CIESC Journal

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SOME THEORETICAL PROBLEMS OF ANIONIC POLYMERIZATION OF BUTADIENE——A Study on the Association Degree of n-BuLi and Polybutadienyl-Li

金关泰; 杨大川; 杨晓勤   

  1. Beijing Institute of Chemical Technology, Beijing
  • 收稿日期:1990-05-22 修回日期:1990-08-20 出版日期:1991-12-28 发布日期:1991-12-28
  • 通讯作者: 金关泰

SOME THEORETICAL PROBLEMS OF ANIONIC POLYMERIZATION OF BUTADIENE——A Study on the Association Degree of n-BuLi and Polybutadienyl-Li

JIN Guantai; YANG Dachuan; YANG Xiaoqin

  

  1. Beijing Institute of Chemical Technology, Beijing
  • Received:1990-05-22 Revised:1990-08-20 Online:1991-12-28 Published:1991-12-28
  • Contact: JIN Guantai

摘要: This paper determined the association degree of n-BuLi and polybutadinyllithium(PBLi)by UV spec-trometry and viscometry.The experimental results of UV spectrometric analysis showed that the associationdegree of n-BuLi as well as PBLi is dependent mainly on their concentration in solutions;there may be specieswith three and two degrees of association in cyclohexane solvent respectively for n-BuLi and PBLi,i.e.the asso-ciation degree for the former is equal to 2,4 and 6;and for the latter it equals to 2 and 4.Similarly,the experi-mental results obtained by viscometric measurement showed that the average association degree N of PBLiin cyclohexane changed from 2 to 4 with increasing of its concentration in solution and decreased with addi-tion of a small amount of polar additive into the above mentioned system.Furthermore,in pure polar solvent,such as dimethoxyethane(DME),tetrahydrofuran(THF)or dioxane(DOX),PBLi is completely dissociatedinto monomeric species;however,in pure diethyl ether,due to its weak polarity a part of associated species stillcan be found.Generally speaking,all of the above results were consistent with the results of kinetic studies in-vestigated by us before.

Abstract: This paper determined the association degree of n-BuLi and polybutadinyllithium(PBLi)by UV spec-trometry and viscometry.The experimental results of UV spectrometric analysis showed that the associationdegree of n-BuLi as well as PBLi is dependent mainly on their concentration in solutions;there may be specieswith three and two degrees of association in cyclohexane solvent respectively for n-BuLi and PBLi,i.e.the asso-ciation degree for the former is equal to 2,4 and 6;and for the latter it equals to 2 and 4.Similarly,the experi-mental results obtained by viscometric measurement showed that the average association degree N of PBLiin cyclohexane changed from 2 to 4 with increasing of its concentration in solution and decreased with addi-tion of a small amount of polar additive into the above mentioned system.Furthermore,in pure polar solvent,such as dimethoxyethane(DME),tetrahydrofuran(THF)or dioxane(DOX),PBLi is completely dissociatedinto monomeric species;however,in pure diethyl ether,due to its weak polarity a part of associated species stillcan be found.Generally speaking,all of the above results were consistent with the results of kinetic studies in-vestigated by us before.