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Synthesis of aromatic polyethers by ion-radical reactions

Wang, James Hongxue
http://rave.ohiolink.edu/etdc/view?acc_num=case1059492813

Abstract Details

1991, Doctor of Philosophy, Case Western Reserve University, Macromolecular Science.
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 ω-(2,6-dimethylphenol) chain end (PPO-OH). The PTC copolymerization of BDMP with 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane yielded α,ω-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′-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 α,ω-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 ω-(ρ-vinylbenzyl) ether macromonomer of PPO (PFO-VBE, M2) in copolymerization with methyl methacrylate (M1)was investigated as a function of macromonomer concentration and the nature of polymerization solvents. The reactivity of the PPO-VBE macromonomer, 1/r1, 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 1H-NMR spectroscopy. The concentration and solvent effects were interpreted based on the micelle formation during the copolymerization. (Abstract shortened with permission of author.)
Virgil Percec (Advisor)
445 p.
Chemistry, Polymer
Polyethers, aromatic; Ion-radical reactions

Recommended Citations

Citations

  • Wang, J. H. (1991). Synthesis of aromatic polyethers by ion-radical reactions [Doctoral dissertation, Case Western Reserve University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=case1059492813

    APA Style (7th edition)

  • Wang, James. Synthesis of aromatic polyethers by ion-radical reactions. 1991. Case Western Reserve University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=case1059492813.

    MLA Style (8th edition)

  • Wang, James. "Synthesis of aromatic polyethers by ion-radical reactions." Doctoral dissertation, Case Western Reserve University, 1991. http://rave.ohiolink.edu/etdc/view?acc_num=case1059492813

    Chicago Manual of Style (17th edition)

case1059492813
652
© 1991, all rights reserved.
This open access ETD is published by Case Western Reserve University School of Graduate Studies and OhioLINK.