高等学校化学学报

高等学校化学学报 ›› 2011, Vol. 32 ›› Issue (5): 1200.

• 研究论文 • 上一篇    下一篇

含溴α-二亚胺镍(Ⅱ)配合物的合成、表征及催化乙烯聚合反应

袁建超,梅铜简,王学虎,刘玉凤   

  1. 西北师范大学化学化工学院, 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, 兰州 730070
  • 收稿日期:2010-08-05 修回日期:2010-09-30 出版日期:2011-05-10 发布日期:2011-04-11
  • 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(批准号: 20964003)、2009年教育部留学回国人员科研启动基金(批准号: [2009]1341)和2009年人力资源和社会保障部留学人员科技活动项目择优资助项目(批准号: 2009[416])资助.

Synthesis and Characterization of α-Diimine Nickel(Ⅱ) Catalyst Containing Br Groups for Ethylene Polymerization

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

  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, China
  • Received:2010-08-05 Revised:2010-09-30 Online:2011-05-10 Published:2011-04-11
  • Contact: YUAN Jian-Chao E-mail:jianchaoyuan@nwnu.edu.cn
  • Supported by:

    国家自然科学基金(批准号: 20964003)、2009年教育部留学回国人员科研启动基金(批准号: [2009]1341)和2009年人力资源和社会保障部留学人员科技活动项目择优资助项目(批准号: 2009[416])资助.

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摘要： 合成了一种新型含溴?-二亚胺及其镍配合物, 采用1H NMR、13C NMR、FT-IR、元素分析和XPS表征. 配合物作为催化剂以MAO(甲基铝氧烷)为助催化剂催化乙烯聚合得到高支化度的聚乙烯，并研究了聚合条件如Al/Ni摩尔比、聚合温度以及配体结构对催化活性的影响，表明在反应温度为25?C，Al/Ni摩尔比为800,该催化剂催化乙烯聚合活性高达5.50 ×106gPE/(molNi?h?Bar)，且催化剂具有较好的热稳定性. 与不含吸电子基团Br的同类催化剂比较，活性相当，催化剂的热稳定性和聚合所得聚乙烯支化度有较大程度的提高. 聚合物测定采用1H NMR、13C NMR、GPC、TG、DSC表征.

关键词: 　含溴α-二亚胺, 镍(Ⅱ)配合物, 乙烯聚合, 支化聚乙烯

Abstract: A new Br-substituted alpha-diimine compound and its corresponding Ni(II) complex, {bis[N,N’-(3-bromo-2,4,6-trimethylphenyl)imino]acenaphthene}dibromonickel was successfully synthesized, and characterized by 1H NMR, 13C NMR, elemental analysis, FT-IR and XPS. The pre-catalyst 2 activated by methylaluminoxane (MAO) was tested in the polymerization of ethylene, showed to be highly active (5.50×106gPE/ (molNi.h.bar)). The catalyst system 2/MAO showed the highest activity with the 800 of Al/Ni molar ratio at 25 ?C. It was found that the catalyst containing electron-withdrawing groups Br showed better thermal stability and almost the same catalytic activity. At same time, branching degrees was increased in the presence of electron-withdrawing groups Br. The polymer were characterized by 1H NMR, 13C NMR, GPC、TG、DSC.

Key words: alpha-Diimine ligand Bromo-containing, Nickel (II) complexes, Ethylene polymerization, Branched Polyethylene

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