Bifunctional Additive-Driven Shape Transitions of Block Copolymer Particles through Synergistic Quaternization and Protonation

Abstract

Block copolymer (BCP) particles with tailored shapes and nanostructures hold promise for applications in cell adhesion, photonic system, and energy storage due to their unique optical and rheological properties. Conventional approaches relying on surfactant-mediated self-assembly often limit particle geometries to simple structures. Herein, we present a versatile approach to expand the morphology of poly(styrene-block-2-vinylpyridine) (PS-b-P2VP) BCP particles through the incorporation of 9-bromononanoic acid (BNA), a bifunctional additive that facilitates synergistic quaternization and protonation. Increasing the BNA-to-2VP molar ratio enhances P2VP hydrophilicity and reduces the pH value, driving dramatic shape transitions from onion-like spheres to tulip bulbs, ellipsoids, discs, and Janus cups. This morphological diversity is attributed to synergetic interfacial instability-driven water infiltration and pH-induced repulsion of protonated P2VP chains. Additives with a single functional group, however, yield limited morphologies, such as tulip bulbs or onion-like spheres. Notably, Janus cups fabricated via this strategy exhibit selective cargo-loading capabilities, highlighting the importance of precise control over the internal composition and structure of BCP particles.