Abstract: | The effects of 2‐hydroxyalkyl methacrylates (HEMA and HPMA) on the styrene miniemulsion polymerizations stabilized by SDS/lauryl methacrylate (LMA) or SDS/stearyl methacrylate (SMA) were investigated. A mixed mode of particle nucleation (monomer droplet nucleation and homogeneous nucleation) is operative during polymerization. Homogeneous nucleation plays a crucial role in the polymerizations stabilized by SDS/LMA, whereas monomer droplet nucleation becomes more important in the polymerizations stabilized by SDS/SMA. The polymerization kinetics is insensitive to the type of 2‐hydroxyalkyl methacrylates, but the difference in the relative importance of monomer droplet nucleation and homogeneous nucleation is detected. Incorporation of 1‐pentanol (C5OH) into the reaction mixture also shows a significant influence on the polymerizations stabilized by SDS/LMA or SDS/SMA. This is attributed to the formation of a close‐packed structure of SDS and C5OH on the droplet surface, which acts as a barrier to the incoming oligomeric radicals. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 3188–3199, 2000 |