SYNTHESIS OF NOVEL THIOPHENEDIMETHYLENE BRIDGED HOMOBINUCLEAR METALLOCENES AND THEIR CATALYTIC PROPERTIES FOR ETHYLENE POLYMERIZATION

作     者：Xi-jie Liu Jun-quan Sun Hai-ying Zhang Xiao-hui Xiao and Feng Lin Department of Chemical Engineering,College of Material and Chemical Engineering,Zhejiang University,Hangzhou 310027,China 

作者机构：Department of Chemical Engineering College of Material and Chemical Engineering Zhejiang University Hangzhou 310027 

出 版 物：《Chinese Journal of Polymer Science》 (高分子科学（英文版）)

年 卷 期：2006年第24卷第1期

页      面：21-27页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 0817[工学-化学工程与技术] 08[工学] 070305[理学-高分子化学与物理] 080501[工学-材料物理与化学] 0805[工学-材料科学与工程（可授工学、理学学位）] 0703[理学-化学] 

基　　金：This work was financially supported by the National Natural Science Foundation of China(Nos.20374043 20074028)China Petroleum & Chemical Corporation(No.X503027) 

主　　题：Binuclear metallocene Thiophenedimethylene bridged Ethylene polymerization. 

摘      要：By treating disodium（thiophenedimethylene）dicyclopentadienide C4H2S（CH2C5H4Na）2 with two equivalent of CpTiCl3 or CpZrC13 DME at 0℃ in THF, two new thiophenedimethylene bridged binuclear metallocenes [Cl2MC5H5][C5H4CH2C4H2SCH2C5H4][C5H5MCl2] （M = Ti 3, M = Zr 4） were synthesized in high yield and their structures were characterized by ^1H-NMR. These complexes were used as catalysts for ethylene polymerization in the presence of methylaluminoxane （MAO）. The effects of polymerization temperature, time, concentration of catalyst, molar ratio of MAO/Cat on polymerization were studied in detail. The catalytic activities of thiophenedimethylene bridged binuclear metallocene catalysts （3, 4） reached 2.44 × 10^5 g PE mol^-1 cat^-1· h^-1, 9.61 × 10^5 g PE mol^-1 · cat^-1· h^-1 respectively, which are higher than that of pheneyldimethylene bridged binuclear metallocene catalysts and much higher than that of corresponding mononuclear metallocenes （Cp2TiCl2 and Cp2ZrCl2）. The molecular weight distribution curves of polyethylenes produced by binuclear metallocene catalysts （3, 4） and by mononuclear metallocene catalyst have only single peak, but the former （MWD = 3.5-4.7） is obviously broader than the latter （MWD = 2.0-2.2）.