Janus Nanostructures from ABC/B Triblock Terpolymer Blends

Lamella-forming ABC triblock terpolymers are convenient building blocks for the synthesis of soft Janus nanoparticles (JNPs) by crosslinking the B domain that is "sandwiched" between A and C lamellae. Despite thorough synthetic variation of the B fraction to control the geometry of the sandwiched microphase, so far only Janus spheres, cylinders, and sheets have been obtained. In this combined theoretical and experimental work, we show that the blending of polybutadiene homopolymer (hPB) into lamella morphologies of polystyrene-block-polybutadiene-block-polymethylmethacrylate (SBM) triblock terpolymers allows the continuous tuning of the polybutadiene (PB) microphase. We systematically vary the volume fraction of hPB in the system, and we find in both experiments and simulations morphological transitions from PB-cylinders to perforated PB-lamellae and further to continuous PB-lamellae. Our simulations show that the hPB is distributed homogeneously in the PB microdomains. Through crosslinking of the PB domain and redispersion in a common solvent for all blocks, we separate the bulk morphologies into Janus cylinders, perforated Janus sheets, and Janus sheets. These studies suggest that more complex Janus nanostructures could be generated from ABC triblock terpolymers than previously expected.