Effect of Small Reaction Locus in Free-Radical Polymerization: Conventional and Reversible-Deactivation Radical Polymerization †

When the size of a polymerization locus is smaller than a few hundred nanometers, such as in miniemulsion polymerization, each locus may contain no more than one key-component molecule, and the concentration may become much larger than the corresponding bulk polymerization, leading to a significantly different rate of polymerization. By focusing attention on the component having the lowest concentration within the species involved in the polymerization rate expression, a simple formula can predict the particle diameter below which the polymerization rate changes significantly from the bulk polymerization. The key component in the conventional free-radical polymerization is the active radical and the polymerization rate becomes larger than the corresponding bulk polymerization when the particle size is smaller than the predicted diameter. The key component in reversible-addition-fragmentation chain-transfer (RAFT) polymerization is the intermediate species, and it can be used to predict the particle diameter below which the polymerization rate starts to increase. On the other hand, the key component is the trapping agent in stable-radical-mediated polymerization (SRMP) and atom-transfer radical polymerization (ATRP), and the polymerization rate decreases as the particle size becomes smaller than the predicted diameter.