Nonclassical Block Copolymer Self‐Assembly Resulting from a Constrained Location of Chains and Junctions

During the self-assembly process of block-copolymers, interfaces are formed as a result of the microphase separation between the blocks. The location of the polymer chains and block junctions with respect to these interfaces is crucial and drives the morphology. It depends on the dispersities (e.g. molecular mass and composition) of the blocks, their architectures (e.g. linear vs star) and the type of interaction (e.g. repulsion vs attraction). In this review, we focus on the formation of unusual morphologies that have been obtained in the following three categories: i) multimodal blends of block polymers, ii) star block polymers and iii) supramolecular assemblies composed of block copolymers. Although these three examples seem to be very different from one another, we will demonstrate in this review that they all share a constrained location of their chains and/or junctions with respect to the interfaces. In this sense, they deviate from the common behavior of simple linear block copolymers, in which the junctions are located on the interface and homogeneously distributed onto it. 2