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

Abstract

Abstract4,4′‐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.