Chain transfer agents in cationic photopolymerization of a bis-cycloaliphatic epoxide monomer: Kinetic and physical property effects
Chain transfer agents in cationic photopolymerization of a bis-cycloaliphatic epoxide monomer: Kinetic and physical property effects
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DOI：
10.1002/pola.26595
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发表时间：
2013-05-01
影响因子：
--
通讯作者：
Jessop, Julie L. P.
中科院分区：
文献类型：
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作者：
Dillman, Brian;Jessop, Julie L. P.
研究了链转移剂（CTA）对3,4-环氧环己基甲基-3,4-环氧环己烷羧酸盐（EEC）阳离子开环聚合反应的影响。EEC在各种cta存在下聚合，并通过拉曼光谱监测环氧化物的转化。制备了聚合物薄膜，并对其进行了动态力学分析。所研究的许多有机醇大大提高了环氧化物的聚合速率和转化水平。聚合物样品的凝胶分数随着辛醇含量的增加而迅速下降（凝胶分数>90%达到0.3当量OH），但随着1,2-丙二醇含量的增加而保持较高（凝胶分数>90%达到0.6当量OH）。增加伯醇尺寸对聚合速率和转化率影响不大。随着醇取代度的增加（1度>2度>3度），聚合速率降低。相对于纯环氧树脂，酸性醇对其转化和聚合速率的影响很小。玻璃化转变温度与CTA的大小和用量成反比。(c) 2013 Wiley Periodicals, Inc.；[J]高分子材料学报，2013,51 (1),2058-2067
The effects of chain transfer agents (CTA) on cationic ring-opening polymerization of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate (EEC) were explored. EEC was polymerized in the presence of various CTAs, and epoxide conversions monitored via Raman spectroscopy. Polymer films were prepared and analyzed by dynamic mechanical analysis. Many of the organic alcohols studied greatly enhanced epoxide polymerization rates and conversion levels. The gel fraction of polymer specimens decreased rapidly with increasing amounts of octanol (gel fraction >90% up to 0.3 equiv OH) but remained high with increasing amounts of 1,2-propanediol (gel fraction >90% up to 0.6 equiv OH). Increasing the size of primary alcohols had little effect on the polymerization rates and conversions. The polymerization rate decreased with increasing alcohol substitution (1 degrees>2 degrees>3 degrees). Acidic alcohols had very low impact on conversion and polymerization rates relative to the neat epoxy resin. The glass transition temperature was inversely related to the size and amount of CTA. (c) 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013, 51, 2058-2067