PREPARATION OF POLYMER-SUPPORTED CATALYSTS CONTAINING PHOSPHORUS PALLADIUM COMPLEXES AND QUATERNARY ONIUM GROUPS, AND THEIR APPLICATION TO THE VINYLATION REACTION

Micron-sized crosslinked polystyrene [poly(ST-DVB)] particles prepared by the concentrated emulsion polymerization method were coated with nonuniform layers of the following functionalized polymers: (I) poly(3- and 4-vinylbenzyl chloride) [poly(VBC)]; (II) a copolymer of VBC and 4-chlorosytrene [poly(VBC)-(CST)] and; (III) a composite of poly(VBC) and poly(3,4-dichloro-1-butene) [poly(VBC)-poly(DCB)]. A fine powder composed of small aggregates of such particles was obtained by grinding. The polymers thus prepared were converted to three types of reactive substrates containing both organophosphorus ligands and quaternary onium groups: (1) (m-sulfonate phenyl) diphenyl phosphine and poly(vinylbenzyl tributyl ammonium chloride) bound to poly(ST-DVB); (2) diphenyl ethylene phosphite and benzyl methyl diethanol ammonium groups bound to poly(ST-DVB); and (3) phosphine oxide and quaternary benzyl tributyl ammonium or phosphonium groups bound to poly(ST-DVB). The polymer-supported catalysts containing phosphorus palladium complexes and quaternary onium groups were then employed in the vinylation reaction of iodobenzene with methyl acrylate. These supported bicatalysts displayed a cooperative effect that increased the yield of vinylation by a factor greater than two when compared to its homogeneous counterpart. The relative locations of palladium complexes and quaternary onium groups are found to influence the yield.