The rate of particle growth in persulfate initiated emulsion polymerization

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Abstract
The initial growth rate of a particle in a polymerizing emulsion is constant with respect to time and also with respect to the aqueous concentration of the initiator. However, as a particle becomes larger, a size is reached where positive deviations from this constant rate are observed. It is shown that the kinetic analysis of Ewart and Smith qualitatively implies this type of behavior. In order to obtain quantitative agreement between theory and experiment, It is necessary to assume that free radicals entering a particle are generated at the particle‐water interface. When this restriction is imposed on the kinetic analysis, the latter gives a highly satisfactory account of the experimental results throughout the region in which the approximation employed in the analysis is valid. The results of the analysis indicate specifically a nontrivial dependence of the kinetics of emulsion polymerization on particle size and initiator concentration.

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