Vinylbenzenesulfonyl fluoride (VBSF)-based binary and ternary copolymers and selective post-polymerization modification via SuFEx click chemistry

Abstract

Restricted by functional-group compatibility and monomer synthesis, functional polymers are difficult to obtain directly, whereas post-polymerization modification (PPM) provides an alternative efficient synthetic approach. Accordingly, efficient and selective orthogonal PPM under mild conditions could provide a higher degree of complexity and diversity. Herein, we propose a novel and efficient strategy for selective orthogonal PPM, which utilizes the high reactivity of aryl silyl ethers toward –SO₂F groups (SuFEx click reaction) and of alkylamines toward pentafluorophenyl esters (active ester–amine chemistry) for sequential PPM of the copolymer of 4-vinylbenzenesulfonyl fluoride (VBSF) and pentafluorophenyl methacrylate (PFPMA) under mild conditions. NMR and GPC characterization studies demonstrate that silyl ethers react selectively with VBSF alone, and that PFPMA units are converted exclusively by alkylamines, while other functional groups remain inert throughout the process, enabling efficient selective orthogonal PPM and the preparation of structurally complex, well-defined polymers. Overall, the introduction of orthogonal functional groups into polymer precursors provides multiple independent reaction sites for PPM, thus offering a new synthetic pathway for functional materials.