Highly Active New a-Diimine Nickel Catalyst for Polymerization of Ethylene

A new a-diimine ligand 1a,bis[N,N'-(4-tert-butyl-2,6-dimethylphenyl)imino]-2,3-butanediylidene and its corresponding Ni(II)complex 2a,{bis[N,N'-(4-tert-butyi-2,6-dimethylphenyi)imino]-2,3-butanediylidene}dibromonickel were successfully synthesized,and characterized by 1H NMR,13C NMR,Fourier transform infrared spectroscope(FTIR),elemental analysis and X-ray photoelectron spectroscopy(XPS).a-Diimine ligand 1b,bis[N,N'-(2,6-dimethylphenyl)imino]-2,3-butanediylidene and its corresponding Ni(Ⅱ)complex 2b,{bis[N,N'-(2,6-dimethylphenyl)imino]-2,3-butanediylidene}dibromonickel were also synthesized and characterized for comparison.The pre-catalyst 2a with sterically bulky,electron-donating group tert-butyl,activated by diethylaluminum chloride (DEAC)and tested in the polymerization of ethylene,was very highly active[2.01 × 107g PE/(mol Ni.h·0.1 MPa)]and led to a very highly branched polyethylene(ca.35-103 branches/1000 C).The state of the polyethylene obtained varied from plastic,elastomer polymers to the oil-like hyperbranched polymers.