Particle Formation in Emulsion Polymerization: Transient Particle Concentration

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Abstract
A general kinetic model of particle formation in emulsion polymerization is presented. This model takes into account homogeneous, micellar, and monomer droplet nucleation mechanisms. Chain transfer and termination in the aqueous phase, capture of oligomer radicals by particles, and coagulation of particles are also considered. A three-parameter analytical solution is obtained for the transient particle consideration: where N and Ns are particle concentrations in number per volume of aqueous phase during the nucleation period and at steady state, respectively; t is time; and A 2 and τ are adjustable model parameters. The model parameters Ns , A 2, and τ can be estimated from basic kinetic parameters and reaction conditions. Model predictions are in agreement with experimental data obtained from the literature. Values of the average rate coefficient for coagulation obtained from fitting the model to the experimental data were used to calculate the coagulation-average particle diameter. These coagulation-average particle diameters are much less than the measured particle diameters because small particles have a much stronger tendency to coagulate than large particles.

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