膦胺铬和双膦铬催化乙烯选择性齐聚研究进展

doi:10.19894/j.issn.1000-0518.200250

摘要/Abstract

摘要： 乙烯选择性齐聚制备线性α-烯烃是在学术界和工业界均受到高度重视,具有目标产物选择性高、产品易分离和经济效益显著等特点。铬系配合物催化剂在催化乙烯选择性齐聚反应中综合性能较好,有良好的发展和应用前景。近年来的研究表明,配体结构对催化剂性能有重要影响;反应体系中通入H₂可以改善齐聚产物的分布并抑制低聚物的生成;开发不以甲基铝氧烷为助催化剂的催化体系可降低催化剂成本;而乙烯选择齐聚机理及金属中心氧化态对催化剂的设计有重要的指导意义。本文主要从以上几个方面介绍了膦胺铬和双膦铬配合物在催化乙烯选择性齐聚中的研究进展,分析了目前乙烯选择性四聚工业化急需解决的问题,展望了该领域未来的发展方向。

关键词: 乙烯选择性齐聚, 线性α-烯烃, 膦胺铬, 双膦铬, 齐聚机理

Abstract: The selective oligomerization of ethylene to prepare linear α-olefins has been highly valued in both academia and industry because of its high target product selectivity, easy product separation, and significant economic benefits. Chromium-based catalysts have good overall performance in catalyzing selective oligomerization of ethylene, and are a class of catalysts with broad application prospects. Recent studies have shown that the ligand structure has an important effect on the catalyst performance; the introduction of hydrogen in the reaction system can improve the distribution of oligomerization products and inhibit the formation of polymers; development of the catalyst without methylaluminoxane as a cocatalyst can reduce the costs of the catalyst; the ethylene selective oligomerization mechanism and the oxidation state of the central metal have important guiding significance to the design of the catalyst. Recent progress in the research of phosphoamine chromium and diphosphinoamine chromium complexes in the selective oligomerization of ethylene is reviewed from the above aspects, with the problems to be solved in the industrializaion of ethylene selective tetramerization and the further development in ethylene selective oligomerization.

Key words: Ethylene selective oligomerization, Linear α-olefin, Phosphoamine chromium, Diphosphinoamine chromium, Oligomerization mechanism

中图分类号:

O614.6

魏雪莹, 吴玮, 乃永宁, 姜梦圆, 田诗伟, 毛国梁. 膦胺铬和双膦铬催化乙烯选择性齐聚研究进展[J]. 应用化学, 2021, 38(2): 136-156.

WEI Xue-Ying, WU Wei, NAI Yong-Ning, JIANG Meng-Yuan, TIAN Shi-Wei, MAO Guo-Liang. Research Progress on the Selective Oligomerization of Ethylene Catalyzed by Phosphoramine Chromium and Diphosphinoamine Chromium[J]. Chinese Journal of Applied Chemistry, 2021, 38(2): 136-156.

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