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Elaborate Tuning in Ligand Makes a Big Difference in Catalytic Performance: Bulky Nickel Catalysts for (Co)polymerization of Ethylene with Promising Vinyl Polar Monomers
Author(s) -
Zhang Yanping,
Mu Hongliang,
Wang Xuling,
Pan Li,
Li Yuesheng
Publication year - 2019
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201900265
Subject(s) - substituent , polymer chemistry , copolymer , catalysis , monomer , polymerization , steric effects , ethylene , moiety , polar effect , acrylate , nickel , chemistry , ethylene glycol , ligand (biochemistry) , methyl acrylate , vinyl ether , materials science , photochemistry , organic chemistry , polymer , biochemistry , receptor
To reveal effect of electronic or steric modification of phosphino‐phenolate nickel complex for preparing optimized catalysts, we take elaborated studies on structure‐performance relationship by finely modifying substituents on ortho ‐phenoxy position or phosphorus moiety of this catalyst. It reveals that these newly synthesized complexes are thermally robust, and exhibits very high activity (up to 10 7 g mol Ni −1 h −1 ) in ethylene polymerization even at 120 °C. Associated with stoichiometric experiments, experimental results prove that nickel complexes bearing electron‐withdrawing substituents on ortho ‐phenoxy position or electron‐donating substituents on phosphorus atom show higher activity than contrastive catalysts toward ethylene polymerization and ethylene–methyl acrylate (MA) copolymerization. Among these catalysts, 3 g bearing a strong electron‐withdrawing substituent on ortho ‐phenoxy position exhibits the highest activity, and produces copolymers with the highest molecular weight and analogous MA incorporation. Various challenging polar vinyl monomers, like polyethylene glycol monomethyl ether acrylate, can be efficiently copolymerized with ethylene.