Short Aromatic Blocks Enhance Styrene Conversion in Polymer Cubosome Formation via Polymerization-Induced Self-Assembly

Macromol Rapid Commun. 2025 Jan 7:e2400891. doi: 10.1002/marc.202400891. Online ahead of print.

Abstract

Polymer cubosomes (PCs) have garnered significant interest in the field of nanomaterials and nanotechnology due to their unique properties and potential applications. However, the fabrication of PCs remains challenging. Polymerization-induced self-assembly (PISA) is recognized as an efficient method for producing a variety of polymer particles, including PCs. Despite the advantages of PISA, the conversion of styrene (St), a core-forming monomer commonly used in PC preparation, is relatively low. Herein, a novel strategy is introduced to enhance the St conversion in PC preparation via PISA by incorporating a short azobenzene-containing block (PMAAz) into the hydrophilic macro-chain transfer agent (macro-CTA). Utilizing PMAAz-tailed poly(poly(ethylene glycol) methyl ether methacrylate), the St conversion is successfully improved from an initial 12.9-13.8% to an enhanced range of 19.1-26.9%. This enhancement in conversion allows for a reduced feeding ratio of St to macro-CTA in the preparation of PCs. Further studies into various blocks consisting of different hydrophobic monomers reveal that the aromatic interactions, derived from these short blocks, are crucial for increasing monomer conversion and facilitating PC formation. This study offers a direct and convenient approach to obtaining PCs with diversified functional groups efficiently, thereby significantly broadening the potential application of these materials.

Keywords: aromatic interaction; block copolymers; polymer cubosomes; polymerization‐induced self‐assembly; styrene conversion.