Synthesis of aromatic polyethers by ion-radical reactions

This dissertation describes the synthesis of aromatic polyethers by both anion-radical and cation-radical reactions. The anion-radical reactions refer to the phase transfer catalyzed (PTC) copolymerization of 4-bromo-2,6-dimethylphenol (BDMP) with a comonomer phenol and the PTC depolymerization of poly(2,6-dimethyl-1,4-phenylene oxide)s (PPO) in the presence of a phenol.; The PTC anion-radical copolymerization of BDMP with a chain initiator - 2,4,6-trimethylphenol (TMP) or 4-tert-butyl-2,6-dimethylphenol (TBDMP) led to PPO with one {dollar}omega{dollar}-(2,6-dimethylphenol) chain end (PPO-OH). The PTC copolymerization of BDMP with 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane yielded {dollar}alpha{dollar},{dollar}omega{dollar}-bis(2,6-dimethylphenol)-PPO (PPO-2OH). The PTC copolymerization of BDMP with 4-hydroxy-3,5-dimethylbenzyl alcohol resulted in a mixture of PPO-2OH and PPO-OH. Chain termination was observed in the PTC copolymerization of BDMP with a 4-substituted-2,6-di-tert-butylphenol. The PTC anion-radical depolymerization of high molecular weight PPO-OH in the presence of either TMP or TBDMP was investigated.; The cation-radical polymerization of a series of bis(aromatic groups) substituted ether monomers was investigated. A series of monomers of different structure were synthesized and polymerized under single electron transfer (SET) oxidation conditions (the Scholl reaction). The substitution of the phenyl rings with electron-donating groups improves both the polymerizability and the solubility of the polymers. The polymerizability of 4,4{dollar}spprime{dollar}-bis(1-naphthoxy)diphenyl sulfone is higher than that of 1,5-bis(1-naphthoxy)pentane. The difference between the reactivity of growing cation-radical species is a dominant factor. The cation-radical copolymerization of {dollar}alpha{dollar},{dollar}omega{dollar}-bis (4-(1-naphthoxy)phenylsulfonyl) perfluoroalkanes and 1,5-bis(1-naphthoxy)diphenyl sulfone indicates that the comonomer of higher oxidizability/nucleophilicity is more favorably incorporated into the copolymers. Fully aromatic polyethers were synthesized by the cation-radical polymerization of bis(1-naphthoxy)aryls.; The "reactivity" of the {dollar}omega{dollar}-({dollar}rho{dollar}-vinylbenzyl) ether macromonomer of PPO (PFO-VBE, M{dollar}sb2{dollar}) in copolymerization with methyl methacrylate (M{dollar}sb1{dollar})was investigated as a function of macromonomer concentration and the nature of polymerization solvents. The reactivity of the PPO-VBE macromonomer, 1/r{dollar}sb1{dollar}, was influenced by both the concentration of the macromonomers and by the nature of polymerization solvents. Micelle formation of the resulting graft copolymers was demonstrated by {dollar}sp1{dollar}H-NMR spectroscopy. The concentration and solvent effects were interpreted based on the micelle formation during the copolymerization. (Abstract shortened with permission of author.)...