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.
出处
《合成橡胶工业》
CAS
CSCD
北大核心
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)