Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 49 Issue 10

15 May 2011

Volume 49, Issue 10

Pages 2107–2313

  1. Articles

    1. Top of page
    2. Articles
    1. Synthesis of novel proton-conducting highly sulfonated polybenzimidazoles for PEMFC and the effect of the type of bisphenyl bridge on polymer and membrane properties (pages 2107–2117)

      Feifei Ng, Jennifer Péron, Deborah J. Jones and Jacques Rozière

      Article first published online: 22 MAR 2011 | DOI: 10.1002/pola.24630

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      Polysulfonated bisphenyl (sulfone, ether, hexafluoroisopropylidene) bridged dicarboxylic acid monomers and their polycondensation with 3,3′-diaminobenzidine give high-molecular-weight sulfonated polybenzimidazoles. Investigation of the influence of the nature of the bisphenyl bridging moiety on the properties of the resulting sulfonated polybenzimidazoles identifies the system containing bridging hexafluoroisopropylidene, both as sulfonated and non-sulfonated units, as introducing an attractive set of mechanical, thermal, and ionic conduction properties.

    2. Embedding multiple site-specific functionalities into polymer chains via nitrone-mediated radical coupling reactions (pages 2118–2126)

      Edgar H. H. Wong, Martina H. Stenzel, Thomas Junkers and Christopher Barner-Kowollik

      Article first published online: 17 MAR 2011 | DOI: 10.1002/pola.24639

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      A novel synthetic concept for the introduction of site-specific functionalities along the polymer backbone via a step growth mechanism employing nitrone-mediated radical coupling (NMRC) reactions is described. Via this procedure secondary functionalities (e.g., alkynes) can be incorporated into nitrones with ease allowing for facile post functionalizations on the newly formed polymer chains. Additionally, the chain length between functionalities can be tuned precisely by simply using polymer precursors with α,ω-halide end groups that are pre-made with the desired molecular weights.

    3. Self-assembly and secondary structures of linear polypeptides tethered to polyhedral oligomeric silsesquioxane nanoparticles through click chemistry (pages 2127–2137)

      Yung-Chih Lin and Shiao-Wei Kuo

      Article first published online: 17 MAR 2011 | DOI: 10.1002/pola.24640

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      Well-defined linear POSS-b-PBLG copolymers were synthesized through ROP of Glu-NCA followed by click reactions with a monofunctional azide-POSS. The self-assembly of POSS-b-PBLG formed a bilayer-like nanostructure featuring α-helical conformation and POSS aggregates, as evidenced using SAXS analysis.

    4. Cucurbit[7]uril moving on side chains of polypseudorotaxanes: Synthesis, characterization, and properties (pages 2138–2146)

      Hui Yang, Jingcheng Hao and Yebang Tan

      Article first published online: 17 MAR 2011 | DOI: 10.1002/pola.24642

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      Novel side chain polypseudorotaxanes with cucurbit[7]uril (CB[7]) threaded onto the side chains are synthesized from a water soluble polymer (P4VBVHeP) and CB[7] in water by simple stirring at room temperature. Interestingly, CB[7] beads could threaded onto the hexyl groups in the side chains of polymer first, and CB[7] beads could move from the hexyl groups to the benzyl and a part of viologen units in the side chains with increasing CB[7]. It is considered that the hydrophobic and charge–dipole interactions of CB[7] are the driving forces.

    5. Redox initiated cationic polymerization: The unique behavior of alkyl glycidyl ethers (pages 2147–2154)

      James V. Crivello

      Article first published online: 28 MAR 2011 | DOI: 10.1002/pola.24644

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      Alkyl glycidyl ethers form metastable oxiranium ions in the presence of strong Brønsted acids (HMtXn) generated by the platinum or palladium catalyzed redox reaction of a diaryliodonium or a triarylsulfonium salt in the presence of silanes bearing Si[BOND]H groups. The thermal destabilization of the oxiranium ion intermediates takes place at low temperatures resulting in rapid and exothermic cationic polymerization of the monomer.

    6. Dual thermo- and pH-sensitive network-grafted hydrogels formed by macrocrosslinker as drug delivery system (pages 2155–2164)

      Ting-Ting Pan, Wei-Dong He, Li-Ying Li, Wen-Xing Jiang, Chen He and Jing Tao

      Article first published online: 17 MAR 2011 | DOI: 10.1002/pola.24645

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      PDMAEMA-g-PNIPAM hydrogels with PDMAEMA as the crosslinked network and PNIPAM as the grafting chain were synthesized through the combination of ATRP, RAFT polymerization, and click chemistry. The resulted hydrogels exhibit dual thermo- and pH-sensitive behavior with excellent swelling/deswelling performance, depending on the degree of crosslinking. The drug release from the hydrogels can be easily modulated with temperature, pH, and hydrogel structure.

    7. Spontaneous Cu(I)Br–PMDETA-mediated polymerization of isobornyl methacrylate in heterogeneous aqueous medium at ambient temperature (pages 2165–2172)

      Kannapiran Rajendrakumar and R. Dhamodharan

      Article first published online: 24 MAR 2011 | DOI: 10.1002/pola.24646

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      Isobornyl methacrylate (IBMA), a bulky hydrophobic methacrylate, undergoes a spontaneous initiator-free polymerization with Cu(I)Br/N,N,N′,N″,N″-pentamethyldiethylenetriamine/ethyl-2-bromoisobutyrate catalytic system in dimethyl sulfoxide–water mixtures, at ambient temperature. The rate of polymerization increases with increasing water content up to 80 mol % and then decreases. The active Cu(0) formed with the disproportionation of Cu(I) species, in aqueous medium, probably plays a vital role for a possible air-initiation of IBMA via single electron transfer-living radical polymerization mechanism. Poly(IBMA) samples of narrow molecular weight distribution (1.1–1.3) are obtained. This observation is specific only to bulky hydrophobic methacrylates, isobornyl methacrylate, and 1-adamantyl methacrylate.

    8. Basic amino acid assisted-fabrication of rectangular nanotube, circular nanotube, and hollow microsphere of polyaniline: Adjusting and controlling effect of pH value (pages 2173–2182)

      Cuiling Gao, Man Ai, Xun Li and Zheng Xu

      Article first published online: 24 MAR 2011 | DOI: 10.1002/pola.24647

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      This article reports an effective method to prepare polyaniline (PANI) nanotubes with rectangular or circular cross section and hollow microspheres by using basic amino acids L-lysine or L-arginine as dopants and pH buffer agents, respectively. And reveal the pH value of the reaction solution at the beginning stage is a crucial factor for the morphology of PANI microstructures. This method provides a novel route to selectively synthesize different PANI microstructures via adjusting and controlling the pH value of reaction solution using basic amino acid, and also supplies a new view on the polymerization process. The magnified SEM images of polyaniline tubes with rectangular cross section doped by L-lysine.

    9. Promoting effects of urethane derivatives of phenols on the ring-opening polymerization of 1,3-benzoxazines (pages 2183–2190)

      Atsushi Sudo, Atsushi Mori and Takeshi Endo

      Article first published online: 22 MAR 2011 | DOI: 10.1002/pola.24648

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      Urethanes derived from phenolic compounds such as resorcinol were used as efficient promoters for the ring-opening polymerization of benzoxazines. The mechanisms for the promoting effect would involve the thermal dissociation of the urethanes into the corresponding isocyanate and phenolic compounds, which exhibited promoting effects on the ring-opening reaction of benzoxazines.

    10. Synthesis and characterization of radiopaque poly(ether urethane) with iodine-Containing diol as chain extender (pages 2191–2198)

      Weiqiang Qu, Weijuan Xia, Chao Feng, Xinlin Tuo and Teng Qiu

      Article first published online: 22 MAR 2011 | DOI: 10.1002/pola.24649

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      A radiopaque iodinated poly(ether urethane) was prepared by using iodine-containing diol as chain extender in a normal two-step condensation polymerization process. In addition of the high radiopacity this material possesses good thermal stability, favorable mechanical properties and noncytotoxicity.

    11. Polyrotaxane derivatives. II. Preparation and characterization of ionic polyrotaxanes and ionic slide-ring gels (pages 2199–2209)

      Jun Araki

      Article first published online: 28 MAR 2011 | DOI: 10.1002/pola.24650

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      Four ionic polyrotaxane derivatives, i.e., carboxymethylated, sulfoethylated, diethylaminoethylated, and trimethylammoniohydroxypropylated polyrotaxanes, were prepared from a parent polyrotaxane consisting of poly(ethylene glycol) and α-cyclodextrins. Degrees of substitution of the derivatives were determined from results of 1H NMR and colloidal titrations. Cross-linking of sulfoethylated and quaternized polyrotaxanes yielded ionic slide-ring gels carrying respective ionic groups on the mobile cross-links. The former gel showed intriguing phenomena, including a large degree of swelling of up to 1147, drastic decrease in degree of swelling by the presence of electrolyte and bending under a moderate applied electric field (7 V/cm).

    12. New polyimides incorporated with diphenylpyrenylamine unit as fluorophore and redox-chromophore (pages 2210–2221)

      Yi-Chun Kung, Wen-Fu Lee, Sheng-Huei Hsiao and Guey-Sheng Liou

      Article first published online: 24 MAR 2011 | DOI: 10.1002/pola.24652

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      New series of polyimides containing electroactive diphenylpyrenylamine unit were prepared from the conventional two-step polycondensation reactions of N,N-di(4-aminophenyl)-1-aminopyrene with aromatic or alicyclic tetracarboxylic dianhydrides. The polymers exhibited good solubility in polar organic solvents and could afford robust films via solution casting. Apart from high Tg values and good thermal stability, these polymers also showed strong blue fluorescence, ambipolar redox behaviors, and multicolored electrochromic properties.

    13. Synthesis of azide end-functionalized isotactic polypropylene building block and renewed modular synthesis of diblock copolymers of isotactic polypropylene and poly(ε-caprolactone) (pages 2222–2232)

      Huahua Huang, Hui Niu and Jin-Yong Dong

      Article first published online: 24 MAR 2011 | DOI: 10.1002/pola.24653

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      The synthesis of i-PP terminated with an azide group (i-PP-t-N3) was detailed. The chemistry is based on a dual-step transformation from a styryl-capped i-PP through 1-chloroethylbezene-terminated intermediate to azide end-functionalized i-PP. 1H NMR and FTIR as well as GPC and DSC results reveal a clean and clear formation of i-PP-t-N3 (Mn in between 10,000 and 40,000 g/mol). The clickable i-PP building block was applied to a renewed, modular synthesis of amphiphilic i-PP-b-PCL (poly(ε-caprolactone)) diblock copolymers. Composition-diversified, structure-well defined diblock copolymers were obtained in high yields.

    14. Poly[methyl(phenyl)silanediyl] modified with dansyl fluorophore: Synthesis and photophysics (pages 2233–2244)

      Věra Cimrová, Drahomír Výprachtický and Hans-Heinrich Hörhold

      Article first published online: 28 MAR 2011 | DOI: 10.1002/pola.24654

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      Novel dansyl-modified polysilanes PMPSi-n-DNS with various length of the spacer (n = 0, 2, 5, 8, and 12) were synthesized by condensation reaction of dansyl amines with formylated poly[methyl(phenyl)silanediyl], yielding Schiff bases. Their photophysical properties were investigated by absorption, steady-state, and time-resolved photoluminescence spectroscopy.

    15. Construction of reversible hydration–dehydration system by a model compound and a novel polymer bearing vicinal tricarbonyl structure (pages 2245–2251)

      Takehito Dei, Kazuhide Morino, Atsushi Sudo and Takeshi Endo

      Article first published online: 24 MAR 2011 | DOI: 10.1002/pola.24656

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      A novel polymer bearing acyclic vicinal tricarbonyl moieties in the side chains was synthesized by radical polymerization of a styrene derivative bearing a 1,3-diketone structure and its oxidation into the corresponding vicinal tricarbonyl moiety. The tricarbonyl moiety was easily hydrated into a geminal diol structure, and the resulting geminal diol was easily dehydrated under vacuum to recover the tricarbonyl moiety, leading to the successful hydration–dehydration cycles.

    16. Polyterephthalates made from Ethylene glycol, 1,4-cyclohexanedimethanol, and isosorbide (pages 2252–2260)

      Robert Quintana, Antxon martínez de Ilarduya, Abdelilah Alla and Sebastián Muñoz-Guerra

      Article first published online: 28 MAR 2011 | DOI: 10.1002/pola.24657

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      Random poly(ethylene terephthalate) terpolyesters containing 1,4-cyclohexanedimethanol and isosorbide (Is) show higher Tg and lower crystallizability as the content in cyclic diols increases, this effect being more pronounced when Is is the replacing monomer.

    17. Synthesis and properties of biobased epoxy resins. part 1. Glycidylation of flavonoids by epichlorohydrin (pages 2261–2270)

      Hélène Nouailhas, Chahinez Aouf, Christine Le Guerneve, Sylvain Caillol, Bernard Boutevin and Hélène Fulcrand

      Article first published online: 28 MAR 2011 | DOI: 10.1002/pola.24659

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      The possibility to partially replace bisphenol A by catechin, a representative of the monomeric unit of condensed tannins, was evaluated. Biobased epoxy resins were formulated from the glycidyl ether of catechin (GEC). Their thermal properties, dynamic mechanical properties, and swelling percentage were investigated and compared to a commercial diglycidyl ether of bisphenol A (DGEBA). For instance, when incorporated into DGEBA resin, GEC did not modify the glass transition temperature but induced a decrease of the swelling percentage, suggesting that GEC enhanced crosslinking in the epoxy resin networks.

      Corrected by:

      Erratum: Erratum: Synthesis and properties of biobased epoxy resins. Part 1. Glycidylation of flavonoids by epichlorohydrin

      Vol. 49, Issue 14, 3239, Article first published online: 7 JUN 2011

    18. One-pot synthesis of polyamide 12,T–polyamide-6 block copolymers (pages 2271–2280)

      Theodore F. Novitsky and Lon J. Mathias

      Article first published online: 28 MAR 2011 | DOI: 10.1002/pola.24660

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      CaCl2 was found to decrease the rate of transamidation during anionic polymerization of caprolactam by a PA-12,T macrocoinitiator. Hence, the PA-12,T block size is decreased with reactions performed at lower CaCl2 concentrations. The 10 and 8 mol % CaCl2 samples have PA-12,T sequences long enough to crystallize resulting in swollen and opaque particles in formic acid. The 5 and 2 mol % CaCl2 samples have severely deteriorated PA-12,T blocks, where they cause the polymer to gel rather than fully dissolve in formic acid. Clarity of these gels is due to their inability to crystallize.

    19. Novel suberin-based biopolyesters: From synthesis to properties (pages 2281–2291)

      Andreia F. Sousa, Alessandro Gandini, Armando J. D. Silvestre, Carlos Pascoal Neto, José J. C. Cruz Pinto, Christer Eckerman and Bjarne Holmbom

      Article first published online: 28 MAR 2011 | DOI: 10.1002/pola.24661

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      Suberin, a major component of two important industrially exploited species, cork and birch, is a valuable renewable resource, which can be depolymerized into interesting aliphatic fragments bearing complementary functions for polyester synthesis. In this study, these suberin monomers were used to prepare novel hydrophobic, biodegradable, biopolyesters. Their full characterization both for linear and partly crosslinked architectures suggested valuable potential applications.

    20. Enhancement of OFET performance of semiconducting polymers containing benzodithiophene upon surface treatment with organic silanes (pages 2292–2302)

      Prakash Sista, Mahesh P. Bhatt, Ashton R. Mccary, Hien Nguyen, Jing Hao, Michael C. Biewer and Mihaela C. Stefan

      Article first published online: 28 MAR 2011 | DOI: 10.1002/pola.24663

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      Poly{4,8-bis(4-decylphenylethynyl)benzo[1,2-b:4,5-b′]dithiophene} (P1) homopolymer and poly{4,8-bis(4-decylphenylethynyl)benzo[1,2-b:4,5-b′]dithiophene-alt-thiophene} (P2) alternating copolymer have been synthesized by Stille coupling polymerization. The field-effect mobilities of both polymers were measured on both untreated and silane-treated OFET devices. Various silanes were selected to allow an incremental increase in the hydrophobicity of the silicon dioxide dielectric. A direct correlation was observed between the hydrophobicity of the silicon dioxide dielectric surface and the enhancement of the field-effect mobilities. The highest mobilities for both polymers were measured on the OFET devices treated with heptadecafluoro-1,1,2,2-tetrahydro-decyl-1-trimethoxysilane (FS) which generated the most hydrophobic surface.

    21. Synthesis, self-assembly, fluorescence, and thermosensitive properties of star-shaped amphiphilic copolymers with porphyrin core (pages 2303–2313)

      Tianbin Ren, An Wang, Weizhong Yuan, Lan Li and Yue Feng

      Article first published online: 28 MAR 2011 | DOI: 10.1002/pola.24665

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      Star-shaped amphiphilic poly(ε-caprolactone)-bolck-poly(oligo(ethylene glycol) methyl ether methacrylate) with porphyrin core has been successfully prepared by the combination of ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP). The copolymer can easily self-assemble into micelles in aqueous solution. The copolymer micelles were stable and exhibited a certain degree of cyclical sensitivity to phase transition when aqueous temperature was switched as above and below LCST, therefore benefit for the application as stimuli-responsive nanocontainer.