新型引发转移终止剂引发烯类单体活性自由基聚合及共聚合

引发转移终止剂 (Iniferter)是最早实现活性自由基聚合的方法 ,尽管它对聚合过程控制得不是很好 ,但是可聚合单体多 ,能方便地制备接枝和嵌段共聚物 .因此 ,近 2 0年来 ,它一直是高分子合成化学领域的一个研究热点 ,许多新颖结构的引发转移终止剂被合成并用于制备端基功能化聚合物、遥爪聚合物、大分子单体以及接枝和嵌段聚合物等 .本文扼要综述了引发转移终止剂的发展 ,着重综述了我们研究组在C—C键型高活性热引发转移终止剂、新的光引发转移终止剂、可聚合光引发转移终止剂、新型多功能引发转移终止剂和大分子光引发转移终止剂 5个方面的研究进展

LIVING RADICAL POLYMERIZATION AND COPOLYMERIZATION OF VINYL MONOMERS INITIATED WITH NOVEL INIFERTERS

Iniferter technique is an efficient and convenient method for preparation of well defined vinyl polymers and copolymers,and developing novel iniferters is a continued theme in living radical polymerization area.In this review article,the progress of iniferter studies was summarized.Novel mono functional thermal and photo iniferters,polymerizable iniferters,multi functional iniferter and photo macroiniferters were designed,synthesized and used for preparation of well defined end functionalized polymers,block and graft copolymers.These thermal iniferters are diethyl 2,3 dicyano 2,3 diphenylsuccinate (DCDPS),diethyl 2,3 dicyano 2,3 di( p tolyl)succinate (DCDTS); photo iniferters are N (p tolyl) N′,N′ diethyldithiocarbamylacetamide (TDCA),ethyl N,N diethyldithio\|carbamylacetate (EDCA), n butyl N,N diethyldithiocarbamylacetate (BDCA),benzyl N,N diethyldithio carbamylacetate (BzDCA); polymerizable iniferters are β methacryloxylethyl 2 N,N diethyldithiocarbamylacetate (MAEDCA),allyl 2 N,N diethyldithiocar bamylacetate (ADCA); the multi functional iniferter is diethyl 2,3 dicyano 2,3 di( p diethyldithiocar bamylmethyl)phenylsuccinate (DDDCS); photo macroiniferters are α,ω functionalized polyethylene glycol and polytetrahydrofuran macroiniferters.DCDPS and DCDTS not only can initiate MMA living polymerization at low temperature but also realize St living polymerization successfully in thermal iniferter area for the first time.MAEDCA bearing both vinyl group and DC group is used for synthesis of well defined graft copolymer by two pathways.DDDCS bearing both thermal dissociated and photo dissociated chemical bonds,by alternative heating and irradiation sequence,can be used to synthesize a series of ABA triblock copolymers with controlled compositions and block chain length facilely,especially for PVAc b PSt b PVAc which cannot be prepared by using any other living radical polymerization methods.