Compartmentalized polymerization with oil-soluble initiators. Kinetic effect of single radical formation.

The stationary state distribution of radicals in compartmentalized systems initiated by oil-soluble initiators have been calculated for various cases of single radical formation as well as a simultaneous generation of single radicals and pairs of radicals in the particles. The effect of a contribution from radicals produced by initiator dissolved in the aqueous phase has been considered. Desorption and reabsorption of radicals, aqueous phase termination, total rate of radical formation and the water-solubility of the initiator are quantified in terms of dimensionless parameters. The calculations predict that single radicals generated in the particles are kinetically indistinguishable from radicals produced in the aqueous phase over a wide range of variation of the parameters. It is shown that if the rate of generation of single radicals constitutes only about 10 per cent of the overall rate of radical formation in the particles, the former radicals account for the major part of the rate of polymerization. The mechanisms previously proposed to account for the similar kinetic behaviour observed with water-soluble and oil-soluble initiators are discussed. It is concluded that the present calculations support the view that this similarity is mainly due to radicals produced by the water-soluble fraction of the initiator. (C) 1997 John Wiley & Sons, Inc.