Experimental study of emulsion polymerization with crosslinking

Herein is reported the results of an extensive experimental investigation of the kinetics of emulsion polymerization as affected by crosslinking in the polymer particles. The model monomer system, methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDMA), was chosen for this study due to its earlier comprehensive investigation in bulk polymerization. Standard recipes with sodium dodecylsulfate (SDS) as anionic emulsifier and potassium persulfate (KPS) as initiator were used for the batch emulsion polymerizations. Results, which clearly show the effect of crosslinking on the kinetics, are discussed in detail. These include swellability of polymer particles by monomer; polymer particle nucleation rates, below and above the critical micelle concentration (CMC); average number of radicals per particle; and gel‐sol levels. It was found advantageous to use electron spin resonance (ESR) to follow radical concentrations during crosslinking in polymer particles. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 935–957, 1997