NMP与ROP相结合制备PCL-b-PSt共聚物及其性能研究  

Synthesis and Properties of PCL-b-PSt Copolymer Prepared from the Combination of Nitroxide-Mediated Radical Polymerization and Ring-Opening Polymerization

作　　者：李翠珍[1,2] 刘建静[1] 张琰[1] 郎美东[1] 

机构地区：[1]华东理工大学材料科学与工程学院,超细材料制备与应用教育部重点实验室,上海200237 [2]东华理工大学材料系,江西抚州344000

出　　处：《功能高分子学报》2011年第3期225-230,共6页Journal of Functional Polymers

基　　金：中央高校基本科研业务费(WD0913008,WD1014036);国家自然科学基金资助项目(20804015)

摘　　要：以4-羟基-2,2,6,6-四甲基哌啶氮氧自由基(HTEMPO)为引发剂,通过ε-己内酯(ε-CL)的开环聚合,合成末端基为氮氧自由基的聚己内酯(PCL-T)。在其调控下,进行过氧化苯甲酰(BPO)引发苯乙烯(St)的自由基聚合,合成结构规整的聚己内酯-b-聚苯乙烯(PCL-b-PSt)共聚物。用氢核磁共振(1H-NMR)、电子自旋共振(ESR)、红外光谱(FT-IR)、凝胶渗透色谱(GPC)和热重分析(TGA)等手段对聚合物的结构和性能进行了研究。结果表明:氮氧自由基的存在不影响ε-CL的开环聚合,异辛酸亚锡(Sn(Oct)2)对ε-CL开环聚合的催化作用也对氮氧自由基无破坏性;在PCL-T的调控下,通过St的聚合可合成结构规整的PCL-b-PSt共聚物,且聚合过程具有"活性"聚合的特征;PCL-b-PSt共聚物的热稳定性高于PCL均聚物的热稳定性。Poly（ε-caprolactone）-block-polystyrene（PCL-b-PSt） was prepared by nitroxide-mediated radical polymerization of styrene（St） in the presence of PCL with terminated-nitroxide radical group（PCL-T） together with the ring-opening polymerization of ε-CL with 4-hydroxyl-2,2,6,6-tetramethylpiperidinyl-1-oxy（HTEMPO） as initiator.1H-NMR,ESR,FT-IR,GPC and TGA were employed to analyze the structure and properties of the polymers.Results show that the presence of the nitroxide radical has no effect on the ring-opening polymerization of ε-CL.Also,the ring-opening polymerization of ε-CL with Sn（Oct）2 as the catalyst does not destroy the nitroxide radical group.The well-defined PCL-b-PSt copolymers were synthesized through the polymerization of St at the mediation of PCL-T and the mechanism of polymerization of St fulfilled a typical well-controlled polymerization.The thermal stability of PCL-b-PSt copolymer is better than that of PCL homopolymer.

关 键 词：氮氧稳定自由基聚合 开环聚合 聚苯乙烯 聚己内酯 

分 类 号：O63[理学—高分子化学]