Double Gyroid Morphologies in Precise Ion-Containing Multiblock Copolymers Synthesized via Step-Growth Polymerization

The double gyroid structure was first reported in diblock copolymers about 30 years ago, and the complexity of this morphology relative to the other ordered morphologies in block copolymers continues to fascinate the soft matter community. The double gyroid microphase-separated morphology has co-continuous domains of both species, and the minority phase is subdivided into two interpenetrating network structures. In addition to diblock copolymers, this structure has been reported in similar systems including diblock copolymers blended with one or two homopolymers and ABA-type triblock copolymers. Given the narrow composition region over which the double gyroid structure is typically observed (∼3 vol %), anionic polymerization has dominated the synthesis of block copolymers to control their composition and molecular weight. This perspective will highlight recent studies that (1) employ an alternative polymerization method to make block copolymers and (2) report double gyroid structures with lattice parameters below 10 nm. Specifically, step-growth polymerization linked precise polyethylene blocks and short sulfonate-containing blocks to form strictly alternating multiblock copolymers, and these copolymers produce the double gyroid structure over a dramatically wider composition range (>14 vol %). These new (AB) multiblock copolymers self-assemble into the double gyroid structure by having exceptional control over the polymer architecture and large interaction parameters between the blocks. This perspective proposes criteria for a broader and synthetically more accessible range of polymers that self-assemble into double gyroids and other ordered structures, so that these remarkable structures can be employed to solve a variety of technological challenges.