Radical polymerization of miniemulsions induced by compressed gases

Abstract

Generation of miniemulsions (nanoemulsions) comprising hydrophobic vinyl monomers and water by use of the compressed gases carbon dioxide and ethylene, respectively, has been investigated in the absence of high energy mixing. It is proposed that transparent/translucent miniemulsions are formed at the transparency pressure (P_T) as a result of the refractive index of the dispersed phase being reduced due to expansion with carbon dioxide/ethylene, resulting in refractive index matched miniemulsions with enhanced stability. Radical polymerization of methyl acrylate at 40 °C in miniemulsions induced by carbon dioxide at P_T proceeds as a hybrid miniemulsion/emulsion polymerization system generating particles with diameters less than 100 nm. The experimental data are consistent with particle formation occurring mainly via monomer droplet nucleation (miniemulsion polymerization) but also via secondary nucleation in the aqueous phase (emulsion polymerization). Polymerizations at a range of pressures above and below P_T revealed limited pressure effects on the polymerization rate and particle size for both carbon dioxide and ethylene.