Polymer-supported quaternary onium salts catalysts prepared via concentrated emulsion polymerization

Abstract

A concentrated emulsion has a very large volume fraction of dispersed phase (0.74 – 0.95 in this case) and the appearance of a gel. Three procedures based on concentrated emulsion polymerization are suggested for the preparation of polymer-supported quaternary onium salts. (1) Concentrated emulsions of vinylbenzyl chloride (VBC) in water are subjected to polymerization. The polymer resins thus obtained are composed of particles in the micrometre range. A large fraction of the pendant benzyl-chloride groups present in the poly(VBC) particles are converted to onium chloride by a quaternization reaction. (2) A small amount of VBC is added to a partially polymerized concentrated emulsion of styrene (containing a crosslinking agent) in water under vigorous stirring. The system is subsequently subjected to complete polymerization. The obtained polystyrene-poly (VBC) is found to consist of particles having a non-uniform poly (VBC) shell that covers a crosslinked polystyrene core. This polymer is then subjected to a quaternization reaction in order to generate a polymer substrate with bound quaternary onium chloride. (3) A concentrated emulsion of styrene in an aqueous solution of a quaternary onium chloride monomer is prepared. The onium chloride adsorbed on the surface of the dispersed phase polymerizes simultaneously with styrene when the concentrated emulsion is subjected to polymerization. The polymer-supported onium salts thus prepared were used as phase transfer catalysts in the alkylation of isopropylidene malonates. The catalysts containing larger pores had a higher activity than those with a more compact structure. The catalyst prepared by the second approach had a greater catalytic activity than that prepared by the first approach. The catalyst prepared by the third procedure had a low activity because of the small amount of supported onium salt it contains.