Corona structure on demand: Tailor-made surface compartmentalization in worm-like micelles via random cocrystallization

We present a straightforward approach to well-defined 1D patchy particles utilizing crystallization-induced self-assembly. A polystyrene-block-polyethylene-block-poly(methyl methacrylate) (PS-b-PE-b-PMMA) triblock terpolymer is cocrystallized in a random fashion with a corresponding polystyrene-block-polyethylene-block-polystyrene (PS-b-PE-b-PS) triblock copolymer to yield worm-like crystalline-core micelles (wCCMs). Here, the corona composition (PMMA/PS fraction) can be easily adjusted via the amount of PS-b-PE-b-PMMA triblock terpolymer in the mixture and opens an easy access to wCCMs with tailor-made corona structures. Depending on the PMMA fraction, wCCMs with a mixed corona, spherical PMMA patches embedded in a continuous PS corona, as well as alternating PS and PMMA patches of almost equal size can be realized. Micelles prepared by cocrystallization show the same corona structure as those prepared from neat triblock terpolymers at identical corona composition. Thus, within a certain regime of desired corona compositions the laborious synthesis of new triblock terpolymers for every composition can be circumvented.