Elaborate Tuning in Ligand Makes a Big Difference in Catalytic Performance: Bulky Nickel Catalysts for (Co)polymerization of Ethylene with Promising Vinyl Polar Monomers

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 107 g molNi−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.