Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 52 Issue 1

1 January 2014

Volume 52, Issue 1

Pages i–iv, 1–147

  1. Cover Image

    1. Top of page
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    3. Highlight
    4. Rapid Communication
    5. Articles
    1. You have free access to this content
      Cover Image, Volume 52, Issue 1 (pages i–ii)

      Article first published online: 26 NOV 2013 | DOI: 10.1002/pola.27020

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      A set of segmented, amphiphilic copolymers was prepared by Müge Artar, Takaya Terashima, Mitsuo Sawamoto, E. W. Meijer, and Anja R. A. Palmans on page 12, which comprised hydrophilic side chains, supramolecular or hydrophobic side chains, and ligand units via reversible addition–fragmentation chain transfer (RAFT) polymerization. Copolymers fold into single-chain polymeric nanoparticles (SCPNs) as a result of the helical self-assembly of the pendant BTA units and/or hydrophilic–hydrophobic phase separation. The obtained Ru(II) loaded SCPNs provide hydrophobic, isolated reaction pockets around Ru(II) complexes, and they show transfer hydrogenation of cyclohexanone in water independent of supramolecular units.

    2. You have free access to this content
      Cover Image, Volume 52, Issue 1 (pages iii–iv)

      Article first published online: 26 NOV 2013 | DOI: 10.1002/pola.27021

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      A series of regioregular poly(3-alkylthiophene)s is synthesized with substituents of increasing bulkiness, which is realized by the use of systematically more heavily branched alkyl groups, as presented by Guy Koeckelberghs et al. on page 76. The self-assembly properties are investigated by UV–vis spectroscopy both in poor solvent conditions and thin films and by X-ray diffraction and DSC experiments on powders. This shows that the self-assembly is slowed down and complicated, but not suppressed by increasing the bulkiness, as even poly(thiophene)s with very bulky alkyl substituents self-assembled. The magnetic properties of powders of the neutral polymers are investigated by ESR spectroscopy and magnetometry and are in line with previous findings on the magnetic properties of conjugated polymers. ESR also confirmed the results on the self-assembly.

  2. Highlight

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    3. Highlight
    4. Rapid Communication
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      Pd–phosphinesulfonate bravely battles the “vinyl halide insertion copolymerization” barricade (pages 1–6)

      Shahaji Gaikwad, Satej Deshmukh and Samir H. Chikkali

      Article first published online: 11 OCT 2013 | DOI: 10.1002/pola.26968

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      Insertion (co)polymerization of vinyl halides has long been on the radar of the scientific community. However, none of the catalytic systems could cross the barricade (insertion vs. x-elimination). The crucial design of the Pd–phosphinesulfonate [(PO)Pd] system enables the incorporation of 3.6 mol % of vinyl fluoride in an ethylene-copolymerization reaction. In a significant development, the existence of (PO)Pd[BOND]H species during the polymerization was cleverly spotted, and it was demonstrated that these are indeed responsible for 2,1-insertion and vinyl chloride incorporation (0.4 mol %).

  3. Rapid Communication

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    4. Rapid Communication
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    1. Renewable benzoxazine monomer from Vanillin: Synthesis, characterization, and studies on curing behavior (pages 7–11)

      N. K. Sini, Jayashree Bijwe and Indra K. Varma

      Article first published online: 6 NOV 2013 | DOI: 10.1002/pola.26981

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      A novel renewable based benzoxazine, 3-(furan-2-ylmethyl)-8-methoxy-3,4-dihydro-2H-1,3-benzoxazine-6-formyl (Va-Bz), has been synthesized from a lignin derived chemical vanillin without solvents. Poly(Va-Bz) has high Tg and excellent thermal and adhesive properties. A mechanism of cross-linking, due to electrophilic substitution at the furan and decarboxylation of the carboxylic group of the benzene ring, is suggested.

  4. Articles

    1. Top of page
    2. Cover Image
    3. Highlight
    4. Rapid Communication
    5. Articles
    1. Spotlight Article

      Understanding the catalytic activity of single-chain polymeric nanoparticles in water (pages 12–20)

      Müge Artar, Takaya Terashima, Mitsuo Sawamoto, E. W. Meijer and Anja R. A. Palmans

      Article first published online: 23 OCT 2013 | DOI: 10.1002/pola.26970

      Thumbnail image of graphical abstract

      A set of segmented, amphiphilic copolymers was prepared, which comprised hydrophilic side chains, supramolecular or hydrophobic side chains, and ligand units via reversible addition–fragmentation chain transfer (RAFT) polymerization. Copolymers fold into single-chain polymeric nanoparticles (SCPNs) as a result of the helical self-assembly of the pendant BTA units and/or hydrophilic–hydrophobic phase separation. The obtained Ru(II) loaded SCPNs provide hydrophobic, isolated reaction pockets around Ru(II) complexes, and they show transfer hydrogenation of cyclohexanone in water independent of supramolecular units.

    2. Poly(arylene ether ether nitrile)s containing flexible alkylsulfonated side chains for polymer electrolyte membranes (pages 21–29)

      Li Sheng, Tomoya Higashihara, Mitsuru Ueda and Teruaki Hayakawa

      Article first published online: 18 OCT 2013 | DOI: 10.1002/pola.26971

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      A synthesis of poly(arylene ether ether nitrile)s is investigated. The synthesis contained different chain lengths of the alkylsulfonates with varying ion exchange capacities (IECs) from 1.89 to 2.69 mequiv g−1. The relationship between length of side chain and membrane properties, such as proton conductivity, water uptake, morphology, and oxidative stability, are also investigated and described.

    3. Spotlight Article

      Versatile functional poly(3-hexylthiophene) for hybrid particles synthesis by the grafting onto technique: Core@shell ZnO nanorods (pages 30–38)

      Hussein Awada, Hussein Medlej, Sylvie Blanc, Marie-Hélène Delville, Roger C. Hiorns, Antoine Bousquet, Christine Dagron-Lartigau and Laurent Billon

      Article first published online: 11 OCT 2013 | DOI: 10.1002/pola.26964

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      A novel and efficient grafting strategy to anchor poly(3-hexylthiophene) (P3HT) onto zinc oxide (ZnO) surfaces is presented. Three triethoxysilane-terminated regioregular P3HTs of different molar masses were synthesized via a hydrosilylation reaction from allyl-terminated P3HT. These polymers were then anchored onto the ZnO nanorods to create a macromolecular self-assembled monolayer. Photoluminescence showed a quenching effect of P3HT fluorescence by ZnO when grafted, making these hybrid materials suitable candidates for photovoltaic applications.

    4. Synthesis of water-soluble allyl-functionalized oligochitosan and its modification by thiol–ene addition in water (pages 39–48)

      Nicolas Illy, Mike Robitzer, Rémi Auvergne, Sylvain Caillol, Ghislain David and Bernard Boutevin

      Article first published online: 17 OCT 2013 | DOI: 10.1002/pola.26967

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      Chitosan was depolymerized under microwave irradiation. Subsequently, different functionalities were chemically attached in water to the oligochitosan backbone by an epoxide-amine reaction followed by thiol–ene additions.

    5. Phosphido-diphosphine pincer aluminum complexes as catalysts for ring opening polymerization of cyclic esters (pages 49–60)

      Ilaria D'Auria, Marina Lamberti, Mina Mazzeo, Stefano Milione and Claudio Pellecchia

      Article first published online: 20 OCT 2013 | DOI: 10.1002/pola.26969

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      Phosphido-diphosphine pincer aluminum complexes are able to promote the controlled ring-opening polymerization of several cyclic esters such as l-lactide, ɛ-caprolactone, and δ-valerolactone. Additionally, they produce copolymers of l-lactide and ɛ-caprolactone with microstructures depending on the catalyst architecture.

    6. From curing kinetics to network structure: A novel approach to the modeling of the network buildup of epoxy–anhydride thermosets (pages 61–75)

      Xavier Fernàndez-Francos, Xavier Ramis and Àngels Serra

      Article first published online: 22 OCT 2013 | DOI: 10.1002/pola.26972

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      The curing kinetics and network build-up during curing of epoxy-anhydride formulations using tertiary amines as initiators are reviewed. A mechanism-based kinetic and structural model has been defined, showing better prediction capabilities than previous living polymerization and simple regeneration models. The network buildup has been modeled using a stochastic network buildup model based on the random combination of primary chains generated by the kinetic model.

    7. Spotlight Article

      Influence of the bulkiness of the substituent on the aggregation and magnetic properties of poly(3-alkylthiophene)s (pages 76–86)

      Helmuth Peeters, Mihaela Jivanescu, André Stesmans, Lino M. C. Pereira, Leander Dillemans, Jean-Pierre Locquet, Margriet J. Van Bael, André Persoons and Guy Koeckelberghs

      Article first published online: 29 OCT 2013 | DOI: 10.1002/pola.26973

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      A series of regioregular poly(3-alkylthiophene)s is synthesized with substituents of increasing bulkiness. The self-assembly properties are investigated by UV–vis spectroscopy, X-ray diffraction, and DSC experiments. This shows that the self-assembly is slowed down and complicated, but not suppressed by increasing the bulkiness. The magnetic properties of powders of the neutral polymers are investigated by ESR spectroscopy and magnetometry.

    8. Design and synthesis of fluorescent core–shell nanoparticles with tunable lower critical solution temperature behavior and metal-enhanced fluorescence (pages 87–95)

      Aihua Li, Jingquan Liu, Guozhen Liu, Jizhen Zhang and Shengyu Feng

      Article first published online: 28 OCT 2013 | DOI: 10.1002/pola.26974

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      Novel fluorescent and thermoresponsive core–shell Ag/copolymer nanohybrids with tunable LCST behavior are fabricated by the random copolymerization of OEG-A and DEG-A, followed by grafting on to AgNPs surface. By thermal manipulation of polymer spacer between AgNPs and fluorophores, the tunable and reversible metal-enhanced fluorescence (MEF) effect is achieved. In addition, the phase transition behavior of the thermoresponsive copolymer can also be studied by MEF effect of these core–shell nanohybrids against the solution temperatures.

    9. Preparation, characterization and copolymerization of the 12-membered cyclic diamide 1,6-diazacyclododecane-2,5-dione (pages 96–103)

      Ethem Kaya, Eylem Tarkin-Tas, Scott Osborn, Roger Ayotte, Steven Manning and Lon J. Mathias

      Article first published online: 29 OCT 2013 | DOI: 10.1002/pola.26975

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      A 12-membered cyclic diamide monomer for nylon 64 was successfully synthesized in fairly high yield (∼45%). The yield and the ring size of cyclic diamide were found to depend on the reactants used and their feed ratios. Copolymerization of cyclic diamides with ɛ-caprolactam via an anionic route gave a block copolyamide with two distinct endotherms in the differential scanning calorimetry analysis. However, copolymerization by the hydrolytic route gave only nylon 6 with terminal 64 units.

    10. Spotlight Article

      RAFT/MADIX copolymerization of vinyl acetate and 5,6-benzo-2-methylene-1,3-dioxepane (pages 104–111)

      Giovanna Gomez d'Ayala, Mario Malinconico, Paola Laurienzo, Antoine Tardy, Yohann Guillaneuf, Muriel Lansalot, Franck D'Agosto and Bernadette Charleux

      Article first published online: 29 OCT 2013 | DOI: 10.1002/pola.26976

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      Copolymers of 5,6-benzo-2-methylene-1,3-dioxepane (BMDO) and vinyl acetate (VAc) are synthesized by RAFT using methyl(ethoxycarbonothioyl)sulfanyl acetate (MEA) as controlling agent. Well-defined P(VAc-co-BMDO) copolymers are obtained and their viability is demonstrated by successful chain extension experiments with VAc, although the presence of dead chains is shown. The introduction of ester groups into the polymeric backbone of P(VAc-co-BMDO) copolymers allows their degradation when treated with a mixture of KOH/MeOH.

    11. Synthesis of 3-(tert-Butoxycarbonylmethyl)-N-vinyl-2-caprolactam and Homologous Copolymerization Toward Biocompatible Carboxylated Poly(N-vinyl-2-caprolactam) Responsive to pH and Temperature (pages 112–120)

      Shuangcheng Tang, Yu Cao, Samuel C. Goddard and Wei He

      Article first published online: 29 OCT 2013 | DOI: 10.1002/pola.26977

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      A new monomer derivative of N-vinyl-2-caprolactam (VCL), namely 3-(tert-butoxycarbonylmethyl)-N-vinyl-2-caprolactam (TBMVCL) was synthesized via nucleophilic substitution at the α-carbon to the lactam carbonyl group. The new monomer copolymerized well with VCL and the resulting copolymers exhibited both pH and temperature responsiveness in water on deprotection. The stimuli-responsiveness was found to be dependent on the chemical nature of the carboxyl substitution group. Additionally, biocompatibility of the copolymer was demonstrated to warrant further study for biomedical applications.

    12. A novel polymer gel electrolyte: Direct polymerization of ionic liquid from surface of silica nanoparticles (pages 121–127)

      Heyi Hu, Wen Yuan, Hui Zhao and Gregory L. Baker

      Article first published online: 22 OCT 2013 | DOI: 10.1002/pola.26980

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      A novel polymer electrolyte is synthesized by directly grafting poly(ionic liquid)s onto silica nanoparticles. The kinetic study of this surface-initiated polymerization has also been included. A gel-state electrolyte is formed by mixing this type of polymer/silica nanocomposite with ionic liquids at 60 °C, which exhibits an excellent conductivity of 0.8 mS/cm at room temperature and 14.7 mS/cm at 90 °C. Additionally, the mechanism of gel formation has also been discussed in this article.

    13. Association, emulsifying, and solubilization properties of amphiphilic hyperbranched poly(acrylic acid) with short polystyrene stickers (pages 128–138)

      Lianwei Li, Xu Wang, Chen He and Weidong He

      Article first published online: 29 OCT 2013 | DOI: 10.1002/pola.26982

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      Amphihiphilic hyperbranched copolymer chains of hyperbranched poly(acrylic acid) grafted with short polystyrene stickers (HB-PAAn-g-PSn+1) with different n values (n = 1, 10, 47) have been synthesized and well-characterized by various analytical methods. These amphiphilic chains present very interesting properties compared with their linear triblock analogues, such as weaker tendency of interchain association and stronger tendency of gel formation. However, poorer emulsifying and solubilization abilities are observed for these hyperbranched-graft copolymer chains due to the branching effect.

    14. Polycyclic arene-based D–A polyimide electrets for high-performance n-type organic field effect transistor memory devices (pages 139–147)

      An-Dih Yu, Tadanori Kurosawa, Mitsuru Ueda and Wen-Chang Chen

      Article first published online: 6 NOV 2013 | DOI: 10.1002/pola.26983

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      Memory characteristics of n-type BPE-PTCDI-based OFETs using polycyclic-arene-based D–A polyimide electrets of PI(AMTPA-6FDA), PI(APAN-6FDA), and PI(APAP-6FDA) are explored. The memory device based on PI(APAP-6FDA) exhibited the largest memory window and the best charge retention ability due to the introduction of pyrene into the electron-donating moiety. With the excellent carrier delocalization, pyrene successfully enhanced the charge storage ability and sustained the CT complex for high performance nonvolatile OFET memory applications.

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