以双四氢糠丙烷为极性调节剂的苯乙烯/异戊二烯/丁二烯三元共聚动力学  

Kinetics study on styrene /isoprene /butadiene copolymerization with 2,2-di( tetrahydrofuran-2-yl) propane as polar modifier

作　　者：康新贺[1,2,3] 赵素合[1,2] 王妮妮[3] 刘辉[3] 孙文娟[3] 徐林[3] 李传清[3] 于国柱[3] 

机构地区：[1]北京化工大学有机无机复合材料国家重点实验室,北京100029 [2]北京化工大学北京市新型高分子材料制备与加工重点实验室,北京100029 [3]中国石化北化院燕山分院橡塑新型材料合成国家工程研究中心,北京102500

出　　处：《合成橡胶工业》2014年第3期161-164,共4页China Synthetic Rubber Industry

基　　金：中国石油化工股份有限公司科研资助项目(213001)

摘　　要：以正丁基锂(n-BuLi)为引发剂,双四氢糠丙烷(DTHFP)为极性调节剂,环己烷为溶剂,采用负离子聚合法合成了线型苯乙烯(St)-异戊二烯(Ip)-丁二烯(Bd)三元共聚物,考察了三元共聚合总反应速率的影响因素,研究了三元共聚合反应动力学,并与传统极性调节剂四氢呋喃(THF)体系进行了比较。结果表明,在单体质量分数为12%,St/Ip/Bd(质量比)为20/40/40,设计单臂相对分子质量为10×104的条件下,随着聚合反应温度的升高或DTHFP/n-BuLi(摩尔比)的增加,总转化率和总反应速率逐渐增大,聚合反应的假一级表观增长反应速率常数增大;表观增长反应活化能和频率因子均随DTHFP/n-BuLi值的增加而减小;DTHFP在用量较小的情况下与较大THF用量的效果相当,促进聚合反应速率的能力明显高于THF。The linear styrene（St）-isoprene（Ip）-butadiene （Bd） terpolymer was synthesized with n-BuLi as initiator,2,2-di （tetrahydrofuran-2-yl） propane （DTHFP） as polar modifier,cyclohexane as solvent by anionic polymerization.The influence factors of total reaction rate for St/Ip/Bd copolymerization were investigated,the copolymerization kinetics was studied,and the comparison was conducted with traditional polar modifier tetrahydrofuran（THF）.The results showed that under the conditions of mass fraction of monomers 12％,St/Ip/Bd（mass ratio） 20/40/40,designed singl-arm relative molecular mass 10 × 104,the total conversion,the total reaction rate of copolymerization and the pseudo first order apparent chain propagation reaction rate constants increased gradually with the increase of polymerization temperature and DTHFP/n-BuLi （mole ratio）,and the activation energy and frequency factor of apparent chain propagation reaction decreased with the increase of DTHFP/n-BuLi.A small amount of DTHFP had the same modifying effect as that of a large amount of THF,and DTHFP was superior to THF in accelerating the copolymerization.

关 键 词：苯乙烯-异戊二烯-丁二烯三元共聚物 双四氢糠丙烷 四氢呋喃 正丁基锂 负离子聚合法 转化率 聚合动力学 

分 类 号：O631.5[理学—高分子化学]