Alternating copolymerization of ethylenesulfonyl fluoride and styrene for the synthesis of SuFEx modifiable polymers

Abstract

This work investigates the copolymerization of ethenesulfonyl fluoride (ESF) and styrene, demonstrating this method as a practical approach to access highly functionalised sulfonyl fluoride-containing polymers. Instantaneous copolymer composition data were analyzed using the Mayo-Lewis equation, yielding reactivity ratios of r₁ ≈ 0.062 (ESF) and r₂ ≈ 0.896 (styrene), indicative of a strong tendency toward alternating copolymerisation. Kinetic studies demonstrated controlled radical polymerization characteristics in the presence of a RAFT agent while low dispersities were observed even in the absence of a chain transfer agent. Post-polymerization modification of PS-ESF copolymers was successfully achieved via reaction of the sulfonyl fluoride functionality, enabling versatile transformations for advanced material design. These findings provide a foundation for tailored copolymer architectures and open pathways for new functional material development.