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酶促缩聚和原子转移自由基聚合法合成AB型两亲性嵌段共聚物

李冬霜1, 沙柯1, 李亚鹏1, 刘啸天1, 艾鹏1, 王薇1, 陈亮2, 王静媛1   

    1. 吉林大学化学学院, 麦克德尔米德实验室, 长春 130012;
    2. 吉林大学第一医院, 长春 130023
  • 收稿日期:2005-10-28 修回日期:1900-01-01 出版日期:2006-08-10 发布日期:2006-08-10
  • 通讯作者: 王静媛

Synthesis of Amphiphilic Diblock Copolymer Poly(10-hydroxydecanoic acid)/poly(glycidyl methacrylate) by Combining Enzymatic Condensation Polymerization and ATRP

LI Dong-Shuang1, SHA Ke1, LI Ya-Peng1, LIU Xiao-Tian1, AI Peng1, WANG Wei1, CHEN Liang2, WANG Jing-Yuan1   

    1. Alan G. MacDiarmid Institute, College of Chemistry, Jilin University, Changchun 130012, China;
    2. The First Hospital of Jilin University, Changchun 130023, China
  • Received:2005-10-28 Revised:1900-01-01 Online:2006-08-10 Published:2006-08-10
  • Contact: WANG Jing-Yuan

摘要: Novozyme-435催化10-羟基癸酸进行自缩聚反应得到线性聚酯, 端基分别是羟基(—OH)和羧基(—COOH), 在三乙胺催化下, 分别用α-溴代丙酰溴和三甲基氯硅烷(TMSCL)进行端基官能化生成一个单官能度的大分子引发剂, 在CuCl/2,2'-联吡啶(bpy)催化体系中, 引发甲基丙烯酸环氧丙酯(GMA)的原子转移自由基反应(ATRP), 得到聚(10-羟基癸酸酯)/聚甲基丙烯酸环氧丙酯(PHDA-b-PGMA) AB 型两亲性嵌段共聚物, 其结构及分子量(分布)通过核磁共振和凝胶渗透色谱(GPC)确证. 此AB型两亲性嵌段共聚物在水溶液中能自组装形成纳米粒子, 用原子力显微镜(AFM)观察粒子的形状和大小.

关键词: 酶促缩聚, 原子转移自由基聚合, 嵌段共聚物, 自组装

Abstract: The diblock copolymers poly(10-hydroxydecanoic acid)-block poly(glycidyl methacrylate)(PHDA-b-PGMA) were synthesized by combining enzymatic condensation polymerization of 10-hydroxydecanoic acid(HDA) and atom transfer radical polymerization(ATRP) of glycidyl methacrylate(GMA). PHDA was firstly obtained via enzymatic condensation polymerization catalyzed by Novozyme-435. Subsequently one end of PHDA chains was modified by reaction with α-bromopropionyl bromide and the other was protected by chlorotrimethylsilane(TMSCL), respectively, the resulting monofunctional macroinitiator was used in the ATRP of GMA using CuCl/2,2'-bipyridine(bpy) as the catalyst system to afford the diblock copolymers including biodegradable PHDA blocks and well-defined PGMA blocks. Polymer nanospheres were prepared by the self-assembly behaviors of the amphiphilic diblock copolymers PHDA-b-PGMA in aqueous solvent.

Key words: Enzymatic polymerization, Atom transfer radical polymerization(ATRP), Block copolymer, Self-assembly

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