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

Abstract

Restricted by functional group compatibility and monomer synthesis, functional polymers are difficult to polymerize directly, while post-polymerization modification (PPM) provides an efficient synthetic approach. Accordingly, efficient and selective orthogonal PPM under mild conditions could bring a higher degree of complexity and diversity. Herein, we propose a novel and efficient strategy for selective orthogonal PPM, which utilizes high reactivity of aryl silyl ethers towards -SO₂F groups (SuFEx click reaction) and alkylamines towards pentafluorophenyl esters (active ester-amine chemistry) to sequentially PPM the copolymer of 4-vinylbenzenesulfonyl fluoride (VBSF) and pentafluorophenyl methacrylate (PFPMA) under mild conditions. NMR and GPC characterizations demonstrate that silyl ethers react selectively with VBSF alone, and PFPMA are converted exclusively by alkylamine, while other functional groups remain inert throughout the process, achieving efficient selective orthogonal PPM and the preparation of structurally complex and 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.