Micellar Shape Change and Internal Segregation Induced by Chemical Modification of a Tryptych Block Copolymer Surfactant

We report the detailed characterization of micelles formed by two nonionic, amphiphilic ABC triblock copolymers. Poly(ethylene oxide)-b-poly(styrene)-b-1,2-poly(butadiene) (PEO-b-PS-b-PB) triblock copolymer “OSB” forms core−corona spherical micelles in aqueous solution, and the two hydrophobic blocks S and B are mixed homogeneously within the micelle core. PEO-b-PS-b-PB:C₆F₁₃I triblock copolymer “OSF” was prepared by selective fluorination of the B block in OSB with n-perfluorohexyl iodide. Fluorination of the B block induces internal segregation into an inner F core and an intermediate S shell. Furthermore, the strong incompatibility that results from fluorination drives a shape change into an oblate ellipsoid. These micellar morphologies are confirmed by combined light, neutron, and X-ray scattering measurements, as well as TEM imaging.