化学学报 ›› 2009, Vol. 67 ›› Issue (14): 1663-1667. 上一篇    下一篇

研究论文

ATRP法合成两亲性嵌段共聚物PSt-b-PAA及其在离子液体[BMIM][PF6]中的自组装行为研究

张普玉* 刘 洋 彭李超 郭有钢

  

  1. (河南大学化学化工学院 精细化学与工程研究所 开封 475001)

  • 投稿日期:2008-11-15 修回日期:2009-01-12 发布日期:2009-07-28
  • 通讯作者: 张普玉

Synthesis of AB-Diblock Copolymers by ATRP and Their Self-assembly in an Ionic Liquid [BMIM][PF6]

Zhang, Puyu* Liu, Yang Peng, Lichao Guo, Yougang

  

  1. (Institute of Fine Chemistry and Engineering, College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475001)
  • Received:2008-11-15 Revised:2009-01-12 Published:2009-07-28
  • Contact: Zhang, Puyu

利用原子转移自由基聚合法(ATRP)合成了分子量可控、分子量分布窄的嵌段共聚物聚苯乙烯-b-聚丙烯酸叔丁酯(PSt-b-PtBA), 进而在酸性条件下由水解反应得到了两亲性嵌段共聚物聚苯乙烯-b-聚丙烯酸(PSt-b-PAA), 并通过凝胶渗透色谱(GPC)、傅立叶变换红外光谱(FTIR)、核磁共振(1H NMR)等测试手段对产物进行了表征. 使三种分子量不同的两亲性嵌段共聚物在离子液体1-丁基-3-甲基咪唑六氟磷酸盐([BMIM][PF6])中进行自组装, 通过激光粒度分析仪(DLS)和透射电子显微镜(TEM)研究了聚合物在离子液体中自组装的胶束尺寸和结构形态. 当PSt的链段长度一定时, 胶束的形状主要依赖于PAA链的长度. 当PAA链段较长时, 胶束呈球形; 当PAA链段较短时, 则变成不规则的花生状胶束.

关键词: 原子转移自由基聚合(ATRP), 两亲性嵌段共聚物, 离子液体, 自组装

The block copolymer of poly(styrene)-block-poly(tert-butyl acrylate) (PSt-b-PtBA) has been synthesized by an atom transfer radical polymerization (ATRP) method. Then the amphiphilic block copolymer of poly(styrene)-block-poly(acrylic acid) (PS-b-PAA) was obtained by hydrolysis from PSt-b-PtBA copolymers in HCl solution. Furthermore, the architectures of the copolymers were confirmed by FT-IR and 1H NMR spectra. GPC analysis was used to estimate the molecular weight and the molecular weight distribution of the copolymers. Three amphiphilic copolymers with different molecular weights formed micelles in an ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF6]). The nanostructures of the PSt-b-PAA micelles formed in the ionic liquid were observed by TEM (transmission electron microscopy) and DLS (dynamic light scattering). The self-assembled morphologies of the copolymers are strongly dependent on the length of PAA block chains when the chain length of PSt is fixed. With the increase of molecular weight of PAA in the diblock copolymers, some spherical micelles were obtained. With further decrease of the PAA molecular weight in the copolymers, the spherical morphology was turned to peanut.

Key words: atom transfer radical polymerization, amphiphilic block copolymer, ionic liquid, self-assembly