Infrared and ultraviolet–visible spectroscopic studies of silica, [(Cp)2ZrCl2] and trimethylaluminum interactions

Abstract

Infrared and UV–vis studies of metallocene immobilization on silica are reported here. The results have indicated changes in the Zr coordination sphere of metallocene depending on the immobilization route used. The reaction of [(Cp)2ZrCl2] with silica formed [(Cp)2ZrCl]+[SiO]− species. The same metallocene, reacting with TMA modified silica, formed monomethylated and dimethylated species by the substitution of chloro for methyl ligands, stabilized on the surface by interaction with “MAO-like” species (methylaluminoxane, MAO). These monomethylated and dimethylated cationic zirconium species are the active centers for the polymerization reaction. Different order of TMA addition in the silica modification step generated surface species of a similar nature, differing in their relative quantities. The highest amount of these active species was obtained when the support was added to the TMA solution rather than adding the TMA solution to the silica support. This was the most significant parameter affecting catalytic activity in ethylene polymerization.