乙烯/1-辛烯连续溶液聚合及反应动力学  

Continuous solution polymerization of ethylene/1-octene and its reaction kinetics

作　　者：闫冰 王立娟 张永辉 牟祥升 曹晨刚 姜涛 YAN Bing;WANG Lijuan;ZHANG Yonghui;MU Xiangsheng;CAO Chengang;JIANG Tao(College of Chemical Engineering and Materials Science,Tianjin University of Science&Technology,Tianjin 300457,China;Daqing Chemical Research Center,PetroChina Petrochemical Research Institute,Daqing 163714,China)

机构地区：[1]天津科技大学化工与材料学院,天津300457 [2]中国石油石油化工研究院大庆化工研究中心,黑龙江大庆163714

出　　处：《石油化工》2023年第2期182-187,共6页Petrochemical Technology

基　　金：中国石油科技创新基金研究项目(2021DQ02-0705);中国博士后科学基金面上项目(2022M721431)。

摘　　要：以茂金属化合物Ph_(2)C(C_(5)H_(4))(C_(29)H_(36))ZrCl_(2)为主催化剂,有机硼化物[Ph_(3)C][B(C_(6)F-(5))_(4)]和Al(i-Bu)_(3)为助催化剂,通过连续溶液聚合催化乙烯/1-辛烯共聚,利用NMR、通过改变聚合工艺条件研究了反应动力学。实验结果表明,Ph_(2)C(C_(5)H_(4))(C_(29)H_(36))ZrCl_(2)/[Ph_(3)C][B(C_(6)F-(5))_(4)]/Al(i-Bu)_(3)催化体系下,乙烯/1-辛烯共聚符合一阶马尔可夫模型;乙烯/1-辛烯共聚物呈随机分布,随反应温度的升高,乙烯竞聚率逐渐增大,1-辛烯竞聚率基本不变,提高反应温度可以提高乙烯的插入量;乙烯均聚活化能高于乙烯/1-辛烯共聚活化能,共单体的加入有利于聚合反应的进行。Ethylene/1-octene was copolymerized by continuous solution polymerization using metallocene compound Ph_(2)C(C_(5)H_(4))(C_(29)H_(36))ZrCl_(2) as main catalyst,organo boride[Ph_(3)C][B(C_(6)F-(5))_(4)]and Al(i-Bu)_(3)as cocatalyst,and the kinetics of the reaction was studied through modifying the polymerization conditions and using NMR.The experimental results show that ethylene/1-octene copolymerization under Ph_(2)C(C_(5)H_(4))(C_(29)H_(36))ZrCl_(2)/[Ph_(3)C][B(C_(6)F-(5))_(4)]/Al(i-Bu)_(3)catalyst system followed the first-order Markov model.Ethylene/1-octene copolymers are randomly distributed,and the reactivity ratio of ethylene increases gradually with the increase of reaction temperature,while the reactivity ratio of 1-octene is almost unchanged.The insertion quantity of ethylene can be increased by increasing the reaction temperature.The activation energy of ethylene homopolymerization is higher than that of ethylene/1-octene copolymerization,and the addition of co-monomer is beneficial to the polymerization.

关 键 词：聚烯烃弹性体 聚合反应动力学 茂金属催化剂 高温溶液聚合 

分 类 号：TQ316.333[化学工程—高聚物工业]