Simulation of Mini/Macro Emulsion Polymerizations I. Development of the Model

Modeling of emulsion polymerizations has concentrated on conventional emulsions. Both miniemulsions and macroemulsions are simply special cases of emulsions in general and should be modeled as one since droplet and micellar nucleation can occur in either system. A model has been developed which allows simulation of batch homopolymerizations of both miniemulsions and macroemulsions where particle diameters range over three orders of magnitude. Assumptions employed are valid at both extremes. The equations are detailed and utilize several new techniques to accomplish accurate simulation of the entire range under consideration. An accurate approximation of the dynamic variance allows simple numerical integration of the differential equation representing the radical concentrations within particles.