催化学报

催化学报 ›› 2011, Vol. 32 ›› Issue (4): 657-665.DOI: 10.3724/SP.J.1088.2011.01239

• 研究论文 • 上一篇    下一篇

亚乙基桥联-(4-取代茚)(芴) 锆金属络合物的合成及其催化 α-烯烃聚合反应

黄文忠, 马海燕a, 黄吉玲b   

  1. 华东理工大学金属有机研究室, 上海 200237
  • 收稿日期:2010-12-16 修回日期:2011-02-06 出版日期:2011-04-18 发布日期:2014-08-30

Ethylene-bridged (4-Substituted Indenyl) (Fluorenyl) Zirconium Complexes: Synthesis and Catalytic Behavior for α-Olefins Polymerization

HUANG Wenzhong, MA Haiyana, HUANG Jilingb   

  1. Laboratory of Organometallic Chemistry, East China University of Science and Technology, Shanghai 200237, China
  • Received:2010-12-16 Revised:2011-02-06 Online:2011-04-18 Published:2014-08-30

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摘要： 首次合成了 3 个 C1-对称亚乙基桥联型-(4-取代茚)(芴) 锆络合物 2a~2c. 并以甲基铝氧烷 (MAO) 为助催化剂用于催化丙烯聚合反应, 所得聚丙烯具有较高的等规立构规整度, 且随聚合温度的降低而升高. 0 oC 时茚环 2-位有甲基取代的络合物 2a 表现出最高的等规选择性, 为 93.6%; 而 60 oC 时络合物 2a~2c 都表现出最高的催化活性, 其中络合物 2a 的为 7.80x106 g PP/(mol-Zr.h). 该类络合物也表现出很高的催化乙烯聚合活性, 得到线性宽分布聚乙烯, 其中以茚环 4-异丙基取代的络合物 2c 活性最高, 在 Al/Zr 比低至 500 时仍可达 3.45 x106 g PE/(mol-Zr.h).

关键词: 桥联茂金属络合物, 锆, 聚合, 等规聚丙烯, 聚乙烯

Abstract: Three new ethylene-bridged (4-substituted indenyl) (fluorenyl) zirconium complexes (2a–2c) were successfully synthesized. They exhibited high isotactic selectivity, which increased with the decrease of polymerization temperature for the polymerization of propylene upon the activation of MAO (methylaluminoxane). Complex 2a with 2-methyl group on indenyl displayed the highest isotactic selectivity of 93.6% at 0 oC. At 60 oC, complexes 2a–2c reached their optimum catalytic activity, and complex 2a displayed the highest activity of 7.80x106 g PP/(mol-Zr.h). Meanwhile, complexes 2a–2c were also studied for ethylene homopolymerization and linear polyethylenes with broad molecular weight distributions were obtained. Complex 2c with 4-isopropyl substituent on indenyl showed high activity of 3.45x106 g PE/(mol-Zr.h) even at a low Al/Zr molar ratio of 500.

Key words: ansa-metallocene, zirconium, polymerization, isotactic polypropylene, polyethylene