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Fragmentation Chain Transfer (fragmentation + chain_transfer)
Kinds of Fragmentation Chain Transfer Terms modified by Fragmentation Chain Transfer Selected AbstractsAb initio Emulsion Polymerization by RAFT (Reversible Addition,Fragmentation Chain Transfer) through the Addition of CyclodextrinsHELVETICA CHIMICA ACTA, Issue 8 2006Bojana Apostolovic Abstract A novel process to produce homo- and copolymers by RAFT polymerization in emulsion is presented. It is known that RAFT-controlled radical polymerization can be conducted in emulsion polymerization without disturbing the radical segregation characteristic of this process, thus leading to polymerization rates identical to those encountered in the corresponding nonliving systems. However, RAFT agents are often characterized by very low water solubility and, therefore, they diffuse very slowly from the monomer droplets, where they are initially solubilized, to the reaction loci, i.e., the polymer particles. Accordingly, when used in emulsion polymerization, they are practically excluded from the reaction. In this work, we show that cyclodextrins, well-known for their ability to form water-soluble complexes with hydrophobic molecules, facilitate the transport across the H2O phase of the RAFT agent to the polymer particles. Accordingly, chains grow through the entire process in a controlled way. This leads to the production of low-polydispersity polymers with well-defined structure and end functionalities as well as to the possibility of synthesizing block copolymers by a radical mechanism. [source] Characterization of New Amphiphilic Block Copolymers of N -Vinyl Pyrrolidone and Vinyl Acetate, 1 , Analysis of Copolymer Composition, End Groups, Molar Masses and Molar Mass Distributions,MACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 8 2010Nick Fandrich Abstract New amphiphilic block copolymers consisting of N -vinyl pyrrolidone and vinyl acetate were synthesized via controlled radical polymerization using a reversible addition/fragmentation chain transfer (RAFT)/macromolecular design via the interchange of xanthates (MADIX) system. The synthesis was carried out in 1,4-dioxane as process solvent. In order to get conclusions on the mechanism of the polymerization the molecular structure of formed copolymers was analysed by means of different analytical techniques. 13C NMR spectroscopy was used for the determination of the monomer ratios. End groups were analysed by means of matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. This technique was also used to determine possible fragmentations of the RAFT end groups. By means of a combination of size exclusion chromatography, 13C NMR and static light scattering molar mass distributions and absolute molar masses could be analysed. The results clearly show a non-ideal RAFT mechanism. [source] Quantification of Grafting Densities Achieved via Modular "Grafting-to" Approaches onto Divinylbenzene MicrospheresADVANCED FUNCTIONAL MATERIALS, Issue 12 2010Leena Nebhani Abstract The surface modification of divinylbenzene (DVB)-based microspheres is performed via a combination of reversible addition fragmentation chain transfer (RAFT) polymerization and rapid hetero-Diels,Alder (HDA) chemistry with the aim of quantifying the grafting densities achieved using this "grafting-to" method. Two variants of the RAFT-HDA concept are employed to achieve the functionalization of the microspheres. In the first approach, the microspheres are functionalized with a highly reactive diene, i.e., cyclopentadiene, and are subsequently reacted with polystyrene chains (number-averaged molecular weight, Mn,=,4200,g,mol,1; polydispersity index, PDI,=,1.12.) that carry a thiocarbonyl moiety functioning as a dienophile. The functionalization of the microspheres is achieved rapidly under ambient conditions, without the aid of an external catalyst. The surface grafting densities obtained are close to 1.2,×,1020 chains per gram of microspheres. In the second approach, the functionalization proceeds via the double bonds inherently available on the microspheres, which are reacted with poly(isobornyl acrylate) chains carrying a highly dienophilic thiocarbonyl functionality; two molecular weights (Mn,=,6000,g,mol,1, PDI,=,1.25; Mn,=,26,000,g,mol,1, PDI,=,1.26) are used. Due to the less reactive nature of the dienes in the second approach, functionalization is carried out at elevated temperatures (T,=,60,°C) yet in the absence of a catalyst. In this case the surface grafting density is close to 7,chains,nm,2 for Mn,=,6000,g,mol,1 and 4,chains,nm,2 for Mn,=,26,000,g,mol,1, or 2.82,×,1019 and 1.38,×,1019,chains g,1, respectively. The characterization of the microspheres at various functionalization stages is performed via elemental analysis for the quantification of the grafting densities and attenuated total reflectance (ATR) IR spectroscopy as well as confocal microscopy for the analysis of the surface chemistry. [source] Temperature Responsive Solution Partition of Organic,Inorganic Hybrid Poly(N -isopropylacrylamide)-Coated Mesoporous Silica Nanospheres,ADVANCED FUNCTIONAL MATERIALS, Issue 9 2008Po-Wen Chung Abstract A series of poly(N -isopropylacrylamide)-coated mesoporous silica nanoparticle materials (PNiPAm-MSNs) has been synthesized by a surface-initiated living radical polymerization with a reversible addition,fragmentation chain transfer (RAFT) reaction. The structure and the degree of polymerization of the PNiPAm-MSNs has been characterized by a variety of techniques, including nitrogen sorption analysis, 29Si and 13C solid-state NMR spectroscopy, transmission electron microscopy (TEM), and powder X-ray diffraction (XRD). The thermally induced changes of the surface properties of these polymer-coated core,shell nanoparticles have been determined by examining their partition activities in a biphasic solution (water/toluene) at different temperatures. [source] Synthesis of Inorganic,Organic Diblock Copolymers as a Precursor of Ordered Mesoporous SiCN Ceramic,ADVANCED MATERIALS, Issue 17 2007D. Nghiem A novel poly(vinyl)silazane- block -polystyrene diblock copolymer is successfully synthesized by living free-radical polymerization via a reversible addition fragmentation chain transfer (RAFT) route (see figure). The obtained diblock copolymer, having an inorganic volume fraction of 0.69, leads to phase-separation at the nanoscale to form an ordered nanostructure, which is converted to well-ordered mesoporous SiCN ceramic after heating at 800,°C and maintained up to 1400,°C. [source] Postpolymerization modification of poly(pentafluorophenyl methacrylate): Synthesis of a diverse water-soluble polymer libraryJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 17 2009Matthew I. Gibson Abstract This article explores the feasibility of poly(pentafluorophenyl methacrylate) (PPFMA) prepared by reversible addition fragmentation chain transfer (RAFT) polymerization as a platform for the preparation of diverse libraries of functional polymers via postpolymerization modification with primary amines. Experiments with a broad range of functional amines and PPFMA precursors of different molecular weights indicated that the postpolymerization modification reaction proceeds with good to excellent conversion for a diverse variety of functional amines and is essentially independent of the PPFMA precursor molecular weight. The RAFT end group, which was well preserved throughout the polymerization, is cleaved during postpolymerization modification to generate a thiol end group that provides possibilities for further orthogonal chain-end modification reactions. The degree of postpolymerization modification can be controlled by varying the relative amount of primary amine that is used and random polymethacrylamide copolymers can be prepared via a one-pot/two-step sequential addition procedure. Cytotoxicity experiments revealed that the postpolymerization modification strategy does not lead to any additional toxicity compared with the corresponding polymer obtained via direct polymerization, which makes this approach also of interest for the synthesis of biologically active polymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4332,4345, 2009 [source] Controlled/living heterogeneous radical polymerization in supercritical carbon dioxideJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 15 2009Per B. Zetterlund Abstract Supercritical carbon dioxide (scCO2) is an inexpensive and environmentally friendly medium for radical polymerizations. ScCO2 is suited for heterogeneous controlled/living radical polymerizations (CLRPs), since the monomer, initiator, and control reagents (nitroxide, etc.) are soluble, but the polymer formed is insoluble beyond a critical degree of polymerization (Jcrit). The precipitated polymer can continue growing in (only) the particle phase giving living polymer of controlled well-defined microstructure. The addition of a colloidal stabilizer gives a dispersion polymerization with well-defined colloidal particles being formed. In recent years, nitroxide-mediated polymerization (NMP), atom transfer radical polymerization (ATRP), and reversible addition fragmentation chain transfer (RAFT) polymerization have all been conducted as heterogeneous polymerizations in scCO2. This Highlight reviews this recent body of work, and describes the unique characteristics of scCO2 that allows composite particle formation of unique morphology to be achieved. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3711,3728, 2009 [source] Core-shell particles with glycopolymer shell and polynucleoside core via RAFT: From micelles to rodsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 6 2009Samuel Pearson Abstract Amphiphilic block copolymers were synthesized via the reversible addition fragmentation chain transfer (RAFT) copolymerisation of 2-methacrylamido glucopyranose (MAG) and 5,- O -methacryloyl uridine (MAU). Homopolymerisations of both monomers using (4-cyanopentanoic acid)-4-dithiobenzoate (CPADB) proceeded with pseudo first order kinetics in a living fashion, displaying linear evolution of molecular weight with conversion and low PDIs. A bimodal molecular weight distribution was observed for PMAU at low conversions courtesy of hybrid behavior between living and conventional free radical polymerization. This effect was more pronounced when a PMAG macroRAFT agent was chain extended with MAU, however, in both cases, good control was attained once the main RAFT equilibrium was established. A stability study on PMAU found that its hydrolysis is diffusion controlled, and is accelerated at physiological pH compared with neutral conditions. Self-assembly of four block copolymers with increasing hydrophobic (PMAU) block lengths produced micelles, which demonstrated an increased tendency to form rods as the PMAU block length increased. Interestingly, none of the block copolymers were surface-active. An initial assessment of PMAU's ability to bind the nucleoside adenosine through base pairing was highly promising, with DSC measurements indicating that adenosine is fully miscible in the PMAU matrix. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 1706,1723, 2009 [source] Poly(ethylene glycol)-based amphiphilic model conetworks: Synthesis by RAFT polymerization and characterizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 22 2008Mariliz Achilleos Abstract Poly(ethylene glycol) (PEG)-containing quasi-model amphiphilic polymer conetworks (APCNs) were prepared by reversible addition fragmentation chain transfer (RAFT) polymerization using ,,,-bis(2-cyanoprop-2-yl dithiobenzoate)-PEG as a bifunctional RAFT macrochain transfer agent (macro-CTA) and stepwise additions of a hydrophobic monomer and a crosslinker (crosslinker: macro-CTA = 10:1, reaction time 24 h). Three different types of monomers, methyl methacrylate (MMA), n -butyl acrylate and styrene, were employed as the hydrophobic monomers, whereas ethylene glycol dimethacrylate, ethylene glycol diacrylate and 1,4-divinylbenzene served as the respective crosslinkers. PEG homopolymer hydrophilic quasi-model networks were also prepared by RAFT-polymerizing the three crosslinkers directly onto the two active ends of the PEG-based macro-CTA. From the three ABA triblock copolymers prepared, the MMA-containing one was obtained at the highest polymerization yields. The crosslinking yields of the three ABA triblock copolymers with the corresponding crosslinkers were higher than those of the PEG-based macro-CTA with the same crosslinkers. The degrees of swelling (DSs) of all conetworks were measured in water and in tetrahydrofuran (THF). The DSs of the APCNs in THF were higher than those in water, whereas the reverse was true for the DSs of the hydrophilic homopolymer networks. Finally, the aqueous DSs of the APCNs were lower than those of the corresponding hydrophilic homopolymer networks. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7556,7565, 2008 [source] Branched polystyrene with abundant pendant vinyl functional groups from asymmetric divinyl monomerJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 18 2008Zhong-Min Dong Abstract Branched polystyrenes with abundant pendant vinyl functional groups were prepared via radical polymerization of an asymmetric divinyl monomer, which possesses a higher reactive styryl and a lower reactive butenyl. Employing a fast reversible addition fragmentation chain transfer (RAFT) equilibrium, the concentration of active propagation chains remained at a low value and thus crosslinking did not occur until a high level of monomer conversion. The combination of a higher reaction temperature (120 °C) and RAFT agent cumyl dithiobenzoate was demonstrated to be optimal for providing both a more highly branched architecture and a higher polymer yield. The molecular weights (Mws) increased with monomer conversions because of the controlled radical polymerization characteristic, whereas the Mw distributions broadened showing a result of the gradual increase of the degree of branching. The evolution of branched structure has been confirmed by a triple detection size exclusion chromatography (TRI-SEC) and NMR technique. Furthermore, the double bonds in the side chains were successfully used for chemical modification reactions. 1H NMR and FTIR measurements reveal that the great mass of pendant vinyl groups were converted to the corresponding objective end-groups. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6023,6034, 2008 [source] Simultaneous reversible addition fragmentation chain transfer and ring-opening polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 9 2008Maude Le Hellaye Abstract The simultaneous ring-opening polymerization (ROP) of ,-caprolactone (,-CL) and 2-hydroxyethyl methacrylate (HEMA) polymerization via reversible addition fragmentation chain transfer (RAFT) chemistry and the possible access to graft copolymers with degradable and nondegradable segments is investigated. HEMA and ,-CL are reacted in the presence of cyanoisopropyl dithiobenzoate (CPDB) and tin(II) 2-ethylhexanoate (Sn(Oct)2) under typical ROP conditions (T > 100 °C) using toluene as the solvent in order to lead to the graft copolymer PHEMA- g -PCL. Graft copolymer formation is evidenced by a combination of size-exclusion chromatography (SEC) and NMR analyses as well as confirmed by the hydrolysis of the PCL segments of the copolymer. With targeted copolymers containing at least 10% weight of PHEMA and relatively small PHEMA backbones (ca. 5,000,10,000 g mol,1) the copolymer grafting density is higher than 90%. The ratio of free HEMA-PCL homopolymer produced during the "one-step" process was found to depend on the HEMA concentration, as well as the half-life time of the radical initiator used. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3058,3067, 2008 [source] Polymerization of N -isopropylacrylamide in the presence of poly(acrylic acid) and poly(methacrylic acid) containing ,-unsaturated end-groupsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 18 2007Ronan Mchale Poly(N -Isopropylacrylamide, NIPAM) propagating radicals add to acrylic acid (AA) macromonomer and methacrylic acid polymer containing unsaturated ,-end-group to respectively give novel graft copolymer (represented as , (AA) and , (NIPAM) units) and addition fragmentation chain transfer (AFCT). [Color figure can be viewed in the online issue, which is available at www.interscience.wiley. com.] [source] Kinetic analysis of the cross reaction between dithioester and alkoxyamine by a Monte Carlo simulation,JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 3 2007Yong Ao Abstract A model reaction of dithioester and alkoxyamine is proposed to probe the reversible addition,fragmentation chain transfer (RAFT) process. The kinetics of the model reaction is analyzed and compared with that of pure alkoxyamine homolysis with a Monte Carlo simulation. Although the pure alkoxyamine obeys the law of persistent radical effect, the model reaction results in higher concentration of the persistent radical during the main period of the reaction. However, for a very fast RAFT process or a very low addition rate constant, the time dependence of the persistent radical concentration is quite close to that of pure alkoxyamine. Furthermore, the cross termination between the intermediate and alkyl radicals causes a retardation effect for the model reaction when the intermediate is relatively long-lived. The Monte Carlo simulation indicates that it is feasible to measure the individual rate constants of the RAFT process, such as the rate constant of addition, with a large excess of alkoxyamine. In addition, the special feature of the system with different leaving groups in the alkoxyamine and dithioester is also discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 374,387, 2007 [source] Latices of poly(fluoroalkyl mathacrylate)- b -poly(butyl methacrylate) copolymers prepared via reversible addition,fragmentation chain transfer polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 3 2007Xiaodong Zhou Abstract Poly(fluoroalkyl mathacrylate)- block -poly(butyl methacrylate) diblock copolymer latices were synthesized by a two-step process. In the first step, a homopolymer end-capped with a dithiobenzoyl group [poly(fluoroalkyl mathacrylate) (PFAMA) or poly(butyl methacrylate) (PBMA)] was prepared in bulk via reversible addition,fragmentation chain transfer (RAFT) polymerization with 2-cyanoprop-2-yl dithiobenzoate as a RAFT agent. In the second step, the homopolymer chain-transfer agent (macro-CTA) was dissolved in the second monomer, mixed with a water phase containing a surfactant, and then ultrasonicated to form a miniemulsion. Subsequently, the RAFT-mediated miniemulsion polymerization of the second monomer (butyl methacrylate or fluoroalkyl mathacrylate) was carried out in the presence of the first block macro-CTA. The influence of the polymerization sequence of the two kinds of monomers on the colloidal stability and molecular weight distribution was investigated. Gel permeation chromatography analyses and particle size results indicated that using the PFAMA macro-CTA as the first block was better than using the PBMA RAFT agent with respect to the colloidal stability and the narrow molecular weight distribution of the F-copolymer latices. The F-copolymers were characterized with 1H NMR, 19F NMR, and Fourier transform infrared spectroscopy. Comparing the contact angle of a water droplet on a thin film formed by the fluorinated copolymer with that of PBMA, we found that for the diblock copolymers containing a fluorinated block, the surface energy decreased greatly, and the hydrophobicity increased. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 471,484, 2007 [source] Polymer having a trithiocarbonate moiety in the main chain: Application to reversible addition,fragmentation chain transfer controlled thermal and photoinduced monomer insertion polymerizationsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 21 2006Suguru Motokucho Abstract A polymer having a trithiocarbonate moiety in its main chain was synthesized with a cyclic, five-membered dithiocarbonate as a building block. The trithiocarbonate in the polymer acted as a reversible addition,fragmentation chain transfer reagent to mediate a controlled insertion polymerization of styrene into the polymer main chain, giving the corresponding sequence-ordered polymer having a well-defined polystyrene segment in the main chain. During the polymerization, the polystyrene segment in the main chain gained its molecular weight, which maintained a linear relationship with the conversion of styrene. The insertion polymerization of styrene was induced not only thermally but also by ultraviolet irradiation. This photoinduced polymerization was well controlled by the trithiocarbonate moiety to give the corresponding polymer, whose structure was virtually the same as that obtained by the thermal polymerization. © 2006 Wiley Periodicals, Inc. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6324,6331, 2006 [source] Synthesis and characterization of core,shell-type polymeric micelles from diblock copolymers via reversible addition,fragmentation chain transferJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 10 2006Ping Zhang Abstract A method was developed to enable the formation of nanoparticles by reversible addition,fragmentation chain transfer polymerization. The thermoresponsive behavior of polymeric micelles was modified by means of micellar inner cores and an outer shell. Polymeric micelles comprising AB block copolymers of poly(N -isopropylacrylamide) (PIPAAm) and poly(2-hydroxyethylacrylate) (PHEA) or polystyrene (PSt) were prepared. PIPAAm- b -PHEA and PIPAAm- b -PSt block copolymers formed a core,shell micellar structure after the dialysis of the block copolymer solutions in organic solvents against water at 20 °C. Upon heating above the lower critical solution temperature (LCST), PIPAAm- b -PHEA micelles exhibited an abrupt increase in polarity and an abrupt decrease in rigidity sensed by pyrene. In contrast, PIPAAm- b -PSt micelles maintained constant values with lower polarity and higher rigidity than those of PIPAAm- b -PHEA micelles over the temperature range of 20,40 °C. Structural deformations produced by the change in the outer polymer shell with temperature cycles through the LCST were proposed for the PHEA core, which possessed a lower glass-transition temperature (ca. 20 °C) than the LCST of the PIPAAm outer shell (ca. 32.5 °C), whereas the PSt core with a much higher glass-transition temperature (ca. 100 °C) retained its structure. The nature of the hydrophobic segments composing the micelle inner core offered an important control point for thermoresponsive drug release and the drug activity of the thermoresponsive polymeric micelles. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3312,3320, 2006 [source] Synthesis of comb-like polystyrene with poly(N -phenyl maleimide- alt-p -chloromethyl styrene) as macroinitiatorJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 6 2006Yan Shi Abstract The copolymerization of N -phenyl maleimide and p -chloromethyl styrene via reversible addition,fragmentation chain transfer (RAFT) process with AIBN as initiator and 2-(ethoxycarbonyl)prop-2-yl dithiobenzoate as RAFT agent produced copolymers with alternating structure, controlled molecular weights, and narrow molecular weight distributions. Using poly(N -phenyl maleimide- alt - p -chloromethyl styrene) as the macroinitiator for atom transfer radical polymerization of styrene in the presence of CuCl/2,2,-bipyridine, well-defined comb-like polymers with one graft chain for every two monomer units of backbone polymer were obtained. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2069,2075, 2006 [source] Macromolecular design via reversible addition,fragmentation chain transfer (RAFT)/xanthates (MADIX) polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 22 2005Sébastien Perrier Abstract Among the living radical polymerization techniques, reversible addition,fragmentation chain transfer (RAFT) and macromolecular design via the interchange of xanthates (MADIX) polymerizations appear to be the most versatile processes in terms of the reaction conditions, the variety of monomers for which polymerization can be controlled, tolerance to functionalities, and the range of polymeric architectures that can be produced. This review highlights the progress made in RAFT/MADIX polymerization since the first report in 1998. It addresses, in turn, the mechanism and kinetics of the process, examines the various components of the system, including the synthesis paths of the thiocarbonyl-thio compounds used as chain-transfer agents, and the conditions of polymerization, and gives an account of the wide range of monomers that have been successfully polymerized to date, as well as the various polymeric architectures that have been produced. In the last section, this review describes the future challenges that the process will face and shows its opening to a wider scientific community as a synthetic tool for the production of functional macromolecules and materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43:5347,5393, 2005 [source] Synthesis of well-defined three-armed polystyrene having thiourethane,isocyanurate as the core structure derived from trifunctional five-membered cyclic dithiocarbonateJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 22 2005Akane Suzuki Abstract The synthesis of a three-armed polymer with an isocyanurate,thiourethane core structure is described. Monofunctional reversible addition,fragmentation chain transfer (RAFT) agent 2 and trifunctional RAFT agent 5 were prepared from mercapto-thiourethane and tris(mercapto-thiourethane), which were obtained from the aminolysis of mono- and trifunctional five-membered cyclic dithiocarbonates, respectively. The radical polymerization of styrene in the presence of 2,2,-azobis(isobutyronitrile) and RAFT agent 2 in bulk at 60 °C proceeded in a controlled fashion to afford the corresponding polystyrene with desired molecular weights (number-average molecular weight = 3000,10,100) and narrow molecular weight distributions (weight-average molecular weight/number-average molecular weight < 1.13). On the basis of the successful results with the monofunctional RAFT agents, three-armed polystyrene with thiourethane,isocyanurate as the core structure could be obtained with trifunctional RAFT agent 5 in a similar manner. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5498,5505, 2005 [source] Controlled radical polymerization of a trialkylsilyl methacrylate by reversible addition,fragmentation chain transfer polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 22 2005M. N. Nguyen Abstract The reversible addition,fragmentation chain transfer (RAFT) polymerization of a hydrolyzable monomer (tert -butyldimethylsilyl methacrylate) with cumyl dithiobenzoate and 2-cyanoprop-2-yl dithiobenzoate as chain-transfer agents was studied in toluene solutions at 70 °C. The resulting homopolymers had low polydispersity (polydispersity index < 1.3) up to 96% monomer conversion with molecular weights at high conversions close to the theoretical prediction. The profiles of the number-average molecular weight versus the conversion revealed controlled polymerization features with chain-transfer constants expected between 1.0 and 10. A series of poly(tert -butyldimethylsilyl methacrylate)s were synthesized over the molecular weight range of 1.0 × 104 to 3.0 × 104, as determined by size exclusion chromatography. As strong differences of hydrodynamic volumes in tetrahydrofuran between poly(methyl methacrylate), polystyrene standards, and poly(tert -butyldimethylsilyl methacrylate) were observed, true molecular weights were obtained from a light scattering detector equipped in a triple-detector size exclusion chromatograph. The Mark,Houwink,Sakurada parameters for poly(tert -butyldimethylsilyl methacrylate) were assessed to obtain directly true molecular weight values from size exclusion chromatography with universal calibration. In addition, a RAFT agent efficiency above 94% was confirmed at high conversions by both light scattering detection and 1H NMR spectroscopy. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5680,5689, 2005 [source] Design strategies for controlling the molecular weight and rate using reversible addition,fragmentation chain transfer mediated living radical polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 15 2005Michael J. Monteiro Abstract Living radical polymerization has allowed complex polymer architectures to be synthesized in bulk, solution, and water. The most versatile of these techniques is reversible addition,fragmentation chain transfer (RAFT), which allows a wide range of functional and nonfunctional polymers to be made with predictable molecular weight distributions (MWDs), ranging from very narrow to quite broad. The great complexity of the RAFT mechanism and how the kinetic parameters affect the rate of polymerization and MWD are not obvious. Therefore, the aim of this article is to provide useful insights into the important kinetic parameters that control the rate of polymerization and the evolution of the MWD with conversion. We discuss how a change in the chain-transfer constant can affect the evolution of the MWD. It is shown how we can, in principle, use only one RAFT agent to obtain a polymer with any MWD. Retardation and inhibition are discussed in terms of (1) the leaving R group reactivity and (2) the intermediate radical termination model versus the slow fragmentation model. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3189,3204, 2005 [source] Dendrimers as scaffolds for multifunctional reversible addition,fragmentation chain transfer agents: Syntheses and polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 23 2004Xiaojuan Hao Abstract The synthesis and characterization of novel first- and second-generation true dendritic reversible addition,fragmentation chain transfer (RAFT) agents carrying 6 or 12 pendant 3-benzylsulfanylthiocarbonylsulfanylpropionic acid RAFT end groups with Z-group architecture based on 1,1,1-hydroxyphenyl ethane and trimethylolpropane cores are described in detail. The multifunctional dendritic RAFT agents have been used to prepare star polymers of poly(butyl acrylate) (PBA) and polystyrene (PS) of narrow polydispersities (1.4 < polydispersity index < 1.1 for PBA and 1.5 < polydispersity index < 1.3 for PS) via bulk free-radical polymerization at 60 °C. The novel dendrimer-based multifunctional RAFT agents effect an efficient living polymerization process, as evidenced by the linear evolution of the number-average molecular weight (Mn) with the monomer,polymer conversion, yielding star polymers with molecular weights of up to Mn = 160,000 g mol,1 for PBA (based on a linear PBA calibration) and up to Mn = 70,000 g mol,1 for PS (based on a linear PS calibration). A structural change in the chemical nature of the dendritic core (i.e., 1,1,1-hydroxyphenyl ethane vs trimethylolpropane) has no influence on the observed molecular weight distributions. The star-shaped structure of the generated polymers has been confirmed through the cleavage of the pendant arms off the core of the star-shaped polymeric materials. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5877,5890, 2004 [source] Synthesis of hydrophilic/CO2 -philic poly(ethylene oxide)- b -poly(1,1,2,2-tetrahydroperfluorodecyl acrylate) block copolymers via controlled/living radical polymerizations and their properties in liquid and supercritical CO2JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 10 2004Zhi Ma Abstract Hydrophilic/CO2 -philic poly(ethylene oxide)- b -poly(1,1,2,2-tetrahydroperfluorodecyl acrylate) block copolymers were synthesized via reversible addition,fragmentation chain transfer (RAFT) polymerization, iodine transfer polymerization (ITP), and atom transfer radical polymerization (ATRP) in the presence of either degenerative transfer agents or a macroinitiator based on poly(ethylene oxide). In this work, both RAFT and ATRP showed higher efficiency than ITP for the preparation of the expected copolymers. More detailed research was carried out on RAFT, and the living character of the polymerization was confirmed by an ultraviolet (UV) analysis of the SC(S)Ph or SC(S)SC12H25 end groups in the polymer chains. The quantitative UV analysis of the copolymers indicated a number-average molecular weight in good agreement with the value determined by 1H NMR analysis. The properties of the macromolecular surfactants were investigated through the determination of the cloud points in neat liquid and supercritical CO2 and through the formation of water-in-CO2 emulsions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2405,2415, 2004 [source] Controlled, radical reversible addition,fragmentation chain-transfer polymerization in high-surfactant-concentration ionic miniemulsionsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 4 2004J. B. McLeary Abstract Living free-radical polymerization of methacrylate and styrenic monomers with ionic surfactants was carried out with reversible addition,fragmentation chain transfer in miniemulsion with different surfactant types and concentrations. The previously reported problem of phase separation was found to be insignificant at higher surfactant concentrations, and control of the molar mass and polydispersity index was superior to that of published miniemulsion systems. Cationic and anionic surfactants were used to examine the validity of the argument that ionic surfactants interfere with transfer agents. Ionic surfactants were suitable for miniemulsion polymerization under certain conditions. The colloidal stability of the miniemulsions was consistent with the predictions of a specific model. The living character of the polymer that comprised the latex material was shown by its transformation into block copolymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 960,974, 2004 [source] Living free-radical polymerization (reversible addition,fragmentation chain transfer) of 6-[4-(4,-methoxyphenyl)phenoxy]hexyl methacrylate: A route to architectural control of side-chain liquid-crystalline polymersJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 19 2003Xiaojuan Hao Abstract Side-chain liquid-crystalline polymers of 6-[4-(4,-methoxyphenyl)phenoxy]hexyl methacrylate with controlled molecular weights and narrow polydispersities were prepared via reversible addition,fragmentation chain transfer (RAFT) polymerization with 2-(2-cyanopropyl) dithiobenzoate as the RAFT agent. Differential scanning calorimetry studies showed that the polymers produced via the RAFT process had a narrower thermal stability range of the liquid-crystalline mesophase than the polymers formed via conventional free-radical polymerization. In addition, a chain length dependence of this stability range was found. The generated RAFT polymers displayed optical textures similar to those of polymers produced via conventional free-radical polymerization. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2949,2963, 2003 [source] One-Pot Synthesis of Micelles with a Cross-Linked Poly(acrylic acid) CoreMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 2 2006Genhua Zheng Abstract Summary: Stable micelles with polystyrene (PS) as a shell and cross-linked poly[(acrylic acid)- co -(ethylene glycol diacrylate)] as a core have been successfully prepared by reversible addition fragmentation chain transfer (RAFT) copolymerization of acrylic acid and ethylene glycol diacrylate in a selective solvent with PS-SC(S)Ph as a RAFT agent. For the preparation of stable micelles, the RAFT polymerizations are carried out in different solvents: benzene, cyclohexane, and mixtures of tetrahydrofuran and cyclohexane. The monomer/PS-SC(S)Ph molar ratio and molecular weight of the macro-RAFT agent, PS-SC(S)Ph, influence the RAFT polymerization and the formation of micelles. Block copolymerization in selective solvent with the RAFT agent. [source] Acrylonitrile-Butadiene Rubber (NBR) Prepared via Living/Controlled Radical Polymerization (RAFT)MACROMOLECULAR RAPID COMMUNICATIONS, Issue 18 2010Andreas Kaiser Abstract In the current work we present results on the controlled/living radical copolymerization of acrylonitrile (AN) and 1,3-butadiene (BD) via reversible addition fragmentation chain transfer (RAFT) polymerization techniques. For the first time, a solution polymerization process for the synthesis of nitrile butadiene rubber (NBR) via the use of dithioacetate and trithiocarbonate RAFT agents is described. It is demonstrated that the number average molar mass, , of the NBR can be varied between a few thousand and 60,000,g,·,mol,1 with polydispersities between 1.2 and 2.0 (depending on the monomer to polymer conversion). Excellent agreement between the experimentally observed and the theoretically expected molar masses is found. Detailed information on the structure of the synthesized polymers is obtained by variable analytical techniques such as infrared spectroscopy (IR), nuclear magnetic resonance (NMR) spectroscopy, differential scanning calorimetry, and electrospray ionization-mass spectrometry (ESI-MS). [source] Synthesis of Multiblock Polymer Containing Narrow Polydispersity BlocksMACROMOLECULAR RAPID COMMUNICATIONS, Issue 1 2006Jian Hong Abstract Summary: We have developed a new strategy to prepare multiblock polymers and copolymers via one- or two-step polymerization using a polymerizable cyclic trithiocarbonate (CTTC), 4,7-diphenyl-[1,3]dithiepane-2-thione. CTTC undergoes ring-opening process to incorporate a trithiocarbonate moiety. The trithiocarbonate moiety in turn, functions as a reversible addition fragmentation chain transfer (RAFT) agent. Through this mechanism, multiblock polystyrenes and polystyrene- block - poly(butyl acrylate) copolymers containing various narrow polydispersity blocks can be prepared. Integrated process of ring-opening and RAFT polymerizations involving cyclic trithiocarbonates. [source] Chain Transfer and Efficiency of End-Group Introduction in Free Radical Polymerization of Methyl Methacrylate in the Presence of Poly(methyl methacrylate) MacromonomerMACROMOLECULAR RAPID COMMUNICATIONS, Issue 22 2004Kazuki Miyake Abstract Summary: Experimental and modeling studies of addition,fragmentation chain transfer (AFCT) during radical polymerization of methyl methacrylate in the presence of poly(methyl methacrylate) macromonomer with 2-carbomethoxy-2-propenyl , -ends (PMMA-CO2Me) at 60,°C are reported. The results revealed that AFCT involving PMMA-CO2Me formed in situ during methyl methacrylate polymerization has a negligible effect on the molecular weight distribution. [source] | ||||||||||||||||||||||