Effect of Chain Architecture on Self-Assembled Aggregates from Cyclic AB Diblock and Linear ABA Triblock Copolymers in Solution.

The self-assembly behaviors of two block copolymers with the same chain length but different chain architectures (cyclic AB, linear ABA) in B-selective solvents are investigated using Monte Carlo simulations. A morphological transition sequence, from spherical micelles to cylindrical micelles, to vesicles and then to multicompartment vesicles, is observed for both copolymer systems when the interaction between the solvophobic A-block and the solvent is increased. In particular, toroidal micelles could be formed in triblock systems due to the presence of the bridging chains at the parameter region between cylindrical micelles and vesicles whereas disklike micelles are formed in cyclic systems. The simulation results demonstrated that the architecture of block copolymers could be used to regulate the structural characteristics and thermal stability of these self-assembled aggregates.