Formation of disk-like micelles of triblock copolymers in frustrating solvents

Coil–coil block copolymers rarely self-assemble into flat low-curvature micelles due to the lack of proper interchain association. Here, we report a facile route to prepare disk-like micelles through the self-assembly of amphiphilic polystyrene-b-polybutadiene-b-poly(2-vinylpyridine) triblock copolymers in a mixture of acetone and cyclohexane, which shows distinct selectivity towards the PS, PB and P2VP blocks. Subtle solvation/aggregation of these blocks in this frustrating solvent system provides access to low-curvature micellar structures, and thus favors the formation of uniform disk-like micelles. Further variation of the volume ratio of the mixed solvents also leads to the emergence of other interesting morphologies, including disk arrays, disk clusters and perforated disk-like micelles. This work provides a complementary insight into the solution self-assembly of block copolymers in a view of selective solvents and demonstrates a distinctive pathway to unconventional micellar nanostructures through the use of complex solvent systems.