有机化学 ›› 2017, Vol. 37 ›› Issue (12): 3248-3256.DOI: 10.6023/cjoc201710037 上一篇    下一篇

研究简报

基于苯氧基联烯的两亲性嵌段共聚物的合成

蒋友好a, 陆国林b, 彭文a   

  1. a 上海中医药大学附属普陀医院 上海 200062;
    b 中国科学院上海有机化学研究所 上海 200032
  • 收稿日期:2017-10-31 修回日期:2017-11-09 发布日期:2017-11-15
  • 通讯作者: 彭文 E-mail:13061677336@163.com
  • 基金资助:
    国家自然科学基金(No.21674124)资助项目.

Synthesis of Phenoxyallene-Based Amphiphilic Block Copolymer

Jiang Youhaoa, Lu Guolinb, Peng Wena   

  1. a Putuo Hospital, Shanghai University of Traditional Chinese Medicine, Shanghai 200062;
    b Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
  • Received:2017-10-31 Revised:2017-11-09 Published:2017-11-15
  • Contact: 10.6023/cjoc201710037 E-mail:13061677336@163.com
  • Supported by:
    Project supported by the National Natural Science Foundation of China (No. 21674124).

运用机理转换策略,结合自由基聚合和原子转移自由基聚合(ATRP),制备了含有聚联烯链段的两亲性三嵌段共聚物.设计合成了含有偶氮和ATRP引发基团的双官能团引发剂,先用该双官能团引发剂引发苯氧基联烯单体的自由基聚合,得到了含有ATRP引发基团的聚联烯大分子引发剂,然后该大分子引发剂引发亲水性单体N,N-二乙基氨乙基甲基丙烯酸酯(DEAEMA)的ATRP聚合,制得了聚N,N-二乙基氨乙基甲基丙烯酸酯-聚联烯-聚N,N-二乙基氨乙基甲基丙烯酸酯(PDEAEMA-b-PPOA-b-PDEAEMA).该三嵌段共聚物能在水溶液中形成胶束,通过荧光探针技术分别测定了它在不同离子浓度、不同pH值条件下的临界胶束浓度.实验结果表明,该聚合物胶束的cmc随着pH值增大而减小,随着离子浓度的增大而增大.

关键词: 聚联烯, 嵌段共聚物, 双官能团引发剂, 原子转移自由基聚合

An amphiphilic triblock copolymer comprising double-bond-containing poly(phenoxyallene) (PPOA) was synthesized by a combination of conventional free radical polymerization and atom transfer radical polymerization (ATRP) via the site transformation strategy. A new bifunctional initiator containing azo and ATRP initiating groups was prepared and used for conventional free radical homopolymerization of phenoxyallene (POA) to afford a PPOA-based macroinitiator bearing ATRP initiating groups. Subsequent ATRP of hydrophilic monomer, 2-((diethylamino)ethyl methacrylate) (DEAEMA), initiated by PPOA-based macroinitiator afforded PDEAEMA-b-PPOA-b-PDEAEMA triblock copolymer. This triblock copolymer can self-assemble into micelles, and critical micelle concentration (cmc) of PDEAEMA-b-PPOA-b-PDEAEMA amphiphilic triblock copolymer in aqueous solution was determined by fluorescence probe technique. The dependence of cmc on pH and ion strength was also investigated.

Key words: polyallene, block copolymer, bifunctional initiator, ATRP