有机化学 ›› 2016, Vol. 36 ›› Issue (9): 2105-2120.DOI: 10.6023/cjoc201602034 上一篇    下一篇

综述与进展

均相Cr系催化剂催化乙烯选择性齐聚反应机理研究进展

宋闯a, 毛国梁a, 刘振华a, 宁英男a, 姜涛b   

  1. a 东北石油大学化学化工学院 石油与天然气化工省重点实验室 大庆 163318;
    b 天津科技大学材料科学与化学工程学院 天津 300222
  • 收稿日期:2016-02-29 修回日期:2016-04-21 发布日期:2016-05-03
  • 通讯作者: 毛国梁 E-mail:maoguoliang@nepu.edu.cn
  • 基金资助:

    国家自然科学基金(Nos.51534004,U1362110)和教育部新世纪优秀人才支持计划(No.NCET-07-0142)资助项目.

Advances in Mechanistic Research of Ethylene Selective Oligomeri-zation Catalyzed by Homogeneous Chromium-Based Catalysts

Song Chuanga, Mao Guolianga, Liu Zhenhuaa, Ning Yingnana, Jiang Taob   

  1. a Provincial Key Laboratory of Oil & Gas Chemical Technology, College of Chemistry and Chemical Engineering, Northeast Petroleum University, Daqing 163318;
    b College of Material Science and Chemical Engineering, Tianjin University of Science & Technology, Tianjin 300222
  • Received:2016-02-29 Revised:2016-04-21 Published:2016-05-03
  • Supported by:

    Project supported by the National Natural Science Foundation of China (Nos.51534004, U1362110), and the Program for New Century Excellent Talents in University (No.NCET-07-0142).

线性α-烯烃是一类重要的化工原料,均相Cr系催化剂催化乙烯选择性齐聚制备特定的α-烯烃是近年来得到迅速发展的一个重要的研究方向,其中催化反应机理的研究对新型高效催化剂的研发具有重要的指导作用.综述了示踪原子、预制催化剂前驱体、EPR-XAS、密度泛函理论(DFT)计算等方法在乙烯选择性齐聚的反应路径和金属中心价态研究中的应用,总结了该催化反应机理研究中取得的最新成果,从方法学角度对各位学者的研究进行了比较与讨论,并在此基础上提出了双核Cr金属环机理研究的新观点,对进一步的研究方向进行了展望.

关键词: 乙烯, 铬系催化剂, 配合物, 催化剂活化, 选择性齐聚, 机理研究

Linear α-olefin is an important feed stock for chemical industry. Production of specific α-olefin through selective ethylene oligomerization catalyzed by homogeneous chromium-based catalysts is an important research on orientation under rapid development in recent years. The research of catalytic mechanism plays an important role in guiding the exploration of novel high-efficient catalysts. The application of methods such as labelled atom, organometallic precursor, EPR-XAS, density functional theory (DFT) calculation etc. in the research of reaction path and the metal oxidation state is introduced, with the latest achievement in the mechanistic research summarized. Research works carried out by various researchers are compared and discussed from methodology. New perspective on binuclear Cr metal ring mechanistic research is proposed and an outlook on the further research orientation is presented.

Key words: ethylene, chromium-based catalyst, metal complex, catalyst activation, selective oligomerization, mechanism research