An investigation of the reactivity of the cycloaliphatic diepoxide, 3,4-epoxycyclohexyl 3′, 4′-epoxycycloexane carboxylate (I) in photoinitiated cationic polymerization was carried out with the aid of model compounds. It was shown that the presence of the ester group greatly retards the rate of polymerization of this bisepoxide. Molecular modeling studies indicate that the ester carbonyl group can interact in a number of ways with the initially formed protonated or alkylated oxiranium cation to give bicylic dialkoxycarbenium ions. These latter species are both more sterically hindered and less reactive than the oxiranium cation precursors and undergo propagation at a considerably reduced rate. Reactivity studies em-ploying model compounds also showed that epoxy monomers that contain ester groups undergo polymerization at much slower rates than those in which the ester group is absent. © 1995 John Wiley & Sons, Inc.

中文翻译：

---

3,4-环氧环己基甲基3'，4'-环氧环己羧酸酯在光引发阳离子聚合反应中的反应机理

脂环族二环氧，3,4-环氧环己基3'，4'-环氧环己烷羧酸酯的反应性研究（I）在光引发的阳离子聚合中借助于模型化合物进行。结果表明，酯基的存在大大阻碍了该双环氧化物的聚合速率。分子模型研究表明，酯羰基可以多种方式与最初形成的质子化或烷基化的氧杂鎓阳离子相互作用，生成双环二烷氧基碳鎓离子。后一种物质比氧杂鎓​​阳离子前体在空间位阻上和反应性上都较低，并且以显着降低的速率传播。采用模型化合物的反应性研究还表明，含有酯基的环氧单体的聚合反应速率比不存在酯基的环氧单体要慢得多。版权所有©1995 John Wiley＆Sons，Inc.