有机化学 ›› 2016, Vol. 36 ›› Issue (10): 2344-2352.DOI: 10.6023/cjoc201603048 上一篇    下一篇

综述与进展

膦基苯磺酸(PO)金属配合物催化乙烯与极性单体的共聚反应及其机理研究进展

苏碧云a, 郏佩瑜b, 王彦昭a, 李亚宁a, 黄鹤a, 李谦定a   

  1. a 西安石油大学化学化工学院 西安 710065;
    b 宁波激智科技股份有限公司 宁波 315100
  • 收稿日期:2016-03-30 修回日期:2016-05-11 发布日期:2016-06-08
  • 通讯作者: 苏碧云,E-mail:subiyun@xsyu.edu.cn E-mail:subiyun@xsyu.edu.cn
  • 基金资助:

    陕西省教育厅专项科研基金(No.12JK0620)和陕西省科学技术研究发展计划(No.2013 KJXX-33)资助项目.

Copolymerization of Ethylene/Polar Monomer Catalyzed by Phosphinoarenesulfonate (PO) Metal Catalysts and the Catalytic Mechanism

Su Biyuna, Jia Peiyub, Wang Yanzhaoa, Li Yaninga, Huang Hea, Li Qiandinga   

  1. a College of Chemistry and Chemical Engineering, Xi'an Shiyou University, Xi'an 710065;
    b Ningbo Exciton Technology, Co., Ltd., Ningbo 315100
  • Received:2016-03-30 Revised:2016-05-11 Published:2016-06-08
  • Supported by:

    ProjectProject of Shaanxi Education Department (No.12JK0620) and the Science and Technology Research Program of Shaanxi Province (No.2013 KJXX-33).

含有膦基苯磺酸(PO)配体的烷基金属配合物表现出罕见的烯烃聚合催化性质,其不但可以催化乙烯均聚形成线性聚乙烯,而且可以催化乙烯与众多的极性单体如CH2=CHX、CO等共聚产生功能化线性聚烯烃.总结了PO配体的结构特点和(PO)Pd(Ⅱ)配合物引发的新型聚合反应,综述了(PO)Ni(Ⅱ)催化剂在催化乙烯和极性单体共聚方面的应用,以及含有膦基二磺酸配体OPO的Pd(Ⅱ)、Ru(Ⅳ)催化剂的特殊催化性质.另外,从配体的对称性、柔性和轴向官能团位阻以及纯电子效应等方面对PO金属催化剂的构效关系和共聚催化反应机理进行了探讨.

关键词: 烯烃/极性单体共聚, 膦基苯磺酸配体, Pd(Ⅱ)、Ni(Ⅱ)、Ru(IV)催化剂, 催化机理

The metal catalysts based on phosphinoarenesulfonate (PO) ligand display interesting olefin polymerization prop-erties, which not only polymerize ethylene to linear polyethylene, but also copolymerize ethylene with polar vinyl monomers or CO to functional linear copolymers. The structural features of PO ligand and the novel polymerization reactions initiated by (PO)Pd(Ⅱ) complexes are assumed. Then the application of (PO)Ni(Ⅱ) catalysts in the copolymerization of ethylene with polar monomers, as well as the rare catalytic properties of Pd(Ⅱ), Ru(Ⅳ) catalysts based on phosphine-bis(arenesulfonate) (OPO) ligands are reviewed. At last, the influence of PO ligand structural features such as symmetry, flexibility, steric effect in axial direction, as well as the pure electronic effect on the insertion and polymerization reactivity of PO metal catalyst are explored, at the same time, the catalytic reaction mechanism is also studied.

Key words: olefin/polar monomer copolymerization, phosphinoarenesulfonate ligand, Pd(Ⅱ), Ni(Ⅱ), Ru(IV) catalyst, catalytic mechanism