Poly(arylene ether)s with Pendent 3-Iodophenyl Sulfonyl Groups: Synthesis, Characterization, and Modification

Abstract

A series of poly(arylene ether)s carrying truly pendent functional groups were prepared by the meta activated nucleophilic aromatic substitution (NAS) polycondensation reaction of a new aryl difluoride monomer, 3,5-difluoro-1-((3-iodophenyl)sulfonyl)benzene, followed by Suzuki–Miyaura and Heck cross-coupling reactions. The synthesis of 3,5-difluoro-1-((3-iodophenyl)sulfonyl)benzene was achieved via the one-step reaction of 3,5-difluorodiphenyl sulfone with N-iodosuccinimide. Model reactions and NMR data indicated that the carbon–iodine functionality was stable to NAS conditions, thus allowing the synthesis of the desired iodo functional poly(arylene ether sulfone), I-PAES. The iodo moiety was then subjected to palladium-catalyzed cross-coupling reactions with phenyl, naphthyl, and 4-acetylphenyl boronic acids as well as styrene in order to prepare the corresponding phenyl, naphthyl, 4-acetyl phenyl, and 2-phenylvinyl analogues. The polymers were characterized via NMR spectroscopy, size exclusion chromatography, thermogravimetric analysis, and differential scanning calorimetry. The polymers exhibited moderate thermal stability in air, with 5% weight loss temperatures ranging from 404 to 482 °C, while the glass transition temperatures ranged from 131 to 165 °C.