高等学校化学学报

高等学校化学学报 ›› 2002, Vol. 23 ›› Issue (11): 2089.

• 研究论文 • 上一篇    下一篇

联苯基桥连双核茂锆化合物的合成及催化乙烯聚合

邓小斌1, 徐善生1, 王佰全1,2, 周秀中1, 杨玲3, 李于飞3, 胡友良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. 中国科学院化学研究所, 北京100080
  • 收稿日期:2001-09-11 出版日期:2002-11-24 发布日期:2002-11-24
  • 通讯作者: 王佰全(1968年出生),男,博士,教授,博士生导师,从事金属有机化学及均相催化研究.E-mail:bqwang@public.tpt.t j.cn E-mail:bqwang@public.tpt.t j.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(2001-345)资助

Synthesis and Application in Ethylene Polymerization of p-Biphenylene-bridged Dinuclear Zirconocenes

DENG Xiao-Bin1, XU Shan-Sheng1, WANG Bai-Quan1,2, ZHOU Xiu-Zhong1, YANG Ling3, LI Yu-Fei3, HU You-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;
    3. Institute of Chemistry, Chinese Academy of Sciences, Beijing 100080, China
  • Received:2001-09-11 Online:2002-11-24 Published:2002-11-24

PDF (PC)

被引次数

29

摘要： 4,4′-二溴联苯与n-BuLi反应得到对-联苯基二锂,再与四甲基环戊烯酮进行羰基加成,酸催化脱水,一步得到对-联苯基桥连四甲基环戊二烯配体4-(C5Me4H)C6H4-C6H4(C5Me4H)-4(1).配体1相继与n-BuLi和ZrCl4反应得到相应的联苯基桥连双(单茂三氯化锆)4-(C5Me4ZrCl3)C6H4—C6H4(C5Me4ZrCl3)-4,不经分离直接与环戊二烯基锂或茚基锂反应得到相应的双核锆化合物4-(C5MeZrCl2Cp′)C6H4—C6H4·(C5Me4ZrCl2Cp′)-4[Cp′=C5H5(2),C9H7(3)].研究了在MAO(MethylAluminoxane)助催化下,化合物2和3对乙烯聚合的催化性能.化合物2和3都显示了非常高的催化活性,并在较高的温度下达到最高活性.

关键词: 茂金属化合物, 双核, 锆, 茚基

Abstract: ?Dibromobiphenyl reacted with n-BuLi to form 4,4′-dilithiobiphenyl, which further reacted with 2,3,4,5-tetramethylcyclopent-2-enone following the elimination of water to give the ligand 4-(C5Me4H)C6H4—C6H4(C5Me4H)-4(1). Ligand 1 reacted with n-BuLi and ZrCl4 to form the p-biphenylene-bridged dinuclear tetramethylcyclopentadienyl zirconium trichlorides 4-(C5Me4ZrCl3)·C6H4—C6H4(C5Me4ZrCl3)-4, which reacted in situ with cyclopentadienyl lithium(CpLi) or indenyl lithium(IndLi) to give the corresponding p-biphenylene-bridged dinuclear zirconocenes 4-(C5Me4ZrCl2Cp′)C6H4-C6H4(C5Me4ZrCl2Cp′)-4 [Cp′= Cp(2), Ind(3)]. The zirconocenes 2 and 3 were characterized by 1H NMR, MS spectra and elemental analysis, and were studied for ethylene polymerization with methyl aluminoxane(MAO) as cocatalyst. Both 3 and 4 show very high activities and reach the maximum at a higher temperature, indicating that the introduction of the p-biphenylene-bridge increased the catalytic activity and thermal stability of the dinuclear zirconocene catalysts.

Key words: Metallocene, Dinuclear, Zirconium, Indenyl

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