Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 48 Issue 9

1 May 2010

Volume 48, Issue 9

Pages 1851–2056

  1. Articles

    1. Top of page
    2. Articles
    3. Rapid Communication
    1. Proton conduction in 1H-1,2,3-triazole polymers: Imidazole-like or pyrazole-like? (pages 1851–1858)

      Chikkannagari Nagamani, Craig Versek, Michael Thorn, Mark T. Tuominen and S. Thayumanavan

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23932

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      Proton conduction in 1H-1,2,3-triazole polymers was investigated by systematically comparing the proton transfer dynamics in structurally analogous N-heterocyclic and benz-N-heterocyclic polymers and it has been observed that the proton transfer in triazole systems is assisted predominantly by the imidazole-like pathway, while the pyrazole-like pathway makes a negligible contribution.

    2. Iridium complex grafted to 3,6-carbazole-alt-tetraphenylsilane copolymers for blue electrophosphorescence (pages 1859–1865)

      Teng Fei, Gang Cheng, Dehua Hu, Wenyue Dong, Ping Lu and Yuguang Ma

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23934

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      Novel 3,6-carbazole-alt-tetraphenylsilane copolymers grafted with FIrpic in the side chains were synthesized. Energy transfer from the polymer backbones to iridium complex in solid state was realized. Phase separation in the polymers was suppressed, which can be identified by atomic force microscopy and designed electroluminescent (EL) devices. EL devices based on the polymers exhibited blue phosphorescence from FIrpic. The luminous efficiency of preliminary devices reached 2.3 cd/A and the efficiency roll-off at high current densities was suppressed.

    3. Chain internal/chain end latent crosslinking in thermoset polymer systems (pages 1866–1877)

      Piotr P. Matloka, Zachary Kean and Kenneth B. Wagener

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23941

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      Acyclic diene metathesis polycondensation has been used to produce fully “latent reactive” carbosilane/carbosiloxane copolymers. The reactive methoxy groups remain dormant during polymerization process yielding in linear copolymer; subsequent exposure to moisture triggers hydrolysis/condensation processes leading to a chemically crosslinked thermoset. Different lengths of siloxanes and numbers of methylene groups between them in the polymer backbone have been investigated to explore structure/property relationship. Resultant materials have been subjected to mechanical tests; generated stress/strain curves have shown fully elastic behavior.

    4. End-linked amphiphilic polymer conetworks: Synthesis by sequential atom transfer radical polymerization and swelling characterization (pages 1878–1886)

      Maria D. Rikkou, Maria Kolokasi, Krzysztof Matyjaszewski and Costas S. Patrickios

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23951

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      Sequential atom transfer radical polymerization (ATRP) of hydrophilic 2-(dimethylamino)ethyl methacrylate (DMAEMA, light blue circles), hydrophobic methyl methacrylate (MMA, dark green circles) and ethylene glycol dimethacrylate (EGDMA, cross-linker, black dumbbells) was employed for the first time to prepare amphiphilic polymer conetworks based on end-linked gradient ABA triblock copolymers. These conetworks were subsequently characterized in terms of their aqueous swelling properties as a function of the degree of ionization of the DMAEMA weakly basic units.

    5. Facile one-pot synthesis and thermal cyclopolymerization of aryl bistrifluorovinyl ether monomers bearing reactive pendant groups (pages 1887–1893)

      Kaizheng Zhu, Scott T. Iacono, Stephen M. Budy, Jianyong Jin and Dennis W. Smith Jr.

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23953

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      A diverse pool of aryl bistrifluorovinyl ether (BTFVE) compounds with reactive pendant groups were prepared in a facile, high yielding three step “one-pot” synthesis from commercial 4-bromo(trifluorovinyloxy)benzene. Aryl BTFVE compounds were thermally polymerized to afford perfluorocyclobutyl (PFCB) aryl ether polymers that have high thermal stability, are solution processable producing optically transparent films, and possess the ability to be postfunctionalized.

    6. Polymethylene-b-polystyrene diblock copolymer: Synthesis, property, and application (pages 1894–1900)

      Jian-Zhuang Chen, Qiao-Ling Zhao, Hui-Chao Lu, Jin Huang, Shao-Kui Cao and Zhi Ma

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23954

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      Well-defined polymethylene-b-polystyrene (PM-b-PS) diblock copolymers were synthesized through the mechanism transformation from living polymerization of ylides to ATRP of styrene. PM6k-b-PS15k micellization can be formed in THF and give spherical precipitated aggregate with the size of 600 nm. Honeycomb microporous films (average pore size = 3.0 μm and 6.0 μm, respectively) were successfully fabricated via breath-figure (BF) method using different concentration of PM6k-b-PS12k (3.0 wt % and 1.5 wt %) in CS2 under a static humid condition. The cross-sections of LDPE/PC blends with and without PM10k-b-PS20k were observed by SEM, revealing that such PM-b-PS diblock copolymer is effective compatibilizer for LDPE/PC blend.

    7. Polymerization of 1,3-dienes and styrene catalyzed by cationic allyl Ni(II) complexes (pages 1901–1912)

      Abby R. O'Connor and Maurice Brookhart

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23955

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      The polymerizations of butadiene, isoprene, 2,3-dimethylbutadiene, the functionalized diene, 2,3-bis(4-trifluoroethoxy-4-oxobutyl)-1,3-butadiene, and styrene catalyzed by cationic complexes (2-R-allyl)Ni(mes)+ (R = H, 13, or CH3, 14) and [(2-R-allyl)Ni] [B(ArF)4] (R = H, 5, or CH3, 6) are described. Highly cis-enchained polymers with moderate molecular weights are observed for the poly-1,3-dienes. Styrene polymerization is achieved with (2-methallyl)Ni(mes)+, 14, as catalyst, yielding polystyrene with Mn = 4–5 K and a MWD of ∼2. NMR studies have been used to identify intermediates during the polymerization reaction.

    8. Organic soluble deoxyribonucleic acid (DNA) bearing carbazole moieties and its blend with phosphorescent Ir(III) complexes (pages 1913–1918)

      Min Ju Cho, U Ra Lee, Youn Sun Kim, Jicheol Shin, Young Min Kim, Young Wook Park, Byeong-Kwon Ju, Jung-Il Jin and Dong Hoon Choi

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23958

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      We prepared an organic soluble DNA (Cz-DNA) bearing carbazole moieties in the side chain of DNA. We also investigated the phosphorescence behavior in Ir(Cz-ppy)3 doped Cz-DNA system by comparing the emission behavior of PCzSt with Ir(Cz-ppy)3. Electrophosphorescent polymer light-emitting diodes (PLEDs) were fabricated using deoxyribonucleic acid functionalized with carbazolyl ammonium (Cz-DNA) lipid as a triplet host material to study device performances. A highly soluble iridium complex with carbazolyl-substituted 2-phenylpyridine ligands (Ir(Cz-ppy)3) was employed in 5,4-tert-butylhenyl-1,3,4-oxadiazole (PBD)-doped Cz-DNA to fabricate multilayered electrophosphorescence devices.

    9. Synthesis and physicochemical characterization of biodegradable and pH-responsive hydrogels based on polyphosphoester for protein delivery (pages 1919–1930)

      Jinlin He, Peihong Ni, Sai Wang, Haiyan Shao, Mingzu Zhang and Xiulin Zhu

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23959

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      A new class of biodegradable and pH-responsive hydrogels based on polyphosphoester is provided, and their swelling/deswelling as well as degradation behaviors were investigated in detail. The results demonstrated that crosslinking density and pH values of media strongly influenced both the swelling ratio and the degradation rate of the hydrogels. MTT assay and “live/dead” cell staining assay showed that these hydrogels were compatible to fibroblast cells, not exhibiting apparent cytotoxicity even at a high concentration, showing their potential in biomedical applications. Moreover, the preliminary study on the potential applications of these hydrogels in protein release was also investigated and the release rate was inversely proportional to the crosslinking density of hydrogels.

    10. Thermal cured epoxy resins using certain calixarenes and their esterified derivatives as curing agents (pages 1931–1942)

      Shengang Xu, Hiroto Kudo, Tadatomi Nishikubo, Shinya Nakamura and Shunichi Numata

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23960

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      Calixarenes (CAs), which are cyclic oligomers with many reactive groups in one small molecule, could be looked as perfectly defined cyclic phenolic oligomers. In this article, the cured epoxy resins with high glass temperature and high thermal stability were successfully prepared by the thermal curing reaction of two commercial epoxy resins with 13 kinds of CAs and their esterified derivatives. Among these cured materials, Tg and Tmath image of cured materials of jER 828 using CRA as curing agents were 241 °C and 404 °C, respectively, which could suit for the requirement in the field of electrical encapsulation and advanced materials.

    11. Two main chain polymeric metal complexes as dye sensitizers for dye-sensitized solar cells based on the coordination of the ligand containing 8-hydroxyquinoline and phenylethyl or fluorene units with Eu(III) (pages 1943–1951)

      Lifen Xiao, Yuan Liu, Qian Xiu, Lirong Zhang, Lihui Guo, Hailiang Zhang and Chaofan Zhong

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23961

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      The π-conjugated systems between the donor (fluorene or phenylethyl group) and the acceptor (Euq3): 1,4-Dioctyloxy-2,5-bis[2-(8-hydroxyquinoline)-vinyl]-benzene Eu(III) and 2,7-bis[2-(8-hydroxyquinoline)-vinyl]-9,9′-diocthylfluorene Eu(III) were synthesized. They have shown solar-to-electricity conversion efficiency 2.25% and 3.04%, respectively, under the illumination of AM1.5G, 100 mW/cm2.

    12. Structured multistimuli-responsive functional polymer surfaces obtained by interfacial diffusion of amphiphilic block copolymers (pages 1952–1961)

      Antoine Bousquet, Emmanuel Ibarboure, Eric Papon, Christine Labrugère and Juan Rodríguez-Hernández

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23962

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      We report on the preparation of structured multistimuli-responsive surfaces able to change reversibly their chemical composition depending on the environment and their surface behavior by varying either/both the pH or/and the temperature. More interestingly, the surfaces of the blends exhibit structuration as a result of the microphase separation of the block copolymers at the interface. Thus, either micellar structures or “donut-like” morphologies were obtained by using THF or toluene respectively, as solvent.

    13. Synthesis and electrical properties of polyaniline/polyaniline grafted multiwalled carbon nanotube mixture via in situ static interfacial polymerization (pages 1962–1972)

      In-Yup Jeon, Loon-Seng Tan and Jong-Beom Baek

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23963

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      PANi/PANi-g-MWNT mixture was prepared from in situ static interfacial polymerization. Without proton doping, the conductivity of the mixture was 4.9 S/cm, which is in the range of semimetallic transport property. The excellent electronic conductivity should be because MWNT severed as nonvolatile dopant and conducting bridge. The capacitance of the mixture was also greatly enhanced and its capacitance decay with respect to cycle times was significantly reduced.

    14. Synthesis, characterization, and field-effect transistor performance of poly[2,6-bis(3-tridecanoxythiophen-2-yl)benzo[1,2-b;4,5-b′]dithiophene] (pages 1973–1978)

      Mark A. M. Leenen, Tim Meyer, Fabio Cucinotta, Heiko Thiem, Ralf Anselmann and Luisa De Cola

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23964

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      We have synthesized a copolymer of benzo[1,2-b:4,5-b′]dithiophene and 3,3′-bis(tridecanoxy)-5,5′-bithiophene by Stille copolymerization. The bis(alkoxythiophene) monomer was synthesized through an AgF-mediated, Pd-catalyzed homocoupling of 2-bromo-3-tridecanoxythiophene, in which the bromide functional groups were preserved instead of consumed. The alkoxy chains decrease the band gap of the polymer, compared to alkyl side chains, by increasing (less negative) the HOMO energy level of the polymer, as determined by UV photoelectron spectroscopy in air. OFETs fabricated from this polymer show a hole mobility of 2 × 10−3 cm2/Vs and an on/off ratio of over 106 in practically hysteresis-free transfer characteristics.

    15. Tough interconnected polymerized medium and high internal phase emulsions reinforced by silica particles (pages 1979–1989)

      Ranting Wu, Angelika Menner and Alexander Bismarck

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23965

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      A series of macroporous nanocomposites, containing silylated silica particles as reinforcement, were prepared via emulsion templating. After polymerization of the continuous phase of high and medium internal phase emulsion templates, low density, high porosity, tough, and permeable macroporous nanocomposites were obtained. The functionalized silica particles were incorporated into the polymer, which resulted in a significant improvement of the mechanical properties of the macroporous nanocomposites without affecting the interconnected and permeable pore structures.

    16. Synthesis and characterization of polyfluorenes containing bisphenazine units (pages 1990–1999)

      Ming Wang, Hui Tong, Yanxiang Cheng, Zhiyuan Xie, Lixiang Wang, Xiabin Jing and Fosong Wang

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23966

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      To improve the electron injection properties and enhance the recombination efficiency of electrons and holes, a series of novel polyfluorenes containing bisphenazine (BP) units in the main chains were synthesized. The electroluminescence performance of the single-layer device based on all copolymers surpassed that of PFO. To optimize the structure of the diodes, a multilayer device showed the best performance, with a current efficiency of 10.01 cd/A and a maximum brightness of 5939 cd/m2.

    17. Frontal cationic curing of epoxy resins (pages 2000–2005)

      Sergio Scognamillo, Chris Bounds, Michael Luger, Alberto Mariani and John A. Pojman

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23967

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      Frontal curing of a triepoxy resin was achieved using two different BF3-amine initiators in the presence of various amounts of two fillers: fumed silica and kaolin clay. Because of heat losses due to the presence of such inert materials, large amounts of filler could be used only if relatively high initiator concentrations were used. However, the velocity and front temperature showed the same trends as with kaolin clay. In all cases, front velocities were ∼1 cm/min, and front temperatures around 200 °C.

    18. Air-tolerantly surface-initiated AGET ATRP mediated by iron catalyst from silica nanoparticles (pages 2006–2015)

      Qiang Li, Lifen Zhang, Zhengbiao Zhang, Nianchen Zhou, Zhenping Cheng and Xiulin Zhu

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23968

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      Surface-initiated atom transfer radical polymerization using activators generated by electron transfer (AGET ATRP) mediated by iron catalyst was used to synthesize well-defined polymer–nanoparticle hybrids. The kinetics of the surface-initiated AGET ATRP of methyl methacrylate (MMA) from the silica nanoparticles was studied in detail. The chemical composition of the nanocomposites was characterized by FTIR spectroscopy, X-ray photoelectron spectroscopy (XPS), and 1H nuclear magnetic resonance (1H NMR) spectroscopy.

    19. Effect of crosslinker multiplicity on the gel point in ATRP (pages 2016–2023)

      Wim Van Camp, Haifeng Gao, Filip E. Du Prez and Krzysztof Matyjaszewski

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23970

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      The effect of various types of crosslinkers containing different numbers of vinyl groups per molecule (up to six) on the gelation behavior was studied during the ATRP of methyl acrylate, using a constant ratio of branching vinyl groups to initiator, as well as using a constant molar concentration of crosslinkers.

    20. Conjugated polymers atypically prepared in water (pages 2024–2031)

      Michael A. Invernale, Samuel A. Pendergraph, Mustafa S. Yavuz, Matthew Ombaba and Gregory A. Sotzing

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23972

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      Electrochromic polymers that are not typically synthesized in water were herein prepared using the precursor approach. A soluble, insulating precursor polymer was patterned onto an electrode and was oxidatively converted in a brine electrolyte to its conjugated, electrochromic form. Subsequently, it was switched between its colored states with no loss of color or function when compared with organic-converted precursors (confirmed by UV–vis spectra and colorimetry). Both main-chain (figure) precursors and pendant side-chain precursor systems were used in this study. Brine offers a less costly and also a greener and more environmentally friendly method of processing for these systems.

    21. Stimulus-responsive polymers based on 2-hydroxypropyl acrylate prepared by RAFT polymerization (pages 2032–2043)

      Cong-Duan Vo, Julien Rosselgong, Steven P. Armes and Nicola Tirelli

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23973

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      Narrow molecular weight distribution 2-hydroxypropyl acrylate (HPA) homopolymers have been prepared using reversible addition fragmentation chain transfer (RAFT) chemistry in tert-butanol at 80 °C. The PHPA homopolymers showed different thermoresponsive behavior depending on their mean degree of polymerization and nature of the chain-end groups. Selected HPA-based diblock copolymers can self-assemble into micelles upon heating their aqueous solutions.

    22. Synthesis of polystyrene-based random copolymers with balanced number of basic or acidic functional groups (pages 2044–2052)

      Ivaylo Dimitrov, Katja Jankova and Søren Hvilsted

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23974

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      Pairs of polystyrene-based copolymers with stoichiometrically balanced number of pendant acidic or basic groups were synthesized utilizing the template strategy. The same platform random copolymer of styrene and 4-hydroxystyrene was modified in quantitative manner through direct alkylation of the phenolic groups or through the “click” chemistry approach. The oppositely charged copolymers were characterized by NMR spectroscopy and thermal analyses. The presence of different side functional groups strongly affects the copolymers' thermal stability and glass transition temperature.

  2. Rapid Communication

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    2. Articles
    3. Rapid Communication
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      Reversible click chemistry at the service of macromolecular materials. 2. Thermoreversible polymers based on the Diels-Alder reaction of an A-B furan/maleimide monomer (pages 2053–2056)

      Alessandro Gandini, Armando J. D. Silvestre and Dora Coelho

      Article first published online: 22 MAR 2010 | DOI: 10.1002/pola.23957

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      A novel structure was synthesized from renewable resources, bearing a furan and a masked maleimide as terminal moieties. Its thermal deprotection generated in situ the Diels-Alder (DA) A-B monomer, which was polymerized (forward DA) and then depolymerized (retro DA) in several cycles, as a function of the medium temperature. The ensuing linear polyadduct represents the first thermally reversible macromolecular material prepared from a furan-maleimide A-B monomer.