Kinetic analysis of seeded emulsion polymerization of vinyl acetate

Particle number and size data from a series of seeded, emulsifier-free, vinyl acetate emulsion polymerization experiments have been analyzed with the aid of polymerization and particle growth models. A secondary population of particles, with a significantly greater number concentration than the seed, was nucleated in all experiments. The two populations (seed and new) had rather narrow size distributions and large diameters. Hence the reactions were in the area normally associated with Smith–Ewart Case III kinetics. Water-phase termination reactions can be important in this reaction region but radical desorption from such large particles does not significantly influence the kinetics. The results of the analysis were used to evaluate the magnitude of water-phase termination; to estimate radical capture coefficients; and to evaluate competitive particle growth.