Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 48 Issue 7

1 April 2010

Volume 48, Issue 7

Pages 1461–1675

  1. Articles

    1. Top of page
    2. Articles
    1. Synthesis of bipolar charge transporting block copolymers and characterization for organic light-emitting diode (pages 1461–1468)

      Kousuke Tsuchiya, Hidemasa Kasuga, Akira Kawakami, Hideo Taka, Hiroshi Kita and Kenji Ogino

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23853

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      Block copolymers consisted of bipolar charge transporting segments, namely triphenylamine and oxadiazole units for hole and electron transport respectively, were prepared by living radical polymerization using an alkoxyamine initiator. The performances of OLED devices were investigated among random, block, and blend polymers with same composition, and the relationship between the morphology and the device performance was discussed.

    2. Electrochromic material containing unsymmetrical substituted N,N,N′,N′-tetraaryl-1,4-phenylenediamine: Synthesis and their optical, electrochemical, and electrochromic properties (pages 1469–1476)

      Han-Yu Wu, Kun-Li Wang, Der-Jang Liaw, Kueir-Rarn Lee and Juin-Yih Lai

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23880

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      A novel dibromo compound containing unsymmetrical substituted N,N,N ′,N ′- tetraaryl-1,4-phenylene diamine was synthesized. A electrochromic conjugated polymer was prepared via the Suzuki coupling from the newly prepared dibromide and 9,9-dioctylfluorene-2,7-bis(trimethyleneboronate). The polymer films revealed excellent stability of electrochromic characteristics, with a color change from yellow green to the dark blue at applied potentials ranging from 0 to 1.3 V. The color switching time was found to be about 5 s and bleaching time was about 7 s. In electrochromic behavior, it revealed excellent continuous cyclic stability.

    3. Synthesis of MWCNTs-core/thiophene polymer-sheath composite nanocables by a cationic surfactant-assisted chemical oxidative polymerization and their structural properties (pages 1477–1484)

      Kakarla Raghava Reddy, Han Mo Jeong, Youngil Lee and Anjanapura Venkataramanaiah Raghu

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23883

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      The MWCNTs-thiophene polymer core-sheath composite nanocables were synthesized by chemical oxidative polymerization of 3,4-ethylenedioxythiophene (EDOT) with oxidant (FeCl3) in the presence of cationic surfactant, deceyltrimethyl ammonium bromide (DTAB) that acts as the structure-directing agen. In the polymerization process, DTAB surfactant molecules were adsorbed on the surface of MWCNTs and forms MWCNTs-DTAB soft template. On the addition of EDOT and oxidant, the polymerization takes place on the surface of MWCNTs, and PEDOT is gradually deposited on the surface of MWCNTs. The resulting nanocomposites have the nanocable structure as shown in the scheme. The structural, morphological, thermal, optical, and electrical properties of the synthesized nanocomposites were fully characterized by using various techniques. The mechanism for the formation of composite nanocables was explained on the basis of self-assembly of micelles. The reported self-assembly strategy for the synthesis of PEDOT-coated MWCNTs in micellar medium is a rapid, versatile, potentially scalable, stable, and making it useful for further exploitation in various types of applications.

    4. Polymerization of trimethylene carbonate in aqueous solutions: Reaction mechanism and characterization (pages 1485–1492)

      Takao Okada, Yukari Imamura and Takehisa Matsuda

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23891

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      Polymerization of trimethylene carbonate (TMC) in an aqueous solution was performed without using any additive or catalyst by a three-step reaction. In the polymerization reaction, 1,3-propanediol was added to the monomer and eliminated from the oligomer. This three-step reaction is a new method for polymerization of TMC.

    5. The nature of Cu(II) species in ATRP: New insights via EPR (pages 1493–1501)

      Ignacio Caretti, Bart Dervaux, Filip E. Du Prez and Sabine Van Doorslaer

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23907

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      Via electron paramagnetic resonance (EPR), up to five different paramagnetic species—one organic radical and four copper-based species—were identified during the Cu(I)Br-catalyzed atom transfer radical polymerization (ATRP). Based on the time evolution of the individual EPR contributions, it has been revealed that kinetic studies based on the summed Cu(II) EPR signal, as commonly used in literature, are too simplistic and not correct.

    6. A novel mesogen-jacketed liquid crystalline electroluminescent polymer with both thiophene and oxadiazole in conjugated side chain (pages 1502–1515)

      Qian Yang, Yiding Xu, Hao Jin, Zhihao Shen, Xiaofang Chen, Dechun Zou, Xinghe Fan and Qifeng Zhou

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23908

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      We synthesized a series of mesogen-jacketed liquid crystalline polymers with both electron-transport oxadiazole and hole-transport thiophene in the side chain. Electroluminescence study with the device configuration of ITO/PEDOT/PVK/polymer/TPBI/Ca/Ag showed maximum brightness and current efficiency of 541 cd/m2 and 0.10 cd/A, which proved that the introduction of directly connected electron- and hole-transport units could greatly improve the EL property of side-chain conjugated polymers. The phase structures of the polymers were confirmed to be smectic A phase through the results of PLM and WAXD.

    7. Polymerized pickering HIPEs: Effects of synthesis parameters on porous structure (pages 1516–1525)

      Inna Gurevitch and Michael S. Silverstein

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23911

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      A cross-section through a polymerized Pickering HIPE is shown in the transmission electron micrograph. A polyHIPE is a crosslinked, highly porous polymer synthesized within the external phase of a high internal phase emulsion (HIPE). The polyHIPEs were synthesized thorough the copolymerization of ethylhexyl acrylate (EHA) and divinylbenzene (DVB) within surfactant-free Pickering HIPEs stabilized with silane-modified silica nanoparticles. The P(EHA-co-DVB) wall (a stripe of light gray) is seen between two poly(methyl methacrylate)-filled voids (dark gray). Two rows of silica nanoparticle aggregates can be seen within the wall (black lines within the light gray). The nanoparticle shells are brought together through the close packing of the HIPE droplets (schematic illustration).

    8. A new strategy for the synthesis of methacrylate end-functionalized macromonomers by ATRP (pages 1526–1537)

      Sandie Piogé, Laurent Fontaine, Jean-Claude Soutif, Erwan Nicol and Sagrario Pascual

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23905

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      Well-defined poly(ethylene oxide)-b-poly(ethyl acrylate) PEO-b-PEA with a high bromine chain-end functionality was obtained by ATRP. The halogen end-groups of PEO-b-PEA were converted into hydroxyl end-groups by an original method using mercaptoalcohols. A quantitative functionalization was observed using the 6-mercaptohexan-1-ol. The resulting ω-hydroxy-PEO-b-PEA was transformed into methacrylate end-functionalized macromonomers with well-defined molecular weights and low polydispersities.

    9. Photoresponsive poly(methyl methacrylate)-b-azodendron block copolymers prepared by ATRP and click chemistry (pages 1538–1550)

      Jesús del Barrio, Luis Oriol, Rafael Alcalá and Carlos Sánchez

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23920

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      The combination of ATRP and Click Chemistry is employed in the synthesis of photoaddressable linear-dendritic block copolymers (BCs). The length of the PMMA block and the generation number of the dendritic block influence the BC morphology and photo-induced anisotropy, with the latter also determined by the spacer length of the cyanoazobenzene units at the periphery of the dendritic block.

    10. Colorimetric naked-eye recognizable anion sensors synthesized via RAFT polymerization (pages 1551–1556)

      Jianbing Jiang, Xiao Xiao, Ping Zhao and He Tian

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23922

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      Both TH and PTH solutions showed yellow-to-orange change in low anion concentrations, and only F resulted in further orange-to-purple change in high concentrations, which was attributed to the protonation of the thiourea N[BOND]H.

    11. Multiarm star triblock terpolymers via sequential double click reactions (pages 1557–1564)

      Hakan Durmaz, Aydan Dag, Duygu Gursoy, A. Levent Demirel, Gurkan Hizal and Umit Tunca

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23925

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      Multiarm star triblock terpolymers were obtained by using two different click reactions sequentially: Cu(I) catalyzed azide–alkyne and Diels–Alder. The synthetic strategy is described as follows: (poly(methyl methacrylate))n-(polystyrene)m-poly(divinyl benzene)) ((PMMA)n-(PS)m-polyDVB) multiarm star diblock copolymer was first obtained from an azide–alkyne click reaction of (alkyne-PS)m-polyDVB multiarm star polymer with α-anthracene-ω-azide PMMA (anth-PMMA-N3), followed by a Diels–Alder click reaction of the anthracene groups at the star periphery with α-maleimide poly (tert-butyl acrylate) (PtBA-MI) or α-maleimide poly(ethylene glycol) (PEG-MI) leading to target (PtBA)k-(PMMA)n-(PS)m-polyDVB and (PEG)p-(PMMA)n-(PS)m-polyDVB multiarm star triblock terpolymers.

    12. Fluorine-substituted azobenzene destabilizes polar form of optically switchable fulgimide unit in copolymer system (pages 1565–1578)

      Saravanan Chinnusamy and Kannan Palaninathan

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23926

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      Fulgimide and various size and electronic nature of substituents on terminal position of azobenzenes in the pendant containing homo/copolymethacrylates were synthesized and their optical property studied by UV–Vis and fluorescence spectroscopy. Polar form fulgimide absorption in F-co-FL is appeared around 482 nm, which is 40 nm lower than other polar form absorption of copolymers; similarly, fluorescence pattern of F-co-FL by UV irradiation exhibited emission intensity slowly increased to certain level then decreases with two new emissions emerged at 430 and 480 nm attributed to terminal position of fluorine atom on azobenzene destabilizes polar form fulgimide unit in copolymer.

      Corrected by:

      Erratum: Fluorine-substituted azobenzene destabilizes polar form of optically switchable fulgimide unit in copolymer system

      Vol. 48, Issue 10, 2256, Version of Record online: 8 APR 2010

    13. Stereospecific styrene polymerization and ethylene–styrene copolymerization with titanocenes containing a pendant amine donor (pages 1579–1585)

      Kyung-Sun Son and Robert M. Waymouth

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23912

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      Monocyclopentadienyl titanium complexes containing a pendant amine group are active catalyst precursors for syndiospecific styrene polymerization and ethylene– styrene copolymerization at 70 °C. The pendant amine donor exhibits a significant influence on the product distribution for ES copolymerizations. Titanocenes with the amine group yield syndiotactic polystyrene at 70 °C, but only atactic polystyrene at 120 °C. At 70 °C, these complexes afford high molecular weight ethylene–styrene copolymers containing 39–71 mol % styrene depending on the monomer feed ratios. Simultaneously, syndiotactic polystyrene is produced, implicating that two active forms of the catalyst are generated under these conditions.

    14. Modeling of reinitiation ability of polymer brushes grown by surface-initiated photoiniferter-mediated photopolymerization (pages 1586–1593)

      Santosh B. Rahane, Andrew T. Metters and S. Michael Kilbey II

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23913

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      A rate-based model is used to examine reinitiation ability of polymer layers synthesized by surface-initiated photoiniferter-mediated photopolymerization in the presence of the deactivator, tetraethylthiuram disulfide (TED). Model predictions show that while increases in [TED] and decreases in light intensity affect overall rates of chain growth in similar fashions, the reinitiation ability is improved by increasing [TED], but is not improved by decreasing the light intensity. Model predictions suggest that tethered chains synthesized in the presence of TED are more likely to form surface-tethered block copolymers upon reinitiation compared to those synthesized without TED and at lower light intensity.

    15. Tailored composite polymer–metal nanoparticles by miniemulsion polymerization and thiol-ene functionalization (pages 1594–1606)

      Kim Y. van Berkel and Craig J. Hawker

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23917

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      A simple and modular synthetic approach, based on miniemulsion polymerization, has been developed for the fabrication of composite polymer-metal nanoparticle materials. This methodology readily permits the incorporation of multiple metal domains into a single polymeric particle, while still preserving the useful optical and magnetic properties of the metal nanoparticles and allows the surface chemistry to be modified using thiol-ene chemistry.

    16. Jacket-like structure of donor–acceptor chromophores-based conducting polymers for photovoltaic cell applications (pages 1607–1616)

      Yi-Lung Yang, Yi-Huan Lee, Chun-Jie Chang, Ang-Jhih Lu, Wei-Chun Hsu, Leeyih Wang, Man-Kit Leung and Chi-An Dai

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23921

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      A novel jacket-like structure of two-dimensionally donor–acceptor type conducting polymer PCPQT via Stille coupling polymerization was designed, synthesized, and investigated. The HOMO and LUMO energy levels of PCPQT could be determined from cyclic voltammetry measurement to be −5.36 and −3.59 eV, respectively. The solar cell made from PCPQT exhibited a high Voc (∼0.75 V). Further improvements are anticipated through a rational design of the new low band-gap conducting polymer.

    17. A new titanium (IV) complex bearing phenoxyimine-fluorene ligand and its use as catalyst for ethylene homo- and copolymerization (pages 1617–1621)

      Liang Zhong, Kun Cui, Peng Xie, Jian-Zhuang Chen and Zhi Ma

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23927

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      A new titanium (IV) complex (TPIF) bearing phenoxyimine-fluorene ligand was synthesized and used as catalyst for ethylene homopolymerization and copolymerizations in presence of modified methylaluminoxane (MMAO). The complex exhibited good catalytic activities for ethylene homo- and copolymerizations and good capability of incorporating various comonomers such as 1-hexene, 1-octene and norbornene into polyethylene backbone. The broad molecular weight distribution of resulting polymer indicated that the multiple active species were formed during polymerization.

    18. Controlled synthesis and functionalization of PEGylated methacrylates bearing cyclic carbonate pendant groups (pages 1622–1632)

      Satyasankar Jana, Han Yu, Anbanandam Parthiban and Christina L.L. Chai

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23928

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      PEG-based difunctional macroinitiators were synthesized and used for the synthesis of (co)polymers bearing cyclic carbonate (CC) pendant groups. The CC unit was subsequently subjected to ring opening reaction with mono- or diamines to yield polymers with enhanced solubility characteristics and crosslinked materials respectively. The wettability characteristics were studied by measuring the contact angle of polymers before and after ring opening reaction. Lithium ion conductivity of some of the polymers was also measured by impedance spectroscopy.

    19. Effects of Br connected groups on atom transfer nitroxide radical coupling reaction and its application in the synthesis of comb-like block copolymers (pages 1633–1640)

      Guowei Wang, Yannan Zhang and Junlian Huang

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23929

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      The effect of Br connected groups played an important effect on ATNRC reaction. The versatile ATNRC reaction with high efficiency could be realized by transforming the higher active Br connected groups into the lower one by the addition of small amount of St monomers. This strategy would largely facilitate the designing of the ATNRC precursors and enriched the kind of complicated copolymers.

    20. Synthesis of poly(vinyl ether) polyols with pendant oxyethylene chains and properties of hydrophilic, thermo-responsive polyurethanes prepared therefrom (pages 1641–1648)

      Tamotsu Hashimoto, Ayumi Takahashi, Michio Urushisaki and Toshikazu Sakaguchi

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23930

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      Hydroxy-terminated telechelic poly(vinyl ether)s with pendant oxyethylene chains were synthesized by the end-group transformation of bifunctional living cationic polymers of oxyethylene chain-containing vinyl ethers and new type of water-soluble polyurethanes were obtained therefrom. The aqueous solutions of these polyurethanes exhibited thermally-induced precipitation at a particular temperature depending on the sort of the thermosensitive poly(vinyl ether) segments containing oxyethylene side chains.

    21. Phosphorus-containing renewable polyester-polyols via ADMET polymerization: Synthesis, functionalization, and radical crosslinking (pages 1649–1660)

      Lucas Montero de Espinosa, Michael A. R. Meier, Juan C. Ronda, Marina Galià and Virginia Cádiz

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23887

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      The acyclic diene metathesis (ADMET) copolymerization of two α,ω-dienes prepared from plant oil derived chemicals, afforded a series of new renewable phosphorus containing linear polyester-polyols. Acrylation of the pendant hydroxyl groups followed by radical polymerization yielded a family of flame retardant crosslinked polymers that have been fully characterized.

    22. Nanoparticles consisting of optically active helical polymers: Preparation via aqueous catalytic miniemulsion polymerization and the effects of particles size on their optical activity (pages 1661–1668)

      Xiaofeng Luo, Naiwen Kang, Lei Li, Jianping Deng and Wantai Yang

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23924

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      An N-propargylamide monomer is initiated to undergo catalytic miniemulsion polymerization in aqueous medium in the presence of Rh-based catalyst, providing optically active nanoparticles consisting of helical polymers. The optical activity of the nanoparticles increases with decreasing the particle size. Optically active composite films are further prepared from the obtained polymer nanoparticles, attesting to the utility of the obtained nanoparticles.

    23. Synthesis and characterization of a narrow-bandgap polymer containing alternating cyclopentadithiophene and diketo-pyrrolo-pyrrole units for solar cell applications (pages 1669–1675)

      Guan-Yu Chen, Chien-Ming Chiang, Dhananjay Kekuda, Shang-Che Lan, Chih-Wei Chu and Kung-Hwa Wei

      Version of Record online: 18 FEB 2010 | DOI: 10.1002/pola.23931

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      A conjugated polymer (PCTDPP) containing alternating cyclopentadithiophene and diketo-pyrrolo-pyrrole units possesses a broad absorption band extending from 350 to 1000 nm and a low bandgap of 1.31 eV. Solar cell devices based on this polymer exhibited power conversion efficiencies of up to 2.27%.