Thermodynamics and kinetics of diblock copolymer micelles: chain architecture effect*

Diblock copolymers are actively used in various application, thus understanding the factors affecting thermodynamics and kinetics of self-assembly is of obvious importance. Computer modelling is a useful tool to analyze and compare behavior of various complex systems including diblock copolymers. Using dissipative particle dynamics simulations we investigate the effect of chain architecture on diblock copolymer self-assembly and the chain exchange kinetics using the example of diblock copolymers with a ring-shaped core or corona block in comparison with their linear diblock copolymer counterpart. We found a striking difference in both the equilibrium micelle size and kinetics of chain exchange in these systems. Furthermore, mixed micelles containing block copolymers of both types exhibit an unexpected synergism of chain exchange, which is not present in mixed micelles composed solely of linear chains. The origin of this effect and its implication for micelle self-assembly and practical applications of self-assembled nanostructures will be discussed.