高等学校化学学报 ›› 2004, Vol. 25 ›› Issue (10): 1962.

• 研究论文 • 上一篇    下一篇

氯乙烯/N-取代马来酰亚胺共聚竞聚率及共聚物组成

杜淼, 翁志学, 单国荣, 黄志明, 潘祖仁   

  1. 浙江大学高分子工程研究所, 杭州310027
  • 收稿日期:2003-07-02 出版日期:2004-10-24 发布日期:2004-10-24
  • 基金资助:

    国家教育部博士学科点专项基金(批准号:9533504)资助

Reactivity Ratios and Copolymer Composition of Vinyl Chloride and N-Substituted Maleimide Copolymerization

DU Miao, WENG Zhi-Xue, SHAN Guo-Rong, HUANG Zhi-Ming, PAN Zu-Ren   

  1. Institute of Polymer Engineering, Zhejiang University, Hangzhou 310027, China
  • Received:2003-07-02 Online:2004-10-24 Published:2004-10-24

摘要: 研究了氯乙烯(VC)与多种N-取代马来酰亚胺的溶液共聚合,求得各对单体的竞聚率.结果表明,各种马来酰亚胺的竞聚率都远高于VC的竞聚率,即N-取代马来酰亚胺单体的活性均比VC单体活性高.计算得到N-取代马来酰亚胺Qe值.由于苯环的共轭效应,N-苯基及N-取代苯基马来酰亚胺具有较大的Q值.各对单体的e值差别较大,表明有形成交替共聚物的倾向.此外,还考察了聚合过程中共聚物组成的变化,用递推法预测了这类体系共聚物瞬时和累积组成随转化率的变化.

关键词: 氯乙烯, N-取代马来酰亚胺, 共聚物组成, 竞聚率

Abstract: Radical copolymerization of vinyl chloride(VC) with N-substituted maleimide were conducted in tetrahydrofuran at 60℃ with AIBN as initiator. Based on the copolymer composition and monomer composition, the copolymerization parameters(r1, r2, Q and e) of each monomer pair were determined. The reactivity ratios of N-substituted maleimide monomers were all larger than that of VC, indicating that these monomers were more active. The effects of substituted groups on reactivity ratios were also discussed, and N-substituted maleimide monomer had a larger Q value than that of VC, especially for phenyl substituted maleimide monomer. It was believed that this phenomenon was related to the conjugated effect of phenyl group in N-substituted maleimide. The location of substituent on phenyl would influence Q value of N-substituted phenyl maleimide monomer. para-Substituent(i.e. p-ClPMI and p-MPMI) phenyl maleimide has a large Q value than that of ortho- and meta-substituted phenyl maleimides. In addition, there is a larger difference between e1 and e2, which means the large alternating tendency of the copolymerization of N-substituted maleimide with VC. The copolymer compositions for VC/N-substituted maleimide solution copolymerization varied greatly with conversion, especially for small N-substituted maleimide feed ratios. Subsequently, recurrence method deduced from Mayo-Lewis was used for predicting the change of copolymer composition with conversion. In addition, this method is also used to calculate the critical weight [(xw)c] conversion for VC/N-substituted maleimide copolymerization systems at different VC monomer feed fractions.

Key words: Vinyl chloride, N-Substituted maleimide, Copolymer composition, Reactivity ratio

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