Catalytic Behavior of Cobalt Complexes Bearing Pyridine–Oxime Ligands in Isoprene Polymerization

Abstract

Several cobalt(II) complexes Co1–Co3 bearing pyridine–oxime ligands (L1 = pyridine-2-aldoxime for Co1; L2 = 6-methylpyridine-2-aldoxime for Co2; L3 = phenyl-2-pyridylketoxime for Co3) and picolinaldehyde O-methyl oxime (L4)-supported Co4 were synthesized and well characterized by FT-IR, mass spectrum and elemental analysis. The single-crystal X-ray diffraction of complex Co2 reveals that the cobalt center of CoCl2 is coordinated with two 6-methylpyridine-2-aldoxime ligands binding with Npyridine and Noxime atoms, which feature a distorted octahedral structure. These Co complexes Co1–Co4 displayed extremely high activity toward isoprene polymerization upon activation with small amount of AlClEt2 in toluene, giving polyisoprene with high activity up to 16.3 × 105 (mol of Co)−1(h)−1. And, the generated polyisoprene displayed high molecular weights and narrow molecular distribution with a cis-1,4-enriched selectivity. The type of cobalt complexes, cocatalyst and reaction temperature all have effects on the polymerization activity but not on the microstructure of polymer.