Modelling particle growth under saturated and starved conditions in emulsion polymerization

Abstract

AbstractModelling of particle growth under saturated and starved conditions in emulsion polymerization was investigated in order to allow describing the broadening of the particle size distribution and account for the effects of restricted diffusion inside the monomer‐swollen polymer particles. In emulsion polymerization, if particle nucleation and coagulation are avoided, the reaction proceeds as a consequence of radical capture, desorption, and termination reactions inside the particles. Therefore, first, investigation of radical entry and desorption models was done under saturation of polymer particles with monomer, where diffusion parameters are constant. The discrimination criterion of the different models was based on fitting the reaction and the total particle size distribution. Indeed, the broadening of the particle size distribution was found to reveal a dependency of radical capture on the particle size; such an effect would be misestimated if only the mean particle size is considered. Second, the models for starved conditions that account for the variation of radical diffusion inside the polymer particles, such as the gel and glass effects, were investigated with comparison to a wide variety of experimental conditions spanning from weak to strong gelation. The dominating mechanisms as well as the interests of both intervals are highlighted.