COPOLYMERIZATION OF ETHYLENE AND 1-HEXENE WITH TiCl_4/MgCl_2 CATALYSTS MODIFIED BY 2,6-DIISOPROPYLPHENOL  

作　　者：Sheng-jie Xia Zhi-sheng Fu Xiao-yan Liu 范志强 

机构地区：[1]MOE Key Laboratory of Macromolecular Synthesis and Functionalization,Department of Polymer Science and Engineering,Zhejiang University

出　　处：《Chinese Journal of Polymer Science》2013年第1期110-121,共12页高分子科学（英文版）

基　　金：supported by the National Natural Science Foundation of China (No. 20874084);the Special Research Fund for the Doctoral Program of Higher Education (No. 20100101110136)

摘　　要：A supported TiCl4/MgCl2 catalyst without internal electron donor （O-cat） was prepared firstly. Then it was modified by 2,6-diisopropylphenol to make a novel modified catalyst （M-cat）. These two catalysts were used to catalyze ethylene/l-hexene copolymerization and l-hexene homopolymerization. The influence of cocatalyst and hydrogen on the catalytic behavior of these two catalysts was investigated. In ethylene/l-hexene copolymerization, the introduction of 2,6- iPr2C6H3O- groups did not deactivate the supported TiCl4/MgCl2 catalyst. Although the 1-hexene incorporation in ethylene/1- hexene copolymer prepared by M-cat was lower than that prepared by O-cat, the composition distribution of the former was narrower than that of the latter. Methylaluminoxane （MAO） was a more effective activator for M-cat than triisobutyl- aluminium （TIBA）. MAO led to higher yield and more uniform chain structure. In 1-hexene homopolymerization, the presence of 2,6-ipr2C6H3O- groups lowered the propagation rate constants. Two types of active centers with a chemically bonded 2,6-iprzCaH3O- group were proposed to explain the observed phenomena in M-cat.A supported TiCl4/MgCl2 catalyst without internal electron donor （O-cat） was prepared firstly. Then it was modified by 2,6-diisopropylphenol to make a novel modified catalyst （M-cat）. These two catalysts were used to catalyze ethylene/l-hexene copolymerization and l-hexene homopolymerization. The influence of cocatalyst and hydrogen on the catalytic behavior of these two catalysts was investigated. In ethylene/l-hexene copolymerization, the introduction of 2,6- iPr2C6H3O- groups did not deactivate the supported TiCl4/MgCl2 catalyst. Although the 1-hexene incorporation in ethylene/1- hexene copolymer prepared by M-cat was lower than that prepared by O-cat, the composition distribution of the former was narrower than that of the latter. Methylaluminoxane （MAO） was a more effective activator for M-cat than triisobutyl- aluminium （TIBA）. MAO led to higher yield and more uniform chain structure. In 1-hexene homopolymerization, the presence of 2,6-ipr2C6H3O- groups lowered the propagation rate constants. Two types of active centers with a chemically bonded 2,6-iprzCaH3O- group were proposed to explain the observed phenomena in M-cat.

关 键 词：Supported Ziegler-Natta catalyst 2 6-Diisopropylphenol Ethylene copolymerization Active center distribution. 

分 类 号：O631.3[理学—高分子化学]