Kinetics of emulsion polymerisation in the unsteady state

Abstract

Equations are developed which show how the number of free radicals in polymer particles changes with time in emulsion polymerisation. The treatment is confined to cases where the total number of particles is constant. Unlike the procedures which have been published previously, the present treatment, which is relatively simple, allows for both radical desorption from the particles and radical combination within the particles. Inclusion of intraparticle combination leads to predictions of more realistic values of the numbers of radicals within the particles. The new procedure is shown to apply over a wider range of operating variables than the previous treatments. If the rate at which radicals enter the particles is time-independent, the efficiency of radical capture by the particles is expected to be low.