Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Journal of Polymer Science Part A: Polymer Chemistry

1 March 2003

Volume 41, Issue 5

Pages 625–724

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      Bicyclobutanes and cyclobutenes: Unusual carbocyclic monomers (pages 625–635)

      H. K. Hall Jr. and Anne Buyle Padias

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/pola.10618

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      Bicyclobutanes and cyclobutenes substituted with electron-attracting groups readily undergo free-radical and anionic polymerizations to give high polymers consisting of 1,3- and 1,2-enchained cyclobutane rings, respectively. These polymers display numerous attractive properties in comparison with their vinyl counterparts.

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    1. Hydrogen-bonding-aided synthesis of novel ladderlike organobridged polysiloxane containing side-chain naphthyl groups (pages 636–644)

      Jin Sun, Huadong Tang, Jinqiang Jiang, Xiaoshu Zhou, Ping Xie, Rongben Zhang and Peng-Fei Fu

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/pola.10607

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      With a hydrogen-bonding template, a novel soluble aryl amide-bridged ladderlike polysiloxane (ALPS), containing naphthyl as the side-chain group, has been successfully synthesized via a stepwise coupling polymerization. The analytical results (Fourier transform infrared, 1H NMR, 29Si NMR, X-ray diffraction, differential scanning calorimetry, and vapor pressure osmometry) show that the polymer possesses an ordered ladderlike architecture.

    2. Substituted propenyl end groups as reactive intermediates in radical polymerization (pages 645–654)

      Bunichiro Yamada, Fuminori Oku and Takahiro Harada

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/pola.10587

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      The addition of propagating radicals of methyl acrylate (MA) and styrene (St) to CH2[DOUBLE BOND]C(CO2CH3)CH2[BOND] and CH2[DOUBLE BOND]C(C6H5)CH2[BOND] ω-end groups of poly(methyl methacrylate) (PMMA) and polystyrene (PSt) was investigated. The unsaturated end groups were as reactive as MA and St toward the respective propagating radicals. However, adduct radicals derived from the PMMA end group and poly(methyl acrylate) (PMA) radical exclusively underwent β fragmentation to yield PMMA radicals and end groups bound to PMA chain. The addition of PSt radicals to the same end groups bound to PMMA resulted in adduct radicals that underwent (1) β fragmentation and (2) addition to St or (3) coupling with PSt radicals.

    3. Multifunctional coupling agents: Synthesis and model reactions (pages 655–667)

      L. Jakisch, H. Komber and F. Böhme

      Version of Record online: 17 JAN 2003 | DOI: 10.1002/pola.10612

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      New coupling agents with 2-oxazoline, oxazinone, and one allyl ether groups were prepared. Model reactions showed that the 2-oxazoline groups and the oxazinone groups reacted selectively with carboxylic and amino groups, respectively, whereas the allyl ether group remained unaffected. The conversion of the coupling agents with 11-aminoundecanoic acid resulted in an allyloxy-functionalized poly(ester amide). Furthermore, the utilization of the coupling agents for the preparation of telechelic poly(propylene glycol) was described.

    4. Grafting of poly(styrene-co-p-chloromethyl styrene) with ethyl methacrylate via atom transfer radical polymerization catalyzed by CuCl/1,2-dipiperidinoethane (pages 668–673)

      Mehmet Coşkun and Mehmet Mürşi̇t Temüz

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/pola.10620

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      Poly(styrene-graft-ethyl methacrylate) graft copolymer was prepared by atom transfer radical polymerization (ATRP) with poly(styrene-co-p-chloromethyl styrene)s in various compositions as macroinitiator in the presence of CuCl/1,2-dipiperidinoethane at 130 °C in N,N-dimethylformamide. 1,2-Dipiperidinoethane was an effective ligand of CuCl for ATRP in the graft copolymerization.

    5. Synthesis and properties of new ultraviolet–blue-emissive fluorene-based aromatic polyoxadiazoles with confinement moieties (pages 674–683)

      Nam Choul Yang, Young Hoon Park and Dong Hack Suh

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/pola.10616

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      New 2,7-di(5-phenyl-1,3,4-oxadiazole)-9,9′-didodecylfluorene-based polymers with different confinement linkages in the main chain have successfully been synthesized with a two-step method. They show efficient blue luminescence and high oxidation potentials and are considered promising blue-emitting and hole-blocking electroluminescent materials.

    6. Block copolymers of acrylic acid and butyl acrylate prepared by reversible addition–fragmentation chain transfer polymerization: Synthesis, characterization, and use in emulsion polymerization (pages 684–698)

      Nicolas Gaillard, Alain Guyot and Jerome Claverie

      Version of Record online: 17 JAN 2003 | DOI: 10.1002/pola.10606

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      Amphiphilic block copolymers of poly(acrylic acid-b-butyl acrylate) were prepared by reversible addition–fragmentation transfer polymerization in a one-pot reaction. The aggregation characteristics of the copolymers corresponded to those theoretically predicted for a star micelle. In an emulsion polymerization, low amounts of these copolymers could stabilize latices with solid contents up to 50%.

    7. Cationic ring-opening polymerization behavior of a five-membered cyclic thiocarbonate having a spiro-linked adamantane moiety (pages 699–707)

      Nobukatsu Nemoto, Yoshinori Ito and Takeshi Endo

      Version of Record online: 17 JAN 2003 | DOI: 10.1002/pola.10617

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      The synthesis and cationic ring-opening polymerization behavior of a novel five-membered cyclic thiocarbonate bearing a spiro-linked adamantane moiety, tricyclo[,7]decane-2-spiro-4′-(1′,3′-dioxolane-2′-thione) (TC2), are described. The cationic ring-opening polymerization of TC2 did not proceed with trifluoromethanesulfonic acid, methyl trifluoromethanesulfonate, triethyloxonium tetrafluoroborate (Et3OBF4), boron trifluoride etherate (BF3OEt2), titanium tetrachloride, or methyl iodide as the initiator, presumably because of the steric hindrance of the adamantane moiety. However, the cationic ring-opening copolymerization of TC2 with five- or six-membered cyclic thiocarbonates, that is, 1,3-dioxolane-2-thione (TC3), 1,3-dioxane-2-thione (TC4), 5-methyl-1,3-dioxane-2-thione (TC5), or 5,5-dimethyl-1,3-dioxane-2-thione (TC6), initiated by BF3OEt2 or Et3OBF4, proceeded to afford the corresponding copolymer via a selective ring-opening direction. The increase in the feed ratio of TC2 in the copolymerization increased the unit ratio derived from TC2 in the copolymer; however, the molecular weight of the copolymer decreased.

    8. Synthesis and properties of π-conjugated dithiafulvene oligomers by addition of a monofunctionalized compound (pages 708–715)

      Kensuke Naka, Adriana Gelover-Santiago, Takashi Uemura and Yoshiki Chujo

      Version of Record online: 16 JAN 2003 | DOI: 10.1002/pola.10614

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      Dithiafulvene oligomers (3) were prepared by cycloaddition polymerization of aldothioketenes with their alkynethiol tautomers derived from 1,4-diethynylbenzene (2) with the addition of 1-ethynyl-4-methylbenzene (1) as a monofunctionalized compound. The structures of 3 were confirmed by IR and 1H NMR spectroscopies. Gel permeation chromatographic and 1H NMR analysis suggested that the number-average degree of polymerization (DP) increased with an increasing feed ratio of 2/1. The ultraviolet–visible spectra of 3 demonstrated that the absorption maxima of 3 increased with increasing DP. These redshifts are ascribed to an effective expansion of the π-conjugation system in 3. The oligomers exhibited a maximum conjugation length of seven repeating units. The oxidation half-peak potentials (Ep/2) of 3 were cathodically shifted with increasing DP.

    9. Real-time Fourier transform infrared study of free-radical UV-induced polymerization of hybrid sol–gel. I. Effect of silicate backbone on photopolymerization kinetics (pages 716–724)

      O. Soppera and C. Croutxé-Barghorn

      Version of Record online: 17 JAN 2003 | DOI: 10.1002/pola.10622

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      The influence of the inorganic part of free-radical photocurable hybrid sol–gel was investigated by 29Si NMR and real-time Fourier transform infrared spectroscopy. The condensation state of the silicate network was of crucial importance in the photopolymerization process. The presence of the silicate backbone did not limit the final conversion ratio. On the contrary, photopolymerization occurred more efficiently for systems with a higher degree of condensation. The inhibition role of oxygen is also underlined throughout this article.