Controversies on the mechanism and kinetics of emulsion polymerization: An updated critical review

Conventional emulsion polymerization (EP) is a process via free radicals whose driving force for its development has been its versatility to generate polymer colloids with ad hoc characteristics for a wide variety of applications, as well as its friendly character to the environment since the continuous medium is water. Although through decades of research, considerable progress has been made in understanding its mechanism and kinetics, some aspects are still not entirely clear. Furthermore, new ideas and experimental results have appeared in the literature that challenge the accepted knowledge about some aspects of EP. This work is a personal vision and an updated critical review on those controversial aspects whose precedent is the review with the same approach published by the author and collaborators almost 20 years ago (J. Macromol. Sci. Part C Polym. Rev., 2004;44:207-229). This review covers advances, aspects that are open to discussion or need improvement regarding what happens in the aqueous phase and in the interface (initiator decomposition, entry and exit of radicals, monomer transport) as well as in the polymer particles (free-radical propagation and termination, swelling, average number of radicals per particle). Special attention is paid to particle formation (nucleation) and its interrelation with colloidal stability and the evolution of the particle size distribution (PSD), which is one of the most fundamental and controversial issues of EP. The Smoluchowski collision rate coefficient to describe diffusion-controlled processes has practically become a paradigm despite the fact that there is evidence that questions its applicability. For this reason, this review also emphasizes this point and the alternatives that have been proposed to mathematically describe the diffusive stages of particle coagulation, the entry of radicals, and the termination reaction. Challenges in improving our understanding of the mechanism and kinetics of emulsion polymerization are pointed out.