The Multifaceted Role of Methylaluminoxane in Metallocene-Based Olefin Polymerization Catalysis

In single-site olefin polymerization catalysis, a large excess of cocatalyst is often required for the generation of highly active catalysts, but the reason for this is unclear. In this work, fundamental insight into the multifaceted role of cocatalyst methylaluminoxane (MAO) in the activation, deactivation, and stabilization of group 4 metallocenes in the immobilized single-site olefin polymerization catalyst was gained. Employing probe molecule FT-IR spectroscopy, it was found that weak Lewis acid sites, inherent to the silica-supported MAO cocatalyst, are the main responsible species for the genesis of active metallocenes for olefin polymerization. These weak Lewis acid sites are the origin of AlMe₂⁺ groups. Deactivation of metallocenes is caused by the presence of silanol groups on the silica support. Interaction of the catalyst precursor with these silanol groups leads to the irreversible formation of inactive metallocenes. Importantly, a high concentration of MAO (14 wt% Al) on the silica support is necessary to keep the metallocenes immobilized, hence preventing metallocene leaching and consequent reactor fouling. Increasing the loading of the MAO cocatalyst leads to larger amounts of AlMe₂⁺, fewer silanol groups, and less metallocene leaching, which all result in higher olefin polymerization activity.