摘要
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.
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.
出处
《有机化学》
SCIE
CAS
CSCD
北大核心
2016年第10期2344-2352,共9页
Chinese Journal of Organic Chemistry
基金
陕西省教育厅专项科研基金(No.12JK0620)
陕西省科学技术研究发展计划(No.2013 KJXX-33)资助项目~~
