Self-assembly of block copolymer micelles in an ionic liquid

Four amphiphilic poly((1,2-butadiene)-block-ethylene oxide) (PB-PEO) diblock copolymers were shown to aggregate strongly and form micelles in an ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF ₆]). The universal micellar structures (spherical micelle, wormlike micelle, and bilayered vesicle) were all accessed by varying the length of the corona block while holding the core block constant. The nanostructures of the PB-PEO micelles formed in an ionic liquid were directly visualized by cryogenic transmission electron microscopy (cryo-TEM). Detailed micelle structural information was extracted from both cryo-TEM and dynamic light scattering measurements, with excellent agreement between the two techniques. Compared to aqueous solutions of the same copolymers, [BMIM][PF₆] solutions exhibit some distinct features, such as temperature-independent micellar morphologies between 25 and 100 °C. As in aqueous solutions, significant nonergodicity effects were also observed. This work demonstrates the flexibility of amphiphilic block copolymers for controlling nanostructure in an ionic liquid, with potential applications in many arenas.