Assembly of Disordered Cocontinuous Morphologies by Multiblock Copolymers with Random Block Sequence and Length Dispersity

Among the wide variety of nanostructures accessible by self-assembly of block copolymers, cocontinuous morphologies are of great interest for separations, catalysis, sensing, and energy storage because of their ability to integrate distinct properties of the constituent polymers. Here, we investigate the tendency to form disordered cocontinuous phases of multiblock copolymers (MBCs) with random block sequence and length dispersity prepared by step-growth polymerization of premade telechelic polymers, specifically using thiol-Michael addition between diacrylate functionalized polystyrene and poly (d,l-lactide) chains and a small molecule dithiol. In the phase diagram so established, disordered cocontinuous nanostructures occupy a wide window (≈25% vol) at a modest segregation strength of χN = 15, close to the critical value for microphase separation. At a higher segregation strength of χN = 30, only a moderately wide (≈10 vol %) cocontinuous window is found, with MBCs instead tending to form ordered nanostructures. Although the breadth of the cocontinuous window is less than that found in prior work on analogous randomly end-linked copolymer networks, the MBC architecture offers offsetting advantages in terms of solution and melt processability.