Programmable Morphology Evolution of Rod-Coil-Rod Block Copolymer Assemblies Induced by Variation of Chain Ordering.

Morphology transition of block copolymer assemblies in response to external stimuli has attracted considerable attention. However, our knowledge about the mechanism of such a transition is still limited, especially for rod-coil block copolymers. Here, we report a programmable morphology evolution of assemblies induced by variation of chain ordering for rod-coil-rod triblock copolymers. A sequence of morphology transition from ellipsoids to disks, bowls, and vesicles is observed by increasing the solution temperature. At high temperatures, the mobility of the rod chain increases and the rigidity of the rod chain decreases. This gives rise to an ellipsoid-to-vesicle morphology transition. Dissipative particle dynamics theoretical simulations were performed to reveal the mechanism of this morphology transition process. It was found that the increase of rod chain mobility and the decrease of rod chain rigidity induce a decrease of chain ordering of rod blocks as temperature increases, which results in an ellipsoid-to-vesicle morphology transition. The gained information can guide the construction of nanoassemblies based on the rod-coil block copolymers.