Versatile Method to Expand the Morphology Library of Block Copolymer Solution Self-Assemblies with Tubular Structures

Self-assembly of block copolymers (BCPs) in solution is a powerful technology to achieve a broad range of structures, such as spheres, cylinders, vesicles, and other hierarchical structures. However, the BCP self-assembly library is limited, especially with respect to tubular structures. Here we show a versatile strategy to expand the morphology library of block copolymer solution self-assemblies with tubular structures (including tubular dumbbells and tubules) via self-assembly of the most common diblock copolymers P4VP-b-PS BCPs in methanol. No special chemistry is needed in this strategy, which proves the universality of this method. The novelty of the strategy is to keep the BCPs both highly asymmetric and with very high molecular weight. The underlying formation mechanism and kinetics of these tubular structures were elucidated. The prepared tubular structures expand the structure library of BCP solution self-assemblies and open up a new avenue for the further applications of a variety of tubular materials.