Emulsion polymers are “products by process” whose main properties are determined during polymerization. In this scenario of margins reduction, increasing competition, and public sensitivity to environmental issues, the challenge is to achieve an efficient production of high‐quality materials in a consistent, safe, and environmentally friendly way. This highlight reviews the investigations carried out at The University of the Basque Country to develop a knowledge‐based strategy to achieve these goals. First, the research in fundamental mechanisms is discussed. This includes studies in radical entry and exit, oil‐soluble initiators, propagation‐rate constants of acrylic monomers, processes involved in the formation of branched and crosslinked polymers, microstructure modification by postreaction operations, the formation of particle morphology, and reactive surfactants. The advanced mathematical models developed in the group are also reviewed. In the second part, the advances in process development (optimization, online monitoring and control, monomer removal, production of high‐solids, low‐viscosity latices, and process intensification) are presented. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1025–1041, 2004

Recently, self-healing polymers based on disulfide compounds have gained attention due to the versatile chemistry of disulfide bonds and easy implementation into polymeric materials. However, the underlying mechanisms of disulfide exchange which induce the self-healing effect in poly(disulfide)s remain unclear. In this work, we elucidate the process of disulfide exchange using a variety of spectroscopic techniques. Comparing a model exchange reaction of 4-aminophenyl disulfide and diphenyl disulfide with modified reactions in the presence of additional radical traps or radical sources confirmed that the exchange reaction between disulfide compounds occurred via a radical-mediated mechanism. Furthermore, when investigating the effect of catalysts on the model exchange reaction, it could be concluded that catalysts enhance the disulfide exchange reaction through the formation of S-based anions in addition to the radical-mediated mechanism.

Polymer colloids are complex materials that have the potential to be used in a vast array of applications. One of the main reasons for their continued growth in commercial use is the water-based emulsion polymerization process through which they are generally synthesized. This technique is not only highly efficient from an industrial point of view but also extremely versatile and permits the large-scale production of colloidal particles with controllable properties. In this perspective, we seek to highlight the central challenges in the synthesis and use of polymer colloids, with respect to both existing and emerging applications. We first address the challenges in the current production and application of polymer colloids, with a particular focus on the transition toward sustainable feedstocks and reduced environmental impact in their primary commercial applications. Later, we highlight the features that allow novel polymer colloids to be designed and applied in emerging application areas. Finally, we present recent approaches that have used the unique colloidal nature in unconventional processing techniques.