Polymerization‐Induced Self‐Assembly: From Macromolecular Engineering Toward Applications

Abstract Polymerization‐induced self‐assembly (PISA) is nowadays a well‐established technology that is gaining more and more attention from academics and in the industry. It relies on the extension of a solvophilic reactive chain in heterogeneous polymerization conditions. An amphiphilic block copolymer is generated and concomitantly to the growth of the solvophobic block, self‐assembly occurs. PISA was initially developed to achieve radical emulsion polymerizations in the absence of low molecular weight surfactants in order to produce surfactant‐free latexes. Shortly after, it became clear that this technology had also great potential to synthesize well‐defined amphiphilic block copolymers. Finally, researchers became more and more interested in the formed particles themselves (mainly spheres, but also worm and vesicles) and tried to functionalize them for a large variety of applications. In this article, we will start with reviewing the different PISA polymerization techniques, and highlight the possibility to use PISA as a tool to synthesize well‐defined, functional, and complex macromolecular architectures. We will then discuss the main parameters that control the particle morphology, before presenting applications of PISA‐derived particles and dispersions. The article cites more than 400 references, and presents for each polymerization technique a great number of the existing systems in tabular format.