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Free Radical Polymerization (free + radical_polymerization)
Selected AbstractsChain 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] "Living" Free Radical Polymerization in Tubular Reactors.MACROMOLECULAR REACTION ENGINEERING, Issue 6 2007Abstract This is the first of a series of works aiming at developing a tool for designing "living" free radical polymerization processes in tubular reactors, in order to achieve tailor-made MWDs. A mathematical model of the nitroxide-mediated controlled free radical polymerization is built and implemented to predict the complete MWD. It is shown that this objective may be achieved accurately and efficiently by means of the probability generating function (pgf) transformation. Comparison with experimental data is good. The potential of the resulting model for optimization activities involving the complete MWD is also shown. [source] Free Radical Polymerization of Acrylonitrile in Green Ionic LiquidsMACROMOLECULAR SYMPOSIA, Issue 1 2004Liang Cheng Abstract Free radical polymerization of acrylonitrile (AN) in ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), 2,2;m1-azobisisobutyronitrile (AIBN) as initiator was investigated. Early investigations on polymerizations using ionic liquids indicate that they serve as especially good solvents to achieve high molecular weight polymers. Free radical polymerizations result in higher molecular weight polymers, for ionic liquids have low chain transfer constants and act to stabilize the active radical during the process of polymerization. The thermal stability of polymers synthesized in ionic liquids have be improved obviously than that in traditional solvents. [source] Stable Free Radical Polymerization in Emulsion: Modeling the Thermodynamics of Monomer Transfer between Droplets and ParticlesMACROMOLECULAR THEORY AND SIMULATIONS, Issue 2-3 2008Jordan Pohn Abstract A mathematical model is developed from polymer solution thermodynamics and stable free radical polymerization kinetics to predict the monomer swelling behavior of large droplets and small particles that coexist during the seeded polymerization of styrene in emulsion. This model is used to predict the sensitivity of polymerized latex stability (based on the persistence of large particles) to changes in seed particle size and final latex target molecular weight. Simulation results show that the use of small seed particles (diameter,,,50 nm) in recipe formulation will lead to polymerization occurring preferentially in the large droplets, and offers theoretical evidence that TEMPO-mediated ab initio emulsion polymerizations will not be feasible. Our predictions are consistent with experimental evidence suggesting that the presence of large particles leads to the formation of undesirable coagulum in the final product. [source] Effect of Intramolecular Transfer to Polymer on Stationary Free Radical Polymerization of Alkyl Acrylates, 2,MACROMOLECULAR THEORY AND SIMULATIONS, Issue 2 2006Improved Consideration of Termination Abstract Summary: Procedures are developed to estimate kinetic rate coefficients from available rate data for the free radical solution polymerization of butyl acrylate at 50,°C. The analysis is based upon a complete mechanistic set that includes the formation of mid-chain radicals through backbiting and their subsequent reaction, and contains no assumptions on how the rate coefficient for cross-termination of mid-chain and end-chain radicals is related to the two homo-termination rate coefficients. After a thorough statistical analysis, the results of the fitting are combined with other recent literature data to provide a complete set of individual rate coefficients for the butyl acrylate system. Monomer addition to a mid-chain radical is estimated to be slower than addition to a chain-end radical by a factor of more than 400. The termination of two mid-chain radicals is estimated to be two orders of magnitude slower than termination of two end-chain radicals, with the cross-termination rate coefficient close to the geometric mean. Formation of a mid-chain radical by intramolecular chain transfer to polymer by a chain-end radical. [source] Transient Behavior and Gelation of Free Radical Polymerizations in Continuous Stirred Tank ReactorsMACROMOLECULAR THEORY AND SIMULATIONS, Issue 4 2005Rolando C. S. Dias Abstract Summary: Using the authors' previously developed method for the general kinetic analysis of non-linear irreversible polymerizations, the simulation of free radical homogeneous polymerization systems with terminal branching and chain transfer to polymer has been carried out for continuous stirred tank reactors. Its improved accuracy on the numerical evaluation of generating functions has been exploited in order to perform their numerical inversion and chain length distributions could also be estimated with or without the presence of gel. A comparison with alternative techniques emphasizing the effect of their simplifying assumptions on the accuracy of calculations is also presented. Predicted CLD before gelation (t,=,1 h), after gelation (t,=,15 h, steady state), and close to gel point for a free radical polymerization with transfer to polymer in a CSTR with ,,=,60 min. [source] Free Radical Polymerization of Acrylonitrile in Green Ionic LiquidsMACROMOLECULAR SYMPOSIA, Issue 1 2004Liang Cheng Abstract Free radical polymerization of acrylonitrile (AN) in ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), 2,2;m1-azobisisobutyronitrile (AIBN) as initiator was investigated. Early investigations on polymerizations using ionic liquids indicate that they serve as especially good solvents to achieve high molecular weight polymers. Free radical polymerizations result in higher molecular weight polymers, for ionic liquids have low chain transfer constants and act to stabilize the active radical during the process of polymerization. The thermal stability of polymers synthesized in ionic liquids have be improved obviously than that in traditional solvents. [source] Morphology and mechanical properties of impact modified polypropylene blendsPOLYMER ENGINEERING & SCIENCE, Issue 11 2008Nathan Tortorella Isotactic polypropylene (PP) has been reactively blended with various grades of an ethylene,octene copolymer (EOC) in a twin-screw extruder. Free radical polymerization of styrene and a multifunctional acrylate during melt extrusion has resulted in an enhancement of mechanical properties over the binary blend. The reactive blend exhibits a notched Izod impact strength over 12 times that of pure polypropylene and greater than double the performance of the binary blend. Electron microscopy shows that by grafting onto the polymers, elastomer particle size and interparticle distance decrease, while particle shape becomes less spherical. The acrylate is crucial to achieve superior performance, as infrared spectra correlate an increase in graft yield to improvements in stress,strain behavior and impact strength. In addition, melt flow index (MFI) and melt strength data indicate a reduction in unwanted side reactions of polypropylene and the presence of long-chain branching. Dynamic-mechanical analysis reveals that the reaction promotes miscibility between polypropylene and the EOC and reduces molecular mobility at their glass-transition temperatures. Mechanical properties, graft yield, and MFI are shown to be highly dependent upon the elastomer's concentration, density, and molecular weight, initiator and monomer concentration, as well as processing temperature. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers [source] Free radical polymerization of methyl methacrylate initiated by the diphosphine Mo(0) complexesAPPLIED ORGANOMETALLIC CHEMISTRY, Issue 11 2006Ayfer Mente Abstract The polymerization of methyl methacrylate MMA catalyzed by [Mo(CO)4L2] [L2 = diphenylphosphinomethane (dppm), diphenylphosphinoethane (dppe) or diphenylphosphinopropane (dppp)] has been studied. The activity of these single-component catalysts depends on the length of the (CH2)n bridge of diphosphine ligand. Thus, the dppm derivative displays higher activity than dppe or dppp ligands. These complexes, as free radical initiators, afforded the methyl methacrylate polymerization in chlorinated solvents. The mechanism of the polymerization was discussed and a radical mechanism was proposed. Copyright © 2006 John Wiley & Sons, Ltd. [source] Free Radical Polymerization of Acrylonitrile in Green Ionic LiquidsMACROMOLECULAR SYMPOSIA, Issue 1 2004Liang Cheng Abstract Free radical polymerization of acrylonitrile (AN) in ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF4]), 2,2;m1-azobisisobutyronitrile (AIBN) as initiator was investigated. Early investigations on polymerizations using ionic liquids indicate that they serve as especially good solvents to achieve high molecular weight polymers. Free radical polymerizations result in higher molecular weight polymers, for ionic liquids have low chain transfer constants and act to stabilize the active radical during the process of polymerization. The thermal stability of polymers synthesized in ionic liquids have be improved obviously than that in traditional solvents. [source] Evaluation of the potential of polymeric carriers based on chitosan- grafted -polyacrylonitrile in the formulation of drug delivery systemsJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2010A. A. Sarhan Abstract Graft copolymerization of chitosan with acrylonitrile (AN) was carried out by free radical polymerization using KMnO4 and oxalic acid as a combined redox initiator system. Graft copolymerization was confirmed by Fourier transform infrared spectra (FTIR), proton nuclear magnetic resonance spectra (1H-NMR), thermal gravimetric analysis (TGA) measurements, and wide angle X-ray diffraction (WAXD). In addition, further modification of the cyano groups of the grafted copolymers was performed by partial hydrolysis into carboxylic function groups with various extents. The extent of hydrolysis was monitored using FTIR spectroscopy. The potential of the hydrolyzed and unhydrolyzed grafted copolymers as polymeric carriers for drug delivery systems was extensively studied by preparation of tablets incorporated with methyl orange (MO) as a drug model. In vitro drug release was carried out in simulated gastric and intestinal conditions. The effects of grafting percentage (GP) and the extent of hydrolysis on the release kinetics were evaluated. Release continued up to 24 h for both hydrolyzed and unhydrolysed chitosan- g -PAN copolymers. The nature of drug transport through the polymer matrices was studied by comparing with power law or Kormeyer-Peppas equation. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] Analyzing the real advantages of bifunctional initiator over monofunctional initiator in free radical polymerizationJOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2010Paula F. de M. P. B. Machado Abstract Monofunctional initiators are extensively used in free radical polymerization. To enhance productivity, a higher temperature is usually used; however, this leads to lower molecular weights. Bifunctional initiators can increase the polymerization rate without decreasing the average molecular weight and this can be desirable. A bifunctional initiator is an important issue to be investigated, and it is of great interest to industries. The objective of this work is to study polymerization reactions with mono- and bi-functional initiators through comprehensive mathematical models. Polystyrene is considered as case study. This work collects and presents some experimental data available in literature for polymerization using two different types of bifunctional initiators. Model prediction showed good agreement with experimental data. It was observed that the initial initiator concentration has a huge impact on the efficiency of initiators with functionality bigger than one and high concentrations of bifunctional initiator make the system behave as if it were a system operating with monofunctional initiator. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] Synthesis, characterization, and antimicrobial properties of novel quaternary amine methacrylate copolymersJOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2008Supriya Punyani Abstract A novel amine methacrylate monomer trimethylolpropane trimethacrylate,piperazine,ethyleneglycol dimethacrylate (TMPTMA-PPZ-EGDMA) was synthesized by amination of trimethylolpropane trimethacrylate (TMPTMA) with excess of piperazine (PPZ) followed by reaction with ethyleneglycol dimethacrylate (EGDMA). Copolymerization of TMPTMA-PPZ-EGDMA with 2-hydroxyethyl methacrylate (HEMA) was carried out by free radical polymerization using ammonium persulfate (APS) and N,N,N,,N,-tetramethyl ethylenediamine (TEMED) as a redox initiator. The copolymers obtained were then quaternized with 1-iodooctane. The monomers were characterized by FTIR and 1H NMR spectral studies. The molecular weights and polydispersity values of the monomers were determined with gel permeation chromatography. Quaternized copolymers containing more than 20% amine methacrylate monomer showed microporosity in the range of 9.9,10.4 ,m. The antibacterial activity of the quaternized copolymers against Escherichia coli and Staphylococcus aureus was studied using UV,vis spectrophotometer and scanning electron microscopy. Quaternized copolymers showed broad-spectrum contact-killing antibacterial properties without releasing any active agent as checked by iodide selective ion meter. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Influence of the copolymer architecture and composition on the response and mechanical properties of pH-sensitive fibersJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2007Anasuya Sahoo Abstract A series of copolymers based on acrylonitrile (AN) and acrylic acid (AA) with varying architecture and composition were synthesized using free radical polymerization. The distribution of monomers in the copolymer chains could be successfully controlled by regulating the addition of more reactive monomer (AA). Copolymers having nearly random distribution of comonomer moieties to block type distribution with different composition (10,50 mol % AA) were synthesized to investigate the effect of polymer architecture and composition on pH response and mechanical properties of resultant structures. These copolymers were solution spun from dimethylformamide-water system, drawn in coagulation bath, and annealed at 120°C for 2 h to make pH-sensitive fibers which were structurally stable without the need of chemical crosslinking. The fibers from block copolymers showed significantly better tensile strength (34.3 MPa), higher retractive forces (0.26 MPa), and enhanced pH response (swelling 3890%) in comparison with fibers from random copolymer (13.55 MPa, 0.058 MPa, and 1723%, respectively). The tensile strength and retractive forces could be further improved to a value of 72 MPa and 0.36 MPa, respectively, by changing the composition of the block copolymer while retaining the swelling percentage similar to the random copolymer mentioned above. It is proposed that on processing to fibers, the block copolymers could form a segregated domain structure with separate domains of AA and AN, where AN domains were responsible for high structural integrity by providing connectivity among polymer chains, while AA domains showed improved response to changing pH of the environment. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007 [source] Radical polymerization of n -butyl methacrylate initiated by stibonium ylideJOURNAL OF APPLIED POLYMER SCIENCE, Issue 4 2007Sumita Srivastava Abstract 1,2,3,4-Tetraphenylcyclopentadiene triphenyl stibonium ylide initiated radical polymerization of n -butyl methacrylate (n -BMA) in dioxane at (60 ± 0.2)°C for 90 min under nitrogen atmosphere has been carried out. The system follows nonideal kinetics, i.e., Rp , [ylide]0.2 [n -BMA]1.8. The value of k/kt and overall energy of activation have been computed as 0.133 × 10,2 L mol,1 s,1, 33 kJ/mol, respectively. The FTIR spectrum shows a band at 1745 cm,1 due to acrylate group of n -BMA. The 1H NMR spectrum shows a peak of two magnetically equivalent protons of methylene group at 2.1 , ppm. The DSC curve shows glass transition temperature (Tg) as 41°C. The presence of six hyperfine lines in ESR spectrum indicates that the system follows free radical polymerization and the initiation is brought about by phenyl radical. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2457,2463, 2007 [source] Characterization of the physicochemical, antimicrobial, and drug release properties of thermoresponsive hydrogel copolymers designed for medical device applicationsJOURNAL OF BIOMEDICAL MATERIALS RESEARCH, Issue 2 2008David S. Jones Abstract In this study, a series of hydrogels was synthesized by free radical polymerization, namely poly(2-(hydroxyethyl)methacrylate) (pHEMA), poly(4-(hydroxybutyl)methacrylate) (pHBMA), poly(6-(hydroxyhexyl)methacrylate) (pHHMA), and copolymers composed of N -isopropylacrylamide (NIPAA), methacrylic acid (MA), NIPAA, and the above monomers. The surface, mechanical, and swelling properties (at 20 and 37°C, pH 6) of the polymers were determined using dynamic contact angle analysis, tensile analysis, and thermogravimetry, respectively. The Tg and lower critical solution temperatures (LCST) were determined using modulated DSC and oscillatory rheometry, respectively. Drug loading of the hydrogels with chlorhexidine diacetate was performed by immersion in a drug solution at 20°C ( New straightforward route for the synthesis of some 1-oxa-2-silacyclopentane derivativesJOURNAL OF HETEROCYCLIC CHEMISTRY, Issue 2 2008Kazem D. Safa Tris(dimethylsilyl)methyl lithium, (HSiMe2)3CLi, reacts with allyl, phenyl, benzyl, n -propyl and n -butyl glycidyl ethers in THF at -5 °C to give 1-oxa-2-silacyclopentane derivatives. It seems that ring closure is facilitated by conversion of the SiH bond into an SiO bond. Glycidyl methacrylate (GM) random copolymers with 4-methyl- and 4-methoxy styrene, synthesized by solution free radical polymerization at 70 (±1) °C with ,,,-azobis(isobutyronitrile) (AIBN) as initiator, contained pendant epoxide functions. Treatment of these with (HSiMe2)3CLi did not lead to intramolecular nucleophilic attack as found for simple epoxides. [source] Characterization of crosslinking effects on the physicochemical and drug diffusional properties of cationic hydrogels designed as bioactive urological biomaterialsJOURNAL OF PHARMACY AND PHARMACOLOGY: AN INTERNATI ONAL JOURNAL OF PHARMACEUTICAL SCIENCE, Issue 10 2005David S. Jones This study examined the effects of concentration and type of crosslinker (tetraethyleneglycol diacrylate, TEGDA; diethyleneglycol dimethacrylate, DEGDMA; and polyethyleneglycol dimethacrylate, PEGDMA) on the mechanical and drug diffusional properties of hydrogels that had been selected as candidate coatings for bioactive medical devices. Hydrogels (dimethylaminoethylmethacrylate-covinylpyrrolidone; 1:1) were prepared by free radical polymerization and characterized using tensile analysis, dynamic contact angle analysis and analysis of swelling at pH 6.0. The release of fusidic acid and chlorhexidine was evaluated using buffered medium at pH 6.0 and, in addition, using dissolution medium that had been buffered to pH 9 in the presence and absence of elevated concentrations of calcium, representative of urinary encrustation. Crosslinker concentration, but not type, affected the advancing and receding contact angles. Conversely, both crosslinker type and concentration affected the mechanical and swelling properties of the hydrogels. Maximum swelling and elongation at break were associated with the PEGDMA-crosslinked hydrogels whereas TEGDA-crosslinked hydrogels exhibited the maximum ultimate tensile strength and Young's modulus. Drug release from all systems occurred by diffusion. The mass of chlorhexidine and fusidic acid released was dependent on crosslinker type and concentration, with hydrogels crosslinked with PEGDMA offering the greatest mass of drug released at each sampling period. The mass of fusidic acid but not chlorhexidine released at pH 9.0 in a calcium augmented medium was lower than that released in the same medium devoid of elevated calcium, due to the formation of the poorly soluble calcium salt. In conclusion, this study has uniquely examined the effects of crosslinker type and concentration on physicochemical and drug release properties essential to the clinical and non-clinical performance of bioactive hydrogels for medical device application. [source] Free radical and nitroxide mediated polymerization of hydroxy,functional acrylates prepared via lipase,catalyzed transacylation reactionsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 12 2010Dragos Popescu Abstract 3-Hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-methyl-3-hydroxypropyl acrylate, 2-hydroxypropyl acrylate, neopentyl glycol acrylate, glyceryl acrylate, and dihydroxyhexyl acrylate were prepared via transacylation reaction of methyl acrylate with diols and triols catalyzed by Candida antarctica lipase B. After removal of the enzyme by filtration and the methyl acrylate by distillation, the monomers were polymerized via free radical polymerization (FRP) with azobisisobutyronitrile as initiator and nitroxide mediated polymerization (NMP) employing BlocbuilderÔ alkoxyamine initiator and SG-1 free nitroxide resulting in hydroxy functional poly(acrylates). The NMP kinetics are discussed in detail. In addition, the polymers obtained by FRP and NMP are compared and the results are related to the amount of bisacrylates that are present in the initial monomer mixtures resulting from the transacylation reactions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2610,2621, 2010 [source] Tailoring the liquid crystalline property via controlling the generation of dendronized polymers containing azobenzene mesogenJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 5 2010Chang-An Yang Abstract The first- and second-generation dendronized polymers containing azobenzene mesogen were designed and successfully synthesized via free radical polymerization. The chemical structures of the monomers were confirmed by elemental analysis, 1H NMR, and 13C NMR. The molecular characterizations of the polymers were performed with 1H NMR and gel permeation chromatography. The phase structures and transition behaviors were studied using differential scanning calorimetry, polarized light microscopy, and small-angle X-ray scatter experiments. The experiment results revealed that the first-generation dendronized polymer exhibited liquid crystalline behavior of the conventional side-chain liquid crystalline polymer with azobenzene mesogen, that is, the polymer exhibited smectic phase structure at lower temperature and nematic phase structure at higher temperature. However, the second-generation dendronized polymers exhibited more versatile intriguing liquid crystalline structures, namely smectic phase structure at lower temperature and columnar nematic phase structure at higher temperature, and moreover, the phase structure still remained before the decomposition temperature. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1149,1159, 2010 [source] Synthesis of polymeric 1-iminopyridinium ylides as photoreactive polymersJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 4 2010Daniel Klinger Abstract Two synthetic routes to polymeric 1-imino pyridinium ylides as new photoreactive polymeric architectures were investigated. In the first approach, polymerization of newly synthesized 1-imino pyridinium ylide containing monomers yielding their polymeric analogues was achieved by free radical polymerization. Alternatively, reactive precursor polymers were synthesized and converted into the respective 1-imino pyridinium ylide polymers by polymer analogous reactions on reactive precursor polymers. Quantitative conversion of the reactive groups was achieved with pentafluorophenyl ester containing polymers and newly synthesized photoreactive amines as well as by the reaction of poly(4-vinylbenzoyl azide) with a photoreactive alcohol. The polymers obtained by both routes were examined regarding their photoreaction products and kinetics in solution as well as in thin polymer films. Contact angle measurements of water on the polymer films before and after irradiation showed dramatic changes in the hydrophilicity of the polymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 832,844, 2010 [source] Mapping the characteristics of the radical ring-opening polymerization of a cyclic ketene acetal towards the creation of a functionalized polyesterJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 18 2009Peter Plikk Abstract Radical ring-opening polymerization of cyclic ketene acetals is a means to achieve novel types of aliphatic polyesters. 2-methylene-1,3-dioxe-5-pene is a seven-membered cyclic ketene acetal containing an unsaturation in the 5-position in the ring structure. The double bond functionality enables further reactions subsequent to polymerization. The monomer 2-methylene-1,3-dioxe-5-pene was synthesized and polymerized in bulk by free radical polymerization at different temperatures, to determine the structure of the products and propose a reaction mechanism. The reaction mechanism is dependent on the reaction temperature. At higher temperatures, ring-opening takes place to a great extent followed by a new cyclization process to form the stable five-membered cyclic ester 3-vinyl-1,4-butyrolactone as the main reaction product. Thereby, propagation is suppressed and only small amounts of other oligomeric products are formed. At lower temperatures, the cyclic ester formation is reduced and oligomeric products containing both ring-opened and ring-retained repeating units are produced at higher yield. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4587,4601, 2009 [source] Dual responsive poly(N -isopropylacrylamide) hydrogels having spironaphthoxazines as pendant groupsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 13 2009Erandimala U. Kulawardana Abstract Stimuli responsive hydrogels (PNIPAAm-MSp) with a thermoresponsive backbone and photochromic pendant groups were synthesized via free radical polymerization using N -isopropylacrylamide, modified spironaphthoxazines with a polymerizable double bond (MSp) as photochromic monomer, the crosslinker N,N,-methylenebis(acrylamide) and the initiator 2,2,-azobis(isobutyronitrile) in dimethylsulfoxide. The polymers are dual responsive, in that poly(N -isopropylacrylamide) (PNIPAAm) responds to temperature changes whereas the pendant spironaphthoxazines respond to light. Irradiation enhanced the water absorption of the polymers while increases in temperature decreased it. The irradiated PNIPAAm-MSp showed best water absorption at 0 °C (Q = 3.25) while water desorbed at higher temperatures (35 °C; Q = 0.30); where Q is the amount of water absorbed by a gram of dry polymer. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3318,3325, 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] The role of mid-chain radicals in acrylate free radical polymerization: Branching and scissionJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 23 2008Thomas Junkers Abstract The past 5 years have seen a significant increase in the understanding of the fate of so-called mid-chain radicals (MCR), which are formed during the free radical polymerization of monomers that form highly reactive propagating radicals and contain an easily abstractable hydrogen atom. Among these monomers, acrylates are, beside ethylene, among the most prominent. Typically, a secondary propagating acrylate-type macroradical (SPR) can easily transfer its radical functionality via a six-membered transition state to a position within the polymer chain (in a so-called backbiting reaction), creating a tertiary MCR. Alternatively, the radical function can be transferred intramolecularly to any position within the chain (also forming an MCR) or intermolecularly to another polymer strand. This article aims at providing a comprehensive overview of the up-to-date knowledge about the rates at which MCRs are formed, their secondary reactions as well as the consequences of their occurrence under variable reaction conditions. We explore the latest aspects of their detection (via electron spin resonance spectroscopy) as well as the characterization of the polymer structures to which they lead (via high resolution mass spectrometry). The presence of MCRs leads to the formation of branched polymers and the partial formation of polymer networks. They also limit the measurement of kinetic parameters (such as the SPR propagation rate coefficient) with conventional methods. However, their occurrence can also be used as a synthetic handle, for example, the high-temperature preparation of macromonomers. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7585,7605, 2008 [source] Introduction of pH-sensitivity into mechanically strong nanoclay composite hydrogels based on N -isopropylacrylamideJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 19 2008Siddharthya K. Mujumdar Abstract pH-sensitive nanoclay composite hydrogels based on N -isopropylacrylamide (NIPA) were synthesized by copolymerization with cationic and anionic comonomers. Laponite nanoclay particles served as multifunctional crosslinkers, producing hydrogels with exceptionally high mechanical strengths, as measured by elongation at break. Cationic copolymer gels based on NIPA and dimethylaminoethylmethacrylate were prepared by aqueous free radical polymerization, adopting a procedure reported by Haraguchi (Adv Mater 2002, 14, 1120,1124). Without modification, this technique failed to produce anionic copolymer gels of NIPA and methacrylic acid (MAA), due to flocculation of clay particles. Three methods were conceived to incorporate acidic MAA into nanoclay hydrogels. First, NIPA was copolymerized with sodium methacrylate under dilute conditions, producing hydrogels with good pH-sensitivity but weak mechanical characteristics. Second, NIPA was copolymerized with methyl methacrylate, which was then hydrolyzed to generate acid sidegroups, yielding hydrogels that were much stronger but less pH sensitive. Third, NIPA was copolymerized with MAA following modification of the nanoclay surface with pyrophosphate ions. The resulting hydrogels exhibited both strong pH-sensitivities at 37 °C and excellent tensile properties. Optical transparency changed during polymerization, depending on hydrophobicity of the components. This work increases the diversity and functionality of nanoclay hydrogels, which display certain mechanical advantages over conventionally crosslinked hydrogels. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6630,6640, 2008 [source] Styrene 4-vinylbenzocyclobutene copolymer for microelectronic applicationsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 8 2008Ying-Hung So Abstract Styrene and 4-vinylbenzocyclobutene (vinyl-BCB) random copolymers were prepared by free radical polymerization and studied for suitability as a dielectric material for microelectronic applications. The percentage of vinyl-BCB in the copolymer was varied from 0 to 26 mol % to optimize the physical and mechanical properties of the cured copolymer as well as the cost. Copolymer in which 22 mol % of vinyl-BCB was incorporated along with styrene produced a thermoset polymer which, after cure, did not show a Tg before decomposition at about 350 °C. The polymeric material has a very low dielectric constant, dissipation factor, and water uptake. The fracture toughness of the copolymer was improved with the addition of 20 wt % of a star-shaped polystyrene- block -polybutadiene. Blends of the poly(styrene- co -vinyl-BCB) with the thermoplastic elastomer provided material that maintained high Tg of the cured copolymer with only a slight decrease in thermal stability. The crosslinked styrenic polymer and toughened blends possess many properties that are desirable for high frequency-high speed mobile communication applications. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2799,2806, 2008 [source] Energetic polymer salts from 1-vinyl-1,2,4-triazole derivativesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 7 2008Hong Xue Abstract Energetic polymers salts from 1-vinyl-1,2,4-triazole derivatives have been synthesized via free radical polymerization of 1-vinyl-1,2,4-triazolium monomer salts or by protonation of poly(1-vinyl-1,2,4-triazole) with inorganic or organic acids. Standard enthalpies of formation of the new monomer salts were calculated using the computationally feasible DFT(B3LYP) and MP2 methods in conjunction with an empirical approach based on densities of salts. Compared with the monomer salts, the polymer salts have good thermal properties with high densities > 1.5 g cm,3. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2414,2421, 2008 [source] Synthesis of PS and PDMAEMA mixed polymer brushes on the surface of layered silicate and their application in pickering suspension polymerizationJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 24 2007Yongfang Yang Abstract An ammonium free radical initiator was ion exchanged onto the surface of clay layers. Polystyrene (PS) and poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) mixed polymer brushes on the surface of clay layers were prepared by in situ free radical polymerization. PS colloid particles armored by clay layers with mixed polymer brushes were prepared by Pickering suspension polymerization. Transmission electron microscopy (TEM), atomic force microscopy (AFM), and scanning electron microscopy (SEM) were used to characterize the structure and morphology of the colloid particles. Clay layers on the surface of PS colloid particles can be observed. Because of the cationic nature of the PDMAEMA brushes the colloid particles have positive zeta potentials at low pH values. X-ray photoelectron spectroscopy (XPS) was used to analyze the surface of the colloid particles. N1s binding energy of PDMAEMA chains on the surface of clay layers was detected by XPS. The two peaks of the N1s binding energy indicate two different nitrogen environments on the surface of clay layers. The peak with a lower binding energy is characteristic of neutral nitrogen on PDMAEMA chains, and the peak with a higher binding energy is attributed to protonated nitrogen on PDMAEMA chains. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5759,5769, 2007 [source] PS/PMMA mixed polymer brushes on the surface of clay layers: Preparation and application in polymer blendsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 22 2007Jian Zhang Abstract Polystyrene (PS) and poly(methyl methacrylate) (PMMA) mixed polymer brushes on the surface of clay layers were prepared by using in situ free radical polymerization. Free radical initiator molecules with two quaternary ammonium groups at both ends were intercalated into the interlayer spacing of clay layers. The amount of polymer brushes grafted on the surface of clay layers can be controlled by controlling the polymerization time. Thermogravimetric analysis, X-ray diffraction, and high-resolution transmission electron microscope results indicated successful preparation of the mixed polymer brushes on the surface of clay layers. The kinetics of the grafting of the monomers was also studied. The mixed polymer brushes on the surface of clay layers were used as compatibilizers in blends of PS and PMMA. In the blends, the intercalated clay particles tend to locate at the interface of two phases reducing the interfacial tension. In the meanwhile, PMMA homopolymer chains tend to intercalate into clay layers. The driving force for the intercalation is the compatibility between homo-PMMA chains and PMMA brushes on the surface of clay layers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5329,5338, 2007 [source]
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