Iodo Containing Sulfone and Sulfonamide Based Poly(arylene ether)s

In an ongoing project involving the synthesis of functionalized poly(arylene ether)s that carry pendent phenyl sulfonyl groups, the introduction of an iodo group was desired. The effects of fluorine position on the electrophilic iodination of the 2,4-, 2,6-, and 2,5- and 3,5-isomers of difluorodiphenylsulfone, DFDPS were studied. The relative reactivity, toward EAS, was probed via ¹³C NMR spectroscopy and verified experimentally by iodination with N-iodosuccinimide. The product mixtures and corresponding structures indicated that intermediate stability did not always correlate to reactivity. Model studies were also conducted on DFDPS isomers that successfully carry in iodo groups in a pendent position.

2,4- and 3,5- Isomers of difluoro-N,N-diphenylbenzene sulfonamide have been synthesized for polymerization by nucleophilic aromatic substitution. Their properties were characterized by ¹H, ¹³C, and ¹⁹F NMR spectroscopy and elemental analysis. The 2,4- and 3,5- isomers of difluoro-N,N-diphenylbenzene were polymerized with Bisphenol-A and the resultant polymers were characterized by TGA, DSC, and SEC. The isomers were successfully iodinated with N-iodosuccinimide. Model studies and polymerization reactions on the resultant 3,5-difluoro-N,N-bis(4-iodo)diphenylbenzene sulfonamide were conducted.