Structure Regulation of Block Copolymer Assemblies in Emulsion Droplets by Adding a Selective Solvent

Abstract Generally, nanostructured polymer particles are prepared by 3D confined self‐assembly (3D‐CSA) of block copolymers (BCPs), while micelles are obtained through self‐assembly of BCPs in dilute solutions. Herein, a facile yet robust strategy is developed to regulate the assembled structures of BCP, poly(styrene‐ block ‐4‐vinylpyridine) (PS‐ b ‐P4VP), from nanostructured particles to micelles. The assemblies are prepared by an emulsion‐solvent diffusion‐induced self‐assembly route, which is conducted by dialysis. A key feature of this strategy is that a P4VP‐selective solvent (e.g., ethanol) is added to the dialysate to tune the interfacial behavior of the droplets and assembled structures of PS‐ b ‐P4VP. The authors’ results reveal that in the presence of slight ethanol, the surface and internal structural transitions of nanostructured particles are caused by changes in the interfacial selectivity and packing parameter. Interestingly, interfacial instability, which results in the formation of micelles, is observed when the dialysate contains 50 vol% ethanol or more. The reason can be ascribed to the decreased interface tension, which is induced by the increase in ethanol and enhanced solubility of P4VP. This facile strategy provides a new opportunity to bridge the gap between traditional 3D‐CSA and solution self‐assembly of BCPs, offering a promising route to engineer morphologies and nanostructures of polymeric assemblies.