Ethylene homopolymerization with P,O-chelated nickel catalysts

Abstraction of phosphine from the nickel(II) P, O-chelated complexes, NiPh₂PCH?C(Ph)O] (Ph)(PPh₃), and related species converts them from olefin oligomerization to olefin polymerization catalysts. Phosphine acceptors such as Rh(acetylacetonate)(C₂H₄)₂ or Ni(1,5-cyclooctadiene)₂ are most effective. Alternatively, nickel complexes in which the phosphine ligand is replaced with weakly coordinated pyridine can be prepared. These active, homogeneous catalysts can be tuned to give either low or high molecular weight, linear low or high density polyethylene. Depending on the diluent, the same catalytic complex can be used as heterogeneous or homogeneous catalyst. They are tolerant of oxygenated, hydroxylic, or polar molecules that would poison normal early transition metal-based Ziegler-Natta catalysts. In fact, the polymerizations can be run in solvents such as ethanol or acetone, but hydrocarbon solvents are preferred.