两亲性接枝共聚物P(MMA-co-GMA)-g-mPEG的合成  

Synthesis of amphiphilic grafted copolymer P(MMA-co-GMA)-g-mPEG

作　　者：张勇林[1] 王梦元[1] 姚军善[1] 刘超[1] 叶妮雅[1] 雷良才[1] 李海英[1] 

机构地区：[1]辽宁石油化工大学化学与材料科学学院,抚顺113001

出　　处：《化工新型材料》2015年第7期95-98,110,共5页New Chemical Materials

基　　金：国家自然科学基金"生物相容性环状聚乳酸及其功能化共聚物的合成"资助项目(20974042)

摘　　要：借助原子转移自由基聚合(ATRP)技术和环氧功能基团的大分子后修饰反应合成具有梳型结构的两亲性接枝共聚物P(MMA-co-GMA)-g-mPEG)。首先,采用ATRP方法,以2-溴代丙酸乙酯(EPN-Br)为引发剂,氯化亚铜(CuCl)/2,2′-联二吡啶(bpy)为催化体系,引发甲基丙烯酸甲酯(MMA)和甲基丙烯酸环氧丙酯(GMA)无规共聚,合成二元无规共聚物P(MMA-co-GMA);然后,在催化剂BF3/Et2O的作用下,无规共聚物P(MMA-co-GMA)的环氧基团开环,与单甲氧基封端的聚乙二醇(mPEG)发生接枝(grafting-onto)反应,获得具有梳型结构的两亲性接枝共聚物P(MMA-coGMA)-g-mPEG。采用红外光谱(IR)、凝胶色谱(GPC)、核磁共振氢谱(1 H-NMR)及差示扫描量热仪(DSC)等技术对聚合物的结构和性能进行表征。研究的特点是无规共聚物的合成可控性好,后修饰反应获得两亲性接枝共聚物的效率高,为研究接枝共聚物结构与性能的关系提供了物质依据。The synthesis of an amphiphilic comb-like grafted copolymer,i.e.,P（MMA-co-GMA）-g-mPEG by the combination of ATRP and the post-modification of the epoxy groups was reported.Firstly,a random copolymer,P（MMAco-GMA）,was obtained by atom transfer radical copolymerization of the comonomers,methyl methacrylate and glycidyl methacrylate,using 2-bromine propionic acid ethyl ester as an initiator and CuCl/2,2′-bipyridine（bpy）as a catalyst.Then the monomethyl polyethylene glycol（mPEG）was reacted with the epoxy groups and finally grafted onto the random copolymer in the presence of BF3/Et2 O,with formation of an amphiphilic comb-like grafted copolymer,P（MMA-co-GMA）-gmPEG.The resulting polymers were characterized by infrared spectroscopy（IR）,gel permeation chromatography（GPC）,proton nuclear magnetic resonance spectroscopy（1 H-NMR）and differential scanning calorimetry（DSC）technologies.GPC results showed that the molecular weight of grafted copolymer significantly increased with lower polydispersity compared with random copolymer.The main point of the strategy was that a well-defined random copolymer was synthesized and the amphiphilic graftied copolymer was readily prepared with high efficiency.It was very important for the reliable establishment of macromolecular structure-properties relationships of copolymers.

关 键 词：原子转移自由基聚合 聚(甲基丙烯酸甲酯-co-甲基丙烯酸环氧丙酯) 单甲氧基封端的聚乙二醇 两亲性梳型接枝共聚物P(MMA-co-GMA)-g-mPEG 

分 类 号：TQ316.343[化学工程—高聚物工业]