SYNTHESIS OF AROMATIC POLYETHERS BY SCHOLL REACTION .2. ON THE POLYMERIZABILITY OF 4,4'-BIS(PHENOXY) DIPHENYL SULFONES AND OF 4,4'-BIS (PHENYLTHIO) 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 H-1-NMR spectroscopy. The mechanism of termination and the side reactions occurring during this polymerization process were discussed based on the structure of the resulting polymers.