화학공학소재연구정보센터
Journal of Polymer Science Part A: Polymer Chemistry, Vol.45, No.17, 4054-4061, 2007
Effects of hydrogen in ethylene polymerization and oligomerization with magnesium chloride-supported bis(imino)pyridyl iron catalysts
The effects of hydrogen in ethylene polymerization and oligomerization with different bis(imino)pyridyl iron(II) complexes immobilized on supports of type MgCl2,/AlEtn(OEt)(3-n) have been investigated. Hydrogen has a significant activating effect on polymerization catalysts containing relatively bulky bis(imino)pyridyl ligands, but this is not the case in ethylene oligomerization with a catalyst containing relatively little steric bulk in the ligand. It was found that the presence of hydrogen in the latter system led to decreased activity and an overall increase rather than a decrease in product molecular weight, indicating deactivation of active species producing low molecular weight polymer and oligomer. Decreased formation of vinyl-terminated oligomers in the presence of hydrogen can therefore contribute to the activating effect of hydrogen in ethylene polymerization with immobilized iron catalysts, if it is assumed that hydrogen activation is related to chain transfer after a 2,1-insertion of a vinyl-terminated oligomer into the growing polymer chain.