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化学学报
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化学学报 ›› 2012, Vol. 70 ›› Issue (04): 505-511.DOI: 10.6023/A1108302 上一篇    下一篇

研究论文

ARGET ATRP 与ROP 结合制备pH 响应两亲性聚合物分子刷及其自组装研究

杨友强, 孙清清, 张灿阳, 郭新东, 章莉娟, 文秀芳   

  1. 华南理工大学化学与化工学院 广州 510640
  • 投稿日期:2011-08-30 修回日期:2011-10-30 发布日期:2011-11-09
  • 通讯作者: 章莉娟
  • 基金资助:

    国家自然科学基金(No. 21176090)、广东省自然科学基金团队项目(No. S2011030001366)、广东省自然科学基金(No. 9251064101000009)、广州市应用基础研究计划(No. 2009J1-C511-2)和中央高校基本科研业务费专项资金(No. 2011ZM0041)资助项目.

Synthesis of pH-Sensitive Amphiphilic Copolymer Brush by the Combination of ARGET ATRP with ROP and Its Self-Assembly Behavior

Yang Youqiang, Sun Qingqing, Zhang Canyang, Guo Xindong, Zhang Lijuan, Wen Xiufang   

  1. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640
  • Received:2011-08-30 Revised:2011-10-30 Published:2011-11-09
  • Supported by:

    Project supported by the National Natural Science Foundation of China (No. 21176090), Team Project of Natural Science Foundation of Guangdong Province (No. S2011030001366), Guangdong Province Science Foundation (No. 9251064101000009), Guangzhou Municipal Bureau of Science and Technology (No. 2009J1-C511-2) and the Fundamental Research Funds for the Central Universities (No. 2011ZM0041).

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结合电子转移活化剂再生-原子转移自由基聚合(ARGET ATRP)和开环聚合(ROP)法合成了一种具有无规疏水/ pH 响应结构的两亲性聚合物分子刷聚(甲基丙烯酸聚丙交酯酯-co-甲基丙烯酸)-b-聚甲基丙烯酸单甲氧基聚乙二醇酯 [P(PLAMA-co-MAA)-b-PPEGMA]. 通过核磁共振氢谱(1H NMR)和凝胶渗透色谱(GPC)表征了聚合物的结构、分子量及分子量分布. 优化了反应条件并合成出分子量可控、分子量分布窄的聚合产物. 采用动态光散射法(DLS)、扫描电子显微镜(SEM)研究了聚合物分子刷在水溶液中自组装胶束的粒径、形貌及pH 响应行为. P(PLAMA-co-MAA)-b-PPEGMA 自组装形成粒径分布均匀的球形胶束. 且随着溶液pH 值从7 降低至3, 胶束中的PMAA 逐渐去离子化, 溶胀的胶束逐渐收缩, 粒径由200～300 nm 减小至150 nm 左右; 但当pH 值减小到2 以下, 胶束表面电荷量非常小, 胶束聚集, 使得粒径增大.

关键词: pH 响应, 聚合物分子刷, 自组装胶束, ARGET ATRP, ROP

A random hydrophobic/pH-sensitive copolymer brush poly(polylactide methacrylate-comethacrylic acid)-b-poly(poly(ethylene glycol) methyl ether methacrylate) [P(PLAMA-co-MAA)-b-PPEGMA] was synthesized by the combination of activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) with ring opening polymerization (ROP). The chemical structure, molecular weight and polydispersity index were characterized by nuclear magnetic resonance hydrogen spectrum (1H NMR) and gel permeation chromatography (GPC). The reaction conditions of polymerization were optimized and polymer products with controllable molecular weight and narrow distribution were obtained. The self-assembly behavior (micelle size, morphology and pH-sensitive properties) of the polymer brush was investigated by dynamic light scattering (DLS) and scanning electron microscopy (SEM). The P(PLAMA-co-MAA)-b-PPEGMA self-assembled micelles were sphere in morphology and with an uniform particle size. As the solution pH decreased from 7 to 3, the deionization of carboxyl groups of PMAA contributed to the shrinking of micelle structure, which made the micelle size decreased from 200～300 nm to about 150 nm. When the solution pH decreased to below 2, the surface charge of micelle became very small which resulting in the aggregation of micelles and the increase of micelle size.

Key words: pH-sensitive, polymer brush, self-assembled micelle, ARGET ATRP, ROP