Microgel with a Core—Shell Particulate Structure Formed via Spinodal Decomposition of a Diblock Ionomer Containing a Doped Hydrophobic Moiety

This study explored the formation of soft colloidal particles from a diblock ionomer (DI) with the monomeric composition (acrylonitrile)_x-co-(glycidyl methacrylate)_y-b-(3-sulfopropyl methacrylate potassium)_z-abbreviated as (A_xG_y)S_z, where x >> z > y. A colloidal dispersion was generated by introducing water into the pre-prepared DMSO solutions of DI, which led to micelle formation and subsequent coagulation. The assembly of the hydrophobic (A_xG_y) blocks was influenced by water content and chain conformational flexibility (the ability to adopt various forms of conformation). The resulting microgel structure (in particle form) consists of coagulated micelles characterized by discrete internal hydrophobic gel domains and continuous external hydrophilic gel layers. Characterization methods included light scattering, zeta potential analysis, and particle size distribution measurements. In contrast, the copolymer (A_xG_y) chains form random coil aggregates in DMSO-H₂O mixtures, displaying a chain packing state distinct from the hydrophobic gel domains as aforementioned. Additionally, the amphiphilic glycidyl methacrylate (G) units within the (A_xG_y) block were found to modulate the microgel dimensions. Notably, the nanoscale hydrogel corona exhibits high accessibility to reactive species in aqueous media. The typical microgel has a spherical shape with a diameter ranging from 50 to 120 nm. It exhibits a zeta potential of -65 mV in a neutral aqueous medium; however, it may precipitate if the metastable colloidal dispersion state cannot be maintained. Its properties could be tailored through adjusting the internal chain conformation, highlighting its potential for diverse applications.