Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 48 Issue 13

1 July 2010

Volume 48, Issue 13

Pages 2733–2959

  1. Articles

    1. Top of page
    2. Articles
    3. Rapid Communications
    1. Synthesis of thermosensitive guar-based hydrogels with tunable physico-chemical properties by click chemistry (pages 2733–2742)

      Morgan Tizzotti, Marie-Pierre Labeau, Thierry Hamaide, Eric Drockenmuller, Aurélia Charlot and Etienne Fleury

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24015

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      Guar chains bearing alkyne functions have been successfully crosslinked using a α,ω-diazido-poly[(ethylene glycol)-co-(propylene glycol)] in water via a click chemistry coupling. The resulting biohybrid hydrogels were obtained with short gelation times and were proved to have physicochemical properties (rheological and water uptake) easily tunable by molecular parameters and experimental conditions. Thermosensitive behavior is obtained through an appropriate chemical composition and preliminary data concerning their use as drug-release devices is also reported.

    2. Low-band gap copolymers containing thienothiadiazole units: Synthesis, optical, and electrochemical properties (pages 2743–2756)

      Ivan Kmínek, Drahomír Výprachtický, Jaroslav Kříž, Jiří Dybal and Věra Cimrová

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24022

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      This study deals with synthesis, optical, and electrochemical characterization of three novel soluble low-band gap copolymers containing 4,6-di(2-thienyl)thieno[3,4-c][1,2,5]thiadiazole and/or its 3,3″′-dialkyl derivatives. The introduction of alkyl chains to the thiophene units increases the molecular weights of soluble fractions and solubility of the final copolymers leading to the improved processability of thin films. The copolymers absorb in visible spectral region with long wavelength absorption up to 1000 nm in thin films. Because of their low-band gap, high electron affinity, and ambipolar redox properties, they are promising for photovoltaic and electrochromic applications.

    3. Highly sulfonated multiblock copoly(ether sulfone)s for fuel cell membranes (pages 2757–2764)

      Kazuhiro Nakabayashi, Tomoya Higashihara and Mitsuru Ueda

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24023

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      The synthesis of highly sulfonated multiblock copoly(ether sulfone)s and their membranes' properties, such as proton conductivity, water uptake, mechanical strength, oxidative stability, and morphology have been investigated.

    4. Novel low-bandgap oligothiophene-based donor-acceptor alternating conjugated copolymers: Synthesis, properties, and photovoltaic applications (pages 2765–2776)

      Yaowen Li, Zaifang Li, Chunyu Wang, Hui Li, Hongguang Lu, Bin Xu and Wenjing Tian

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24025

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      A series of novel soluble donor-acceptor low-bandgap-conjugated polymers consisting of different electron-donating oligothiophene coupled to 2-pyran-4-ylidenemalononitrile-based unit were synthesized by Stille or Suzuki coupling polymerization. The structures, optical physics properties, electrochemical properties, and morphology of the copolymers were investigated. We also obtained bulk heterojunction photovoltaic devices by using the copolymers as donors and (6,6)-phenyl C61-butyric acid methyl ester (PC61BM) as acceptor. Power conversion efficiencies of the devices were measured between 0.61 and 0.99% under simulated AM 1.5 solar irradiation of 100mW/cm2.

    5. Substituent effects of N-alkyl groups on thermally induced polymerization behavior of 1,3-benzoxazines (pages 2777–2782)

      Atsushi Sudo, Long-Chao Du, Shoji Hirayama and Takeshi Endo

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24026

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      Thermally induced polymerizations of a series of 1,3-benzoxazines were investigated to clarify the dependences of the polymerization rates and the weight loss during the polymerizations on bulkiness of N-alkyl group.

    6. Water-soluble, thermoresponsive, hyperbranched copolymers based on PEG-methacrylates: Synthesis, characterization, and LCST behavior (pages 2783–2792)

      Mario Luzon, Cyrille Boyer, Carmen Peinado, Teresa Corrales, Michael Whittaker, Lei Tao and Thomas P. Davis

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24027

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      A series of water-soluble thermoresponsive hyperbranched copoly(oligoethylene glycol)s via reversible addition fragmentation chain transfer polymerization. Polymers were characterized by size exclusion chromatography and nuclear magnetic resonance analyses. According to the monomer composition the lower critical solution temperature (LCST) could be tuned from 25 °C to 90 °C.

    7. The application of copper(II) deactivator on the single-electron transfer living radical polymerization of tert-butyl acrylate (pages 2793–2797)

      Wuyang Ren, Long Jiang, Weiwei Wang and Yi Dan

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24031

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      This article describes the living radical polymerization of tert-butyl acrylate (tBA) applying the novel SET mechanism, copper(II) deactivator is observed necessary to be introduced into the catalyst system for the purpose of getting control on the SET-LRP polymerization of tBA. GPC and 1H NMR analyses confirmed the controllable SET-LRP of tBA and the expected structure of the resulting polymer. This method is helpful to the SET-LRP of the other monomers and promotes the development of the SET-LRP methodology.

    8. Fluorescent and electrochromic aromatic polyamides with 4-tert-butyltriphenylamine chromophore (pages 2798–2809)

      Sheng-Huei Hsiao, Guey-Sheng Liou, Yi-Chun Kung and Yu-Ming Chang

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24033

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      A series of novel fluorescent and electrochromic aromatic polyamides with 4-tert-butyltriphenylamine chromophore have been prepared from the polycondensation reactions of a newly synthesized dicarboxylic acid monomer, 4-(tert-butyl)-4′,4″-dicarboxytriphenylamine, with various aromatic diamines. Apart from high Tg and Ts values, high thermal stability, good mechanical property, and strong fluorescence, the polymers also revealed a high degree of redox and electrochromic reversibility.

    9. The effects of abstractable hydrogen in radical photopolymerization of maleate/vinyl ether monomers studied with EPR and photo-RTIR (pages 2810–2816)

      Tommy Haraldsson, Mats Johansson and Anders Hult

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24050

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      We show that the well-accepted alternating copolymerization between vinyl ethers and maleates is disturbed via reinitiation from a radical that results from an abstraction event. The sterically hindered maleate radical has a high propensity for hydrogen abstraction and the resulting electron-rich, vinyloxy-like radical preferentially reacts with a maleate monomer, as is shown via photo-RTIR and eletron paramagnetic resonance (EPR).

    10. Phosphonated fully aromatic polyethers for PEMFCs applications (pages 2817–2827)

      Konstantinia D. Papadimitriou, Aikaterini K. Andreopoulou and Joannis K. Kallitsis

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24055

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      Fully aromatic homopolymers and copolymers bearing side phosphonate ester or phosphonic acid units have been synthesized and investigated as potential polymer electrolyte membranes for fuel cells applications. The copolymers, which are based on a pyridine diol comonomer, presented high thermal stability, due to acid–base interactions between the pyridine and the side phosphonic acid groups, with no weight loss up to 550 °C.

    11. A novel aromatic–aliphatic copolyester consisting of poly(1,4-dioxan-2-one) and poly(ethylene-co-1,6-hexene terephthalate): Preparation, thermal, and mechanical properties (pages 2828–2837)

      Jie Gong, Xiao-Jie Lou, Wen-Da Li, Xin-Ke Jing, Hong-Bing Chen, Jian-Bing Zeng, Xiu-Li Wang and Yu-Zhong Wang

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24056

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      The synthetic process of PEHT (B) in which terephthalate copolyesters was made by random polycondensation of ethylene glycol and hexanediol with DMT has been revised as a process in which DMT reacted with each alcohol separately and then ester exchange was used for the copolymerization.

    12. A mixed cyclodextrin-biphenyl thermotropic liquid crystal: Synthesis, liquid-crystalline properties, and supramolecular organization (pages 2838–2845)

      Li Chen, Tian-Hui Hu, He-Lou Xie and Hai-Liang Zhang

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24060

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      Intriguing supramolecular structures were observed via the combination of liquid crystal and cyclodextrin. These investigations had shown that the supramolecular structure of H6B-β-CD consisted of a large-scale ordered lamellar structure and a small-scale ordered structure (SmE) formed by biphenyl mesogens at low temperature region.

    13. Proton conductive polyimide ionomer membranes: Effect of NH, OH, and COOH groups (pages 2846–2854)

      Jumpei Saito, Manabu Tanaka, Kenji Miyatake and Masahiro Watanabe

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24061

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      A series of sulfonated polyimide ionomers containing NH, OH, or COOH groups were synthesized, among which triazole and carbazole groups were effective in improving mechanical and proton conductive properties of the ionomer membranes.

    14. Micelles and reverse micelles with a photo and thermo double-responsive block copolymer (pages 2855–2861)

      Qiao Jin, Gongyan Liu and Jian Ji

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24062

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      Micelles and reverse micelles were constructed by photo and thermo double-responsive block copolymer PSPMA-b-PDEGMMA in aqueous solution. At 15 °C under visible light irradiation, the block copolymer self-assembled to form PSPMA-core micelles. In contrast, at 30 °C under UV light irradiation, PDEGMMA-core micelles were formed.

    15. Surface modification of UV-cured epoxy resins by click chemistry (pages 2862–2868)

      Yasemin Yuksel Durmaz, Marco Sangermano and Yusuf Yagci

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24063

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      A novel method for surface modification of photochemically cured epoxy network was described. Photoinitiated cationic copolymerization of a bisepoxide, namely 3,4-epoxy cyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (EEC) with epibromohydrine (EBH) by using a cationic photoinitiator, [4-(2-methylpropyl)phenyl]4-methylphenyl-iodonium hexafluorophosphate, in propylene carbonate solution was studied. Epoxy network possessing bromomethyl functional groups on the glass surface were converted to azide functionalities with sodium azide. Independently prepared alkyne functional poly(ethylene glycol) (PEG) was subsequently anchored to azide-modified epoxy surface by a “click” reaction to enhance surface hydrophilicity. Surface modification of the network through incorporation of hydrophilic PEG chain was evidenced by contact angle measurements.

    16. Cationic methacrylate copolymers containing primary and tertiary amino side groups: Controlled synthesis via RAFT polymerization, DNA condensation, and in vitro gene transfection (pages 2869–2877)

      Caihong Zhu, Sooyeon Jung, Guoying Si, Ru Cheng, Fenghua Meng, Xiulin Zhu, Tae Gwan Park and Zhiyuan Zhong

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24064

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      A versatile family of cationic PDMAEMA copolymers containing varying amounts of primary and tertiary amine groups were designed and synthesized by controlled RAFT copolymerization. These novel copolymers showed improved DNA condensation and dramatically enhanced gene transfection as compared with the PDMAEMA homopolymer. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    17. Synthesis and properties of thermoplastic polyimides with ether and ketone moieties (pages 2878–2884)

      Xiaohui Yu, Xiaogang Zhao, Changwei Liu, Zewei Bai, Daming Wang, Guodong Dang, Hongwei Zhou and Chunhai Chen

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24065

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      A series of thermoplastic polyimides containing ether and ketone moieties were synthesized and characterized. All obtained films showed very low glass transition temperatures (<225 °C) and also exhibited outstanding mechanical properties and thermooxidative stability. The films had excellent thermoplasticity (drop of E′ at Tg > 103), which indicated that they may be suitable for the melt processing. The film PI-a can potentially be used to fabricate materials such as PI fiber, ultra-thin film and ultra high strength, high-modulus film due to its outstanding ductility.

    18. Unsaturated, biobased polyesters and their cross-linking via radical copolymerization (pages 2885–2895)

      Lidia Jasinska and Cor E. Koning

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24067

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      The biobased, unsaturated polyesters from isosorbide, maleic anhydride, and succinic acid were synthesized via solvent-free bulk polycondensation catalyzed by titanium(IV) n-butoxide. 2D NMR, MALDI-Tof-MS, and FT-IR spectroscopy as well as TGA and DSC techniques were used for examination of the structure and thermal properties of the obtained products. The reported polyesters were successfully cured with unsaturated monomers. Good thermal properties and solvent resistance, make these cross-linked, predominantly biobased polyesters promising materials for coating applications.

    19. Synthesis of novel tetrahydrofuran-epichlorohydrin [poly(THF-b-ECH)] macromonomeric peroxy initiators by cationic copolymerization and the quantum chemically investigation of initiation system effects (pages 2896–2909)

      Murat Misir, Temel Ozturk, Mustafa Emirik and Sevil S. Yilmaz

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24069

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      This article describes the synthesis of poly(THF-b-ECH) macroperoxy initiators obtained from the cationic polymerization of THF and ECH with t-BuBP and BBP in the presence of AgSbF6 or ZnCl2. Poly(THF-b-ECH) macroperoxy initiators were used to synthesize poly(THF-b-ECH-b-MMA) poly(THF-b-ECH-b-S) block copolymers with methyl methacrylate (MMA) or styrene (S). Then, we synthesized poly(THF-b-ECH-g-PBd) graft copolymers by the copolymerization of poly(THF-b-ECH) macroperoxy initiators and PBd. Moreover, we investigated the effects of t-BuBP, BBP/AgSbF6, ZnCl2 initiating systems on the cationic copolymerization of THF and ECH as quantum chemically by using HYPERCHEM 7.5 program.

    20. Photosensitized alkoxyamines as bicomponent radical photoinitiators (pages 2910–2915)

      Davy-Louis Versace, Jacques Lalevée, Jean-Pierre Fouassier, Didier Gigmes, Yohann Guillaneuf and Denis Bertin

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24071

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      This article shows the ability of four alkoxyamines in the presence of a photosensitizer to act as efficient two-component photoinitiating systems under UV/near visible lights. Laser flash photolysis, electron spin resonance, and MO calculations support a photosensitized C[BOND]O bond cleavage through energy transfer leading to the formation of a carbon-centered initiating radical R and a nitroxide radical N[BOND]O.

    21. Photopolymerization of biocompatible phosphorus-containing vinyl esters and vinyl carbamates (pages 2916–2924)

      Claudia Dworak, Thomas Koch, Franz Varga and Robert Liska

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24072

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      Radical photopolymerization is a widely used tool for the curing of coatings and films, but also gains increasing interest in the field of biomedical applications. Many of biochemically relevant molecules contain organo-phosphorus features. Therefore, we focused on the development of different types of phosphorus containing vinyl esters and vinyl carbamates, which displayed high photoreactivity, surprisingly low cytotoxicity, and formed polymers with good mechanical properties.

    22. Polynorbornene with pentafluorophenyl imide side chain groups: Synthesis and sulfonation (pages 2925–2933)

      Arlette A. Santiago, Joel Vargas, Serguei Fomine, Rubén Gaviño and Mikhail A. Tlenkopatchev

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24073

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      Polynorbornene with pentafluorophenyl imide side chain groups was synthesized via ring opening metathesis polymerization using ruthenium alkylidene catalysts. The new polynorbornene bearing highly fluorinated sulfonic acid groups was obtained by the reaction of the hydrogenated poly(N-pentafluorophenyl-norbornene-5,6-dicarboximide) with sodium 4-hydroxybenzenesulfonate dihydrate.

    23. C2-symmetry dimethylated zirconocenes activated with triisobutyl aluminum as effective homogeneous catalysts for copolymerization of olefins (pages 2934–2941)

      N. M. Bravaya, A. N. Panin, E. E. Faingol'd, O. N. Babkina and A. Razavi

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24074

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      TIBA was found to act as an effective activator for several dimethylated bisindenylzirconocenes in homopolymerizations and copolymerizations of olefins at low AlTIBA/Zr ratios (100–300 mol/mol). As compared with the borate cocatalyst, Me2NHPhB(C6F5)4, TIBA does not admit successive incorporation of two and more α-olefin molecules into a copolymer chain, thus restricting the formation of XXX, XXE, and XEX triads (here E = ethylene and X = propylene or hexene-1).

    24. Preparation of remarkably tough polyHIPE materials via polymerization of oil-in-water HIPEs involving 1-vinyl-5-aminotetrazole (pages 2942–2947)

      Carlos Youssef, Rénal Backov, Mona Treguer, Marc Birot and Hervé Deleuze

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24075

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      A new class of “reverse” polyHIPE monoliths were prepared via oil-in-water emulsion templating. The main monomer used was the water-soluble 1-vinyl-5-amino[1,2,3,4]tetrazole, a specially designed vinylic heterocycle. Exceptionally tough, low density, high porosity macroporous monoliths were obtained. The interconnected voids morphology of these materials is typical of emulsion-templated polymer materials as already reported.

  2. Rapid Communications

    1. Top of page
    2. Articles
    3. Rapid Communications
    1. You have free access to this content
      Synthesis of polybenzamide-b-polystyrene block copolymer via combination of chain-growth condensation polymerization and atom transfer radical polymerization (pages 2948–2954)

      Chih-Feng Huang, Akihiro Yokoyama and Tsutomu Yokozawa

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24068

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      We present an efficient and easy approach using chain-growth condensation polymerization (CGCP) followed by atom-transfer radical polymerization (ATRP) to synthesize well-defined polybenzamide-b-polystyrene diblock copolymers with π[BOND]π interactions of aromatic rings, as well as strong intermolecular multiple hydrogen bonding between amide linkages after removal of the protecting group on amide nitrogen.

    2. You have free access to this content
      Time-lapse thiol-acrylate polymerization using a pH clock reaction (pages 2955–2959)

      Gang Hu, Christopher Bounds, John A. Pojman and Annette F. Taylor

      Article first published online: 24 MAY 2010 | DOI: 10.1002/pola.24088

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      A clock reaction, which involves a rapid increase in pH after a programable interval, may act as a “time-lapse” system for triggering the Michael addition polymerization of a trithiol and triacrylate dispersed in the clock reaction solution. The increase in pH catalyzes the addition of thiols to acrylates at the interface of the drops. The time-lapse period for the polymerization (as indicated by turbidity) was always longer than the induction period for clock in the same reactant concentrations condition. This is consistent with our claim that the polymerization was caused by the pH change.

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