高等学校化学学报

高等学校化学学报 ›› 2002, Vol. 23 ›› Issue (1): 143.

• 研究论文 • 上一篇    下一篇

新型二茂锆化合物(1,2-Ph2-4-PrCp)2ZrCl2的合成及催化烯烃聚合反应研究

张帆, 母瀛, 陈从喜   

  1. 吉林大学化学系, 长春 130023
  • 收稿日期:2000-05-17 出版日期:2002-01-24 发布日期:2002-01-24
  • 通讯作者: 母瀛(1958年出生),男,博士,教授,博士生导师,从事有机合成及催化方面的研究.
  • 基金资助:

    国家自然科学基金(批准号:29734143;29672013)资助

Synthesis of A Novel Zirconocene Complex (1,2-Ph2-4-PrCp)2ZrCl2 and Catalysis for Olefin Polymerization

ZHANG Fan, MU Ying, CHEN Cong-Xi    

  1. Department of Chemistry, Jilin University, Changchun 130023, China
  • Received:2000-05-17 Online:2002-01-24 Published:2002-01-24

PDF (PC)

摘要： 3,4-二苯基环戊-2-烯-1-酮与丙基锂反应,经酸化脱水得新环戊二烯衍生物1,2-二苯基-4-丙基-1,3-环戊二烯(1).用丁基锂处理1得到相应的环戊二烯基锂,再与ZrCl4在甲苯中反应,生成大立体阻碍二氯二茂锆化合物(1,2-Ph2-4-PrCp)2ZrCl2(2).化合物1和2均经元素分析和核磁共振谱学表征.经甲基铝氧烷(MAO)活化,化合物2在较低Al/Zr比条件下既可有效地催化乙烯聚合,生成高分子量、高熔化温度聚乙烯.2/MAO体系对丙烯聚合表现出高活性,生成低分子量齐聚物,其分子量随聚合温度的降低而升高.

关键词: 茂金属催化剂, 烯烃聚合反应, 二茂锆化合物, 均相催化

Abstract: A new cyclopentadiene derivative 1,2-diphenyl-4-propyl-1,3-cyclopentadiene(1) was synthesized by reaction of 3,4-diphenyl-2-cyclopentenone with n propyl lithium. 1 was treated with n butyl lithium and then reacted with ZrCl4 in toluene to give sterically bulky unbridged zirconocene dichloride(1,2-Ph2-4-PrCp)2ZrCl2(2). 1H NMR and 13 C NMR spectroscopic analyses reveal its C2v-symmetric conformation in solution. Upon activation with methylaluminoxane(MAO), 2 effectively polymerizes ethylene and produces high molecular weight polyethylenes with high melting transition temperatures at low Al/Zr ratios. At ambient conditions, 2/MAO system shows high catalytic activity in propylene polymerization and produces oily oligomers.

Key words: Metallocene catalyst, Zirconocene, Olefin polymerization, Homogeneous catalysis

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