Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 49 Issue 11

1 June 2011

Volume 49, Issue 11

Pages 2315–2527

  1. Articles

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Notes
    1. A novel approach to modify poly(vinylidene fluoride) via iron-mediated atom transfer radical polymerization using activators generated by electron transfer (pages 2315–2324)

      Tao Zhao, Lifen Zhang, Zhengbiao Zhang, Nianchen Zhou, ZhenPing Cheng and XiuLin Zhu

      Version of Record online: 6 APR 2011 | DOI: 10.1002/pola.24651

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      The iron(III) salt was successfully used as the catalyst for the atom transfer radical polymerization using activators generated by electron transfer of different monomers [i.e., methyl methacrylate and poly(ethylene glycol) methyl ether methacrylate] directly from the secondary fluorine atoms on the poly(vinylidene fluoride) (PVDF) backbone in the presence of limited amounts of air. The grafted molecular weights could easily be adjusted by the polymerization time or the molar ratio of monomer to PVDF repeat unit.

    2. Novel sulfonated block copolymer containing pendant alkylsulfonic acids: Syntheses, unique morphologies, and applications in proton exchange membrane (pages 2325–2338)

      Hsing-Chieh Lee, Herman Lim, Wei-Fang Su and Chi-Yang Chao

      Version of Record online: 8 APR 2011 | DOI: 10.1002/pola.24655

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      A series of novel block polyelectrolyte, poly(styrene-block-sulfonated hydroxystyrene) (PS-b-sPHS), containing alkylsulfonic acids attached to the polymer backbone via flexible propyl spacers were synthesized. By changing the molecular weights, compositions, and the forms of the sulfonic acids, the interplays between the morphologies and the transportation properties of the resulting proton exchange membranes were systematically studied systematically. Some unique morphologies, including hallow channels and lamellar arrangement of strings of beads, were observed as a consequence of equilibrium between microphase separation and columbic interactions between the electrolytes and these microstructures were believed to be the key for the improvement in the performance of the PEMs.

    3. Synthesis and characterization of semicrystalline triblockcopolymers of isotactic polystyrene and polydimethylsiloxane (pages 2339–2345)

      Barbara T. Gall, Ralf Thomann and Rolf Mülhaupt

      Version of Record online: 8 APR 2011 | DOI: 10.1002/pola.24658

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      iPS-b-PDMS-b-iPS triblock copolymers were synthesized by hydrosilylation of vinyl-terminated isotactic polystyrene and α,ω-bis(dimethylsilane)-terminated poly(dimethylsiloxane). It was possible to vary the molar composition over a wide range and, therefore, to tailor the molecular architectures, which govern the morphology development of the triblock copolymers. Crystallization of the iPS side chains can be induced by thermal postpolymerization treatment.

    4. Unusual collapse of highly hydrated polyelectrolyte multilayers with the ionic strength (pages 2346–2352)

      J. J. Iturri Ramos, I. Llarena and S. E. Moya

      Version of Record online: 8 APR 2011 | DOI: 10.1002/pola.24662

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      Highly hydrated polyelectrolyte multilayers composed of PDADMAC/PSS polyelectrolyte pairs exhibited unusual reversible shrinkage/collapse behavior upon exposure to changes in the ionic strength of the bulk solution. Such response is only observed for multilayers with PDADMAC as outermost layer whereas multilayers with PSS on top remained unaltered. The combination of QCMD and ellipsometry in a single device permitted an in situ quantification of both thickness and water content variations along the collapse/re-swelling process of the multilayer.

    5. Synthesis of novel hyperbranched polymer through cationic ring-opening multibranching polymerization of 2-hydroxymethyloxetane (pages 2353–2365)

      Toshifumi Satoh, Masaki Tamaki, Tsukasa Taguchi, Hideki Misaka, Nguyen To Hoai, Ryosuke Sakai and Toyoji Kakuchi

      Version of Record online: 31 MAR 2011 | DOI: 10.1002/pola.24664

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      The cationic ring-opening multibranching polymerization of 2-hydroxymethyloxetane as a novel latent AB2-type monomer was carried out using trifluoromethane sulfonic acid or trifluoroboron diethyl etherate by a slow-monomer-addition method. The resulting polymer is composed of a highly branched structure, i.e., the hyperbranched poly (2-hydroxymethyloxetane).

    6. A versatile single-electron-transfer mediated living radical polymerization route to galactoglucomannan graft-copolymers with tunable hydrophilicity (pages 2366–2372)

      Jens Voepel, Ulrica Edlund and Ann-Christine Albertsson

      Version of Record online: 31 MAR 2011 | DOI: 10.1002/pola.24666

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      Galactoglucomannan graft-copolymers with tunable hydrophilicity synthesized from a functionalized hemicellulose-based macroinitiator.

    7. Supramolecular fuzzy recognition leads to effective differentiation of similar molecules (pages 2373–2381)

      Decheng Wan, Hongting Pu, Ming Jin, Guowei Wang and Junlian Huang

      Version of Record online: 11 APR 2011 | DOI: 10.1002/pola.24667

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      Core engineering of a roughly defined macromolecular nanocapsule can lead to effective recognition of similar guests via a supramolecular fuzzy recognition mechanism, which is promoted by appropriate combination of nonspecific elementary interaction styles.

    8. Synthesis of raspberry-like organic–inorganic hybrid nanocapsules via pickering miniemulsion polymerization: Colloidal stability and morphology (pages 2382–2394)

      Zhihai Cao, Anika Schrade, Katharina Landfester and Ulrich Ziener

      Version of Record online: 6 APR 2011 | DOI: 10.1002/pola.24668

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      Pickering-stabilized miniemulsions with silica particles as the sole emulsifier and hexadecane (HD) as liquid template were used to prepare raspberry-like hybrid nanocapsules with a hydrophobic liquid core and a polymeric shell of poly(styrene-co-divinylbenzene-co-4-vinylpyridine). There is a strong influence of pH, weight content of HD, divinylbenzene, and 4-vinylpyridine, and of particle size on the particle morphology.

    9. Multiarm star poly(glycidol)-block-poly(ε-caprolactone) of different arm lengths and their use as modifiers of diglycidylether of bisphenol a thermosets (pages 2395–2406)

      Mireia Morell, Albena Lederer, Xavier Ramis, Brigitte Voit and Angels Serra

      Version of Record online: 6 APR 2011 | DOI: 10.1002/pola.24670

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      Well-defined multiarm star copolymers, hyperbranched poly(glycidol)-b-poly(ε-caprolactone), with an average of 100–110 arms per molecule and different molecular weight of arms were synthesized by cationic ring-opening polymerization of ε-caprolactone from a poly(glycidol) core and used to modify diglycidylether of bisphenol A formulations. It has been proved that PGOH-b-PCLx star-like structures are suitable modifiers for epoxy resins enhancing toughness, reducing shrinkage and providing reworkability without affecting negatively the curing process and processability.

    10. A green approach toward oleic- and undecylenic acid-derived polyurethanes (pages 2407–2416)

      R. J. González-Paz, C. Lluch, G. Lligadas, J. C. Ronda, M. Galià and V. Cádiz

      Version of Record online: 8 APR 2011 | DOI: 10.1002/pola.24671

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      Naturally-occurring oleic and undecylenic acids were used as raw materials for the synthesis of novel diols and derived polyurethanes. The application of environmentally friendly thiol-ene additions to 10-undecenoate and oleate derivatives was studied to obtain the corresponding renewable diols. Ultrasound irradiation has been tested to improve the synthesis of polyurethane. The chemical structures of polyurethanes were assessed by FTIR and NMR spectroscopy. The thermal, mechanical properties, and MTT test of the synthesized TPUs have been studied.

    11. ABC type miktoarm star copolymers through combination of controlled polymerization techniques with thiol-ene and azide-alkyne click reactions (pages 2417–2422)

      Birol Iskin, Gorkem Yilmaz and Yusuf Yagci

      Version of Record online: 8 APR 2011 | DOI: 10.1002/pola.24672

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      PS-PCL-PEG as an ABC type miktoarm star copolymer was synthesized by the combination of ATRP, ROP, and double click (thiol-ene and CuAAC type) reactions and characterized. For this purpose, an organic core with alkene, hydroxide ([BOND]OH) and azide functionality was synthesized in a one step reaction, almost with quantitative yield. Next, monodisperse thiol functional polystyrene (PS-SH) was synthesized with very high conversions (95%) in two sequential steps starting from polystyrene bromide (obtained by ATRP). Then, PS-SH was successfully thiol-ene clicked onto the organic core. In the following step, PCL was grafted from the [BOND]OH functionality of the core. Finally, PEG-acetylene was clicked onto the core by CuAAC type click reaction to yield the miktoarm star copolymer.

    12. A unique stepped multifunctionality of perfluorinated aryl compound and its versatile use in synthesizing grafted polymers with controlled structures and topologies (pages 2423–2433)

      Zhenhua Zhao, Xiaohua Ma, Aixin Zhang and Naiheng Song

      Version of Record online: 6 APR 2011 | DOI: 10.1002/pola.24673

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      A unique stepped multifunctionality of perfluorinated aryl compound was discovered and studied. Four levels of distinctively different reactivity were revealed for the para and ortho C[BOND]F of 2,5-dipentafluorophenyl-1,3,4-oxadiazole (FPOx), which could be easily triggered by the reaction temperature in the range of r.t. to 160 °C to enable clean and quantitative reactions with nucleophiles. Versatile applications of such a multistepped reactivity of FPOx in quantitative postpolymerization functionalization of polymers and one-pot syntheses of grafted polymers with well-controlled structures and topologies were successfully demonstrated.

    13. A fully biobased epoxy resin from vegetable oils: From the synthesis of the precursors by thiol-ene reaction to the study of the final material (pages 2434–2444)

      M. Stemmelen, F. Pessel, V. Lapinte, S. Caillol, J.-P. Habas and J.-J. Robin

      Version of Record online: 8 APR 2011 | DOI: 10.1002/pola.24674

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      A vegetable oil-based polyamine issued from grapeseed oil was prepared using cysteamine chloride by thiol-ene coupling (TEC). Its use as curing agent in presence of epoxidized linseed oil for bio-based epoxy resin was investigated by DSC and rheology.

    14. Synthesis and characterization of sulfone containing main chain oligobenzoxazine precursors (pages 2445–2450)

      Cagatay Altinkok, Baris Kiskan and Yusuf Yagci

      Version of Record online: 14 APR 2011 | DOI: 10.1002/pola.24675

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      This study demonstrates an approach that utilizes aromatic sulfone diamine, bisphenol-A, and formaldehyde in Mannich-type polycondesation to prepare polybenzoxazine precursor. The precursor contained both sulfone and benzoxazine ring structures in the backbone. It was shown that small amount of ring-opened phenolic groups were also present. Thermally activated self-curing behavior of precursor in the absence of catalyst and thermal properties of the cured polymers were studied.

    15. Hydrogen-bonded supramolecular polymers from derivatives of α-amino-ε-caprolactam: A bio-based material (pages 2451–2460)

      Eylem Tarkin-Tas, Christopher A. Lange and Lon J. Mathias

      Version of Record online: 8 APR 2011 | DOI: 10.1002/pola.24676

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      Hydrogen-bonded supramolecular polymers were prepared from the derivatives of α-amino-ε-caprolactam. Several self-complimentary bis- or tetra-caprolactam monomers were synthesized by varying the number of carbons of the spacer between the hydrogen-bonding end groups. Biscaprolactams are crystalline solids at room temperature; however, when heated above their melting points and then cooled to room temperature, DSC second heating scans display glass transitions (Tg), exotherms due to crystallization (Tc), and finally endotherms due to melting (Tm). This clearly shows that under suitable experimental conditions, the compounds display semicrystalline linear polymer-like behavior because of their macromolecular self-associated architectures.

    16. Rendering polyureas melt processible (pages 2461–2467)

      Jungmee Kang, Gabor Erdodi and Joseph P. Kennedy

      Version of Record online: 11 APR 2011 | DOI: 10.1002/pola.24677

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      The figure shows idealized micromorphologies of polyureas in the absence and presence of HACE. The conventional polyurea (left) contains strong bidentate H-bonds between the urea units, and, consequently, its flow temperature (Tflow) is high, which obviates thermal processibility. In contrast, H-bonds in polyureas prepared with HACEs are looser (right), which lowers the Tflow and leads to thermal processibility without reducing mechanical properties.

    17. Mesomorphic and conducting properties of dendritic-linear copolymers via ion-doped additives (pages 2468–2473)

      Jin-Woo Choi and Byoung-Ki Cho

      Version of Record online: 8 APR 2011 | DOI: 10.1002/pola.24678

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      Conductivity of liquid crystalline block copolymers increases as the amount of ionic additives increases. The conductivity growth can be interpreted by means of the morphological change and the plasticization effect of the additive.

    18. Cyclization tendencies in the free radical polymerization of allyl acrylate derivatives: A computational study (pages 2474–2483)

      Özlem Karahan, Mehtap Işi̇k, Gülşah Çifci, İlke Uǧur, Duygu Avci and VIktorya AvIyente

      Version of Record online: 13 APR 2011 | DOI: 10.1002/pola.24680

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      In this study density functional theory (DFT) has been used to model the elementary steps and rationalize the free radical polymerization kinetics in allyl methacrylate (AMA), allyl 2-cyanoacrylate (ACA) and methyl α-[(allyloxy)methyl]acrylate.

    19. Comparative study on polyimides from isomeric 3,3′-, 3,4′-, and 4,4′-linked bis(thioether anhydride)s (pages 2484–2494)

      Haibing Wei, Xueliang Pei and Xingzhong Fang

      Version of Record online: 11 APR 2011 | DOI: 10.1002/pola.24681

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      A novel asymmetric bis(thioether anhydride), 3,4′-PTPKDA, was synthesized by four steps. Based on 3,4′-PTPKDA and two other symmetric dianhydride isomers, 3,3′-PTPKDA and 4,4′-PTPKDA, a series of isomeric polyimides was prepared by a conventional two-step method. The glass transition temperature followed the decreasing order of the polyimides based on 3,3′-PTPKDA, 3,4′-PTPKDA, and 4,4′-PTPKDA. 3,3′-PTPKDA- and 3,4′-PTPKDA-based polyimides showed improved solubility compared with 4,4′-PTPKDA. The polyimide resin 3,3′-PTPKDA/4,4′-oxydianiline/phthalic anhydride exhibited better rheological properties and melt stability than the other two isomers.

    20. Chemical modification of chain end in nylon 4 and improvement of its thermal stability (pages 2495–2503)

      Koichiro Tachibana, Kazuhiko Hashimoto, Noriyuki Tansho and Haruki Okawa

      Version of Record online: 11 APR 2011 | DOI: 10.1002/pola.24682

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      Two kinds of nylon 4 having an acyllactam group at one or both chain ends were synthesized by the anionic ring-opening polymerization of 2-pyrrolidone using N-benzoyl-2-pyrrolidone or N,N′-isophthaloylbis-2-pyrrolidone as an initiator. The quantitative conversion of the terminal acyllactam to carboxy and amine groups in the solution condition was found to improve the thermal stability of nylon 4 from the TGA. In addition, the direct heating of the acyllactam-telechelic nylon 4 mixed with diamines also led to significantly improve its thermal stability by chain extension through the polyaddition reaction.

    21. Polymerization mechanism of trimethylene carbonate carried out with zinc(II) acetylacetonate monohydrate (pages 2504–2512)

      Malgorzata Pastusiak, Piotr Dobrzynski, Bozena Kaczmarczyk and Janusz Kasperczyk

      Version of Record online: 11 APR 2011 | DOI: 10.1002/pola.24683

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      Monohydrate zinc(II) acetylacetonate, which is simple in structure, stable, and relatively inexpensive zinc compound, proved to be a very effective catalyst for the homopolymerization of cyclic carbonates. The first stage of the reaction, which is the decarboxylation of the TMC molecule, results in the formation of 1,3-propandiol and the emission of CO2. The diol, similar to oligodiol and polydiol, which are formed at further stages as a result of the chain propagation process, acts as cocatalyst for the studied polymerization process. The chain propagation occurs because of the repeating activation of the TMC monomer through the formation of an active structure resulting in the exchange/transfer reaction between the zinc complex and the monomer, with its following attachment to the hydroxyl groups, with carbonate ring opening and formation of another carbonic unit of the growing chain.

  2. Rapid Communications

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Notes
    1. Self-assembly of ABC nonamphiphilic fluorosilicone triblock copolymers in dilute solutions: The first example (pages 2513–2519)

      Jing-Jing Qiu and Zheng-Hong Luo

      Version of Record online: 8 APR 2011 | DOI: 10.1002/pola.24669

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      The aggregate properties of PDMS65-PMMA21-PHFBMA15 in a THF/ethyl acetate mixture solution were investigated. It was found that PDMS65-PMMA21-PHFBMA15 can self-assemble in a solution to form aggregates of abundant morphologies. To the best of our knowledge, this work is the first example of self-assembly of ABC nonamphiphilic fluorosilicone triblock copolymers in a dilute solution.

  3. Notes

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Notes
    1. You have free access to this content
      Metallocene-mediated cationic ring-opening polymerization of 2-methyl- and 2-phenyl-oxazoline (pages 2520–2527)

      Maria-Evgenia Kourti, Georgios C. Vougioukalakis, Nikos Hadjichristidis and Marinos Pitsikalis

      Version of Record online: 11 APR 2011 | DOI: 10.1002/pola.24679

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      Metallocene complexes activated by fluoroaryl borates have been efficiently used for the cationic ring-opening polymerization of 2-methyl-2-oxazoline and 2-phenyl-2-oxazoline for the first time. Under the appropriate experimental conditions, products of relatively narrow molecular weight distribution were obtained in quantitative yields. The kinetics of polymerization using several initiation systems was examined.