Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 51 Issue 21

1 November 2013

Volume 51, Issue 21

Pages i–iv, 4489–4715

  1. Cover Image

    1. Top of page
    2. Cover Image
    3. Articles
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      Cover Image, Volume 51, Issue 21 (pages i–ii)

      Version of Record online: 22 SEP 2013 | DOI: 10.1002/pola.26931

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      An efficient synthetic method for the production of stabilized cyclo-olefin polymer (COP) latexes catalyzed by a well-defined ruthenium carbene catalyst in aqueous solution is reported by Hoang The Ban, Masahiro Shigeta, Tsutomu Nagamune, and Mitsugu Uejima on page 4584. The COP latexes exhibit an exceptionally high compatibility with well-dispersed carbon nanotubes (CNTs) in aqueous solution due to strong π[BOND]π interactions between the graphitic surfaces of the CNTs with the C[DOUBLE BOND]C bonds located on the COP main chains. Accordingly, a binary blending of these two well-dispersed colloidal systems in aqueous solution leads to the fabrication of highly homogeneous COP/CNT composite nanoparticles that possess high electrical conductivities due to the presence of uniformly CNT-based networks made from individually interconnected CNTs deposited on the interface of COP nanoparticles as observed in the cover image.

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      Cover Image, Volume 51, Issue 21 (pages iii–iv)

      Version of Record online: 22 SEP 2013 | DOI: 10.1002/pola.26932

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      The solid state self-assembly of single-walled carbon nanotubes (SWCNTs) and pyrenyl-terminated poly(γ-benzyl-L-glutamate)s (py-PBLG) is presented by Haoyu Tang and Donghui Zhang on page 4489. Py-PBLGs are prepared by controlled polymerization of γ-benzyl-L-glutamic acid based N-carboxyanhydride using an amine initiator. Py-PBLGs effectively enhance the dispersion of SWCNTs in organic solvents and the PBLG solid through π-π interactions. The cover image depicts the disparate orientation of SWCNTs relative to the PBLG main chain, which is dictated by the polymer conformation (α-helix and β-sheets) and the location of pyrenyl moieties. The relative packing structure also affects the intermolecular interaction among the PBLGs differently.

  2. Articles

    1. Top of page
    2. Cover Image
    3. Articles
    1. Solid state self-assembly of the single-walled carbon nanotubes and poly(γ-benzyl-l-glutamate)s with different conformations (pages 4489–4497)

      Haoyu Tang and Donghui Zhang

      Version of Record online: 22 JUL 2013 | DOI: 10.1002/pola.26856

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      Single-walled carbon nanotubes (SWCNTs) were shown to significantly enhance the hexagonal packing order of the poly(γ-benzyl-l-glutamate) (PBLG) rods in the solid state. By contrast, the lamellar packing order of the PBLG β-sheets consisting of short PBLG chains is weakened. The differing effect has been attributed to the disparate orientation of SWCNTs relative to the PBLG main chain, which is dictated by the polymer conformation and the location of pyrenyl moieties.

    2. Chain center-functionalized amphiphilic block polymers: Complementary hydrogen bond self-assembly in aqueous solution (pages 4498–4504)

      Sang-Ho Lee, Makoto Ouchi and Mitsuo Sawamoto

      Version of Record online: 7 AUG 2013 | DOI: 10.1002/pola.26880

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      The hydrophobic segment of a designed amphiphilic triblock copolymer bearing multiple hydrogen bonding sites at the center of the polymer backbone was promoted due to complementary H-bonding interaction with a hydrophobic DAD-functionalized polymer. In water, hydrophobic interaction supported self-aggregation. The aggregates in aqueous media were relatively stable and uniform in size, which most likely stems from the intermolecular complementary hydrogen bond interaction at the polymer chain centers.

    3. ATNRC/SET-NRC synthesis of graphene/polyisobutylene nanocomposites (pages 4505–4514)

      Zhanzhan Liu, Yongjun Li, Yang Yang, Yongsheng Li and Xiaoyu Huang

      Version of Record online: 27 AUG 2013 | DOI: 10.1002/pola.26892

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      Well-defined polyisobutylene prepared by cationic polymerization was grafted onto graphene sheets via CuBr-catalyzed atom transfer nitroxide radical coupling and Cu-catalyzed single electron transfer–nitroxide radical coupling reactions. At room temperature, this grafting strategy resulted in polyisobutylene/graphene sheet nanocomposites with excellent dispersibility in organic solvents.

    4. Photo-triggered redox frontal polymerization: A new tool for synthesizing thermally sensitive materials (pages 4515–4521)

      Minghui He, Xun Huang, Zhaohua Zeng and Jianwen Yang

      Version of Record online: 26 AUG 2013 | DOI: 10.1002/pola.26896

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      A highly effective strategy for creating thermally sensitive materials is presented. Via photo-triggered redox-induced low temperature frontal polymerization based on the photocaged superbase and peroxides, this strategy affords comprehensive spatiotemporal control of the redox reaction. Superior performance is also demonstrated, lowering the front temperature while improving front velocity and conversion rate.

    5. Stable heterocumulene monomer in water; Synthesis and polymerization of (meth)acrylates having an isothiocyanate structure (pages 4522–4529)

      Ryota Seto, Kozo Matsumoto and Takeshi Endo

      Version of Record online: 31 JUL 2013 | DOI: 10.1002/pola.26868

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      Novel methacrylate and acrylate monomers with an isothiocyanate structure were synthesized using 2-isothiocyanatoethyl methacrylate (ITEMA) and 2-isothiocyanatoethyl acrylate (ITEA). Their radical polymerizations were examined, respectively. Isothiocyanato groups in the monomers did not react with water in an acetone solution at 60 °C for 24 h, showing their tolerance to water. Because of this water-stable characteristic of isothiocyanato groups, ITEMA and ITEA can be polymerized in a water-containing solvent.

    6. Poly(ionic liquid)s based on imidazolium hydrogen carbonate monomer units as recyclable polymer-supported N-heterocyclic carbenes: Use in organocatalysis (pages 4530–4540)

      Paul Coupillaud, Julien Pinaud, Nicolas Guidolin, Joan Vignolle, Maréva Fèvre, Ellen Veaudecrenne, David Mecerreyes and Daniel Taton

      Version of Record online: 30 JUL 2013 | DOI: 10.1002/pola.26869

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      Poly(1-vinyl-3-alkylimidazolium hydrogen carbonate) (poly([NHC(H)][HCO3])) can be readily accessed and serve as air-stable polymer-supported pre-catalysts for organocatalyzed molecular reactions, including benzoin condensation, transesterification, and cyanosilylation. The in situ generation of related polymer-supported N-heterocyclic carbenes (poly(NHC)s), occurs by a loss of H2O and CO2 in solution. Recarboxylation of poly(NHC)s allows recycling of polymer precursors.

    7. 9,9-Diaryl-4,5-diazafluorene-based Cardo polymer; Synthesis and characteristic properties (pages 4541–4549)

      Hitoshi Okuda, Yasuhito Koyama, Takahiro Kojima and Toshikazu Takata

      Version of Record online: 30 JUL 2013 | DOI: 10.1002/pola.26870

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      Diol-functionalized cardo monomers involving 4,5-diazafluorene polymerize with difluoroarenes to give poly(ether ketone)s (N-PEKs). The characteristic properties of the resulting polymers such as optical and thermal properties are evaluated. Additionally, the network polymers are afforded by the partial protonation of 4,5-diazafluorene moieties. The hydrogen bond network formation induces excellent optical and mechanical properties.

    8. New selenophene-based low-band gap conjugated polymers for organic photovoltaics (pages 4550–4557)

      Ching-Chih Chang, Chih-Ping Chen, Ho-Hsiu Chou, Chuang-Yi Liao, Shu-Hua Chan and Chien-Hong Cheng

      Version of Record online: 29 JUL 2013 | DOI: 10.1002/pola.26871

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      Two new low-band gap selenophene-based polymers were synthesized successfully. The differences of optoelectronic and photovoltaic properties and space-charge-limited currents were compared with those of related thiophene-based polymers. Organic photovoltaic devices, based on blends of these polymers and PC71BM, were fabricated; the maximum power conversion efficiency of the device based on PSPSBT and PC71BM was 3.1%.

    9. Hybrid organic–inorganic block copolymer nano-objects from RAFT polymerization-induced self-assembly (pages 4558–4564)

      Yuanming Deng, Cangjie Yang, Conghui Yuan, Yiting Xu, Julien Bernard, Lizong Dai and Jean-François Gérard

      Version of Record online: 31 JUL 2013 | DOI: 10.1002/pola.26872

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      A simple route to POSS containing organic–inorganic hybrid nano-objects with different morphologies through polymerization and (or) cooling-induced block copolymer self-assembly was described. The cooling procedure and chain length of macro-CTA was proven to be a crucial step to generate particles with a unique morphology.

    10. Facile synthesis of poly(l-tryptophan) through polycondensation of activated urethane derivatives (pages 4565–4571)

      Shuhei Yamada, Sudo Atsushi, Mitsuaki Goto and Takeshi Endo

      Version of Record online: 30 JUL 2013 | DOI: 10.1002/pola.26873

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      A facile synthetic route has been developed to produce poly(l-tryptophan) by the polycondensation of N-phenoxycarbonyl-l-tryptophan. The polycondensation proceeded smoothly at 60 °C in N,N-dimethylacetamide (DMAc) in the presence of amines (n-butylamine, diethylamine, and triethylamine). The structural analysis by MALDI-TOF mass spectrometry revealed that n-butylamine or diethylamine was successfully incorporated into the chain end of the polypeptide. Furthermore, synthesis of diblock copolymer by utilizing amine-terminated poly(ethylene glycol) as a source of the polyether segment was established.

      Corrected by:

      Erratum: Erratum: Facile Synthesis of Poly(l-tryptophan) through Polycondensation of Activated Urethane Derivatives

      Vol. 53, Issue 6, 829, Version of Record online: 1 FEB 2015

    11. Synthesis of amphiphilic A4B4 star-shaped copolymers by mechanisms transformation combining with thiol-ene reaction (pages 4572–4583)

      Qianqian Guo, Chenyan Liu, Tingting Tang, Jian Huang, Xinge Zhang and Guowei Wang

      Version of Record online: 1 AUG 2013 | DOI: 10.1002/pola.26874

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      A series of amphiphilic A4B4 star-shaped copolymers (PEO)4(PCL)4, (PEO)4(PS)4, and (PEO)4(PtBA)4 were successfully synthesized using the core-first strategy by combination of ring-opening polymerization and atom transfer radical polymerization with thiol–ene reaction. This synthetic method might be a versatile one for various AnBn (n≥3) star-shaped copolymers with defined structure and compositions.

    12. Synthesis of cyclo-olefin copolymer latexes and their carbon nanotube composite nanoparticles (pages 4584–4591)

      Hoang The Ban, Masahiro Shigeta, Tsutomu Nagamune and Mitsugu Uejima

      Version of Record online: 30 JUL 2013 | DOI: 10.1002/pola.26875

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      A highly efficient and environmentally benign synthetic method for the production of cyclo-olefin copolymer latexes using an emulsion ring opening metathesis polymerization catalyzed by the 2nd generation Grubbs catalyst in aqueous solution was reported. The as-prepared cyclo-olefin copolymer latexes show exceptionally high compatibility with a well-dispersed carbon nanotube in aqueous solution. A binary blending of these stabilized colloidal systems in aqueous solution thus led to the fabrication of highly electrical conductive cyclo-olefin copolymer/carbon nanotube composite nanoparticles.

    13. Preparation of highly sensitive sensors based on polystyrene microspheres for the detection and removal of Hg2+ ions (pages 4592–4600)

      Yun Yu, Xinjian Cheng, Huijuan Zhang, Shengli Hu, Xianghong Li and Aiqing Zhang

      Version of Record online: 31 JUL 2013 | DOI: 10.1002/pola.26878

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      Fluorescent monomers were prepared and introduced to polystyrene microsphere chemosensors. The microspheres could detect Hg2+ ions by the change of color and fluorescence. Moreover, the microspheres could separate Hg2+ ions by centrifugation.

    14. Synthesis of H-shaped complex macromolecular structures by combination of atom transfer radical polymerization, photoinduced radical coupling, ring-opening polymerization, and iniferter processes (pages 4601–4607)

      Binnur Aydogan Temel, Julia Amici, Marco Sangermano and Yusuf Yagci

      Version of Record online: 7 AUG 2013 | DOI: 10.1002/pola.26879

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      ABCBD-type H-shaped complex copolymer was prepared by combining atom transfer radical polymerization (ATRP), photoinduced radical coupling reaction, ring-opening polymerization (ROP), and iniferter processes. α-Benzophenone functional BP–PS and BP–PMMA, prepared by ATRP, were photocoupled to obtain benzpinacole together with hydroxyl and iniferter functionalities. Further ROP of ɛ-CL and thermal iniferter polymerization of tBA gave the target polymer (PCL)(PS)PtBA(PMMA)(PCL).

    15. Synthesis of functional polymer particles by dispersion polymerization in organic media: A tool toward stable electrophoretic inks (pages 4608–4617)

      Antoine Charbonnier, Cyril Brochon, Eric Cloutet, Christophe Navarro and Georges Hadziioannou

      Version of Record online: 7 AUG 2013 | DOI: 10.1002/pola.26881

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      The synthesis of functional polymer particles in organic media has grown in importance because of the large advance of all electronic papers applications. The use of a NMRP macroinitiator soluble in apolar media shows great efficiency in producing functional polymer particles in one step, bearing ionizable groups like pyridine or carboxylic acid. The process allows synthesis in a controlled way, producing very stable particles on a wide scale (75 nm to 20 μm).

    16. Organic–inorganic interpenetrating polymer networks and hybrid polymer materials prepared by frontal polymerization (pages 4618–4625)

      Javier Illescas, Roberta Sanna, Valeria Alzari, Daniele Nuvoli, Mariano Casu, Roberta Sanna, Ernesto Rivera and Alberto Mariani

      Version of Record online: 1 AUG 2013 | DOI: 10.1002/pola.26882

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      Original series of well-defined composite hybrid hydrogels are presented and synthesized by frontal polymerization. Comparison between two different acidic media is performed and there is evidence that indicates that the amount of the inorganic moiety affects the hydrophilicity, as well as the thermal stability of the composite. Therefore, swelling ratio, thermal, contact angle, and morphology studies are performed and the results of these studies are highlighted.

    17. Photo-initiated thiol–ene “click” hydrogels from RAFT-synthesized poly(N-isopropylacrylamide) (pages 4626–4636)

      Huey Wen Ooi, Kevin S. Jack, Andrew K. Whittaker and Hui Peng

      Version of Record online: 7 AUG 2013 | DOI: 10.1002/pola.26883

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      Photo-initiated thiol–ene is demonstrated as an alternative “click” reaction to synthesize thermoresponsive poly(N-isopropylacrylamide) “model networks.” RAFT-synthesized poly(N-isopropylacrylamide) with thiol and ene moieties are used as network precursors. The ability of these polymers to crosslink is found to be dependent on steric effects of the polymer end groups and the sensitivity of thiol groups to air, which could potentially lead to oxidation to form disulfides. As a result, the ene moieties provide more success in preparing “model networks.”

    18. Thiol–ene polymerizations using imide-based monomers (pages 4637–4642)

      Kate A. Murphy, Aidan S. Zebertavage, Brianne E. Kiliman and Devon A. Shipp

      Version of Record online: 7 AUG 2013 | DOI: 10.1002/pola.26884

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      Imide-containing diene and dithiol monomers were synthesized and used in thiol–ene polymerizations that yield poly(imide-co-thioether)s. These linear polymers exhibit limited solubility in various organic solvents and show increased glass transition temperature (Tg) as the imide content increases.

    19. Comparison of the growth and degradation of poly(glycolic acid) and poly(ε-caprolactone) brushes (pages 4643–4649)

      Xinfang Hu, Gongfang Hu, Kaitlyn Crawford and Christopher B. Gorman

      Version of Record online: 9 AUG 2013 | DOI: 10.1002/pola.26885

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      Poly(glycolic acid) and poly(ɛ-caprolactone) brushes were grown from hydroxy-terminated silicon surfaces via ring opening polymerization using tin (octanoate) as the catalyst. Poly(ɛ-caprolactone) brushes grew thicker at elevated temperatures but the thickest poly(glycolic acid) brushes grew at room temperature. The confined surface polyester brushes only degraded under neutral or basic conditions. Through a blocking experiment, the terminal hydroxyl groups of these brushes were demonstrated to be essential to the degradation process, indicating a preferential backbiting mechanism.

    20. Photoresponsive polyamides containing pentamethylated norbornadiene moieties: Synthesis and photochemical properties under sunlight irradiation (pages 4650–4656)

      Ahmed Oueslati, Imen Abdelhedi, Régis Mercier, Eric Drockenmuller and Hatem Ben Romdhane

      Version of Record online: 13 AUG 2013 | DOI: 10.1002/pola.26886

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      Soluble, thermally stable, and photoresponsive polyamides are obtained via the Yamazaki polyaddition between a pentamethylated norbornadiene dicarboxylic acid and several aromatic diamines. Characterization by 1H and 13C NMR, SEC, FTIR, DSC, TGA, and viscosimetry is performed. The photochemical isomerization of the norbornadiene units into quadricyclane ones is studied by UV/Vis spectroscopy. The thermal release of the stored energy associated to the reverse transformation of quadricyclane groups into norbornadiene ones is about 90–95 kJ mol−1 as measured by DSC.

    21. Poly(tetrafluorostyrenephosphonic acid)–polysulfone block copolymers and membranes (pages 4657–4666)

      Zhecheng Shao, Arindam Sannigrahi and Patric Jannasch

      Version of Record online: 19 AUG 2013 | DOI: 10.1002/pola.26887

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      Polysulfone with terminal benzyl bromide groups was used as a bifunctional macroinitiator for atom transfer radical polymerization of 2,3,4,5,6-pentafluorostyrene. The fluorostyrene blocks of the ABA triblock copolymers were selectively and quantitatively phosphonated with tris(trimethylsilyl)phosphite and hydrolyzed to form poly(2,3,5,6,-tetrafluorostyrene-4-phosphonic acid). Solvent cast copolymer membranes had a high thermal stability, and showed a nanophase-separated morphology and high proton conductivity at 80 mS cm−1 at 120 oC under fully hydrated conditions.

    22. V-shaped graft copolymers via triple click reactions: Diels–alder, copper-catalyzed azide–alkyne cycloaddition, and nitroxide radical coupling (pages 4667–4674)

      Ufuk Saim Gunay, Bengu Ozsoy, Hakan Durmaz, Gurkan Hizal and Umit Tunca

      Version of Record online: 20 AUG 2013 | DOI: 10.1002/pola.26888

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      A simple and universal synthetic pathway is reported. Covering triple click reactions, Diels–Alder, copper-catalyzed azide–alkyne cycloaddition, and nitroxide radical coupling, the pathway is used to prepare well-defined graft copolymers with V-shaped side chains.

    23. Precision synthesis of graft copolymers via living cationic polymerization of p-acetoxystyrene followed by friedel–crafts-type termination reaction (pages 4675–4683)

      Yu Shinke, Hidehiro Yamamoto, Arihiro Kanazawa, Shokyoku Kanaoka and Sadahito Aoshima

      Version of Record online: 23 AUG 2013 | DOI: 10.1002/pola.26889

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      A Friedel–Crafts-type termination, a common side reaction, of cationically prepared living polymers proved a powerful reaction for the highly efficient synthesis of graft copolymers. A well-defined graft copolymer was obtained from the reaction of pendant alkoxynaphthyl groups, more nucleophilic than a phenyl counterpart, in poly(vinyl ether) with a living polymer of p-acetoxystyrene, the ideal living cationic polymerization of which was performed for the first time using SnCl4 in the presence of ethyl acetate.

    24. Selectively degradable alternating copolymers of isobutyl vinyl ether and plant-derived aldehydes with acyclic side chains: Effects of side group structures on copolymerization behaviors (pages 4684–4693)

      Yasushi Ishido, Arihiro Kanazawa, Shokyoku Kanaoka and Sadahito Aoshima

      Version of Record online: 27 AUG 2013 | DOI: 10.1002/pola.26890

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      Relationships between side group structures of plant-derived aldehydes and their copolymerization behaviors with vinyl ether were investigated. Conjugated aldehydes were cationically copolymerized in alternating fashion, some of which were controlled to produce copolymers with well-defined structures. The product alternating copolymers were selectively degradable by acid hydrolysis into other conjugated aldehydes. Judging from copolymerization results using various plant-derived aldehydes with acyclic or cyclic structures, bulkiness and electron-donating ability of side groups would be crucial for copolymerization behaviors.

    25. Synthesis of novel polydiazocine for electroactive materials based on diazocine (pages 4694–4701)

      Jianzhong Li and Xiaobo Wan

      Version of Record online: 20 AUG 2013 | DOI: 10.1002/pola.26891

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      A novel class of ladder-type polymer named polydibenzoyl[b,f][1,5]diazocine and polydimethoxybenzoyl[b,f][1,5]diazocines based on a diazocine unit were developed for electrochemical actuator materials. The polydiazocines may exhibit a conformation change from zigzag or helix conformation to planar structure of their diazocine ring upon redox processes. This may simulate electrical response of the muscle.

    26. Fluorescent, thermoresponsive copolymers via nitroxide-mediated polymerization: Synthesis and effect of fluorescent groups on phase transitions in an ionic liquid (pages 4702–4715)

      Chi Zhang and Milan Maric

      Version of Record online: 26 AUG 2013 | DOI: 10.1002/pola.26895

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      The synthesis and characterizations of a series of statistical copolymers of benzyl methacrylate with 2–11 mol% 9-(4-vinylbenzyl)-9H-carbazole is examined. The synthesis via nitroxide-mediated polymerization using BlocBuilder as the initiator at 90 °C was demonstrated to be relatively well controlled. These copolymers exhibit fluorescent and thermoresponsive properties, as well as an interesting phase separation–triggered fluorescent enhancement behavior in a hydrophobic ionic liquid (C2mim)(NTf2), which are comprehensively studied and discussed.