耐高温茂金属催化剂催化乙烯与降冰片烯共聚  

Copolymerization of ethylene/norbornene catalyzed by high temperature resistant metallocene catalyst

作　　者：张永辉 葛腾杰[2] 牟祥升 窦洪鑫 闫冰 曹晨刚 姜涛 Zhang Yonghui;Ge Tengjie;Mu Xiangsheng;Dou Hongxin;Yan Bing;Cao Chengang;Jiang Tao(College of Chemical Engineering and Materials Science,Tianjin University of Science&Technology,Tianjin 300457,China;Daqing Chemical Research Center of China,CNPC 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]中国石油天然气股份有限公司石油化工研究院大庆化工研究中心,黑龙江大庆163714

出　　处：《合成树脂及塑料》2024年第3期7-10,20,共5页China Synthetic Resin and Plastics

基　　金：中国石油科技创新基金项目(2021DQ02-0705)。

摘　　要：合成了一种用于乙烯与降冰片烯高温溶液共聚合的高活性耐高温茂金属催化剂,研究了反应温度、茂金属催化剂浓度、n(Al)∶n(Zr)、降冰片烯浓度等对催化剂活性的影响,并对乙烯-降冰片烯共聚物进行了分析和表征,确定了制备乙烯-降冰片烯共聚物的高温溶液聚合工艺条件。结果表明:反应温度为140℃时,催化剂活性高达6.7×10^(6)g/(mol·h),催化剂寿命达到30 min以上。最佳聚合条件:反应温度为140℃,茂金属催化剂浓度为6×10^(-5)mol/L,乙烯压力为1 MPa,n(Al)∶n(Zr)为250,n(B)∶n(Zr)为1.1,反应时间为30 min;最佳聚合条件下共聚物中的降冰片烯插入率达34.44%(y),密度约为0.98 g/cm^(3),玻璃化转变温度为135.8℃。A high activity and high temperature resistant metallocene catalyst for high-temperature solution copolymerization of ethylene/norbornene was synthesized.The effects of reaction temperature,molar ratio of Al to Zr,metallocene catalyst and norbornene concentration on the activity of the catalyst system were studied.The ethylene-norborene copolymer was characterized and whose polymerization conditions were determined.The results show that the activity of the catalyst system is up to 6.7×10^(6)g/(mol·h)and the catalyst life is longer than 30 min at 140℃.The optimum polymerization condition is as follows:the reaction temperature is 140℃,the concentration of metallocene catalyst is 6×10^(-5)mol/L,the ethylene pressure is 1 MPa,the molar ratio of Al to Zr is 250,the molar ratio of B to Zr is 1.1,and the reaction time is 30 min.Under the optimal conditions the insertion rate of norbornene in the polymer is as high as 34.44%(y),the density is about 0.98 g/cm3,and tg is 135.8℃.

关 键 词：茂金属催化剂 乙烯-降冰片烯共聚物 溶液聚合 相对分子质量分布 熔体流动速率 

分 类 号：TQ317[化学工程—高聚物工业]