Radical ring-opening polymerization of five-membered cyclic vinyl sulfone using p-toluenesulfonyl halides

Radical ring‐opening polymerizations of a five‐membered cyclic vinyl sulfone monomer, 2‐vinylthiolane‐1,1‐dioxide (VTDO), was carried out by using p‐toluenesulfonyl iodide (TosI) and bromide (TosBr) as radical initiators, and the corresponding ring‐opened polymer (PVTDO) was obtained. Both TosI and TosBr were found to work as the radical initiators for the polymerization of VTDO in bulk. The use of TosI gave PVTDOs with a broad, multimodal distribution of molecular weight in low yields. When 10 mol % of TosBr was employed, the isolated yield of PVTDO reached 49%, and the obtained PVTDO had a relatively narrow, monomodal molecular weight distribution of 1.8 with an Mn of 4100. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013 Radical ring‐opening polymerization of a five‐membered cyclic vinyl sulfone monomer, 2‐vinylthiolane‐1,1‐dioxide (VTDO), proceeded in bulk by use of p‐toluenesulfonyl iodide (TosI) or bromide (TosBr) as a radical initiator. When 10 mol % of TosBr was used, the isolated yield of PVTDO reached 49%. The PVTDO synthesized using TosBr had an Mn of 4100 with a relatively narrow, monomodal distribution of molecular weight of 1.8.