Quinolinyl Imidazolidin-2-imine Nickel Catalyzed Efficient Copolymerization of Norbornene with para-Chlorostyrene

A series of novel quinolinyl imidazolidin-2-imine nickel complexes with different substituents on the imidazolidin-2-imine ligand were synthesized and characterized. The complexes in the presence of methylaluminoxane (MAO) as a cocatalyst catalyzed the copolymerization of norbornene (N) and styrene (S) or para-chlorostyrene (CS) with high activity (up to 1070 kg·mol−1·h−1). The installation of sterically bulky substituents on the imidazolidine-2-imine ligand was effective for the increase of the molecular weight and the comonomer content, affording high molecular weight copolymers with tunable CS content (0.57 mol%–11.7 mol%), in which the existence of Cl group can provide reaction site for the further functionalization of copolymers as well as the synthesis of graft or cross-linked polymers. The linear relationship between the comonomer content and the glass transition temperature of the copolymers and the monomer reactivity ratios in the copolymerization indicated the formation of the expected functionalized cyclic olefin copolymers (COC).