Controlling the phase behavior of block copolymers via sequential block growth

Block copolymers remain one of the most extensively investigated classes of polymers due to their abilities to self-organize into various nanostructures and modify polymer/polymer interfaces. Despite fundamental and technological interest in these materials, only a handful of experimental phase diagrams exist due to the laborious task of preparing such diagrams. In this work, two copolymer series are each synthesized from a single macromolecule via sequential living anionic polymerization to yield molecularly asymmetric diblock and triblock copolymers systematically varying in composition. The phase behavior and morphology of these copolymers are experimentally interrogated and quantitatively compared with predictions from mean-field theories, which probe copolymer phase behavior beyond current experimental conditions.