The self-assembly of AB diblock copolymers in solution has been extensively studied for more than fifty years. It is well known that the copolymer morphology is dictated by the relative volume fractions of the A and B blocks, with the most common nano-objects being spheres, worms (or cylinders) and vesicles (or polymersomes). Traditionally, such nano-objects have been prepared in dilute solution via post-polymerization processing. However, the recent development of polymerization-induced self-assembly (PISA) has enabled the efficient preparation of a wide range of diblock copolymer nano-objects. Herein we report the PISA synthesis of a new amphiphilic AB diblock copolymer in concentrated aqueous solution that can form polydisperse vesicles at 47°C, highly anisotropic worms at around 20°C and near-monodisperse spheres at 2°C. These vesicle-to-worm and worm-to-sphere morphological transitions have been studied by TEM, and DLS and SAXS. The latter technique suggests that the variable degree of hydration of the core-forming block is the key to understanding this remarkably rich self-assembly behaviour, which is unprecedented for a <i>single </i>diblock composition.

Every which way but loose: A single thermoresponsive diblock copolymer can form spheres, worms or vesicles in aqueous solution

255th National Meeting (2018)

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