文献类型：期刊文献

中文题名：负载双核茂金属催化剂催化乙烯聚合反应动力学研究(英文)

英文题名：Study on Kinetics of Ethylene Polymerization Catalyzed by Supported Binuclear Metallocene

作者：米普科[1,2];许胜[2];刘敏[2];程琳[1]

机构：[1]华侨大学材料工程学院,厦门福建361021;[2]华东理工大学材料与工程学院,上海200237

年份：2012

卷号：26

期号：6

起止页码：537

中文期刊名：分子催化

外文期刊名：Journal of Molecular Catalysis(China)

收录：CSTPCD;;Scopus;北大核心:【北大核心2011】；CSCD:【CSCD2011_2012】；

基金：National Natural Science Foundation of China(U1162111)

语种：中文

中文关键词：乙烯聚合;动力学;负载双中心茂金属

外文关键词：kinetics; ethylene polymerization; supported binuclear metallocene

摘要：以SiO2为载体,制备了负载的双核茂金属[(η5-C5H5)Zr Cl2]2[μ,μ-(SiMe2)2(η5-allyl C5H2)2]/MAO/SiO2催化剂,以己烷为溶剂进行了淤浆条件下乙烯聚合反应,研究了扩散因素、乙烯聚合压力和聚合温度对乙烯淤浆聚合动力学参数的影响,测定了聚合反应级数和表观活化能,采用动力学和相对分子质量法计算了负载催化剂的活性中心浓度,并对链增长速率常数等动力学参数进行了计算.结果表明,以负载双核茂金属催化剂催化乙烯淤浆聚合反应速率对单体浓度呈1.11级依赖,反应活化能Ea为72.47 kJ/mol,活性中心浓度C*为0.33 mol/mol,链增长速率常数Kp为1.06×106L.(mol.h)-1.
The kinetics of ethylene polymerization catalyzed by supported binuclear metallocene catalyst [（η 5-C 5 H 5） ZrCl 2 ] 2 [μ,μ-（SiMe 2） 2（η 5-allyl C 5 H 2） 2 ]/MAO/SiO 2 in slurry phase was investigated.The effects of polymerization factors,such as diffusion index,polymerization pressure and temperature on the kinetics were studied.The kinetics parameters such as reaction order（n）,the apparent activation energy（E a） and the chain propagation rate constant（K p） were determined and the concentration of active site（C ＊） was obtained by kinetic extrapolation method.The result indicates that the supported binuclear metallocene / MAO catalyst system exhibits a higher catalytic activity than that of mononuclear system,attributed to the higher C ＊ concentration and higher K p of the former.The slurry phase polymerization reaction rates show 1.11 order dependency on monomer concentration,and E a = 72.47 kJ / mol,C ＊ = 0.33 mol / mol and K p = 1.06×10 6 L.（mol.h）-1 are found.