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Vinyl Monomers (vinyl + monomer)
Selected AbstractsControlled Radical Polymerization of Vaporized Vinyl Monomers on Solid Surfaces under UV IrradiationMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 4 2004Mikio Yasutake Abstract Summary: In order to prepare well-defined polymers on solid surfaces in the gas phase, a gas phase-assisted surface polymerization (GASP) of vinyl monomers was carried out on solid surfaces pre-coated with a photoiniferter, 2-cyanoprop-2-yl N,N,-dimethyldithiocarbamate, under UV irradiation. The GASP of methyl methacrylate (MMA) resulted in the formation of polymer on the surfaces and showed a proportional relationship between and polymer yield. Consecutive copolymerization of MMA and styrene led to the formation of a block copolymer, which was confirmed by a selective solvent fractionation method. These results demonstrate that controlled radical polymerization of vaporized monomer occurred on the solid surfaces. Expected mechanism of GASP under UV irradiation. [source] Free Radical Grafting of Polyethylene with Vinyl Monomers by Reactive ExtrusionMACROMOLECULAR THEORY AND SIMULATIONS, Issue 9 2007Guofang Zhang Abstract The free radical grafting of polyethylene with vinyl monomers by reactive extrusion was studied numerically. Numerical computation expressions of key variables, such as the concentrations of the initiator and polymer, grafting degree, average molecular weight and apparent viscosity, were deduced. The evolutions of the above variables were predicted by means of an uncoupled semi-implicit iterative algorithm. The monomer conversion monotonically increases with decreasing throughput or increasing initial initiator concentration; with increasing barrel temperature, the monomer conversion first increases then decreases. The simulated results are nearly in good agreement with the experimental results. [source] High-Speed Living Polymerization of Polar Vinyl Monomers by Self-Healing Silylium CatalystsCHEMISTRY - A EUROPEAN JOURNAL, Issue 34 2010Dr. Yuetao Zhang Abstract This contribution describes the development and demonstration of the ambient-temperature, high-speed living polymerization of polar vinyl monomers (M) with a low silylium catalyst loading (, 0.05,mol,% relative to M). The catalyst is generated in situ by protonation of a trialkylsilyl ketene acetal (RSKA) initiator (I) with a strong Brønsted acid. The living character of the polymerization system has been demonstrated by several key lines of evidence, including the observed linear growth of the chain length as a function of monomer conversion at a given [M]/[I] ratio, near-precise polymer number-average molecular weight (Mn, controlled by the [M]/[I] ratio) with narrow molecular weight distributions (MWD), absence of an induction period and chain-termination reactions (as revealed by kinetics), readily achievable chain extension, and the successful synthesis of well-defined block copolymers. Fundamental steps of activation, initiation, propagation, and catalyst "self-repair" involved in this living polymerization system have been elucidated, chiefly featuring a propagation "catalysis" cycle consisting of a rate-limiting CC bond formation step and fast release of the silylium catalyst to the incoming monomer. Effects of acid activator, catalyst and monomer structure, and reaction temperature on polymerization characteristics have also been examined. Among the three strong acids incorporating a weakly coordinating borate or a chiral disulfonimide anion, the oxonium acid [H(Et2O)2]+[B(C6F5)4], is the most effective activator, which spontaneously delivers the most active R3Si+, reaching a high catalyst turn-over frequency (TOF) of 6.0×103,h,1 for methyl methacrylate polymerization by Me3Si+ or an exceptionally high TOF of 2.4×105,h,1 for n -butyl acrylate polymerization by iBu3Si+, in addition to its high (>90,%) to quantitative efficiencies and a high degree of control over Mn and MWD (1.07,1.12). An intriguing catalyst "self-repair" feature has also been demonstrated for the current living polymerization system. [source] A paradigm for the mechanisms and products of spontaneous polymerizationsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 24 2009H. K. Hall Jr. Abstract In spontaneous vinyl and ring-opening copolymerizations, polar and resonance effects on the intermediates from bond-forming initiation offer a continuous spectrum of reactivities and polymer structures. In bond-forming initiation, an electron-rich donor monomer forms a bond to an acceptor monomer. The donor monomer may be a vinyl monomer with O, N, or aryl substituent or it may be an aza- or oxacycle. The acceptor monomer may be a vinyl monomer carrying CN, COOR, or SO2R substituent or it may be a cyclic anhydride or maleimide. Beyond this, the donor may have a ,-like strained single bond, whereas the acceptor may be an electrophilic quinodimethane. Lewis acids may be used to enhance the electrophilicity of acceptor monomers. Reaction rates and polymer composition are determined by systematically varying the stability of the first intermediate, designated P (for polymethylene). The nature of the intermediate will vary from a highly reactive trans biradical, which initiates chain alternating copolymerization, to a cis/gauche zwitterion, which can initiate chain ionic homopolymerization, to an extremely stabilized zwitterion, which cannot add monomer, but builds up in concentration and terminates by combination, forming alternating copolymer. This model embraces the existing literature for a wide variety of monomers and possesses predictive power. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2009 [source] Synthesis of polar vinyl monomer,olefin copolymers by ,-diimine nickel catalystPOLYMER INTERNATIONAL, Issue 5 2001Maria M Marques Abstract Vinyl acetate, methyl methacrylate, acrylonitrile and methyl vinyl ketone were investigated for co- and terpolymerization with ethylene and ethylene,propylene. Precursor [bis(N,N,,-dimesitylimino)acenaphthene]dibromonickel, activated by methylaluminoxane was used as a catalyst system and trialkylaluminium was employed to block the polar groups for these polymerizations. Polymerization activities of the order of magnitude of 106 in the case of vinyl acetate and methyl methacrylate, and 105 in the case of acrylonitrile were achieved. Microanalysis and GPC of acrylonitrile copolymers found about 17 units of acrylonitrile per polymer chain. Copolymers with very different properties from the parent homopolymers were obtained in all cases except that of methyl vinyl ketone. © 2001 Society of Chemical Industry [source] Combinatorial Initiated CVD for Polymeric Thin Films,CHEMICAL VAPOR DEPOSITION, Issue 11 2006P. Martin Abstract A new combinatorial initiated (i)CVD system is fabricated and used to efficiently determine the deposition kinetics for two new polymeric thin films, poly(diethylaminoethylacrylate) (PDEAEA) and poly(dimethylaminomethylstyrene) (PDMAMS). The results of combinatorial depositions are compared to blanket iCVD under identical conditions using the appropriate vinyl monomer with tert -amylperoxide as the initiator. Fourier transform infrared spectroscopy (FTIR) reveals similar chemical structure in blanket and combinatorial films. FTIR also shows that functional groups are retained in iCVD of PDMAMS, whereas essentially all fine chemical structure of the material is destroyed in plasma-enhanced (PE)CVD. The maximum observed growth rates of PDEAEA and PDMAMS were 43 and 11,nm,min,1, respectively. The activation energy of growth with respect to filament temperature (Ea,filament) was 88.4±1.6 kJ,mol,1 for PDEAEA and 42.0±1.7 kJ,mol,1 for PDMAMS. Activation energies for growth with respect to substrate temperature (Ea,substrate) are ,59.5±2.7 kJ,mol,1 for PDEADA and ,82.7±2.6 kJ,mol,1 for PDMAMS, with the negative values consistent with adsorption-limited kinetics. The molecular weight of PDEAEA films ranges from 1 to 182 kDa as a function of substrate temperature. It is found that in all cases the combinatorial system agreed (within experimental uncertainty) with results of blanket iCVD, thus validating the use of the combinatorial system for future iCVD studies. [source] Surface modification of nylon-6 fibers for medical applicationsJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2007S. E. Shalaby Abstract Hydroxyethylmethacrylate (HEMA) is considered to be one of the important vinyl monomers. The ability of polyhydroxyethyl-methacylate (PHEMA) graft sites to consecutive chemical modification makes the use of nylon-6 fibers grafted with PHEMA a feasible bed for immobilization of a wide range of biologically active reagents, specially enzymes, drugs, cells, and immunadsorbents. Stemming from the above discussions, in this article, the graft copolymerization of HEMA onto modified nylon-6 fibers containing Polydiallyldimethylammonium chloride (PDADMAC) in the presence of Cu2+,K2S2O8 as a redox initiating system was carried out, with very high rate and almost without homopolymer formation. The factors affecting the grafting reaction (monomer, K2S2O8 and cupric ion concentrations, the amount of PDADMAC as well as the reaction temperature) were studied. Kinetic investigation revealed that the rate of grafting (Rp) of HEMA onto modified nylon-6 fibers is proportional to [HEMA]1, [CuSO4.5H2O] 0.7, [PDADMAC]0.4, and [K2S2O8]1.4. The overall activation energy was calculated (71 KJ/mol). The fine structure, surface topography, thermal and electrical properties of parent and grafted nylon-6 fibers were investigated. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 3788,3796, 2007 [source] Polystyrene nanocomposite materials by in situ polymerization into montmorillonite,vinyl monomer interlayersJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2007Ahmed Akelah Abstract A different series of new polystyrene,clay nanocomposites have been prepared by grafting polymerization of styrene with vinyl-montmorillonite (MMT) clay. The synthesis was achieved through two steps. The first step is the modification of clay with the vinyl monomers, such as N,N -dimethyl- n -octadecyl-4-vinylbenzyl-ammonium chloride, n -octadecyl-4-vinylbenzyl-ammonium chloride, triphenyl-4-vinylbenzyl-phosphonium chloride, and tri- n -butyl-4-vinylbenzyl-phosphonium chloride. The second step is the polymerization of styrene with different ratios of vinyl-MMT clay. The materials produced were characterized by different physical and chemical methods: (1) IR spectra, confirming the intercalation of the vinyl-cation within the clay interlayers; (2) thermogravimetric analysis (TGA), showing higher thermal stability for PS,nanocomposites than polystyrene (PS) and higher thermal stability of nanocomposites with of phosphonium moieties than nanocomposites with ammonium moieties; (3) swelling measurements in different organic solvents, showing that the swelling degree in hydrophobic solvents increases as the clay ratio decreases; (4) X-ray diffraction (XRD), illustrating that the nanocomposites were exfoliated at up to a 25 wt % of organoclay content; and (5) scanning electron microscopy (SEM), showing a complete dispersion of PS into clay galleries. Also, transmission electron microscopy (TEM) showed nanosize spherical particles of , 150,400 nm appearing in the images. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3739,3750, 2007 [source] Poly(ethylene glycol)-thioxanthone prepared by Diels,Alder click chemistry as one-component polymeric photoinitiator for aqueous free-radical polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 10 2010Hakan Akat Abstract Novel water-borne macrophotoinitiator containing thioxanthone (TX) end group was successfully synthesized by using Diels,Alder (DA) [4 + 2] click chemistry strategy. For this purpose, thioxanthone-anthracene (TX-A) and maleimide end-functionalized poly(ethylene glycol) (PEG-MI) were reacted in toluene at reflux temperature for 48 h. The final polymer (PEG-TX) and the intermediates were characterized in detail by spectral analysis. PEG-TX possesses absorption characteristics similar to the parent TX. The one-component photoinitiating nature of the photointiator was demonstrated by photopolymeization of several hydrophilic vinyl monomers, such as acrylic acid, acrylamide, 2-hydroxyethyl acrylate, and 1-vinyl-2-pyrrolidone. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2109,2114, 2010 [source] Dispersion polymerization of vinyl monomers in supercritical carbon dioxide in the presence of drug molecules: A one-pot route for the preparation of controlled delivery systemsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 22 2008Alessandro Galia Abstract The polymerization of 1-vinyl-2-pyrrolidone in supercritical carbon dioxide in the presence of ibuprofen as a model drug was investigated as a new one-pot process for the preparation of polymer-based drug delivery systems (DDSs). The composites were prepared at 65 °C and P = 31,42 MPa by changing the initial concentration of the drug and the concentration of a crosslinking agent and that of a hydrophobic comonomer. The effects of these parameters on the performances of the polymerization and on the in vitro release kinetics of ibuprofen were studied. In all the experiments, part of the drug was entrapped inside the polymer particles and dissolved more slowly with respect to the pure compound. Copolymerization with methyl methacrylate was the most effective route to obtain a DDS with sustained temporal release of the drug molecule. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7429,7446, 2008 [source] Cyclometalated 2-phenylpyridine complex [RuII(o -C6H4 -py)(MeCN)4]PF6 as a tunable catalyst for living radical polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 12 2008F. Diaz Camacho Abstract The cyclometalated complex [RuII(o -C6H4 -py)(MeCN)4]PF6 (1) with a ,-RuC bond and four substitutionally labile acetonitrile ligands mediates radical polymerization of different vinyl monomers, viz. n -butyl acrylate, methyl methacrylate, and styrene, initiated by three alkyl bromides: ethyl 2-bromoisobutyrate, methyl 2-bromopropionate, and 1-phenylethyl bromide. The polymerization requires the presence of Al(OiPr)3 and occurs uncontrollably as a conventional radical process. The variation of the molar ratio of the components of the reaction mixture, such as initiator, Al(OiPr)3 and catalyst, affected the polymerization rates and the molecular weights but did not improve the control. A certain level of control has been achieved by adding 0.5 eq of SnCl2 as a reducing agent. Tin(II) chloride decreased the rate of polymerization and simultaneously the molecular weights became conversion-dependent and the polydispersities were also narrowed. Remarkably, the level of control was radically improved in the presence of excess of the poorly soluble catalyst (1), when the added amount of (1) was not soluble any more, i.e., under heterogeneous conditions, the system became adjustable and the living polymerization of all three monomers was finally achieved. Possible mechanisms of the (1)-catalyzed polymerization are discussed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4193,4204, 2008 [source] Facile syntheses of 4-vinyl-1,2,3-triazole monomers by click azide/acetylene couplingJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 9 2008Kenichi Takizawa Abstract Synthetic strategies for the preparation of a new family of vinyl monomers, 4-vinyl-1,2,3-triazoles, have been developed. These monomers are noteworthy as they combine the stability and aromaticity of styrenics with the polarity of vinylpyridines and the structural versatility of acrylate/methacrylate derivatives. To enable the wide adoption of these unique monomers, new methodologies for their synthesis have been elaborated which rely on Cu-catalyzed azide/acetylene cycloaddition reactions,"click chemistry",as the key step, with the vinyl substituent being formed by either elimination or Wittig-type reactions. In addition, one-pot "click" reactions have been developed from alkyl halides, which allow for monomer synthesis without isolation of the intermediate organic azides. The high yield and facile nature of these procedures has allowed a library of new monomers including the parent compound, 1- H -4-vinyl-1,2,3-triazole, to be prepared on large scales. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2897,2912, 2008 [source] Novel synthesis of rod-coil block copolymers by combination of coordination polymerization and ATRPJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 17 2007Koji Ishizu Abstract Combination of coordination polymerization and atom transfer radical polymerization (ATRP) was applied to a novel synthesis of rod-coil block copolymers. The procedure included the following steps: (1) monoesterification reaction of ethylene glycol with 2-bromoisobutyryl bromide yielded a ,-bromo, ,-hydroxy bifunctional initiator, (2) CpTiCl3 (bifunctional initiator) catalyst was prepared from a mixture of trichlorocyclopentadienyl titanium (CpTiCl3) and bifunctional initiator. Coordination polymerization of n- butyl isocyanate initiated by such catalyst provided a well-defined macroinitiator, poly(n- butyl isocyanate)-Br (PBIC-Br), and (3) ATRP method of vinyl monomers using PBIC-Br provided rod (PBIC)-coil block copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4037,4042, 2007 [source] Divergent synthesis of dendrimer-like macromolecules through a combination of atom transfer radical polymerization and click reactionJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 15 2007Qingchun Liu Abstract This article describes a divergent strategy to prepare dendrimer-like macromolecules from vinyl monomers through a combination of atom transfer radical polymerization (ATRP) and click reaction. Firstly, star-shaped polystyrene (PS) with three arms was prepared through ATRP of styrene starting from a three-arm initiator. Next, the terminal bromides of the star-shaped PS were substituted with azido groups. Afterwards, the azido-terminated star-shaped PS was reacted with propargyl 2,2-bis((2,-bromo-2,-methylpropanoyloxy)methyl)propionate (PBMP) via click reaction. Star-shaped PS with six terminal bromide groups was afforded and served as the initiator for the polymerization of styrene to afford the second-generation dendrimer-like PS. Iterative process of the aforementioned sequence of reactions could allow the preparation of the third-generation dendrimer-like PS. When the second-generation dendrimer-like PS with 12 bromide groups used as an initiator for the polymerization of tert -butyl acrylate, the third-generation dendrimer-like block copolymer with a PS core and a poly (tert -butyl acrylate) (PtBA) corona was afforded. Subsequently PtBA segments were selectively hydrolyzed with hydrochloric acid, resulting an amphiphilic branched copolymer with inner dendritic PS and outer linear poly(acrylic acid) (PAA). Following the same polymerization procedures, the dendrimer-like PS and PS- block -PtBA copolymers of second generation originating from six-arm initiator were also synthesized. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3330,3341, 2007 [source] Synthesis of dithiocarbamate bearing azobenzene group and use for RAFT polymerization of vinyl monomersJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 14 2007Xiaoming Wan Abstract A novel dithiocarbamate bearing azobenzene group, 2-(phenylazo-phenoxy-carbonyl) prop-2-yl 9H-carbazole-9-carbodithioate (APCDT), was synthesized and used as a RAFT agent in the polymerization of methyl methacrylate (MMA). The results showed that the controllability to the polymerization of MMA was promoted with APCDT as RAFT agent compared to 2-(ethoxycarbonyl) prop-2-yl 9H-carbazole-9-carbodithioate (EPCDT) under the same experimental conditions. The reason was attributed to the higher chain transfer constant of APCDT than that of EPCDT in the presence of more bulkier and more electrophilic azobenzene moiety. In addition, the RAFT polymerizations of St and methylacrylate (MA) using APCDT as the RAFT agent were also carried out. The ultraviolet spectrum and fluorescence spectrum of the obtained polymers were investigated. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2886,2896, 2007 [source] Grafting of polymers onto and/or from silica surface during the polymerization of vinyl monomers in the presence of ,-ray-irradiated silicaJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 9 2006Akiko Tsuchida Abstract The effects of radicals on silica surface, which were formed by ,-ray irradiation, on the polymerization of vinyl monomers were investigated. It was found that the polymerization of styrene was remarkably retarded in the presence of ,-ray-irradiated silica above 60 °C, at which thermal polymerization of styrene is readily initiated. During the polymerization, a part of polystyrene formed was grafted onto the silica surface but percentage of grafting was very small. On the other hand, no retardation of the polymerization of styrene was observed in the presence of ,-ray-irradiated silica below 50 °C; the polymerization tends to accelerate and polystyrene was grafted onto the silica surface. Poly(vinyl acetate) and poly(methyl methacrylate) (MMA) were also grafted onto the surface during the polymerization in the presence of ,-ray-irradiated silica. The grafting of polymers onto the silica surface was confirmed by thermal decomposition GC-MS. It was considered that at lower temperature, the grafting based on the propagation of polystyrene from surface radical ("grafting from" mechanism) preferentially proceeded. On the contrary, at higher temperature, the coupling reaction of propagating polymer radicals with surface radicals ("grafting onto" mechanism) proceeded to give relatively higher molecular weight polymer-grafted silica. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2972,2979, 2006 [source] Bicyclobutanes and cyclobutenes: Unusual carbocyclic monomersJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 5 2003H. K. Hall Jr. Abstract Bicyclobutanes and cyclobutenes substituted with electron-attracting groups represent novel classes of reactive monomers. They readily undergo free-radical and anionic polymerizations to give high polymers consisting of 1,3- and 1,2-enchained cyclobutane rings, respectively. They also copolymerize readily with conventional vinyl monomers. These polymers display numerous attractive properties in comparison with their vinyl counterparts, including enhanced thermal stability, superior optical properties, and higher glass-transition temperatures. The syntheses of these monomers are reviewed, and suggestions toward future larger scale production are made. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 625,635, 2003 [source] Tetraalkylammonium salt as photoinitiator of vinyl polymerization in organic and aqueous media: A mechanistic and laser flash photolysis studyJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 7 2002María L. Gómez Abstract N -Dimethyl- N -[2-(N,N -dimethylamino)ethyl]- N -(1-methylnaphthyl)ammonium tetrafluoroborate (I) was synthesized with the aim of obtaining a versatile photoinitiator for vinyl polymerization in organic solvents and water. Salt I was able to trigger the polymerization of acrylamide, 2-hydroxyethylmethacrylate and styrene even at very low concentrations of the salt (,1.0 × 10,5 M). Using laser flash photolysis and fluorescence techniques and analyzing the photoproduct distribution, we were able to postulate a mechanism for the photodecomposition of the salt. With irradiation, I undergoes an intramolecular electron-transfer reaction to form a radical ion pair (RIP). The RIP intermediate decomposes into free radicals. The RIP and the free radicals are active species for initiating the polymerization. Depending on the concentration of the vinyl monomers studied, the initiation mechanism of the polymerization reaction changes. At large monomer concentrations, the RIP state is postulated to trigger the reaction by generating the anion radical of the olefin substrate. At a low monomer concentration, the free radicals produced by the decomposition of I are believed to start the chain reaction. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 901,913, 2002; DOI 10.1002/pola.10166 [source] Search for highly resolved electron spin resonance spectra of the transient radical in radical polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 3 2002Mikiharu Kamachi Abstract The detection of highly resolved spectra in electron spin resonance (ESR) measurements of radical polymerization is presented. Well-resolved ESR spectra of the propagating radical were detected in the radical polymerization of several vinyl monomers with a specially designed cavity and cell. More highly resolved ESR spectra of the propagating radicals of vinyl and diene compounds were observed with aconventional spectrometer without the specially designed cavity and cell. On the basis of the ESR spectra, propagation rate constants and dynamic behavior of propagating radicals are discussed. Moreover, the application of time-resolved ESR spectroscopy to research on the initiation process in radical polymerization is shown. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 269,285, 2002 [source] Controlled Radical Polymerization of Vaporized Vinyl Monomers on Solid Surfaces under UV IrradiationMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 4 2004Mikio Yasutake Abstract Summary: In order to prepare well-defined polymers on solid surfaces in the gas phase, a gas phase-assisted surface polymerization (GASP) of vinyl monomers was carried out on solid surfaces pre-coated with a photoiniferter, 2-cyanoprop-2-yl N,N,-dimethyldithiocarbamate, under UV irradiation. The GASP of methyl methacrylate (MMA) resulted in the formation of polymer on the surfaces and showed a proportional relationship between and polymer yield. Consecutive copolymerization of MMA and styrene led to the formation of a block copolymer, which was confirmed by a selective solvent fractionation method. These results demonstrate that controlled radical polymerization of vaporized monomer occurred on the solid surfaces. Expected mechanism of GASP under UV irradiation. [source] Architecture of Polymeric Superstructures Constructed by Mesoscopically Ordered Cubic LatticesMACROMOLECULAR RAPID COMMUNICATIONS, Issue 4 2003Koji Ishizu Abstract Highly monodisperse crosslinked core-shell polymer microspheres could be prepared easily by introducing special crosslinking reagents into the segregated core in block copolymer assembly films. The crosslinked core was stabilized sterically by highly branched shell chains in solution. These microspheres moved like pseudo-latex. The microspheres formed a lattice with a body-centered cubic (BCC) structure near the overlap threshold (C*). This structure changed to a face-centered cubic (FCC) lattice in the bulk region of the films. Photofunctionalized core-shell microspheres were prepared by introducing dithiocarbamate (DC) groups into shell parts by means of polymer reactions, where DC groups could be propagated using vinyl monomers such as methyl methacrylate (MMA) with living radical mechanism. Polymeric superstructure (three microphase-separated structure) films were constructed by graft copolymerization of MMA initiated with photofunctionalized microspheres such as macroinitiators under UV irradiation, exhibiting self-coloring due to Bragg diffraction. These materials can be used for the construction of optical devices such as for the fabrication of light modulators. Photograph of a solution of the microsphere in MMA. [source] Free Radical Grafting of Polyethylene with Vinyl Monomers by Reactive ExtrusionMACROMOLECULAR THEORY AND SIMULATIONS, Issue 9 2007Guofang Zhang Abstract The free radical grafting of polyethylene with vinyl monomers by reactive extrusion was studied numerically. Numerical computation expressions of key variables, such as the concentrations of the initiator and polymer, grafting degree, average molecular weight and apparent viscosity, were deduced. The evolutions of the above variables were predicted by means of an uncoupled semi-implicit iterative algorithm. The monomer conversion monotonically increases with decreasing throughput or increasing initial initiator concentration; with increasing barrel temperature, the monomer conversion first increases then decreases. The simulated results are nearly in good agreement with the experimental results. [source] Copolymerization of ethylene with aromatic vinyl monomers using metallocenesPOLYMER INTERNATIONAL, Issue 4 2001K Rajesh Kumar Abstract Copolymerization of ethylene with styrene, allyl benzene and 4-phenyl-1-butene was examined using different metallocene catalysts. We separated the bulky phenyl group of styrene from its double bond using methylene spacers and studied the effect on its copolymerization behaviour with ethylene. The extent of incorporation of the comonomer is in the order 4-phenyl-1-butene,>,allyl benzene,>,styrene for all catalysts. The comonomer incorporation was found to be less than 10,mol% under the experimental conditions employed in the present study. © 2001 Society of Chemical Industry [source] Silane reduction of onium saltsAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 3 2010James V. Crivello Abstract Novel redox initiators for cationic polymerizations were developed consisting of an onium salt together with a SiH functional silane or siloxane. The reduction of the onium salt by the silane is catalyzed by noble metal complexes or certain transition metal compounds and takes place spontaneously at room temperature. The redox reaction of the onium salt with the silane results in the liberation of a strong Brønsted acid that can be subsequently used to initiate cationic polymerizations. Typical onium salts that have been employed in these redox initiator systems are diaryliodonium salts, triarylsulfonium salts and S,S -dialkyl- S -phenacylsulfonium salts. Studies of the effects of variations in the structures of the onium salt, the silane and the type of noble metal catalyst were carried out. In principle, the redox initiator systems are applicable to all types of cationically polymerizable monomers and oligomers, including the ring-opening polymerizations of such heterocyclic monomers as epoxides and oxetanes and, in addition, the polymerization of vinyl monomers such as vinyl ethers, N -vinylcarbazole and styrenic monomers. The use of these novel initiator systems for carrying out commercially attractive crosslinking polymerizations for coatings, composites and encapsulations is discussed. Copyright © 2009 John Wiley & Sons, Ltd. [source] High-Speed Living Polymerization of Polar Vinyl Monomers by Self-Healing Silylium CatalystsCHEMISTRY - A EUROPEAN JOURNAL, Issue 34 2010Dr. Yuetao Zhang Abstract This contribution describes the development and demonstration of the ambient-temperature, high-speed living polymerization of polar vinyl monomers (M) with a low silylium catalyst loading (, 0.05,mol,% relative to M). The catalyst is generated in situ by protonation of a trialkylsilyl ketene acetal (RSKA) initiator (I) with a strong Brønsted acid. The living character of the polymerization system has been demonstrated by several key lines of evidence, including the observed linear growth of the chain length as a function of monomer conversion at a given [M]/[I] ratio, near-precise polymer number-average molecular weight (Mn, controlled by the [M]/[I] ratio) with narrow molecular weight distributions (MWD), absence of an induction period and chain-termination reactions (as revealed by kinetics), readily achievable chain extension, and the successful synthesis of well-defined block copolymers. Fundamental steps of activation, initiation, propagation, and catalyst "self-repair" involved in this living polymerization system have been elucidated, chiefly featuring a propagation "catalysis" cycle consisting of a rate-limiting CC bond formation step and fast release of the silylium catalyst to the incoming monomer. Effects of acid activator, catalyst and monomer structure, and reaction temperature on polymerization characteristics have also been examined. Among the three strong acids incorporating a weakly coordinating borate or a chiral disulfonimide anion, the oxonium acid [H(Et2O)2]+[B(C6F5)4], is the most effective activator, which spontaneously delivers the most active R3Si+, reaching a high catalyst turn-over frequency (TOF) of 6.0×103,h,1 for methyl methacrylate polymerization by Me3Si+ or an exceptionally high TOF of 2.4×105,h,1 for n -butyl acrylate polymerization by iBu3Si+, in addition to its high (>90,%) to quantitative efficiencies and a high degree of control over Mn and MWD (1.07,1.12). An intriguing catalyst "self-repair" feature has also been demonstrated for the current living polymerization system. [source] Modeling of the Nitroxide-Mediated Radical Copolymerization of Styrene and DivinylbenzeneMACROMOLECULAR REACTION ENGINEERING, Issue 5-6 2009Julio C. Hernández-Ortiz Abstract A mathematical model for the copolymerization kinetics with crosslinking of vinyl/divinyl monomers in the presence of nitroxide controllers has been developed and validated using experimental data of TEMPO-mediated copolymerization of styrene (STY) and divinylbenzene (DVB). Polymerization rate, molecular weight development, gelation point, evolution of sol and gel weight fractions, crosslink density, and copolymer composition, as well as concentrations of the species participating in the reaction mechanism can be calculated with the model. Diffusion-controlled effects were assessed and found unimportant. The presence of nitroxide controllers seems to favor the production of more homogeneous polymer networks, but this effect decreases as the initial fraction of crosslinker is increased. [source] | |||||||||||||