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Small-molecule surfactants have long been a “necessary evil” in dispersed phase polymerizations as they are required to impart kinetic stability to a thermodynamically unstable system, but their ability to readily diffuse to interfaces and leach from products leads to undesirable performance properties. The use of amphiphilic polymers as stabilizers in emulsion polymerization and miniemulsion polymerization (hereafter collectively referred to as “(mini)emulsion polymerization” presents a highly tunable option to help mitigate the associated drawbacks of small-molecule surfactants. Although the stabilizer is used in relatively small amounts (typically ∼3 wt% of the total polymer), it has large impacts on (mini)emulsion polymerization from a mechanistic perspective as well as on final product properties. This review outlines considerations that need to be taken into account when using polymeric stabilizers in (mini)emulsion polymerization. For the convenience of the reader, this review starts with some background on (mini)emulsion polymerization and colloidal stabilization. Next, the mechanistic aspects to consider when using polymeric stabilizers in emulsion polymerization are outlined, with a large focus on the complexity of the nucleation stage. This discussion is then extended to miniemulsion polymerization. As stabilizers are present on the particle surface post-polymerization, the impact on rheological properties and film formation is then discussed, followed by various applications of polymer particles enabled using polymer particles. Special focus is drawn to how the stabilizer itself can be used to tailor the surface of particles for various applications. Finally, we conclude with a summary and an outlook on the state of polymeric stabilizers in (mini)emulsion polymerization.
Smeltzer et al. (Fri,) studied this question.