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化学学报
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化学学报 ›› 2011, Vol. 69 ›› Issue (18): 2173-2178. 上一篇    下一篇

研究论文

两亲性嵌段共聚物PCL-b-PNVP的合成及其自组装行为的研究

李翠珍1,2，张琰1，刘建静1，郎美东*,1   

  1. (1华东理工大学材料科学与工程学院 超细材料制备与应用教育部重点实验室 上海 200237)
    (2东华理工大学放射性地质与勘探技术国防重点学科实验室 抚州 344000)
  • 投稿日期:2011-04-27 修回日期:2011-05-10 发布日期:2011-05-20
  • 通讯作者: 郎美东 E-mail:mdlang@ecust.edu.cn
  • 基金资助:

    中央高校基本科研业务费专项资金;国家自然科学基金;高等学校博士学科点专项科研基金;上海市自然科学基金

Synthesis and Self-Assembly Behavior of Amphiphilic Poly- (ε-caprolactone)-b-poly(N-vinylpyrrolidone) Copolymer

Li Cuizhen1,2 Zhang Yan1 Liu Jianjing1 Lang Meidong*,1   

  1. (1 Key Laboratory for Ultrafine Materials of Ministry of Education, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237)
    (2 Key Laboratory of Radioactive Geology and Exploration Technology Fundamental Science for National Defense, East China Institute of Technology, Fuzhou 344000)
  • Received:2011-04-27 Revised:2011-05-10 Published:2011-05-20
  • Contact: Lang Ｍｅｉｄｏｎｇ E-mail:mdlang@ecust.edu.cn

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以4-羟基-2,2,4,4-四甲基哌啶氮氧自由基为引发剂, 通过ε-己内酯(ε-CL)的开环聚合反应, 合成氮氧稳定自由基为末端基的聚己内酯(PCL-T)|在其“介调”下, 进行乙烯基吡咯烷酮(NVP)的氮氧稳定自由基聚合(NMP), 得到结构规整聚己内酯和聚乙烯吡咯烷酮两亲性的嵌段共聚物(PCL-b-PNVP). 通过核磁共振氢谱(1H NMR)、红外光谱(FTIR)、电子自旋共振(ESR)和凝胶渗透色谱(GPC)对聚合物的结构进行了表征. 利用荧光光谱、动态光散射(DLS)、透射电镜(TEM)等手段分析共聚物自组装行为. 结果表明, 在聚己内酯大分子氮氧自由基“介调”下, 合成了结构规整的PCL-b-PNVP共聚物, 该共聚物在水中可自组装成粒径100 nm左右的核壳结构球形胶束|且共聚物表现出良好的生物相容性, 可作为疏水性药物的载体材料.

关键词: 两亲性的嵌段共聚物, 聚乙烯吡咯烷酮, 聚己内酯, 胶束

Amphiphilic poly(ε-caprolactone)-block-poly(N-vinyl pyrrolidone) (PCL-b-PNVP) copolymer was synthesized by nitroxide-mediated radical polymerization of N-vinyl pyrrolidione (NVP) at the mediation of PCL with terminated-nitroxide radical group (PCL-T)|PCL-T has been prepared by the ring-opening polymerization of ε-CL with 4-hydroxy-2,2,6,6-tetramethyl-piperidinooxy (HTEMPO) as initiator. The hydrogen nuclear magnetic resonance (1H NMR), electron spin resonance (ESR), fourier transform infrared spectroscopy (FTIR) and gel permeation chromatography (GPC) were employed to characterize the structure of the polymers. The self-assembly behavior of the copolymers in aqueous media was studied by fluorescence spectra, dynamic light scanning (DLS) and transmission electron microscope (TEM). The results showed that the well-defined PCL-b-PNVP copolymer could be synthesized by combination of ring-opening polymerization and nitroxide-mediated radical polymerization, and the obtained copolymer could be self-assembled into well-dispersed core-shell spherical micelles with a size of 100 nm in aqueous solution. Moreover, the copolymer displayed good biocompatibility and could be acted as the hydrophobic drug carrier.

Key words: amphiphilic block copolymer, poly(N-vinyl pyrrolidone), poly(ε-caprolactone), micelles