(Mini)emulsion polymerization kinetics using oil-soluble initiators

The mechanisms involved in the initiation of (mini)emulsion polymerization using oil-soluble initiators were investigated by means of a first principles model. The model was assessed by comparing its predictions with experimental data. The model shows that desorption of initiator radicals from droplets and particles is the key mechanism controlling the kinetics of miniemulsion polymerization and particle growth in emulsion polymerization. For these systems, the contribution of the fraction of the initiator dissolved in the aqueous phase is minor. In ab initio emulsion polymerization, the fraction of the initiator dissolved in the aqueous phase was the main contributor to micellar nucleation.