Abstract
Mononuclear neutral nickel catalyst Ni1 and binuclear complexes Ni2 and Ni3 based on rigid 9,9-dimethylxanthene frameworks featuring short Ni−Ni distances were synthesized, characterized and applied in ethylene (co)polymerization. Binuclear catalyst Ni2 exhibited higher activity in ethylene polymerization than corresponding mononuclear Ni1, and produce higher molecular weight polymer with a bimodal molecular weight distribution. Catalyst Ni2 is remarkably thermally robust, and still displaying promising activity at 93 °C. The polymer microstructure produced by Ni1 reveals a hyperbranched structure with a variety of branch types, while Ni2 product features methyl branches primarily. In the presence of comonomer 1,5-hexadiene, 1,7-octadiene, and methyl 10-undecenoate, mononuclear Ni1 suffers from either low catalytic activity or poor incorporation efficiency, while binuclear catalyst Ni2 effectively enchained these comonomers into the polymer chain, giving copolymer with unique microstructures.
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