Synthesis of aromatic polyethers by Scholl reaction. II. On the polymerizability of 4,4′-bis(phenoxy)diphenyl sulfones and of 4,4′-bis(phenythiol)diphenyl sulfone

4,4′-Bis(phenoxy)diphenyl sulfone ( 1 ), 4,4′-bis(phenylthio)diphenyl sulfone ( 2 ), and 1 substituted with various electron-donating groups in the phenoxy units were synthesized and polymerized under oxidative reaction conditions. The presence of methyl, tert-butyl, and methoxy groups as substituents on the phenoxy groups of 1 increases both the yield and the solubility of the resulting polymers. The structure-reactivity relationship of the monomers and of the growing species were discussed based on a radical-cation mechanism of polymerization. Monomers of high nucleophilicity and resonance stabilized radical-cation growing species are crucial to achieve polymers of high molecular weight. The structure of the polymers and in several cases of their chain ends were determined by ¹H-NMR spectroscopy. The mechanism of termination and the side reactions occuring during this polymerization process were discussed based on the structure of the resulting polymers.