高等学校化学学报 ›› 2005, Vol. 26 ›› Issue (3): 571.

• 研究论文 • 上一篇    下一篇

四甲基环戊二烯基苯氧基二氯化钛衍生物的合成及催化烯烃聚合研究

张越涛, 母瀛, 吕春胜, 张帆, 陈丛喜   

  1. 吉林大学化学学院, 超分子结构与材料教育部重点实验室 长春 130012
  • 收稿日期:2004-02-17 出版日期:2005-03-10 发布日期:2005-03-10
  • 通讯作者: 母 瀛(1958年出生),男,博士,教授,博士生导师,从事有机和金属有机合成及催化研究.E-mail:ymu@mail.jlu.edu.cn E-mail:ymu@mail.jlu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号:20374023和29734143)资助.

Synthesis of Tetramethylcyclopentadienyl-phenoxytitanium Dichlorides and Their Catalytic Properties for Ethylene Polymerization

ZHANG Yue-Tao, MU Ying, LV Chun-Sheng, ZHANG Fan, CHEN Cong-Xi   

  1. Key Laboratory for Supramolecular Structure and Materials of Ministry of Education, College of Chemistry, Jilin University, Changchun 130012, China
  • Received:2004-02-17 Online:2005-03-10 Published:2005-03-10

摘要: 4-R1-6-R-2-Me4CpH-PhOH[R1=tBu,R=tBu(1);R1=H,R=tBu(2),Ph(3),Me(4)]经双三甲基硅基化后与TiCl4反应,合成了4种限制几何构型茂金属催化剂4-R1-6-R-2-Me4Cp-PhOTiCl2[R1=tBu,R=tBu(5);R1=H,R=tBu(6),Ph(7),Me(8)],合成产率有较大提高.这些茂金属化合物经过iBu3Al和Ph3C+B(C6F5)4-活化后对乙烯聚合有很好的催化活性,并生成乙基支化聚乙烯.

关键词: 茂金属催化剂, 烯烃聚合反应, 单茂钛化合物, 均相催化

Abstract: Four constrained geometry tetramethylcyclopentadienyl-phenoxytitanium dichlorides 4-R1-6-R-2-Me4Cp-PhOTiCl2[R1= tBu, R= tBu(5); R1=H, R= tBu(6), Ph(7), Me(8)] were successfully prepared from the reaction of TiCl4 with the corresponding trimethylsilyl-functionalized ligands, which was obtained by treating the ligands 4-R1-6-R-2-Me4CpH-PhOH[R1= tBu, R= tBu(1); R1=H, R= tBu(2), Ph(3), Me(4)] with nBuLi and Me3SiCl subsequently. The yields are higher than those previously reported. When activated with iBu3Al and Ph3C+B(C6F5)-4, complexes 5—8 exhibit a reasonable catalytic activity for ethylene polymerization, producing ethyl branched polyethylenes. Influences of the molecular structure of these complexes and polymerization conditions on their catalytic properties were studied. Polyethylenes obtained with these catalysts were characterized.

Key words: Metallocene catalysts, Olefin polymerization, Monocyclopentadienyl titanium complex, Homogeneous catalysis

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