物理化学学报 >> 1993, Vol. 9 >> Issue (05): 610-616.doi: 10.3866/PKU.WHXB19930508

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聚合反应增长自由基ESR谱的交替线宽现象研究

毛友钢; 郑莹光; 王国斌; 沈家骢   

  1. 吉林大学理化所，分析测试中心，化学系，长春 130023
  • 收稿日期:1992-03-02 修回日期:1992-07-29 发布日期:1993-10-15
  • 通讯作者: 毛友钢

The Alternating Broadening Effect of the ESR Spectra for Styrene Propagating Radical in Bulk Polymerization

Mao You-Gang; Zheng Ying-Guang; Wang Guo-Bin; Shen Jia-Cong   

  1. Intitute of Theoretical Chemistry, Department of Chemistry, Jilin University, Changchun 130023
  • Received:1992-03-02 Revised:1992-07-29 Published:1993-10-15
  • Contact: Mao You-Gang

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摘要： 用驰豫矩阵方法处理了甲基β质子各向同性超精细偶合常数在扭曲振荡调翻作用下所引起的ESR谱的交替线宽问题, 得到了构象成连续分布β质子的相关函数, 谱密度函数及在快交换条件下的ESR线宽表达式, 并用其对苯乙烯本体聚合反应的全过程ESR谱的交替线宽现象进行了分析, 结果解释了交替线宽随本体聚合反应的变化, 支持了对苯乙烯增长自由基ESR谱超精细偶合常数的归属.

关键词: 交替增宽效应, ESR谱, 增长自由基, 苯乙烯

Abstract: The relaxation-matrix theory of line width analysis in electron spin resonance spectra has been used to analyze the alternating line width effects arising from the motion of β protons of propagating radical, this motion was treated by using a Brow-nian motion model assuming a torsional oscillations about the C_α—C_β bond. The formula of line-width for β-protons obtained were applied to the analysis of the ESR spectra for styrene radicals in the whole process of bulk polymerization to explain the time dependence on polymerization. The results also support the assignment of the β protons hfs-constants.

Key words: Alternating broaden effect, ESR, Propagating radical, Styrene