4-Vinylbenzenesulfonyl fluoride (VBSF): a highly reactive monomer for RAFT polymerization and exhaustive SuFEx postpolymerization sulfonamidation

We designed and synthesized a 4-fluorosulfonyl styrene monomer, 4-vinylbenzenesulfonyl fluoride (VBSF), for the evaluation of the efficiency of our catalytic sulfonamidation of sulfonyl fluorides in post-polymerization modification. Our preliminary studies indicated that this monomer was compatible with “living”/controlled free radical polymerizations such as RAFT and ATRP. Using the slightly modified protocols of catalytic amidation of sulfonyl fluorides established in our laboratory previously, we have achieved the exhaustive sulfonamidation of poly(4-vinylbenzenesulfonyl fluoride)s. Nucleophiles such as aliphatic amines, aromatic amines and phenols were all viable, and six novel polystyrene-analogous sulfonamide (or sulfonate) polymers were prepared. In addition, the exhaustive amidation of poly(VBSF-co-St) was also investigated.