Scalable preparation of alternating block copolymer particles with inverse bicontinuous mesophases

Block copolymer particles with controlled morphologies are of great significance in nanomaterials and nanotechnology. However, ordered inverse morphologies are difficult to achieve due to complex mechanism and formation conditions. Here we report scalable preparation of amphiphilic alternating block copolymer particles with inverse bicontinuous mesophases via polymerization-induced self-assembly (PISA). Concentrated dispersion copolymerizations (up to 40% solid content) of styrene (St) and pentafluorostyrene (PFS) employing a short poly(N,N-dimethylacrylamide) (PDMA₂₉) stabilizer block lead to the formation of well-defined, highly asymmetric PDMA₂₉-b-P(St-alt-PFS)_x block copolymers with precise compositions and various morphologies, from simple spheres to ordered inverse cubosome mesophases. The particle morphology is affected by the molecular weight, solid content, and nature of the cosolvents. The cubosome structure is confirmed by electron microscopies and small angle X-ray scattering spectroscopy. This scalable PISA approach offers facile access to ordered inverse mesophases, significantly expanding the PISA morphology scope and enabling its applicability to the materials science fields.