Synthesis and catalytic properties for olefin polymerization of new vanadium complexes containing silsesquioxane ligands with different denticity

Abstract

AbstractA series of new vanadium‐silsesquioxanes (2a − 2d) was prepared by reacting VCl4 with not fully condensed silsesquioxanes (having from one to four silanol groups) and evaluated as pre‐catalysts in olefin polymerization. The activation of 2a − 2d with EtAlCl2 generated highly active catalysts for ethylene polymerization, yielding high molar mass polymers with narrow dispersity. Ultra‐high molar mass polyethylenes, Mw up to 4 × 106 g mol−1, were obtained with methylaluminoxane and Al(iBu)3/[Ph3C][B(C6F5)4] as activators. Upon treatment with methylaluminoxane and boron compounds, all vanadium pre‐catalysts were active in 1‐octene polymerization as well, and produced isotactic‐rich poly(1‐octene)s with moderate monomer conversion (up to 23%). The polymerization parameters were optimized and the effect of the silsesquioxane structure on the catalytic activity and polymer properties was studied. © 2017 Society of Chemical Industry