Sulfonic acid groups were anchored on silica surface through the robust Si-C bond. Successive treatment of benzylmagnesium chloride and H2SO4 to dehydroxylated silica afforded the silica tethering -CH2C6H4SO3H groups with high surface coverage (0.50-CH2C6H4SO3H/nm2). Pore structure was well preserved in this surface modification process. The -CH2C6H4SO3H groups on the surface were successfully utilized in preparation of supported catalyst for polyketone production; ?Si-CH2C6H4SO3H groups on surface was reacted with [1,3-bis(di(2-methoxyphenyl)phosphino)propane]Pd(OAc)2 to generate dicationic palladium species which were anchored on silica surface through the ionic interaction with sulfonate anion generated on the surface. The supported catalyst prepared in this way showed a high activity (up to 43 kg/g-Pd or 0.61 Kg/g-cat) in CO/ethylene copolymerization. Morphology of polymer particles replicated that of the silica particles consequently to generate polymer powder of high bulk density (0.30 g/mL) with negligible reactor fouling.
