Journal of Molecular Catalysis A-Chemical, Vol.165, No.1-2, 55-66, 2001
Kinetic investigation of ethylene polymerization catalyzed by nickel-diimine catalysts
The effect of ethylene pressure on the activity of ethylene polymerization with the complex ( 1,4-bis(2,6-diisopropylphenyl))-acenaphtenediimine-dichloronickel(II) (1) and trimethylaluminum was evaluated. At low ethylene concentrations, the polymerization rate is first order with respect to monomer concentration. At higher ethylene concentrations, the polymerization rate has a negative order with respect to monomer concentration. We propose a mechanism where the active sites are in a dynamic equilibrium with latent states, the later having two monomer molecules coordinated to the metal center. In situ spectroscopic observations corroborate the proposed mechanism and show that the cocatalyst nature might affect the ion pair formation.