Emulsion polymerization kinetics. General solutions for Smith–Ewart cases I and II

Abstract

Matrix methods are used to obtain general solutions for the Smith-Ewart case II mechanism for emulsion polymerizations; this relates to systems for which bimolecular termination is considered to be more important than free radical exit from the particles. These solutions are compared with simplified forms of the general solutions derived from case I, wherein exit is assumed to be more significant than termination. In neither case is resort made to the steady state approximation. There appears to be general agreement between theory and the results for the seeded emulsion polymerization of vinyl acetate, although discrepancies were apparent when very stringent comparisons were made.