Atom-Transfer Radical Polymerization of a SuFExable Vinyl Monomer and Polymer Library Construction via SuFEx Click Reaction

Abstract

The advancement in the synthesis of functional polymeric materials has greatly benefited from the development of functionalized monomers and effective polymerization methods. Here, inspired by the controlled radical polymerization and the new generation of click chemistry, sulfur(VI) fluoride exchange (SuFEx), we introduce a SuFExable vinyl monomer, 4-vinylbenzenesulfonyl fluoride (VBSF), which shows a good balance of stability and reactivity and can readily undergo organocatalytic atom-transfer radical polymerization under visible light with good controls and high end-group fidelity, while retaining the sulfonyl fluoride groups intact. Moreover, poly(VBSF) can be further modified with high efficiency via SuFEx reactions with various aryl silyl ethers, thus allowing a rapid construction of a functional polymer library in a click fashion.