Synthesis, characterization and olefin polymerization studies of iron(II) and cobalt(II) catalysts bearing 2,6-bis(pyrazol-1-yl)pyridines and 2,6-bis(pyrazol-1-ylmethyl)pyridines ligands

摘要

The complexes Py(PzR(3))(2)MCl2 (R = H, Me; M = Fe, Cc) and Py(CH2-PzR(3))(2)MCl2 (R = H, Me; M = Fe, Co) have been synthesized, characterized and used in the ethylene polymerization. Treatment of these iron and cobalt complexes with methylaluminoxane (MAO) as cocatalyst leads to active ethylene polymerization catalysts that produced linear polyethylene. In general, iron catalysts were more active than cobalt analogs. The steric and electronic effects of the ligands were study over the catalytic activity toward ethylene polymerization. Complexes with small substituents groups (R = H) on the pyrazolyl ring, increase the catalytic activity in comparison to complexes with bigger substituents groups (R = CH3). Additionally, complexes with methylene groups placed between pyridine and pyrazole rings of ligands have less catalytic activity than complexes without the methylene group (-CH2-). The presence of methyl groups (R = CH3) in iron and cobalt complexes allow to obtain polyethylene with molecular weights higher than the one obtained with complexes without these methyl groups. Additionally, complexes with methylene groups present between pyridine and pyrazole rings generate polyethylenes with molecular weight higher than the ones produced with complexes without these methylene groups. (C) 2004 Elsevier B.V. All rights reserved.