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化学学报
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化学学报 ›› 2006, Vol. 64 ›› Issue (6): 556-562. 上一篇    下一篇

研究论文

N-苯基马来酰亚胺/对氯甲基苯乙烯活性可控超支化交替共聚合的研究

计兵，刘翠华，杨金田，黄卫*，颜德岳*   

  1. (1上海交通大学化学化工学院 上海 200240)
    (2湖州师范学院化学系 湖州 313000)
  • 投稿日期:2005-09-01 修回日期:2005-12-02 发布日期:2006-03-28
  • 通讯作者: 黄卫

Living Controllable Hyperbranched Alternating Copolymerization of N-Phenylmaleimide and p-(Chloromethyl)styrene

JI Bing1,2, LIU Cui-Hua1, YANG Jin-Tian1,2, HUANG Wei*,1, YAN De-Yue*,1   

  1. (1 College of Chemistry and Chemical Technology, Shanghai Jiaotong University, Shanghai 200240)
    (2 Department of Chemistry, Huzhou Teacher College, Huzhou 313000)
  • Received:2005-09-01 Revised:2005-12-02 Published:2006-03-28
  • Contact: HUANG Wei

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采用核磁共振氢谱, 研究了N-苯基马来酰亚胺(NPMI)与对氯甲基苯乙烯(PCMS)在氘代氯仿中的络合性能. 以PCMS作为引发剂单体, 通过原子转移自由基聚合(ATRP)引发NPMI-PCMS电子转移络合物(CTC)进行活性可控超支化共聚合. 考察了单体初始摩尔分数对共聚物组成和其玻璃化转变温度的影响, 用Kelen-Tudos法计算得到两种单体的竞聚率分别为 rNPMI＝0.11和rPCMS＝0.25. 结果表明, 当单体配比fNPMI＝0.4～0.7时, 共聚物具有交替结构, 其耐热性随着NPMI含量的增加而提高. 此外还考察了溶剂、聚合温度等对共聚合反应动力学的影响. 并进一步用所得超支化交替共聚物作为大分子引发剂, 引发甲基丙烯酸甲酯(MMA)聚合, 制得了多臂超支化接枝共聚物 poly(NPMI-co-PCMS)/poly(MMA).

关键词: N-苯基马来酰亚胺, 对氯甲基苯乙烯, 电子转移络合物, 超支化, 交替共聚物

The complexation properties of N-phenylmaleimide (NPMI) and p-(chloromethyl)styrene (PCMS) were studied by 1H NMR in CDCl3 firstly. Novel hyperbranched alternating copolymers were successfully synthesized via living controllable radical copolymerization of the charge transfer complex made from NPMI and PCMS while PCMS was used as an inimer. The monomer reactivity ratios were evaluated to be rNPMI＝0.11 and rPCMS＝0.25 respectively by the Kelen-Tudos method. The resulting hyperbranched copolymers were of alternating structure when the molar fraction of NPMI was varied from 0.4 to 0.7. The glass transition temperature of such hyperbranched copolymer was increased with increasing fNPMI, indicating that the thermal stability of the copolymers had been improved with increasing NPMI. The influences of reaction conditions, such as solvent and the polymerization temperature on the copolymerization kinetics, were also studied. These hyperbranched alternating copolymers were successfully used as functional macroinitiators to synthesize the star-shaped poly(NPMI-co-PCMS)/poly(MMA) block copolymers.

Key words: N-phenylmaleimide, p-(chloromethyl)styrene, charge transfer complex; hyperbranched copolymer, alternate