催化学报

催化学报 ›› 2011, Vol. 32 ›› Issue (3): 490-494.DOI: 10.3724/SP.J.1088.2011.01040

• 研究论文 • 上一篇    下一篇

含吸电子基团配体的 α-二亚胺-Ni(Ⅱ) 上乙烯聚合反应性能

袁建超, 王学虎, 刘玉凤, 梅铜简   

  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, 甘肃兰州 730070
  • 收稿日期:2010-11-08 修回日期:2010-12-27 出版日期:2011-03-04 发布日期:2014-08-01

Catalytic Properties of α-Diimine-Ni (II) Catalyst Containing Electron Withdrawing Substituent for Ethylene Polymerization

YUAN Jianchao*, WANG Xuehu, LIU Yufeng, MEI Tongjian   

  1. Key Laboratory of Eco-Environment-Related Polymer Materials of Ministry of Education, Gansu Key Laboratory of Polymer Materials, College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, Gansu, China
  • Received:2010-11-08 Revised:2010-12-27 Online:2011-03-04 Published:2014-08-01

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摘要： 合成了一种新型的含溴 α-二亚胺配体及其 Ni 配合物, 并采用核磁共振氢谱、核磁共振碳谱、元素分析、傅里叶变换红外光谱和 X 射线光电子能谱进行了表征. 同时以二乙基氯化铝为助催化剂用于乙烯聚合反应, 考察了温度、Al/Ni 摩尔比和配体结构对聚合反应性能的影响. 结果表明, 在 25 ºC, Al/Ni 摩尔比为 600 时, 该催化剂活性最高, 可达 3.73 × 107 g/(mol.h.MPa), 与不含吸电子基团 Br 的同类催化剂活性相当, 且催化剂热稳定性和产物聚乙烯支化度明显提高.

关键词: α-二亚胺, 镍, 配合物, 后过渡金属催化剂, 二乙基氯化铝, 乙烯, 聚合, 聚乙烯

Abstract: A new Br-substituted α-diimine ligand and its corresponding Ni(II) complex, {bis[N,N′-(4-bromo-2, 6-dimethylphenyl)imino] acenaphthene}dibromonicke (2) were successfully synthesized and characterized by 1H and 13C nuclear magnetic resonance, elemental analysis, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The catalytic system, complex 2/diethylaluminium chloride (DEAC) showed higher activity for ethylene polymerization. The highest activity (3.73 × 107 g/(mol.h.MPa)) was obtained with the Al/Ni molar ratio of 600 at 25 ºC. The catalyst containing electron-withdrawing group Br showed better thermodynamic stability and almost the same catalytic activity compared with the Br-free catalyst. Branching degree was increased in the presence of electron-withdrawing group Br.

Key words: α-diimine, nickel, complex, late-transition metal catalyst, diethyllaluminium chloride, ethylene, polymerization, polyethylene