Architectural Design of Block Copolymers

Highly designable architectures of polymers endow the same polymer with different properties. In principle, diverse architectures should enrich the self-assembly behavior of block copolymers, providing a possibility for the formation of many novel ordered phases. However, it is infeasible to simply search the huge library of architectures for the formation of desired new phases, and it requires some valid guiding principles for efficiently designing block copolymers. In the past decade, some sophisticated mechanisms have been proposed in addition to the common mechanism that the self-assembly of block copolymers is dictated by the competition between the interaction energy and the stretching energy. To realize these sophisticated mechanisms in the architectures constitutes the guiding principles for the design of block copolymers. A series of theoretical works have demonstrated that one or more sophisticated mechanisms can be derived for desired novel phases, and thus the architectures of block copolymers can be properly designed to achieve these phases. To date, only the architectures of flexible copolymers are considered. In the future, the concept of designing architectures for the formation of the desired novel phases can be extended to a broader range of block copolymers, e.g., semiflexible and charged. In addition, it would be more useful to design block copolymers for the desired properties that are dictated by not only the chain architecture but also the phase-separated structure.