in water and DMSO is discussed. The wax inhibition effect of hydrophobic polybetaines at a decrease of the pour point temperatures of high paraffinic oils was better in comparison with commercial available ethylene-vinylacetate copolymers (EVA.

  19. Carbonyl-Olefin Exchange Reaction: Present State and Outlook

    Science.gov (United States)

    Kalinova, Radostina; Jossifov, Christo

    The carbonyl-olefin exchange reaction (COER) is a new reaction between carbonyl group and olefin double bond, which has a formal similarity with the olefin metathesis (OM) - one carbon atom in the latter is replaced with an oxygen atom. Till now the new reaction is performed successfully only when the two functional groups (carbonyl group and olefin double bond) are in one molecule and are conjugated. The α, β-unsaturated carbonyl compounds (substituted propenones) are the compounds with such a structure. They polymerize giving substituted polyacetylenes. The chain propagation step of this polymerization is in fact the COER. The question arises: is it possible the COER to take place when the two functional groups are not in one molecule and are not conjugated, and could this reaction became an alternative of the existing carbonyl olefination reactions?

  20. About the activity and selectivity of less well-known metathesis catalysts during ADMET polymerizations

    Directory of Open Access Journals (Sweden)

    Hatice Mutlu

    2010-12-01

    Full Text Available We report on the catalytic activity of commercially available Ru-indenylidene and “boomerang” complexes C1, C2 and C3 in acyclic diene metathesis (ADMET polymerization of a fully renewable α,ω-diene. A high activity of these catalysts was observed for the synthesis of the desired renewable polyesters with molecular weights of up to 17000 Da, which is considerably higher than molecular weights obtained using the same monomer with previously studied catalysts. Moreover, olefin isomerization side reactions that occur during the ADMET polymerizations were studied in detail. The isomerization reactions were investigated by degradation of the prepared polyesters via transesterification with methanol, yielding diesters. These diesters, representing the repeat units of the polyesters, were then quantified by GC-MS.

  1. Pressure-Induced Polymerization of Acetylene: Structure-Directed Stereoselectivity and a Possible Route to Graphane.

    Science.gov (United States)

    Sun, Jiangman; Dong, Xiao; Wang, Yajie; Li, Kuo; Zheng, Haiyan; Wang, Lijuan; Cody, George D; Tulk, Christopher A; Molaison, Jamie J; Lin, Xiaohuan; Meng, Yufei; Jin, Changqing; Mao, Ho-Kwang

    2017-06-01

    Geometric isomerism in polyacetylene is a basic concept in chemistry textbooks. Polymerization to cis-isomer is kinetically preferred at low temperature, not only in the classic catalytic reaction in solution but also, unexpectedly, in the crystalline phase when it is driven by external pressure without a catalyst. Until now, no perfect reaction route has been proposed for this pressure-induced polymerization. Using in situ neutron diffraction and meta-dynamic simulation, we discovered that under high pressure, acetylene molecules react along a specific crystallographic direction that is perpendicular to those previously proposed. Following this route produces a pure cis-isomer and more surprisingly, predicts that graphane is the final product. Experimentally, polycyclic polymers with a layered structure were identified in the recovered product by solid-state nuclear magnetic resonance and neutron pair distribution functions, which indicates the possibility of synthesizing graphane under high pressure. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Quasielastic reactions

    International Nuclear Information System (INIS)

    Henning, W.

    1979-01-01

    Quasielastic reaction studies, because of their capability to microscopically probe nuclear structure, are still of considerable interest in heavy-ion reactions. The recent progress in understanding various aspects of the reaction mechanism make this aim appear closer. The relation between microscopic and macroscopic behavior, as suggested, for example, by the single proton transfer data to individual final states or averaged excitation energy intervals, needs to be explored. It seems particularly useful to extend measurements to higher incident energies, to explore and understand nuclear structure aspects up to the limit of the energy range where they are important

  3. Reactions of uranium hexafluoride photolysis products

    Science.gov (United States)

    Lyman, John L.; Laguna, Glenn; Greiner, N. R.

    1985-01-01

    This paper confirms that the ultraviolet photolysis reactions of UF6 in the B band spectral region is simple bond cleavage to UF5 and F. The photolysis products may either recombine to UF6 or the UF5 may dimerize, and ultimately polymerize, to solid UF5 particles. We use four methods to set an upper limit for the rate constant for recombination of krUF6 and UF5 after laser photolysis of the UF6 gas sample.

  4. Role of a waste-derived polymeric biosurfactant in the sol-gel synthesis of nanocrystalline titanium dioxide

    DEFF Research Database (Denmark)

    Boffa, Vittorio; Perrone, Daniele G.; Magnacca, Giuliana

    2014-01-01

    An inexpensive polymeric biosurfactant isolated from urban bio-wastes is shown to be a useful chemical aid in the synthesis of nanostructured materials with tunable pore size and surface hydrophilicity. Photocatalytic active TiO2 powders were prepared by sol–gel reaction in the presence of variable...

  5. Polymerization of aniline in an organic peroxide system by the inverted emulsion process

    OpenAIRE

    Rao, Palle Swapna; Sathyanarayana, DN; Palaniappan, S

    2002-01-01

    An inverted emulsion process for the synthesis of the emeraldine salt of polyaniline using a novel oxidizing agent, namely benzoyl peroxide, is described. The polymerization is carried out in a nonpolar solvent in the presence of a functionalized protonic acid (sulfosalicylic acid) as the dopant and an emulsifier (sodium lauryl sulfate). The influence of synthesis conditions such as the duration of the reaction, temperature, concentration of the reactants, etc., on the properties of polyanili...

  6. Synthesis of indenyllanthanide amides: the effective initiators for polymerization of methyl methacrylate

    Institute of Scientific and Technical Information of China (English)

    赵群; 姚英明; 沈琪

    2000-01-01

    Diisopropylamido bisindenyl lanthanides ( C9H7)2LnN( i-Pr)2(Ln=Gd (1), Y(2), Er (3)) were successfully synthesized in satisfied yield by the reaction of Ln(N(i-Pr)2)3(THF) with indene in 1:2 molar ratio in toluene. All of the complexes exhibit very high catalytic activity in the polymerization of methyl methacrylate. The resulting polymers have narrow molecular weight distributions and syndiotacticity.

  7. The pentafluorostyrene endeavours with atom transfer radical polymerization - quo vadis?

    DEFF Research Database (Denmark)

    Hvilsted, Søren

    2014-01-01

    The versatility of the atom transfer radical polymerization (ATRP) of pentafluorostyrene (FS) is comprehensively evaluated. The ATRP of a wide range of monomers derived from FS is likewise discussed with emphasis on the potential polymer applications. A large number of block and star copolymers...... centred around polypentafluorostyrene (PFS) and prepared primarily using the bromomacroinitiator concept is surveyed. Here the main emphasis is on the feasibility of the polymer design, but also the very many different applications are highlighted. The potential grafting onto PFS and PFS block copolymers...... by exploitation of the very labile para-fluorine demonstrates new material architecture possibilities through very mild reaction conditions. Finally the utility of PFS in various conducting materials is elaborated. The amphiphilic nature of PFS in triblock copolymers with polyethers has been exploited for Li+ ion...

  8. Waterborne hyperbranched alkyd-acrylic resin obtained by miniemulsion polymerization

    Directory of Open Access Journals (Sweden)

    Edwin Murillo

    Full Text Available Abstract Four waterborne hyperbranched alkyd-acrylic resins (HBRAA were synthesized by miniemulsion polymerization from a hyperbranched alkyd resin (HBR, methyl methacrylate (MMA, butyl acrylate (BA and acrylic acid (AA, by using benzoyl peroxide (BPO and ammonium persulfate (AP as initiators. The reaction between HBR and acrylic monomers was evidenced by differential scanning calorimetric (DSC, nuclear magnetic resonance (NMR and gel permeation chromatography (GPC. The conversion percentage, glass transition temperature (Tg, content of acrylic polymer (determined by soxhlet extraction and molecular weight increased with the content of acrylic monomers used in the synthesis. The main structure formed during the synthesis was the HBRAA. The analysis by dynamic light scattering (DLS showed that the particle size distribution of HBRAA2, HBRAA3 and HBRAA4 resins were mainly monomodal. The film properties (gloss, flexibility, adhesion and drying time of the HBRAA were good.

  9. Design and development of reactive injectable and settable polymeric biomaterials.

    Science.gov (United States)

    Page, Jonathan M; Harmata, Andrew J; Guelcher, Scott A

    2013-12-01

    Injectable and settable biomaterials are a growing class of therapeutic technologies within the field of regenerative medicine. These materials offer advantages compared to prefabricated implants because of their ability to be utilized as part of noninvasive surgical procedures, fill complex defect shapes, cure in situ, and incorporate cells and other active biologics. However, there are significant technical barriers to clinical translation of injectable and settable biomaterials, such as achieving clinically relevant handling properties and benign reaction conditions. This review focuses on the engineering challenges associated with the design and development of injectable and chemically settable polymeric biomaterials. Additionally, specific examples of the diverse chemistries utilized to overcome these challenges are covered. The future translation of injectable and settable biomaterials is anticipated to improve patient outcomes for a number of clinical conditions. Copyright © 2013 Wiley Periodicals, Inc., a Wiley Company.

  10. Polymerization of allyl alcohol by radiation to obtain microencapsulated structure

    International Nuclear Information System (INIS)

    Usanmaz, A.; Saricilar, S.

    1989-01-01

    Allyl alcohol was polymerized by radiation under various conditions. The limiting conversions were about 30 % in bulk, 35 % when containing 0.03 mole fraction AlCl 3 and 50 % when water was contained at 27 % (v/v). Irradiation was done with Co-60 gamma rays at room temperature and under vacuum. The presence of oxygen did not cause any change in the reaction rate. Molecular weights were determined by viscosity and cryoscopic methods. K and α values were found to be 3.57 x 10 -4 and 0.62 for solutions in methanol at 25degC. The polymers up to about 10 % conversion were viscous liquids having microcapsular structures: at high conversions, they became hard and glassy. The microencapsulated structures were also retained in solutions in methanol, acetone, and isopropyl alcohol. The samples were insoluble in water, benzene, and toluence. (author)

  11. Synthesis of Well-Defined Three-Arm Star-Branched Polystyrene through Arm-First Coupling Approach by Atom Transfer Radical Polymerization

    OpenAIRE

    Shahabuddin, Syed; Hamime Ismail, Fatem; Mohamad, Sharifah; Muhamad Sarih, Norazilawati

    2015-01-01

    Here we describe a simple route to synthesize three-arm star-branched polystyrene. Atom transfer radical polymerization technique has been utilized to yield branched polystyrene involving Williamson coupling strategy. Initially a linear polymeric chain of predetermined molecular weight has been synthesized which is further end-functionalized into a primary alkyl bromide moiety, a prime requisition for Williamson reaction. The end-functionalized polymer is then coupled using 1,1,1-tris(4-hydro...

  12. The polymeric nanofilm of triazinedithiolsilane fabricated by self-assembled technique on copper surface. Part 2: Characterization of composition and morphology

    International Nuclear Information System (INIS)

    Wang, Yabin; Liu, Zhong; Huang, Yudong; Qi, Yutai

    2015-01-01

    Highlights: • The chemical reactions between copper and triazinedithiolsilane were revealed. • The structure of triazinedithiolsilane's polymeric nanofilm was demonstrated. • The morphology and microstructure of the polymeric nanofilm was observed. - Abstract: In the first part, a novel design route for metal protection against corrosion was proposed, and a class of triazinedithiolsilane compounds was conceived as protector for copper. The protective capability of the polymeric nanofilm, fabricated by self-assembling one representative (abbreviated as TESPA) of triazinedithiolsilane compounds onto copper surface, has been investigated and evaluated by electrochemical tests. The results show that the polymeric nanofilm significantly inhibits copper corrosion. This study, on the one hand, concentrates on the chemical composition of the TESPA polymeric nanofilm by means of X-ray photoelectron spectroscopy (XPS). The XPS results reveal that the chemical bonds between copper and TESPA monomers, three dimensional disulfide units and siloxane networks are responsible for the satisfactory protection of TESPA polymeric nanofilm against copper corrosion. On the other hand, scanning electron microscope (SEM) and energy-dispersive spectroscopy (EDS) are utilized to reveal the morphology and the uniformity of the TESPA polymeric nanofilm. The SEM-EDS results demonstrate that the copper surfaces are uniformly covered with TESPA self-assembled monolayer and the polymeric nanofilm. The TESPA-covered copper surfaces turn out to be smoother than that of the bare copper surface.

  13. Kinetics of waterborne fluoropolymers prepared by one-step semi-continuous emulsion polymerization of chlorotrifluoroethylene, vinyl acetate, butyl acrylate and Veova 10

    Science.gov (United States)

    Liu, H. Z.; Wang, M. H.; Wang, Z. F.; Bian, J. M.

    2018-01-01

    Due to using gaseous fluorine monomer with toxicity, waterborne fluoropolymers are synthesized by semi-continuous high-pressure emulsion polymerization method which differs from free-pressure emulsion polymerization. To dates, the research on preparing process and kinetics for high-pressure emulsion polymerization is reported relatively less, which hinders researchers from understanding of mechanisms for monomer-fluorinated emulsion polymerization. The paper also provides a new method by element auxiliary analysis to calculate kinetics parameters of high-pressure emulsion polymerization. Based on aforementioned consideration, waterborne fluoropolymers were prepared by copolymerization of chlorotrifluoroethylene (CTFE), vinyl acetate (VAc), butyl acrylate (BA) and vinyl ester of versatic acid (Veova 10) using potassium persulfate as initiator and mixed surfactants. The kinetics of emulsion polymerization of waterborne fluoropolymers was then investigated. Effects of emulsifier concentration, initiator concentration, and polymerization temperature on polymerization rate (Rp) were evaluated, and relationship was described as Rp∝[I]0.10 and Rp∝[E]0.12. The apparent activation energy was determined to be 33.61 kJ·mol-1. Moreover, the relative conversion rate of CTFE with the other monomers was observed, and results indicated that CTFE monomer more uniformly copolymerized with the other monomers. The resulting emulsion properties and pressure change in an autoclave were evaluated at different stirring rates. The initial reaction time, defined as the beginning time of dropwise addition, was determined by the change in solid content and particle size of emulsion.

  14. cycloaddition reactions

    Indian Academy of Sciences (India)

    Unknown

    Molecular Modeling Group, Organic Chemical Sciences, Indian Institute of Chemical Technology,. Hyderabad ... thus obtained are helpful to model the regioselectivity ... compromise to model Diels–Alder reactions involving ...... acceptance.

  15. Possible Role of Ice in the Synthesis of Polymeric Compounds

    Science.gov (United States)

    Monnard, Pierre-Alain; Doerr, Mark; Loeffler, Philipp, M. G.

    COSPAR Session F3.6, Bremen July 18-25, 2010 Possible role of ice in the synthesis of polymeric compounds Doerr, Mark, Loeffler, Philipp M.G and Monnard, Pierre-Alain, University of Southern Den-mark, FLinT Center, Odense M, Denmark. Email: monnard@ifk.sdu.dk Cellular life relies on a collection of linear polymers (among them DNA, RNA, proteins) to perform the functions necessary to its survival. It seems likely that catalytic and informational polymers played essential roles in the emergence of the first living entities, precursors of con-temporary cells. Thus, their detection on other planetary bodies might hint at either emerging, or extant, or past life in these environments. A non-enzymatic synthesis of such polymeric materials or their precursors likely had to rely on a supply of monomers dissolved at low concentrations in an aqueous medium. An aqueous environment represents a clear hurdle to the synthesis of long polymers as it tends to inhibit polymerization due to entropic effects and favors the reverse reaction (decomposition by hy-drolysis). It was therefore proposed that polymerization could occur in a distinct micro-or nanostructured environment that would permit a local increase in the monomer concentration, reduce water activity and protect monomers and polymers from hydrolysis. Several types of micro-or nanostructured environments, among them mineral surfaces [1], lattices of organic molecules, such as amphiphile bilayer structures [2], and the eutectic phase in water-ice [3-8] have been proposed to promote RNA and peptide formation. This last environment might be of particular interest since space exploration has established that water exists on Mars, Europa, Enceladus and comets, mostly as ice. Ice deposits may also have existed on the early Earth. When an aqueous solution is cooled below its freezing point, but above the eutectic point, two aqueous phases co-exist and form the eutectic phase system: a solid (the ice crystals made of pure water

  16. Some regularities of separate and simultaneous radiation polymerization of vinyl acetate and acrylonitrile in adsorption layer on aerosil surface

    International Nuclear Information System (INIS)

    Mund, S.L.; Bruk, M.A.; Abkin, A.D.

    1976-01-01

    The kinetics has been studied of initial stage radiation copolymerization and separate radiation polymerization of aerosil adsorbed vinylacetate (VA) and acrylonitrile (AN). The monomers were irradiated using a Co 60 gamma source or a RUP-400 X-ray unit. Infrared spectroscopy, nuclear magnetic resonance and gravimetry were used in the study. It has been found that in the dose rate interval studied (over 60-450 rad./sec) the break of kinetic chains during the polymerization of VA and its mixtures with AN is due to the reaction of degenerate transfer of the chains to the surface hydroxyl groups. When AN is polymerized, biomolecular break of chains prevails. The effective activation energy of polymerization is 1.5 kcal/mol for VA and 2.5 kcal/mol for AN. The order of polymerization rates by the concentration of adsorbed monomers at 50 deg, as well as by the irradiation dose rate is equal to 1 and 1 for VA and 3/2 and 0.7 for AN, respectively. The calculated values of copolymerization constants coincide with those characteristic of their radical polymerization in liquid phase. Isotherms for adsorption of VA and AN on aerosil at 30, 50 and 70 deg have been studied [ru

  17. A guide to the synthesis of block copolymers using reversible-addition fragmentation chain transfer (RAFT) polymerization.

    Science.gov (United States)

    Keddie, Daniel J

    2014-01-21

    The discovery of reversible-deactivation radical polymerization (RDRP) has provided an avenue for the synthesis of a vast array of polymers with a rich variety of functionality and architecture. The preparation of block copolymers has received significant focus in this burgeoning research field, due to their diverse properties and potential in a wide range of research environments. This tutorial review will address the important concepts behind the design and synthesis of block copolymers using reversible addition-fragmentation chain transfer (RAFT) polymerization. RAFT polymerization is arguably the most versatile of the RDRP methods due to its compatibility with a wide range of functional monomers and reaction media along with its relative ease of use. With an ever increasing array of researchers that possess a variety of backgrounds now turning to RDRP, and RAFT in particular, to prepare their required polymeric materials, it is pertinent to discuss the important points which enable the preparation of high purity functional block copolymers with targeted molar mass and narrow molar mass distribution using RAFT polymerization. The key principles of appropriate RAFT agent selection, the order of monomer addition in block synthesis and potential issues with maintaining high end-group fidelity are addressed. Additionally, techniques which allow block copolymers to be accessed using a combination of RAFT polymerization and complementary techniques are touched upon.

  18. Hydrophobic Coatings on Cotton Obtained by in Situ Plasma Polymerization of a Fluorinated Monomer in Ethanol Solutions.

    Science.gov (United States)

    Molina, Ricardo; Teixidó, Josep Maria; Kan, Chi-Wai; Jovančić, Petar

    2017-02-15

    Plasma polymerization using hydrophobic monomers in the gas phase is a well-known technology to generate hydrophobic coatings. However, synthesis of functional hydrophobic coatings using plasma technology in liquids has not yet been accomplished. This work is consequently focused on polymerization of a liquid fluorinated monomer on cotton fabric initiated by atmospheric plasma in a dielectric barrier discharge configuration. Functional hydrophobic coatings on cotton were successfully achieved using in situ atmospheric plasma-initiated polymerization of fluorinated monomer dissolved in ethanol. Gravimetric measurements reveal that the amount of polymer deposited on cotton substrates can be modulated with the concentration of monomer in ethanol solution, and cross-linking reactions occur during plasma polymerization of a fluorinated monomer even without the presence of a cross-linking agent. FTIR and XPS analysis were used to study the chemical composition of hydrophobic coatings and to get insights into the physicochemical processes involved in plasma treatment. SEM analysis reveals that at high monomer concentration, coatings possess a three-dimensional pattern with a characteristic interconnected porous network structure. EDX analysis reveals that plasma polymerization of fluorinated monomers takes place preferentially at the surface of cotton fabric and negligible polymerization takes place inside the cotton fabric. Wetting time measurements confirm the hydrophobicity of cotton coatings obtained although equilibrium moisture content was slightly decreased. Additionally, the abrasion behavior and resistance to washing of plasma-coated cotton has been evaluated.

  19. Polymerization of phenol by using discharged plasma under hydrothermal state

    Energy Technology Data Exchange (ETDEWEB)

    Mitsugi, M; Yoshida, A; Watanabe, H; Kiyan, T; Takade, M; Miyaji, K; Kuwahara, Y; Akiyama, H; Hara, M; Sasaki, M [Graduate School of Science and Technology, Kumamoto University (Japan); Namihira, T; Goto, M, E-mail: mgoto@kumamoto-u.ac.j [Bioelectrics Research Center, Kumamoto University 2-39-1 Kurokami, Kumamoto 865-8555 Japan (Japan)

    2010-03-01

    Supercritical fluid with plasma is a type of green processing media because this technique does not use catalyst and toxic solvents. In this study, we carried out experiments of organic materials in the presence of discharged plasma in sub- and supercritical water to evaluate the possibility for new reactions. For this purpose, we used SUS316 reactor that generates plasma at temperature and pressure up to 573K and 30MPa, respectively. 100 mmol/L aqueous phenol solution was used as starting material. The reactions were carried out at temperature of 523K and under pressure of 25MPa. After a series of reactions, water-soluble, water-insoluble (oily products), solid residue and gaseous product were obtained. For the analysis of these products, HPLC, GC-MS, TOC, GC-TCD and TOF-MS were used. The highest phenol conversion was 16.96% obtained at 523K, 25MPa and with 4000 times discharged plasma. Polymerized phenol was obtained as a product.

  20. Polymerization of phenol by using discharged plasma under hydrothermal state

    International Nuclear Information System (INIS)

    Mitsugi, M; Yoshida, A; Watanabe, H; Kiyan, T; Takade, M; Miyaji, K; Kuwahara, Y; Akiyama, H; Hara, M; Sasaki, M; Namihira, T; Goto, M

    2010-01-01

    Supercritical fluid with plasma is a type of green processing media because this technique does not use catalyst and toxic solvents. In this study, we carried out experiments of organic materials in the presence of discharged plasma in sub- and supercritical water to evaluate the possibility for new reactions. For this purpose, we used SUS316 reactor that generates plasma at temperature and pressure up to 573K and 30MPa, respectively. 100 mmol/L aqueous phenol solution was used as starting material. The reactions were carried out at temperature of 523K and under pressure of 25MPa. After a series of reactions, water-soluble, water-insoluble (oily products), solid residue and gaseous product were obtained. For the analysis of these products, HPLC, GC-MS, TOC, GC-TCD and TOF-MS were used. The highest phenol conversion was 16.96% obtained at 523K, 25MPa and with 4000 times discharged plasma. Polymerized phenol was obtained as a product.

  1. Synthesis, characterization and polymerization of methacrylates of copper (II), cobalt (II) and molybdenum (II). Generation of new materials

    International Nuclear Information System (INIS)

    Rojas Bolanos, Omar

    2006-01-01

    Coordination compounds of the species copper (II), cobalt (II) and molybdenum (II) with methacrylic acid were synthesized and characterized. Besides, it realized reactions of bromine addition to the doubles links of the species obtained previously, also too like reactions with dry HCl. Finally, it got hybrids materials by polymerization of the first compounds in an acrylic matrix. Research concluded with the characterization of all the products. (author) [es

  2. Effect of the Degree of Polymerization of Inulin on the Rate of Hydrolysis Using Immobilized Inulinase

    Directory of Open Access Journals (Sweden)

    Emanuele Ricca

    2014-01-01

    Full Text Available The present paper addresses two crucial features in the industrial development of fructose production by enzymatic hydrolysis of inulin: the use of immobilized biocatalyst in the hydrolysis of crude extracts of chicory roots and the evaluation of the effect of degree of polymerization of inulin on the overall reaction rate. The immobilized biocatalyst consisted of inulinase covalently bound to Sepabeads® supports. It was demonstrated that its catalytic activity towards crude inulin extract (real substrate was much higher than that exhibited towards pure inulin (synthetic solution. Experiments revealed that, in applications of practical interest with real substrate, the activity of immobilized enzyme was as high as 63 % of that of free enzyme in homogeneous solution. This certainly was a driving force to potential industrial application of this immobilized enzyme preparation. Therefore, the effect of pure and crude substrates on the kinetics of the reaction catalysed by the immobilized enzyme was investigated. The kinetic analysis revealed a Michaelis-Menten dependence of the reaction rate on substrate concentration for both pure (high molecular mass and crude (low molecular mass inulin. Interesting results were derived from the comparison of Km and vmax values in the two cases. In particular, it was found that increasing degree of polymerization of the substrate caused vmax decrease and Km increase. After evaluation of mass transport effects, this was mainly associated with a different substrate/ enzyme affinity when exploiting inulin characterized by different (low or high degree of polymerization.

  3. Electrospun polymeric nanofibers for transdermal drug delivery

    Directory of Open Access Journals (Sweden)

    Mahya Rahmani

    2017-04-01

    Full Text Available Conventional transdermal drug delivery systems (TDDS have been designed for drug delivery through the skin. These systems use the permeability property of stratum corneum, the outermost surface layer of the skin. Applying polymeric micro and nanofibers in drug delivery has recently attracted great attention and the electrospinning technique is the preferred method for polymeric micro-nanofibers fabrication with a great potential for drug delivery. More studies in the field of nanofibers containing drug are divided two categories: first, preparation and characterization of nanofibers containing drug and second, investigation of their therapeutic applications. Drugs used in electrospun nanofibers can be categorized into three main groups, including antibiotics and antimicrobial agents, anti-inflammatory agents and vitamins with therapeutic applications. In this paper, we review the application of electrospun polymeric scaffolds in TDDS and also introduce several pharmaceutical and therapeutic agents which have been used in polymer nanofibrous patches.

  4. Biomimetic polymeric membranes for water treatment

    DEFF Research Database (Denmark)

    Habel, Joachim Erich Otto

    This project is about the interplay of the three major components of aquaporin based biomimetic polymeric membranes (ABPMs): Aquaporins (AQPs), amphiphilic block copolymers, serving as a vesicular matrix for the hydrophobic AQP exterior (proteopolymersomes) and a polymeric membrane as embedment....... The interplay of proteopolymersomes and polymeric mesh support (in this case polyethersulfone, PES) was examined via integration of proteopolymersomes in an active layer (AL) formed by interfacial polymerisation between a linker molecule in aqueous phase and another in organic phase on top of the PES....... The resulting thin-film composite (TFC) membrane was analyzed via cross-flow forward osmosis (FO), scanning electron microscopy (SEM), fourier-transformed infrared spectroscopy (FTIR), as well as in the non-supported form over FTIR and a specialized microfluidic visualization approach. Where no clear dierences...

  5. Cross-linking of polymeric materials

    International Nuclear Information System (INIS)

    Bloom, L.I.; Du Plessis, T.A.; Meij, G.O.

    1991-01-01

    The invention provides a method of producing a cured polymeric artifact from a polymeric thermoplastic starting material, the material of the artifact having reduced thermoplasticity relative to the starting material and exhibiting an enhanced degree of cross-linking relative to the starting material. The method includes subjecting a polymeric thermoplastic starting material, which is capable of being cross-linked by irradiation, to sufficient irradiation partially to cross-linked the starting material to produce a thermoplastic partially cross-linked intermediate material. The thermoplasticity of the intermediate material is then reduced by heating it to raise its melting point. The invention also provides a method of making a partially cross-linked feedstocks and a master batch for use in making such artifacts

  6. Laser microstructuring for fabricating superhydrophobic polymeric surfaces

    Science.gov (United States)

    Cardoso, M. R.; Tribuzi, V.; Balogh, D. T.; Misoguti, L.; Mendonça, C. R.

    2011-02-01

    In this paper we show the fabrication of hydrophobic polymeric surfaces through laser microstructuring. By using 70-ps pulses from a Q-switched and mode-locked Nd:YAG laser at 532 nm, we were able to produce grooves with different width and separation, resulting in square-shaped pillar patterns. We investigate the dependence of the morphology on the surface static contact angle for water, showing that it is in agreement with the Cassie-Baxter model. We demonstrate the fabrication of a superhydrophobic polymeric surface, presenting a water contact angle of 157°. The surface structuring method presented here seems to be an interesting option to control the wetting properties of polymeric surfaces.

  7. Nanoscale control of reversible chemical reaction between fullerene C60 molecules using scanning tunneling microscope.

    Science.gov (United States)

    Nakaya, Masato; Kuwahara, Yuji; Aono, Masakazu; Nakayama, Tomonobu

    2011-04-01

    The nanoscale control of reversible chemical reactions, the polymerization and depolymerization between C60 molecules, has been investigated. Using a scanning tunneling microscope (STM), the polymerization and depolymerization can be controlled at designated positions in ultrathin films of C60 molecules. One of the two chemical reactions can be selectively induced by controlling the sample bias voltage (V(s)); the application of negative and positive values of V(s) results in polymerization and depolymerization, respectively. The selectivity between the two chemical reactions becomes extremely high when the thickness of the C60 film increases to more than three molecular layers. We conclude that STM-induced negative and positive electrostatic ionization are responsible for the control of the polymerization and depolymerization, respectively.

  8. Inflation and Instability of a Polymeric Membrane

    DEFF Research Database (Denmark)

    Neergaard, Jesper; Hassager, Ole

    1999-01-01

    We consider an axisymmetric polymeric membrane inflated by a uniform pressure difference acting across the membrane. The polymeric materialis described by an arbitrary combination of a viscoelastic and a purely viscous component to the stress. Some viscoelastic materials described by a Mooney......-Rivlin model show a monotone increasingpressure during inflation of a spherical membrane. These materials develop a homogeneous membrane thickness in agreement with the Considere-Pearson condition. Molecularly based models such as the neo-Hookean, Doi-Edwards or Tom-Pom model show a pressure maximum when...... inflated. Membranesdescribed by these models develop a local thinning of the membrane which may lead to bursting in finite time....

  9. Polymeric materials obtained by electron beam irradiation

    International Nuclear Information System (INIS)

    Dragusin, M.; Moraru, R.; Martin, D.; Radoiu, M.; Marghitu, S.; Oproiu, C.

    1995-01-01

    Research activities in the field of electron beam irradiation of monomer aqueous solution to produce polymeric materials used for waste waters treatment, agriculture and medicine are presented. The technologies and special features of these polymeric materials are also described. The influence of the chemical composition of the solution to ba irradiated, absorbed dose level and absorbed dose rate level are discussed. Two kinds of polyelectrolytes, PA and PV types and three kinds of hydrogels, pAAm, pAAmNa and pNaAc types, the production of which was first developed with IETI-10000 Co-60 source and then adapted to the linacs built in Accelerator Laboratory, are described. (author)

  10. Mechanism and kinetics of addition polymerizations

    CERN Document Server

    Kucera, M

    1991-01-01

    This volume presents an up-to-date survey of knowledge concerning addition type polymerizations. It contains nine chapters, each of which covers a particular basic term. Whenever necessary, the phenomena are discussed from the viewpoint of both stationary and non-stationary state of radical, ionic (i.e. anionic and cationic) and coordination polymerization. Special attention has been paid to the propagation process. It provides not only a general overview but also information on important special cases (theoretical conditions of propagation, influence of external factors, controlled propagatio

  11. Polymeric matrix materials for infrared metamaterials

    Science.gov (United States)

    Dirk, Shawn M; Rasberry, Roger D; Rahimian, Kamyar

    2014-04-22

    A polymeric matrix material exhibits low loss at optical frequencies and facilitates the fabrication of all-dielectric metamaterials. The low-loss polymeric matrix material can be synthesized by providing an unsaturated polymer, comprising double or triple bonds; partially hydrogenating the unsaturated polymer; depositing a film of the partially hydrogenated polymer and a crosslinker on a substrate; and photopatterning the film by exposing the film to ultraviolet light through a patterning mask, thereby cross-linking at least some of the remaining unsaturated groups of the partially hydrogenated polymer in the exposed portions.

  12. Kinetics of exchange reaction between neodymium(3) transcyclohexanediaminetetraacetate and europium(3)- and holmium(3) aquo-ions in the H/sub 2/O and D/sub 2/O solutions

    Energy Technology Data Exchange (ETDEWEB)

    Nikitenko, S.I.; Martynenko, L.I.; Pechurova, N.I.; Spitsyn, V.I. (Moskovskij Gosudarstvennyj Univ. (USSR))

    1983-10-01

    The exchange reaction between central ions in the NdD/sup -/Ln'/sup 3 +/ systems, where Ln'/sup 3 +/ is a substituting cation (Eu/sup 3 +/ and Ho/sup 3 +/, D/sup 4/=cyclohexanediaminetetraacetate) is studied and the electrophilic substitution mechanism is considered. To study the kinetic isotope effects, the reagents have been solved in heavy water containing 99.9% D/sub 2/O. The electrophilic substitution in the indicated systems proceeds through the dissociative mechanism catalyzed by protons and via the spontaneous dissociation mechanism. The exchange via the acid-catalyzed mechanism is limited by the intermediate protonated complex decay. The associative mechanism of the electrophilic exchange in the studied systems is not realized.

  13. Solid state polymerization: its action on thermal and rheological properties of PET/PC reactive blends

    Directory of Open Access Journals (Sweden)

    Luis C. Mendes

    2013-01-01

    Full Text Available The solid state polymerization (SSP of PET/PC reactive extrusion blends - with and without cobalt catalyst - at different polymer ratios was studied. Thermal and rheological evaluations were performed. DSC results showed changes in the PET's Tg, Tch, Tm and Xc.. The melt flow rate (MFR decreased for PET and the blends. The intrinsic viscosity increased. The variation in calorimetric and rheological properties might be attributed to the PET's chain extension reactions - esterification and transesterification. These reactions led to an increase in the PET's molar mass, consequently shifting the PET's Tg to lower temperature and PET's crystallization, besides reducing the blend miscibility and flowability.

  14. Immobilization of biocatalysts for enzymatic polymerizations : Possibilities, advantages, applications

    NARCIS (Netherlands)

    Miletic, Nemanja; Nastasovic, Aleksandra; Loos, Katja; Miletić, Nemanja; Nastasović, Aleksandra

    Biotechnology also holds tremendous opportunities for realizing functional polymeric materials. Biocatalytic pathways to polymeric materials are an emerging research area with not only enormous scientific and technological promise, but also a tremendous impact on environmental issues. Many of the

  15. Polymerization Initiated at the Sidewalls of Carbon Nanotubes

    Science.gov (United States)

    Tour, James M.; Hudson, Jared L.

    2011-01-01

    A process has been developed for growing polymer chains via anionic, cationic, or radical polymerization from the side walls of functionalized carbon nanotubes, which will facilitate greater dispersion in polymer matrices, and will greatly enhance reinforcement ability in polymeric material.

  16. Interfacial Polymerization of Polyaniline Nanofibers Grafted to Au Surfaces

    National Research Council Canada - National Science Library

    Sawall, D

    2004-01-01

    .... The in-situ polymerization technique of these PANI nanofibers in the presence of sulfonated polystyrene allowed for the growth of PANI 2-D nanostructures embedded in the polymerized sulfonated host...

  17. Direct Reactions

    Energy Technology Data Exchange (ETDEWEB)

    Austern, N. [University of Pittsburgh, Pittsburgh, PA (United States)

    1963-01-15

    In order to give a unified presentation of one point of view, these lectures are devoted only to a detailed development of the standard theories of direct reactions, starting from basic principles. Discussion is given of the present status of the theories, of the techniques used for practical calculation, and of possible future developments. The direct interaction (DI) aspects of a reaction are those which involve only a few of the many degrees of freedom of a nucleus. In fact the minimum number of degrees of freedom which must be involved in a reaction are those required to describe the initial and final channels, and DI studies typically consider these degrees of freedom and no others. Because of this simplicity DI theories may be worked out in painstaking detail. DI processes concern only part of the wave function for a problem. The other part involves complicated excitations of many degrees of freedom, and gives the compound nucleus (CN) effects. While it is extremely interesting to learn how to separate DI and CN effects in an orderly manner, if they are both present in a reaction, no suitable method has yet been found. Instead, current work stresses the kinds of reactions and the kinds of final states in which DI effects dominate and in which CN effects may almost be forgotten. The DI cross-sections which are studied are often extremely large, comparable to elastic scattering cross-sections. (author)

  18. 1H NMR studies of substrate hydrogen exchange reactions catalyzed by L-methionine gamma-lyase

    International Nuclear Information System (INIS)

    Esaki, N.; Nakayama, T.; Sawada, S.; Tanaka, H.; Soda, K.

    1985-01-01

    Hydrogen exchange reactions of various L-amino acids catalyzed by L-methionine gamma-lyase (EC 4.4.1.11) have been studied. The enzyme catalyzes the rapid exchange of the alpha- and beta-hydrogens of L-methionine and S-methyl-L-cysteine with deuterium from the solvent. The rate of alpha-hydrogen exchange was about 40 times faster than that of the enzymatic elimination reaction of the sulfur-containing amino acids. The enzyme also catalyzes the exchange reaction of alpha- and beta-hydrogens of the straight-chain L-amino acids which are not susceptible to elimination. The exchange rates of the alpha-hydrogen and the total beta-hydrogens of L-alanine and L-alpha-aminobutyrate with deuterium followed first-order kinetics. For L-norvaline, L-norleucine, S-methyl-L-cysteine, and L-methionine, the rate of alpha-hydrogen exchange followed first-order kinetics, but the rate of total beta-hydrogen exchange decreased due to a primary isotope effect at the alpha-position. L-Phenylalanine and L-tryptophan slowly underwent alpha-hydrogen exchange. The pro-R hydrogen of glycine was deuterated stereospecifically

  19. Synthesis of Conductive Polymeric Nanocomposites for Applications in Responsive Materials

    Science.gov (United States)

    Chavez, Jessica

    The development of next generation "smart" textiles has emerged with significant interest due to the immense demand for high-performance wearable technology. The economic market for wearable technologies is predicted to increase significantly in both volume and value. In the next four years, the wearable technology market will be valued at $34 billion. This large demand has opened up a new research area involving smart wearable devices and conductive fabrics. Many research groups have taken various paths to study and ultimately fabricate wearable devices. Due to the limiting capabilities of conventional conductors, researchers have centered their research on the integration of conductive polymers into textile materials for applications involving responsive material. Conducive polymers are very unique organic molecules that have the ability to transfer electrons across their molecular structure due to the excess presence of pi-electrons. Conductive polymers are favored over conventional conductors because they can be easily manipulated and integrated into flexible material. Two very common conductive polymers are polyaniline (PANI) and polypyrrole (PPY) because of their large favorability in literature, high conductance values, and environmental stability. Common commercial fibers were coated via the chemical polymerization of PANI or PPY. A series of reactions were done to study the polymerization process of each polymer. The conductive efficiency of each conducting polymer is highly dependent on the type of reactants used, the acidic nature of the reaction, and the temperature of the reaction. The coated commercial fiber nanocomposites produced higher conductivity values when the polymerization reaction was run using ammonium peroxydisulfate (APS) as the oxidizing agent, run in an acidic environment, and run at very low temperatures. Other factors that improved the overall efficiency of the coated commercial fiber nanocomposites was the increase in polymer

  20. Reaction mechanisms

    International Nuclear Information System (INIS)

    Nguyen Trong Anh

    1988-01-01

    The 1988 progress report of the Reaction Mechanisms laboratory (Polytechnic School, France), is presented. The research topics are: the valence bond methods, the radical chemistry, the modelling of the transition states by applying geometric constraints, the long range interactions (ion - molecule) in gaseous phase, the reaction sites in gaseous phase and the mass spectroscopy applications. The points of convergence between the investigations of the mass spectroscopy and the theoretical chemistry teams, as well as the purposes guiding the research programs, are discussed. The published papers, the conferences, the congress communications and the thesis, are also reported [fr

  1. Constructing Functional Ionic Membrane Surface by Electrochemically Mediated Atom Transfer Radical Polymerization

    Directory of Open Access Journals (Sweden)

    Fen Ran

    2016-01-01

    Full Text Available The sodium polyacrylate (PAANa contained polyethersulfone membrane that was fabricated by preparation of PES-NH2 via nonsolvent phase separation method, the introduction of bromine groups as active sites by grafting α-Bromoisobutyryl bromide, and surface-initiated electrochemically atom transfer radical polymerization (SI-eATRP of sodium acrylate (AANa on the surface of PES membrane. The polymerization could be controlled by reaction condition, such as monomer concentration, electric potential, polymerization time, and modifier concentration. The membrane surface was uniform when the monomer concentration was 0.9 mol/L, the electric potential was −0.12 V, the polymerization time was 8 h, and the modifier concentration was 2 wt.%. The membrane showed excellent hydrophilicity and blood compatibility. The water contact angle decreased from 84° to 68° and activated partial thromboplastin increased from 51 s to 84 s after modification of the membranes.

  2. Gamma irradiation effect on acrylated-epoxidized soybean oil: polymerization and characterization

    International Nuclear Information System (INIS)

    Hernandez-lopez, S.; Sanchez-Mendieta, V.; Vigueras-Santiago, E.; Martin Del Campo-Lopez, E.; Urena-Nunez, F.

    2006-01-01

    In this work we present the gamma-irradiation dose effect on acrylated-epoxidized soybean oil (AESO). AESO started to polymerize at 12 kGy and at higher doses (24, 110 and 340 kGy) there is an increase in cross-linking reaction without degradation, thermal or structural changes. Polymeric products were glassy, thermosetting, insoluble, which no longer melt upon heating, and no Tg was observed between -30 to 300 deg C. These polymers were obtained with a specific shape and different properties in comparison with the thermal PolyAESO (rubber) due to higher cross-linking achieved by gamma irradiation. NMR, FT-IR and DSC techniques evidenced these facts. Friction and scratching properties were dependent of irradiation dose. Due to an increase in cross-linking density, lower friction values, reached at high doses (110 and 340 kGy), were accompanied by a lower scratching penetration depth in these polymers. Gamma-ray polymerization could be an alternative and efficient method for in situ synthesis of thermosetting polymers, copolymers and composites with given shapes, controlled polymerization degrees and optimized properties

  3. Polymerization of Oriental Lacquer (Urushi with Epoxidized Linseed Oil as a New Reactive Diluent

    Directory of Open Access Journals (Sweden)

    Takahisa Ishimura

    2015-01-01

    Full Text Available A hybrid lacquer (HBL paint prepared by combining a natural kurome lacquer (KL paint and an amino silane reagent, for example, N-(2-aminoethyl-3-aminopropyl triethoxysilane (AATES, produced a polymerized film faster than the KL paint alone. However, the viscosity of the HBL paint was too viscous for easy handling. Addition of 10 wt% of an epoxidized linseed oil, ELO-6, with 6.4 mol% epoxidation as a reactive diluent to the HBL paint decreased the viscosity by 1/2 from 25476 mPa·s to 12841 mPa·s and improved the ease of coatability. The polymerization mechanism was elucidated by NMR measurements of extracts from the resulting polymerization films, suggesting that amino groups in the HBL paint reacted with epoxy groups of ELO-6 in the lacquer matrix, and then the complex reacted with double bonds of the urushiol side-chain by autooxidation and cross-linking reactions to give a hard polymerized film with a high quality of color and gloss. These results indicate that the addition of ELO-6 improved the polymerizability of both KL and HBL paints without decreasing the quality of the resulting films.

  4. Investigations in the field of solid-state polymerization Pt. 37

    International Nuclear Information System (INIS)

    Mahr, L.; Cser, F.; Kovacs, G.; Hardy, Gy.

    1978-01-01

    Chloranil (CA) and bromanil (BA) which have otherwise similar radiation-chemical properties affect the solid state polymerization of acenaphthylene (ACN) in different manner. CA decreases the rate of polymerization proportionally to its concentration and besides, it also decreases the conversion limit and the molecular weight of the product. BA does not influence the reaction up to a conversion of 20%, but soon afterwards the conversion limit of the polymerization is reached. This limit, above 8M% BA content, is independent of the BA concentration. The reason for the different behaviour is that while BA forms an ideal eutectics with ACN, CA forms a solid solution of limited miscibility at the temperature of the experiments. Both pairs of compounds give charge transfer complex in solid state. The charge transfer complex of BA exists merely at the boundary layer of the crystals, but that of CA is within the crystal lattice of ACN as in a solid solvent. In none of the studied cases could be detected the charge transfer complex with its own specific crystal structure. The effect of CA on the solid state polymerization of ACN is discussed on the basis of the results obtained by PPP and CNDO/2 calculations on ACN and CA. (author)

  5. Polymerizations of beta-substituted allylic arsonium ylides with catalytic amounts of organoboron compounds

    International Nuclear Information System (INIS)

    Mondiere, R.

    2004-01-01

    My Ph.D. work consisted in the generalization and optimization of a new polymerization reaction involving allylic arsonium ylides and catalytic amounts of various boron compounds. Thus, various β-substituted allylic arsonium salts were produced according to synthetic strategies that depended on the nature of the functional group born by the salt. These salts were converted in situ to the corresponding arsonium ylides which were then treated with boron compounds to yield polymers. Our new method of polymerization afforded either non conjugated polyenes that are functionalized every three atoms of carbon, or statistic copolymers, depending on the nature of the group R born on the β position of the ylide. These new polymers cannot be synthesized by usual methods of polymerization. Initial molar ratios of reactants were found to give molar mass control of the synthesized polymers. This controlled polymerization allowed us to produce several bloc copolymers. All the polymers were characterized by NMR techniques, by size exclusion chromatography and, for some of them, by mass spectrometry. Investigation of their physicochemical properties will need additional experiments. (author)

  6. Graft polymerization of styrene onto starch by simultaneous cobalt-60 irradiation

    International Nuclear Information System (INIS)

    Fanta, G.F.; Burr, R.C.; Doane, W.M.; Russell, C.R.

    1977-01-01

    Starch-g-polystyrene copolymers have been prepared by the simultaneous 60 Co irradiation of starch--styrene mixtures, and copolymers have been characterized with respect to weight per cent polystyrene (% add-on) and also the molecular weight and molecular weight distribution of polystyrene grafts. In a typical polymerization, 4g each of starch and styrene were blended with 1 ml water and 1.5 ml of an organic solvent; the resulting semisolid paste was irradiated to a total dose of 1 Mrad. With ethylene glycol, acetonitrile, ethanol, methanol, acetone, and dimethylformamide as the organic solvent, values for % add-on ranged from 24% to 29%. The highest % add-on (43%) and the highest conversion of styrene to grafted polymer (76%) were obtained when the organic solvent was omitted, and water alone was used. When water was also omitted, polymerization of styrene was negligible; however, graft copolymer was formed in the absence of water when either ethylene glycol or ethanol was added. Attempts were unsuccessful to achieve a % add-on greater than 43% by doubling the amount of styrene in the polymerization recipe. Mixtures of equal weights of starch and styrene are relatively nonviscous, but these mixtures thicken when either water or ethylene glycol is blended in. Reasons for this thickening action and the possible influence of thickening on the graft polymerization reaction were explored

  7. Vibrating polymeric microsieves: Antifouling strategies for microfiltration

    NARCIS (Netherlands)

    Girones nogue, Miriam; Akbarsyah, Imam J.; Bolhuis-Versteeg, Lydia A.M.; Lammertink, Rob G.H.; Wessling, Matthias

    2006-01-01

    Constant flux performance in time is achieved with polyethersulfone (PES) polymeric microsieves when filtering protein solutions, skimmed milk and white beer in combination with backpulsing. Such microsieves are fabricated by phase separation micromolding (PSμM) and possess pores around 2 μm. The

  8. Inflation and Failure of Polymeric Membranes

    DEFF Research Database (Denmark)

    Hassager, Ole; Neergaard, Jesper

    2000-01-01

    We consider the inflation of an axisymmetric polymeric membrane.Some membranes composed of viscoelastic materialsdescribed by a Mooney-Rivlin model show a monotone increasingpressure during inflation. These materialsdevelop a homogeneous membrane thickness in agreement with the Considere...... is found to stabilize the inflated polymer membrane....

  9. Gamma Radiation-Induced Template Polymerization Technique

    International Nuclear Information System (INIS)

    Siyam, T.

    2005-01-01

    Gamma radiation induced copolymerization of acrylamide sodiumacrylate (AM-AANa) in the presence and absence of the polymer additive was studied at low monomer concentration(1.4M/l). The results showed that the exponents of the dose rate for the polymerization rate was found to be 1.3 and 1.4 in the absence and in the presence of the polymer additive respectively. The molecular weight of the formed polymer increased by addition of the polymer to the system. In the presence of the polymer the comonomers polymerize on the added polymer. In the absence of the added polymer the comonomers polymerize according to the copolymerization process at the initial stage of the copolymerization. While at high conversion the residual comonomers polymerize on the formed macromolecular chains of the produced polymer. These studies showed that the copolymerization in the presence of added polymer is completely template copolymerization while in the absence of the polymer the copolymerization process is only template process with a high conversion

  10. On viscoelastic instability in polymeric filaments

    DEFF Research Database (Denmark)

    Rasmussen, Henrik Koblitz; Hassager, Ole

    1999-01-01

    The 3D Lagrangian Integral Method is used to simulate the effects of surface tension on the viscoelastic end-plate instability, occuring in the rapid extension of some polymeric filaments between parallel plates. It is shovn that the surface tension delays the onset of the instability. Furthermore...

  11. Polymeric additive performance in closed whitewater systems

    Science.gov (United States)

    T. H. Wegner

    1984-01-01

    “With more stringent requirements on discharge water quality and with escalating water treatment costs, water recycling within the paper mill is of growing importance. A serious problem resulting from more white-water recycling is reduced drainage and fiber or fines retention because of diminished polymeric additive performance. To provide better insight for overcoming...

  12. Latent tracks in polymeric etched track detectors

    International Nuclear Information System (INIS)

    Yamauchi, Tomoya

    2013-01-01

    Track registration properties in polymeric track detectors, including Poly(allyl diglycol carbonate), Bispenol A polycarbonate, Poly(ethylen terephtarate), and Polyimide, have been investigated by means of Fourie transform Infararede FT-IR spectrometry. Chemical criterion on the track formation threshold has been proposes, in stead of the conventional physical track registration models. (author)

  13. Bioactive Polymeric Materials for Tissue Repair

    Directory of Open Access Journals (Sweden)

    Diane R. Bienek

    2017-01-01

    Full Text Available Bioactive polymeric materials based on calcium phosphates have tremendous appeal for hard tissue repair because of their well-documented biocompatibility. Amorphous calcium phosphate (ACP-based ones additionally protect against unwanted demineralization and actively support regeneration of hard tissue minerals. Our group has been investigating the structure/composition/property relationships of ACP polymeric composites for the last two decades. Here, we present ACP’s dispersion in a polymer matrix and the fine-tuning of the resin affects the physicochemical, mechanical, and biological properties of ACP polymeric composites. These studies illustrate how the filler/resin interface and monomer/polymer molecular structure affect the material’s critical properties, such as ion release and mechanical strength. We also present evidence of the remineralization efficacy of ACP composites when exposed to accelerated acidic challenges representative of oral environment conditions. The utility of ACP has recently been extended to include airbrushing as a platform technology for fabrication of nanofiber scaffolds. These studies, focused on assessing the feasibility of incorporating ACP into various polymer fibers, also included the release kinetics of bioactive calcium and phosphate ions from nanofibers and evaluate the biorelevance of the polymeric ACP fiber networks. We also discuss the potential for future integration of the existing ACP scaffolds into therapeutic delivery systems used in the precision medicine field.

  14. Hyaluronan polymeric micelles for topical drug delivery

    Czech Academy of Sciences Publication Activity Database

    Šmejkalová, D.; Muthný, T.; Nešporová, K.; Hermannová, M.; Achbergerová, E.; Huerta-Angelesa, G.; Marek Svoboda, M.; Čepa, M.; Machalová, V.; Luptáková, Dominika; Velebný, V.

    2017-01-01

    Roč. 156, JAN 20 (2017), s. 86-96 ISSN 0144-8617 Institutional support: RVO:61388971 Keywords : Skin penetration * Polymeric micelle * Hyaluronan Subject RIV: CE - Biochemistry OBOR OECD: Biochemistry and molecular biology Impact factor: 4.811, year: 2016

  15. The Morphology of Emulsion Polymerized Latex Particles

    Science.gov (United States)

    Wignall, G. D.; Ramakrishnan, V. R.; Linne, M. A.; Klein, A.; Sperling, L. H.; Wai, M. P.; Gelman, R. A.; Fatica, M. G.; Hoerl, R. H.; Fisher, L. W.

    1987-11-01

    Under monomer starved feed conditions, emulsion polymerization of perdeuterated methyl methacrylate and styrene in the presence of preformed polymethylmethacrylate latexes resulted in particles with a core-shell morphology, as determined by small-angle neutron scattering (SANS) analysis for a hollow sphere. The locus of polymerization of the added deuterated monomer is therefore at the particle surface. In similar measurements a statistical copolymer of styrene and methyl methacrylate was used as seed particles for further polymerization of trideuteromethyl methacrylate. The resulting polymer latex was again shown to have a core-shell morphological structure as determined by SANS. SANS experiments were also undertaken on polystyrene latexes polymerized by equilibrium swelling methods, with deuterated polymer forming the first or second step. The experiments covered a molecular weight range of 6 x 10{sup 4} 10{sup 6} the molecular weights are consistent with the experimental errors, indicating that the deuterium labeled molecules are randomly distributed in the latex. These results led to the finding that the polymer chains were constrained in the latex particles by factors of 2 to 4 from the relaxed coil dimensions. For M molecules. Several models were examined, including the possible development of core-shell structures at lower molecular weights.

  16. Immobilization of Trichoderma reesei by radiation polymerization

    International Nuclear Information System (INIS)

    Zhou Ruimin; Ma Zueteh; Kaetus, Isao; Kumakura, Minoro

    1993-01-01

    Immobilization of Trichoderma reesei was carried out by radiation polymerization. It was found that the activity of fixed cells increased with increasing surface area of the carrier and was affected by the concentration of monomer tetraethylenglycol dimethacrylate and the shape of the substrate composition and structure of cotton textile fabrics. (author)

  17. Polymerization of different lignins by laccase

    NARCIS (Netherlands)

    Mattinen, M.L.; Suortti, T.; Gosselink, R.J.A.; Argyropoulos, D.S.; Evtuguin, D.; Suurnäkki, A.; Jong, de E.; Tamminen, T.

    2008-01-01

    In this study the oxidative polymerization of different lignins, i.e. Flax Soda lignin, Spruce EMAL, and Eucalyptus Dioxane lignin by Trametes hirsuta laccase was compared. Initially the structures of the different lignins were compared by Fourier transform infrared spectroscopy. The reactivity of

  18. Interaction of acetamiprid with extracellular polymeric substances ...

    African Journals Online (AJOL)

    Extracellular polymeric substances (EPS) are important components of activated sludge and it plays an important role in removing pollutants. The interaction between EPS and organic pollutants is still little known. In the present study, the interaction of soluble/bound EPS with acetamiprid, a neonicotinoid insecticide, was ...

  19. Radiation sterilization of polymeric implant materials

    International Nuclear Information System (INIS)

    Bruck, S.D.; Mueller, E.P.

    1988-01-01

    High-energy irradiation sterilization of medical devices and implants composed of polymeric biomaterials that are in contact with tissue and/or blood, may adversely affect their long-term mechanical and/or biological performance (tissue and/or blood compatibility). Since many polymeric implants may contain trace quantities of catalysts and/or other additives, the effect of high-energy radiation on these additives, and possible synergistic effects with the polymer chains under the influence of high-energy radiation, must be considered. It is essential to indicate whether polymeric implants are used in short-term (acute) or long-term (chronic) applications. Relatively small changes in their physicochemical, mechanical, and biological properties may be tolerable in the short term, whereas similar changes may lead to catastrophic failures in long-term applications. Therefore, polymeric implants which are to be sterilized by high-energy irradiation should be carefully evaluated for long-term property changes which may be induced by the radiation

  20. Ion induced polymerization in benzene frozen films

    Energy Technology Data Exchange (ETDEWEB)

    Calcagno, G [Catania Univ. (Italy). Ist. di Fisica; Strazzulla, G [Catania Univ. (Italy). Osservatorio Astrofisico; Fichera, M; Foti, G [Catania Univ. (Italy). Ist. di Radiologia

    1983-07-01

    The cross section of the polymerization process induced by energetic protons colliding with frozen benzene layers has been measured. The results have been described by a simple theory and they show that the process is a volume one occurring along the ion track and interesting all of the crossed layers.