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1.
By combining frontal polymerization and radical‐induced cationic polymerization, it was possible to cure thick samples of an epoxy monomer bleached by UV light. The effect of the relative amounts of cationic photoinitiator and radical initiator was thoroughly investigated and was related to the front's velocity and its maximum temperature. The materials obtained were characterized by quantitative conversion also in the deeper layers, not reached by UV light. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2066–2072, 2004  相似文献   
2.
The cationic polymerization of styrene in a neutral ionic liquid, 1‐butyl‐3‐methylimidazolium hexafluorophosphate, with a 1‐phenetyl chloride/TiCl4 initiating system is reported. The polymerization proceeds to a high conversion, but an analysis of the matrix‐assisted laser desorption/ionization time‐of‐flight spectra of the polymers indicates that chain transfer is significant, leading to a lack of control over the molecular weight and molecular weight distribution. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3230–3235, 2004  相似文献   
3.
The effective propagation rate constant (kp; averaged over all the propagating active centers) was characterized for solvent‐free cationic photopolymerizations of phenyl glycidyl ether over the entire range of conversions, including the high conversion regime in which mass transfer limitations become important. The profile for the kp as a function of conversion was found to exhibit a constant plateau value at low to intermediate conversions, followed by a monotonic increase above a threshold value of conversion. To explain this trend, it is proposed that at high conversion the diffusional mobility of the photoinitiator counterion is reduced whereas the mobility of the cationic active center remains high because of reactive diffusion. Therefore, with increasing conversion, the average distance between the active centers and counterions may increase, resulting in an increase in the propagation rate constant. The profiles for the kp values were investigated as a function of the temperature, photoinitiator anion, and photoinitiator concentration. As the photoinitiator concentration was increased, the plateau value of the effective propagation rate constant decreased whereas the threshold conversion increased. All of the experimental trends are consistent with the proposed increase in ion separation at high conversions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4409–4416, 2004  相似文献   
4.
3,3′,5,5′‐Tetrakis(2‐chloro‐2‐propyl)biphenyl (biphenyl tetracumyl chloride, BPTCC) and 1,3‐bis[3,5‐bis(2‐chloro‐2‐propyl)phenoxy]propane (diphenoxypropane tetracumyl chloride, DPPTCC) were synthesized as initiators for quasiliving cationic polymerization of isobutylene (IB). In the synthesis of BPTCC, tetrafunctionality was achieved via the coupling of dimethyl 5‐bromoisophthalate (DMBI) using nickel dibromide bis(triphenylphosphine) and zinc in the presence of a base; in the synthesis of DPPTCC, two equivalents of dimethyl 5‐hydroxyisophthalate were linked via reaction with 1,3‐dibromopropane in the presence of potassium carbonate. Both initiators were used to initiate the polymerization of IB under quasiliving cationic polymerization conditions. PIB initiated from BPTCC revealed a chain end/molecule value (as determined by 1H‐NMR) of 3.85, verifying the nearly exclusive production of 4‐arm polyisobutylene (PIB). GPC analysis revealed a narrow peak representing the target four‐arm PIB, with a slight shoulder at high elution volumes (low molecular weights). GPC analysis of the PIB initiated by DPPTCC revealed multimodal distributions, suggesting the formation of two‐, three‐, and four‐arm star polymers during the polymerization. This behavior was attributed to Friedel–Crafts alkylation of the initiator core after the addition of one IB unit, which was activated by the electron‐donating oxytrimethyleneoxy linking moiety. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5942–5953, 2004  相似文献   
5.
The irradiation of hybrid photopolymer systems consisting of a free radically polymerizable multifunctional acrylate monomer and a cationically polymerizable epoxide or oxetane monomer was conducted under conditions where only the free radical polymerization takes place. This results in the formation of a free‐standing polyacrylate network film containing quiescent oxonium ions along with the unreacted cyclic ether monomer. The subsequent application of a point source of heat to the film ignites a cationic ring‐opening frontal polymerization that emanates from that site and propagates to all portions of the irradiated sample. This article examines the impact of various molecular structural and experimental parameters on these novel hybrid frontal polymerizations that produce interpenetrating network polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4331–4340, 2007  相似文献   
6.
Curcumin, a naturally occurring, intensely yellow dye extracted from the spice turmeric, is an efficient photosensitizer for diaryliodonium salt photoinitiators at wavelengths ranging from 340 to 535 nm. With curcumin as a photosensitizer, it is possible to carry out the cationic photopolymerization of a wide variety of epoxide, oxetane, and vinyl monomers with long‐wavelength UV and visible light. An example of the photopolymerization of an epoxide monomer with ambient solar irradiation is provided. Several other curcumin analogues were synthesized, and their use as photosensitizers is examined. With such photosensitizers, the range of spectral sensitivity can be extended well into the visible region of the electromagnetic spectrum. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5217–5231, 2005  相似文献   
7.
Photoinitiated cationic polymerization of mono‐ and bifunctional epoxy monomers, namely cyclohexeneoxide (CHO), 4‐epoxycyclohexylmethyl‐3′,4′‐epoxycyclohexanecarboxylate (EEC), respectively by using sulphonium salts in the presence of hydroxylbutyl vinyl ether (HBVE) was studied. The real‐time FTIR spectroscopic, gel content determination, and thermal characterization studies revealed that both hydroxyl and vinyl ether functionalities of HBVE take part in the polymerization. During the polymerization, HBVE has the ability to react via both active chain end (ACE) and activated monomer mechanisms through its hydroxyl and vinyl ether functionalities, respectively. Thus, more efficient curing was observed with the addition of HBVE into EEC‐containing formulations. It was also demonstrated that HBVE is effective in facilitating the photoinduced crosslinking of monofunctional epoxy monomer, CHO in the absence of a conventional crosslinker. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4914–4920, 2007  相似文献   
8.
The nature of the propagation center in the cationic polymerization of N-benzoyl-8-octanelactam initiated by octanoylium hexachlcroantimonate, SbCl5, and Ph3CAsF6 in perdeuterated tetrachloroethane or its mixture with o-dichlorobenzene was studied using 1H, 13C, 19F, 31P, 75As, and 121Sb nuclear magnetic resonance (NMR) of model oligomers and the products of their end-capping with triphenylphosphine. In all cases, the nature of the propagation center has been found to be of an acylium ion pair with an SbCl6? or AsF6? counterion coordinated with the nearest benzoylamide group and cosolvated by the solvent. © 1994 John Wiley & Sons, Inc.  相似文献   
9.
This article describes the development of optical pyrometry (OP) as a new analytical technique for the continuous monitoring of the progress of both free‐radical and cationic photopolymerizations. The method is rapid, reproducible, and very easy to implement. A temperature profile of a photopolymerization can be obtained. Preliminary studies have shown that the temperatures of some polymerizing monomers can easily reach temperatures in excess of 250 °C. The effects of the mass and reactivity of the monomer, light intensity, structures, and concentrations of the photoinitiators and monomers as well as the presence or absence of oxygen on various free‐radical and cationic photopolymerizations were examined with this method. Coupling of real‐time infrared spectroscopy with OP provides a convenient method for simultaneously monitoring both the chemical conversion and the temperature of a photopolymerization. This combined technique affords new insights into the effects of temperature‐induced autoacceleration on the course of photopolymerizations. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 579–596, 2003  相似文献   
10.
The polymerization of cyclopentadiene (CPD) was effectively initiated by methylaluminoxane (MAO) to generate poly(cyclopentadiene) (polyCPD). The effects on the polymerization of some reaction parameters such as the monomer concentration, the initiator concentration, and solvents were investigated. The conversion of CPD was monitored with gas chromatography to investigate the reaction kinetics. The polymerization rate was proportional to the concentrations of MAO in the first order and of the CPD monomer in the second order, and a reasonable cationic polymerization mechanism was suggested on the basis of the kinetic study. PolyCPD obtained at a low temperature could be dissolved in toluene or chloroform, and this indicated lower cross‐coupling during the polymerization reaction. 1H NMR and IR analysis of the polymer indicated that there were almost equal amounts of 1,2‐enchainment and 1,4‐enchainment in the polymer chain. The measurement of polyCPD showed its unique properties as a potential candidate for stable wrappings or electronic packaging materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 264–272, 2006  相似文献   
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