烯丙基缩水甘油醚与丙烯酸甲酯的活性聚合

研究了在咪唑基二硫代甲酸苄酯的存在下,热引发烯丙基缩水甘油醚与丙烯酸甲酯的活性自由基聚合反应.实验结果表明,共聚合反应具有良好的活性特征.聚合物分子量随单体转化率线性增长,分子量分布窄,ln(M]0/M])与聚合反应时间呈线性关系.聚合物结构分析证明生成了含有环氧官能团的聚丙烯酸甲酯.烯丙基缩水甘油醚在聚合物中的含量随着转化率和它在单体中比例的增加而增加.不过当单体中烯丙基缩水甘油醚的比例增大时,反应速率降低.利用聚苯乙烯大分子控制剂,合成了含有环氧官能团的两嵌段共聚物,即聚苯乙烯-聚(烯丙基缩水甘油醚/丙烯酸甲酯)(PS-b-P(MA-co-AGE)).

Living Free-Radical Copolymerization of Allyl Glycidyl Ether with Methyl Acrylate

An investigation of the copolymerization of allyl glycidyl ether(AGE) with methyl acrylate(MA) was performed in the presence of benzyl imidazole-1carbodithioate(BICDT) in the thermal initiation condition.The results show that the process has good characteristics of living free radical polymerization,i.e.the molecular weight of the obtained polymer increases linearly with monomer conversion,molecular weight distribution is very narrow,and a linear relationship between ln(M]_0/M]) and polymerization time exists.The copolymer structure containing epoxy groups was demonstrated from the H NMR spectrum.It was found that the content of AGE incorporation in the copolymer increased with higher monomer conversion and higher molar faction of the AGE in the monomer feed.However, polymerization could slow down when the fraction of AGE increased in the monomer feed.Taking advantages of living polymerization process,functional block copolymers(polystyrene-block-poly(MA-co-AGE)) were prepared in the presence of poly(styrene) RAFT agent.