Insights into the activation of silica-supported metallocene olefin polymerization catalysts by methylaluminoxane

Metallocene-based olefin polymerization catalysts often require large excesses of co-catalyst for optimal catalyst activation. In this work, mechanistic insights into the activation of supported metallocenes by methylaluminoxane as co-catalyst are acquired. UV-vis diffuse reflectance (DR) spectroscopy of five metallocene catalysts with varying co-catalyst loading reveals the presence of different metallocene species on the surface of the catalyst particles. Deconvolution of the obtained spectra, in combination with an extensive TD-DFT study of UV-vis DR spectra of metallocene structures results in a proposed activation mechanism. We find that with increasing MAO loading, more AlMe2+-bound metallocenes are observed with a shift towards the trimethylaluminum-stabilized cationic methylated metallocene compound. This shift can be directly correlated with a higher activity in the olefin polymerization reaction. Based on this finding, we propose a universal metallocene activation mechanism in which the cationic methylated metallocene is the active species. This species is formed through initial interaction with AlMe2+, followed by ligand exchange with MAO and stabilized in complex with trimethylaluminum as a dormant species.