| 正丁基锂-丁二烯-四氢呋喃阴离子聚合体系的动力学研究 |
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| 引用本文： | 金关泰,范立群,徐瑞清.正丁基锂-丁二烯-四氢呋喃阴离子聚合体系的动力学研究[J].石油化工,1989(1). |
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| 作者姓名： | 金关泰 范立群 徐瑞清 |
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| 作者单位： | 北京化工学院高分子系，北京化工学院高分子系，北京化工学院高分子系 |
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| 基金项目： | 中国科学院科学基金资助课题 |
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| 摘 要： | 以正丁基锂为引发剂,四氢映喃(THF)为溶剂,研究丁二烯阴离子聚合增长反应动力学。试验在高纯氮保护下,以膨胀计法进行。结果表明,增长反应对单体浓度和引发剂浓度的反应级数皆为一级关系,增长反应的总速度常数 kp=9.30×10~4exp(-6900/RT)1/mol·min,形成1,4-结构的分速度常数数 k_3-1.05×10~5exp(-8530/RT)1/mol·min,形成1,2-结构的分速度常数k_4=6.73×10~4exp(-6790/RT)1/mol·min,以及在 THF 中产物的1,2-结构含量 a=7.24×10~(-I)exp(110/RT)。
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A Study on Kinetics of Anionic Polymerization of n-BuLi-Butadiene-THF System |
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| Abstract: | The kinetics of anionic polymerization of butadiene in THF initiated by n-BuLi was investigated.In this case the propagation reaction rate was found to befirst-order with respect to both moncmer and initiator concentrations.The acti-vation energy was found to be 28.8kJ/mol(6.9kcal/mol) and the frequency factor-9.3×10~4 1/mol·min respectively.According to butadiene polymerization mech-anism proposed by Jin Guantai and Li Tianhu,the activation energies of the cor-responding reaction rate constants of 1,4-and 1,2-structures formed and the fre-quency factors are obtained as follows:E_(1,4)=35.66kJ/mol (8.53keal/mol)A_(1,4)=1.05×10~5 1/mol·minE(1,2)=28.13kJ/mol (6.79kcal/mol)A(1,2)=6.73×10~4 1/mol·minAt the same time,the relationship between the 1,2-content in polybutadiene(a) and the absolute temperature (T) can be expressed as follows:a=7.24×10~1exp(110/RT) |
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