Copolymerization studies of vinyl chloride and vinyl acetate with ethylene using a transition-metal catalyst

Since the advent of Ziegler-Natta polymerization of ethylene, attempts have been made to extend coordination polymerization to commercially important monomers with polar functionality. In this study we examined the copolymerization of perdeuterated vinyl chloride (VC) and perdeuterated vinyl acetate (VA) with ethylene using a tridentate Fe(II) dichloride pyridine diimine metal catalyst. The resulting ethylene oligomers were examined by GC/MS and 2H NMR spectroscopy. It was shown that VC was inserted once for every ∼180 ethylene monomers and VA was inserted once for every ∼350 ethylene monomers. VC and VA behave as comonomers for coordination/insertion polymerizations with ethylene. However, we find that insertion with either monomer leads to termination of the growing chain via β-elimination processes. The deuterium atoms are exclusively located at the olefin terminus for each of the monomers.