Photopolymerization of cycloaliphatic epoxide and vinyl ether.

摘要

This thesis summarizes experimental and theoretical studies on cationic photopolymerizations of 3,4-epoxycyclohexylmethyl-3' ,4'-epoxycyclohexane carboxylate (ECH), cyclohexene oxide (CHO) and triethyleneglycolmethylvinyl ether (TEGMVE), and the use of Principal Component Analysis (PCA) for the interpretation of the real-time Fourier-transform infrared (FT-IR) spectral data for the photopolymerizations.; Phenomenological kinetic models have been developed for photopolymerizations of monofunctional and difunctional monomers. An autocatalytic model including diffusion-controlled reactions is shown to provide a good fit to the experimental data for photopolymerizations of ECH. A mechanistic model based on the free volume theory has been also developed. This model gives a good fit for the conversion-time relationship and weight-average molecular weights but the predicted number-average molecular weights are lower than the experimental values.; Photopolymerizations of ECH with various mixed initiator systems have been compared with single initiator systems. It has been discovered that a strong synergy leading to much higher than expected rates and conversions occurs in the polymerizations of ECH with mixtures of cyclopentadienyliron(II)cumene hexafluorophosphate (FP) and diaryliodonium hexafluoroantimonate (IA), with mixtures of FP and tolylcumyliodoniumtetrakis(pentafluorophenyl)borate (IB) as well as for polymerizations with mixtures of IA and IB.; The effects of curing temperature on the dark postpolymerization of ECH with different initiators have been examined. ECH-IA and ECH-IB systems show higher values of the heat of reaction and higher shear storage modulus than ECH-SP and ECH-FP systems.; Analytical and kinetic studies of photopolymerizations of the mixtures of ECH and TEGMVE show that ECH and TEGMVE do not polymerize independently and suggest a cross-propagation reaction between oxonium and carbenium ions for polymerizations of mixtures of cycloaliphatic epoxides and vinyl ethers. (Abstract shortened by UMI.)