含有热引发转移终止剂的引发体系在反向原子转移自由基聚合中的应用

原子转移自由基聚合 (ATRP)是实现活性聚合的一种颇为有效的途径 ,可以实现多种单体的活性自由基聚合 .反向原子转移自由基聚合 (ReverseATRP)的概念始提出于 1995年 ,是对传统ATRP的改进和拓展 .近年来关于此体系的引发剂的拓展、过渡金属及单体的适用性都得到了很大发展 .本文简要综述了我们研究组在反向原子转移自由基聚合方面的研究进展

NEW TYPE OF REVERSE ATRP PROCESS WITH INITIATING SYSTEM CONSISTING OF THERMAL INIFERTERS AS THE INITIATOR

Atom transfer radical polymerization (ATRP) is an efficient way for living radical polymerization.Reverse ATRP was first reported by Matyjaszewski in 1995 and it is a development and improvement of conventional ATRP.In this review article,we summarize the progresses of reverse ATRP studies in our research group,especially the initiating systems consisting of thermal iniferter and metalic complex catalyst,that are the 1,1,2,2-tetraphenyl-1,2-ethanediol (TPED)/FeCl3/triphenylphosphine (PPh3),diethyl 2,3-dicyano-2,3-di(p-tolyl)succinate (DCDTS)or diethyl 2,3-dicyano-2,3-diphenylsuccinate (DCDPS)/CuCl2/bipyridine(bipy)and DCDPS/FeCl3/PPh3 initiating systems.Using these initating systems,well-defined PMMA and PSt with high molecular weights and quite narrow molecular weight distributions were successfully synthesized.1H-NMR analysis revealed that the resultant polymers were end functionalized by α-H［or α-C(CN)(C6H5)(CO2C2H5)］ and ω-Cl groups.The polymers with ω-Cl groups can serve as macroinitiators to proceed chain extension reactions with fresh monomer and block copolymerization with a second monomer.The polymerization mechanisms belong to reverse ATRP.