高等学校化学学报 ›› 1993, Vol. 14 ›› Issue (1): 123.

• 研究论文 • 上一篇    下一篇

本体聚合反应全过程苯乙烯增长自由基的ESR谱的研究

毛友钢, 王国斌, 郑莹光, 沈家骢   

  1. 吉林大学理化所、化学系分析测试中心, 长春 130023
  • 收稿日期:1992-01-03 修回日期:1992-07-23 出版日期:1993-01-24 发布日期:1993-01-24
  • 通讯作者: 毛友钢

A Study of ESR Spectra and Conformation of Propagating Radical in Bulk Polymerization Styrene

MAO You-Gang, WANG Guo-Bin, ZHENG Ying-Guang, SHEN Jia-Cong   

  1. Departmeat of Chemistry, Jilin University, Changchun, 130023
  • Received:1992-01-03 Revised:1992-07-23 Online:1993-01-24 Published:1993-01-24

摘要: 本文对苯乙烯本体聚合全过程增长自由基ESR谱进行了研究,对全过程ESR谱的模拟和分析及构象能的计算表明:反应初期12线谱由产生6线谱构象R1和8线谱的构象R2叠加而成,其相对含量R1>R2。反应中期4线谱和6线的ESR谱的模拟结果为:R1<R2,并从热力学和动力学角度详细讨论了构象比随反应变化的原因。

关键词: 蓉乙烯, 增长自由基, ESR谱, 本体聚合反应, 构象

Abstract: All the ESRspectra of propagating radical of styrene observed in bulk polymerization were studied and can be regarded as the superposition of the spectra of the two inner-rotational conformations of the radical A, B, which were obtained not only from the simulation of the spectra and the analysis of the hyperfine coupling constants, but also from the calculations of the conformation energy.The ratio of the conformation A/Bat the beginning stage of the reaction is 3, 0, being consistent with results coming from Boltzmann distribution.However the ratio gradually decreased with the polymerization and reached 0.2 at the end.The cause of the change has been discussed with respect to thermodynamics and dynamics.

Key words: Styrene, Propagating radical, ESR spectra, Bulk polymerization conformation

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