Polymerization-induced self-assembly (PISA) has become a widely-used technique for the design of diblock copolymer nano-objects in concentrated aqueous solution. Depending on the specific PISA formulation, reversible addition-fragmentation chain transfer (RAFT) aqueous dispersion polymerization typically provides straightforward access to either spheres, worms or vesicles. In contrast, RAFT aqueous emulsion polymerization formulations often lead to just kinetically-trapped spheres. This limitation is currently not understood and only a few empirical exceptions have been reported in the literature. In the present work, the effect of monomer solubility on copolymer morphology is explored for an aqueous polymerization-induced self-assembly (PISA) formulation. Using 2-hydroxybutyl methacrylate (20 g dm<sup>-3</sup>) instead of benzyl methacrylate (0.4 g dm<sup>-3</sup>) for the core-forming block allows access to an unusual ‘monkey nut’ copolymer morphology over a relatively narrow range of target degrees of polymerization when using a poly(methacrylic acid) RAFT agent at pH 5. These new nanoparticles have been characterized by transmission electron microscopy, dynamic light scattering, aqueous electrophoresis, shear-induced polarized light imaging (SIPLI) and small-angle X-ray scattering.

Effect of monomer solubility on the evolution of copolymer morphology during polymerization-induced self-assembly in aqueous solution

253rd National Meeting (2017)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.