乙烯基降冰片烯为第三单体的三元乙丙共聚物的合成与表征  

Synthesis and characterization of ethylene-propylene terpolymers with 5-vinyl-2-norbornene as third monomer

作　　者：陈建军 CHEN Jianjun(Sinopec Beijing Research Institute of Chemical Industry Yanshan Branch,National Engineering Research Center for Synthesis of Novel Rubber and Plastic Materials,Beijing 102500,China)

机构地区：[1]中国石化北京化工研究院燕山分院、橡塑新型材料合成国家工程研究中心,北京102500

出　　处：《石油化工》2023年第1期75-81,共7页Petrochemical Technology

基　　金：中国石油化工股份有限公司资助项目(214002)。

摘　　要：以膦亚胺半茂钛为主催化剂、甲基铝氧烷为助催化剂、5-乙烯基-2-降冰片烯(VNB)为第三单体合成了乙烯-丙烯-VNB(E-P-VNB)三元共聚物。利用GPC,IR,DSC,1H NMR,13C NMR等方法分别研究了共聚单体及反应条件的影响、共聚物的硫化特性及耐热氧老化性能。实验结果表明,采用膦亚胺半茂钛催化体系成功合成了分子量高且分子量分布较窄的E-P-VNB。VNB的加入降低了乙丙共聚反应速率及收率,但VNB含量可达4.0%(w),催化活性在106g/(mol·h)以上,未出现可见的凝胶,E-P-VNB中无规结构单元占主导地位。E-P-VNB硫化胶的硫化速度快,交联密度大,高温压缩永久变形小,回弹性和物理机械性能好,耐热氧老化性能更优。The ethylene-propylene-5-vinyl-2-norbornene(E-P-VNB) terpolymers were synthezed by using titanium phosphinimide as main catalyst,methyaluminoxane as cocatalyst,and5-vinyl-2-norbornene(VNB) as third monomer.The effects of comonomer and reaction conditions and the curing properties and thermal aging properties of the terpolymer were investigated by GPC,IR,DSC,~1H NMR and13C NMR.The results show that E-P-VNB with high molecular weight and narrow molecular weight distribution is successfully synthesized by the titaniumphosphinimide catalytic system.The addition of VNB decreases the reaction rate and yield of ethyl-propylene copolymerization,but the content of VNB is up to 4.0%(w) and the catalytic activity is above 10~6 g/(mol·h) without the consequence of producing visible gel.The random structure unit is dominant in E-P-VNB.The E-P-VNB vulcanizate shows fast curing speed,high crosslinking density,little permanent set under high temperature compression,good resilience and mechanical properties,and better thermal oxidative aging performance.

关 键 词：膦亚胺半茂钛 5-乙烯基-2-降冰片烯 烯烃三元共聚 

分 类 号：TQ334.2[化学工程—橡胶工业]