THE POLYMERIZATION RATE OF FRESHLY NUCLEATED PARTICLES DURING EMULSION POLYMERIZATION WITH MICELLAR NUCLEATION

A simple procedure was developed to account for the contribution of fr eshly nucleated particles to the total polymerization rate during mice llar nucleation. It has been shown that the polymerization rate of the freshly nucleated particles cannot be described by a steady-state sol ution for a radical population balance over the particle size distribu tion, i.e., the classical Smith-Ewart recursion relation. Once nucleat ed, the particles grow for a significant period of time with one radic al before either radical desorption or radical absorption, followed by instantaneous bimolecular termination, occur. For most emulsion polym erizations, radical desorption is the dominant process for radical los s of the freshly nucleated particles. A relation for the mean time tha t the freshly nucleated particles grow with one radical was derived. ( C) 1996 John Wiley & Sons, Inc.