高等学校化学学报

高等学校化学学报 ›› 2002, Vol. 23 ›› Issue (4): 595.

• 研究论文 • 上一篇    下一篇

柄型金属有机化合物(V)——锗桥连茚基及取代茚基锆化合物的合成及催化烯烃聚合

徐善生1,2, 田公路1,2, 王佰全1,2, 周秀中1,2, 梁波3, 赵亮3   

  1. 1. 南开大学化学系, 元素有机化学国家重点实验室, 天津 300071;
    2. 中国科学院上海有机化学研究所金属有机化学国家重点实验室, 上海 200032;
    3. 北京化工研究院, 北京 100013
  • 收稿日期:2000-12-22 出版日期:2002-04-24 发布日期:2002-04-24
  • 通讯作者: 王佰全(1968年出生),男,博士,教授,博士生导师,从事金属有机化学研究.E-mail:bqwang@public.tpt.tj.cn E-mail:bqwang@public.tpt.tj.cn
  • 基金资助:

    国家自然科学基金(批准号:29734142)、中国石油化工集团公司和教育部留学回国人员科研启动基金资助.

Ansa-Metallocene Complexes(V)- Synthesis and Application in Olefin Polymerization ofGerma-bridged Indenyl and Substituted Indenyl Zirconium Complexes

XU Shan-Sheng1,2, TIAN Gong-Lu1,2, WANG Bai-Quan1,2, ZHOU Xiu-Zhong1,2, LIANG Bo3, ZHAO Liang3   

  1. 1. Department of Chemistry, State Key laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin 300071, China;
    2. State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China;
    3. Beijing Chemical Research Institution, Beijing 100013, China
  • Received:2000-12-22 Online:2002-04-24 Published:2002-04-24

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摘要： 锗桥连茚及取代茚配体相继与丁基锂及ZrCl4作用,生成锗桥连茚基及取代茚基锆化合物Me2Ge(2-R1-4-R2-Ind)2ZrCl2[R1=R2=H(1);R1=Me,R2=H(2);R1=Me,R2=Ph(3)].化合物1-3均为内消旋和外消旋异构体的混合物,通过多次重结晶得到化合物1和2的纯外消旋异构体及化合物3的内消旋异构体。由元素分析和1H NMR谱表征了化合物的分子结构。研究了在甲基铝氧烷(MAO)的助催化下,化合物1-3对乙烯和丙烯聚合的催化性能。由锗桥连茚基化合物1-3得到的聚乙烯的分子量分布比一般茂金属催化剂略宽。内消旋和外消旋异构体的混合物(3)由于两个催化活性中心不等同而使得到的聚乙烯的分子量分布相当宽。外消旋异构体1和2催化丙烯聚合得到高等规聚丙烯。

关键词: 柄型茂金属化合物, 烯烃聚合, 等规聚丙烯, 锆

Abstract: Germa-bridged indenyl and substituted indenyl ligands react with n-butyl lithium and ZrCl4 togive Germa-bridged indenyl and substituted indenyl zirconium complexes Me,Ge (2-R1-4-R2-Ind)2 ZrCl2[R1=R2=H(1); R1=Me, R2 =H(2);R1=Me, R2=Ph(3) ].Compounds 1-3 are mixture of rac andmeso isomers.After fractional crystallization pure rac-1, rac-2 and meso-3 were isolated.Compounds 1-3were characterized by 1H NMR and elemental analyses and used for the polymerization of ethylene andpropylene in the presence of methyl aluminoxane (MAO).The molecular weight distribution of thepolyethylene obtained with compounds 1-3 is slightly broader than that with general metallocenes.A-mong them, the molecular weight distribution of the polyethylene obtained with the mixture of rac-3 andmeso-3 is much broader due to the two unequal catalytic active centers in the system.Compounds rac-1 andrac-2 catalyzed propylene polymerization to give isotactic polypropylene.

Key words: Ansa-Metallocene, Olefin polymerization, Isotactic polypropylene, Zirconium

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