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化学学报
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化学学报 ›› 2011, Vol. 69 ›› Issue (07): 798-802. 上一篇    下一篇

研究论文

高活性a-二亚胺基Ni(II)配合物的合成、表征及其催化乙烯聚合研究

袁建超*，刘玉凤，梅铜简，王学虎   

  1. (生态环境相关高分子材料教育部重点实验室 甘肃省高分子材料重点实验室
    西北师范大学化学化工学院 兰州 730070)
  • 投稿日期:2010-10-16 修回日期:2010-12-10 发布日期:2010-12-22
  • 通讯作者: 袁建超 E-mail:jianchaoyuan@nwnu.edu.cn
  • 基金资助:

    国家自然科学基金

High Active a-Diimine Nickel(II)/DEAC Catalyst System for Ethylene Polymerization

YUAN Jian-Chao, LIU Yu-Feng, MEI Tong-Jian, WANG Xue-Hu   

  1. (Key Laboratory of Eco-Environment-Related Polymer Materials, Ministry of Education, Gansu Key Laboratory of Polymer Materials, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070)
  • Received:2010-10-16 Revised:2010-12-10 Published:2010-12-22
  • Contact: Jian-Chao YUAN E-mail:jianchaoyuan@nwnu.edu.cn

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设计并合成了一种新型的含有强供电子、大体积基团tert-butyl的α-二亚胺配体1及其Ni(II)配合物2, 并利用1H NMR, 13C NMR, 元素分析, FT-IR, XPS对其进行了表征. 配合物2/氯化二乙基铝(DEAC)组成的催化体系催化乙烯聚合显示了非常高的活性, 最高可达3.15×108 g PE/(mol•Ni•h•MPa). 所得聚乙烯的支化度也较高, 最高可达131 branches/1000C. 并研究了聚合条件如聚合反应温度、Al/Ni物质的量比、反应时间等因素对催化剂活性的影响. 在反应温度为5 ℃, Al/Ni物质的量比为600时, 该催化体系催化乙烯聚合活性最高. 采用1H NMR, GPC, DSC, TG分别对聚合物进行了表征.

关键词: α-二亚胺配体, 镍(II)配合物, 后过渡金属催化剂, 乙烯聚合

A new tert-butyl-substituted α-diimine compound 1 and its corresponding Ni(II) complex, {bis[N,N -(4-tert-butyl-2,6-dimethylphenyl)imino]acenaphthene}dibromonickel (2), were successfully synthesized and characterized by 1H NMR, 13C NMR, elemental analysis, FT-IR and XPS. Complex 2 with sterically bulky, donating group tert-butyl, activated by diethylaluminum chloride (DEAC) produces very active catalyst system for the polymerization of ethylene [3.15×108 g PE/(mol•Ni•h•MPa)] and led to a branched polyethylene (ca. 131 branches/1000 C). The effects of the Al/Ni molar ratio, polymerization temperature and polymerization time on the catalyst activity also were investigated. The catalyst system 2/DEAC showed the highest activity with the 600 of Al/Ni molar ratio at 5 ℃. The polyethylene (PE) samples were characterized by 1H NMR, GPC, DSC and TG.

Key words: α-diimine ligand, Nickel(II) complex, late transition metal catalyst, ethylene polymerization

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