苯乙烯与N-取代马来酰亚胺的可逆加成-断裂链转移交替共聚合  

RAFT ALTERNATING COPOLYMERIZATION OF STYRENE AND N-SUBSTITUTED MALEIMIDES

作　　者：方艳[1] 曹赟[1] 张爱萍[1] 翟光群[1] 孔立智[1] 张东亮[1] 

机构地区：[1]江苏工业学院材料科学与工程系常州市高分子材料重点实验室,常州213164

出　　处：《高分子学报》2010年第1期51-58,共8页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号20674033);江苏省自然科学基金(基金号BK2005404;BK2008142)资助项目

摘　　要：研究了二硫代苯甲酸酯存在下偶氮二异丁腈引发苯乙烯(St)、St与N-对羟基苯基马来酰亚胺(HPM)、St与N-对(2-氯/溴丙酰氧基)苯基马来酰亚胺(CPPM/BPPM)的可逆加成-断裂链转移(RAFT)均/共聚,聚合物的结构由紫外-可见光(UV-Vis)与凝胶渗透色谱(GPC)表征.结果表明,St的RAFT均聚以及St与N-取代马来酰亚胺的RAFT共聚均呈现活性聚合特征,分子量随着转化率上升而增加,且分子量分布较窄.对于St的RAFT均聚,由于双基终止,聚苯乙烯(PSt)链中"戴帽效率"随着转化率上升逐渐下降.对于St与N-取代马来酰亚胺的RAFT共聚合,电荷转移复合物的形成显著地提高了共聚反应速度,并促进交替结构的形成.随后进行了以P(St-alt-BPPM)引发St的原子转移自由基聚合以制备梳型PSt,结果表明在强极性溶剂中进行的聚合过程失去可控性,所得产物分子量极宽,而在本体聚合中所得聚合物分子量相对较窄,有一定的可控性.The RAFT homopolymerization of St and copolymerization of St with N-substituted maleimides such as HPM,CPPM and BPPM,using AIBN as initiator,1-phenylethyl dithiobenzoate or cumyl dithiobenzoate as the chain transfer agent was investigated.The polymers were characterized by UV-Vis and GPC.The results suggested that both the homopolymerization and copolymerization exhibited a living behavior,and the molecular weight increased with the conversion and a narrow molecular weight distribution was achieved.For the homopolymerization,due to the unfavorable bimolecular termination of the PSt radicals,the capping efficiency of the PSt chains decreased gradually with the conversion.For the copolymerization,the charge transfer complex formation not only enhanced the reaction rate but also led to alternating sequence.The P（St-alt-BPPM） was also used as the macroinitiator for the ATRP of St to prepare comb-shaped PSt.The results implied that when NMP was used as solvent,the process proceeded in an uncontrolled fashion;on the other hand,when the reaction was carried out in St bulk,the comb-like PSt had a much narrower MWD.

关 键 词：可逆加成-断裂链转移聚合 苯乙烯 N-取代马来酰亚胺 交替共聚物 原子转移自由基聚合 梳型高聚物 

分 类 号：O631.3[理学—高分子化学]