Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 47 Issue 6

15 March 2009

Volume 47, Issue 6

Pages 1485–1730

  1. Articles

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    2. Articles
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      Degradable star polymers with high “click” functionality (pages 1485–1498)

      James T. Wiltshire and Greg G. Qiao

      Version of Record online: 9 FEB 2009 | DOI: 10.1002/pola.23206

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      Degradable star polymers with multiple pendent acetylene groups in the arms and polyester-based crosslinked core were synthesized via a combination of atom transfer radical polymerization (ATRP) and ring-opening polymerization (ROP). The star polymers contained a high level of acetylene functionality in the corona having an average of 1850 pendent acetylene groups per star. This increased functionality was demonstrated by attaching azide-functionalized linear polystyrene via a copper (I)-catalyzed cycloaddition reaction between the azide and acetylene groups. This resulted in a CCS polymer with “brush-like” arm structures, the grafted segment of which could be liberated via hydrolysis of the polyester star structure to generate molecular brushes. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    2. Amphiphilic block copolymers containing thermally degradable poly(phthalaldehyde) blocks (pages 1499–1509)

      Stefan Köstler, Barbara Zechner, Bernd Trathnigg, Hubert Fasl, Wolfgang Kern and Volker Ribitsch

      Version of Record online: 9 FEB 2009 | DOI: 10.1002/pola.23237

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      Amphiphilic block copolymers were prepared by ionic polymerization of phthalaldehde and coupling of these polyaldehyde blocks with amine-functionalized poly(alkylene oxides). The polyaldehyde block is easily depolymerized at low temperature, allowing controlled thermal degradation of the material in two well-separated decomposition steps. The composition of the block copolymer and the decomposition reactions were investigated using dual-detection SEC and thermal analysis. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    3. Anionic polymerization of methacrylates by samarium (III) enolate on networked polystyrene: Effects of its sterically confined environment on polymerization behavior (pages 1510–1521)

      Daisuke Nagai, Asuka Fujii, Masayoshi Tanaka, Bungo Ochiai, Atsushi Sudo and Takeshi Endo

      Version of Record online: 9 FEB 2009 | DOI: 10.1002/pola.23248

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      Anionic polymerization of methacrylates under sterically confined environment in a spherical beads-shaped networked polystyrene (NwPS) matrix is described. By using an initiator, a samarium enolate supported on NwPS, polymerization of a series of methacrylates were studied to find its two aspects: (1) In the early stages, the polymerization rate for each methacrylate was comparable to that for the corresponding solution polymerization, suggesting that methacrylate can be efficiently supplied to the propagating end. (2) After early stages, the polymerization rate decreased remarkably, implying that permeation of methacrylate was sterically interfered by the formed poly(methacrylate) that filled the confined space in NwPS, as supported by a SEM image of the resulting beads, of which pores were filled with the formed polymers. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    4. Synthesis of polymeric nanocapsules with a crosslinked shell through interfacial miniemulsion polymerization (pages 1522–1534)

      Zhihai Cao and Guorong Shan

      Version of Record online: 9 FEB 2009 | DOI: 10.1002/pola.23255

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      The crosslinked polymeric nanocapsules were elaborated by the interfacial miniemulsion copolymerization of styrene, divinylbenzene, and N-isopropylacrylamide through encapsulation of a hydrocarbon in one step. The oligomer radicals containing poly(N-isopropylacrylamide) units were produced and then separated out of the aqueous phase at the reaction temperature. The separated oligomers were adsorbed by nanodroplets, and then propagated with the styrene and divinylbenzene. The oligomer radicals and the polymer chains were immobilized on the interfaces of latex particles because of the formation of crosslinked structure. The nanocapsules were formed via the accumulation of polymer chains on the interfaces of latex particles. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    5. Functional colloidal particles stabilized by layered silicate with hydrophilic face and hydrophobic polymer brushes (pages 1535–1543)

      Yani Wu, Jian Zhang and Hanying Zhao

      Version of Record online: 9 FEB 2009 | DOI: 10.1002/pola.23256

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      In this study, narrowly dispersed polystyrene (PS) colloid particles stabilized by clay layers with hydrophilic clay faces and hydrophobic PS brushes on the edges were prepared by Pickering suspension polymerization. The PS brushes penetrate into colloidal particles, and negatively charged clay layers stay in aqueous phase.

    6. Novel side-chain naphthalimide polyphenylacetylene as a ratiometric fluorescent chemosensor for fluoride ion (pages 1544–1552)

      Yi Qu, Jianli Hua, Yihua Jiang and He Tian

      Version of Record online: 9 FEB 2009 | DOI: 10.1002/pola.23257

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      Novel polyphenylacetylene (P1) containing naphthalimides units in the side chain was designed and synthesized. The measurements of sensing behavior to various halide anions, reveal that the polymer is a ratiometric fluorescent chemosensors for fluoride ion. The polymer sensor shows spectral shifts and intensity changes in the presence of fluoride, in a wavelength-ratiometric and -colorimetric manner, which can detect fluoride concentrations in range of 10–100 μM at visible wavelengths. The color changes and fluorescence emission response of P1 (1 × 10−3 M) in CH3CN upon addition of 10 equiv. tetrabutylammonium fluoride (TBAF). [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    7. Synthesis of copolyfluorenes containing green chromophores based on triphenylamine unit and their application in light-emitting diodes (pages 1553–1566)

      Bar-Yuan Hsieh and Yun Chen

      Version of Record online: 9 FEB 2009 | DOI: 10.1002/pola.23260

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      Two series of new copolyfluorenes (PFTP, PFTT) were prepared by the Suzuki coupling reaction and applied in white-light-emitting devices. The TP and TT chromophores showed photoluminescence at about 492–510 nm and 526–536 nm. Light-emitting diodes using blends of the copolyfluorenes with poly(9,9-dihexylfluorene) and red-emitting Iridium complex as emitting layer exhibited trichromatic emission. White-light emission was realized on PFTT device with maximum brightness, maximum current efficiency, and CIE coordinate being 6880 cd/m2, 1.64 cd/A, and (0.31, 0.33), respectively.

    8. Synthesis of dendritic terpolymers consisting of polystyrene, polybutadiene, and polyisoprene with different isomerisms (pages 1567–1574)

      Sofia Rangou and Apostolos Avgeropoulos

      Version of Record online: 9 FEB 2009 | DOI: 10.1002/pola.23261

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      Synthesis and molecular characterization of neat dendritic terpolymers is described and the results lead to model polymers, since increased molecular and compositional homogeneity is being exhibited. Anionic polymerization techniques in combination with chlorosilane chemistry are being adopted for the successful synthesis.

    9. Preparation and properties of conductive silver/photosensitive polyimide nanocomposites (pages 1575–1583)

      Tung-Lin Li and Steve Lien-Chung Hsu

      Version of Record online: 9 FEB 2009 | DOI: 10.1002/pola.23262

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      The silver/PSPI nanocomposites showed electrical conductivity at a low silver content of 10 wt %. The electrical conductivity of the silver/PSPI nanocomposites ranged from 10 to 104 S/cm, which was dependent on the silver weight fraction in the resist formulation. Patterns with a resolution of 30 μm were obtained from the silver /PSPI nanocomposites.

    10. Synthesis, photoluminescence, and electrochromism of novel aromatic poly(amine-1,3,4-oxadiazole)s bearing anthrylamine chromophores (pages 1584–1594)

      Hung-Ju Yen and Guey-Sheng Liou

      Version of Record online: 9 FEB 2009 | DOI: 10.1002/pola.23258

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      Two novel poly(amine-hydrazide)s were prepared from the polycondensation reactions of the dicarboxylic acid, 9-[N,N-di(4-carboxyphenyl)amino]anthracene (1), with terephthalic dihydrazide (TPH) and isophthalic dihydrazide (IPH) via the Yamazaki phosphorylation reaction, respectively. The hydrazide polymers could be thermally cyclodehydrated into the corresponding oxadiazole polymers in the range of 300–400 oC. All polymers had good solubility in many polar aprotic solvents, and exhibited high Tg values, good thermal stability, and lower HOMO energy levels with good photoluminescent and electrochromic characteristics. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    11. Synthesis and characterization of fluorene-based copolymers containing siloxane or distilbene moieties on their main chain (pages 1595–1608)

      Hoon-Je Cho, Moo-Jin Park, Do-Hoon Hwang, Taek Ahn, Ji-Won Hong, Jonghee Lee, Nam Sung Cho and Hong-Ku Shim

      Version of Record online: 9 FEB 2009 | DOI: 10.1002/pola.23259

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      We have synthesized two types of polyfluorene copolymers containing siloxane linkages or distilbene moieties on their main-chains. To the best of our knowledge, P2Silo05 and P2Silo15 are the first polyfluorene copolymers that contain siloxane linkages on their main-chains. Interestingly, the CIE coordinates of the polyfluorenes containing siloxane linkages or distilbene moieties ranged from (0.21, 0.21) to (0.17, 0.10), indicating a deeper blue light emission than that of PDHF {CIE coordinates of (0.25, 0.29)}.

    12. Synthesis and characterization of a new ethynyl-linked alternating anthracene/fluorene copolymer for organic thin film transistor (pages 1609–1616)

      Jin Uk Ju, Dae Sung Chung, Seul Ong Kim, Sung Ouk Jung, Chan Eon Park, Yun-Hi Kim and Soon-Ki Kwon

      Version of Record online: 10 FEB 2009 | DOI: 10.1002/pola.23135

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      A new p-type conjugated; polymer: poly(9,10-diethynylanthracene-alt-9,9-didodecylfluorene) (PDADF) was synthesized via a palladium(II)-catalyzed Sonogashira coupling reaction. A thin-film transistor with this polymer was found to exhibit typical p-channel FET characteristics with a hole mobility of 6.0 × 10−4 cm2/Vs and an on/off ratio of 104 with a threshold voltage of −17 V.

    13. Effect of gamma radiation on fluoropolymers (pages 1617–1626)

      A. Contreras-Garcia, E. Bucio, F. León-c, C. J. Booth and P. E. Cassidy

      Version of Record online: 10 FEB 2009 | DOI: 10.1002/pola.23267

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      The effect of gamma radiation was studied in highly fluorinated polyethers containing bisphenols. The radiochemical yields were calculated for several polymers, and 1H NMR spectra showed the changes in the structure after irradiation. Mainly, the polyethers undergo a chain scission at the α-heteroatom benzylic carbon. The polyethers containing a benzylic position between two aromatics rings also showed scission in this position.

    14. CNT templated regioselective enzymatic polymerization of phenol in water and modification of surface of MWNT thereby (pages 1627–1635)

      Yun Peng, Hewen Liu, Xingyuan Zhang, Yuesheng Li and Shiyong Liu

      Version of Record online: 10 FEB 2009 | DOI: 10.1002/pola.23271

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      Carbon nanotubes (CNTs) are used as templates to synthesize regioselective polymers from enzymatic polymerization of phenol in water. About 90% of total polymeric units in the obtained polymers are the highly thermally stable oxyphenylene units. The outer walls of CNTs are thereby chemically modified by using hydroquinone as a linking molecule.

    15. Micelles possessing mixed cores and thermoresponsive shells fabricated from well-defined amphiphilic ABC miktoarm star terpolymers (pages 1636–1650)

      Yanfeng Zhang, Hao Liu, Hefei Dong, Changhua Li and Shiyong Liu

      Version of Record online: 10 FEB 2009 | DOI: 10.1002/pola.23273

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      Amphiphilic ABC miktoarm star terpolymers consisting of polystyrene (PS), poly(ε-caprolactone) (PCL), and poly(N-isopropylacrylamide) (PNIPAM) arms, PS(-b-PNIPAM)-b-PCL, were synthesized via a combination of atom transfer radical polymerization, ring-opening polymerization, and consecutive click reactions. In aqueous solution, the obtained amphiphilic miktoarm star terpolymers self-assembles into micelles possessing mixed PS/PCL cores and thermoresponsive coronas. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    16. Synthesis of hollow crosslinked miktoarm polymer using miniemulsion as templates (pages 1651–1660)

      De'an Xiong, Zhe Li, Rujiang Ma, Yingli An and Linqi Shi

      Version of Record online: 10 FEB 2009 | DOI: 10.1002/pola.23268

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      In the miniemulsion system, the monomer and the catalyst system were dissolved in the oil phase and the macroinitiators were dissolved in the water phase. The hydrophobic terminal group of macroinitiators would penetrate into the oil phase and there are initiator, catalyst, and monomer in the oil phase. Accordingly, the polymerization would be initiated and it would mainly occur at the interphase of oil and water. In the process of polymerization, hollow polymers with a liquid core formed. After removing the butanone by dialysis, hollow Miktoarm polymers formed. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    17. Anionic alternating copolymerization of a bifunctional six-membered lactone and glycidyl phenyl ether: Selective synthesis of a linear polyester having lactone moiety (pages 1661–1672)

      Kazuya Uenishi, Atsushi Sudo and Takeshi Endo

      Version of Record online: 10 FEB 2009 | DOI: 10.1002/pola.23263

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      A bifunctional six-membered lactone 1 underwent an anionic alternating copolymerization with glycidyl phenyl ether to selectively give the corresponding linear polyester having lactone moiety in the side chain. The lactone moiety introduced into the side chain served as a versatile reactive site in the chemoselective modifications of the polymer. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    18. Hydrolytic stability and high Tg of polyimides derived from the novel 4,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]-diamantane dianhydride (pages 1673–1684)

      Yaw-Terng Chern and Jane-Jen Wang

      Version of Record online: 10 FEB 2009 | DOI: 10.1002/pola.23265

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      The diamantane-based polyimides were very stable to hydrolysis. The mechanical properties of the polyimides were found to remain after immersing films of these polyimides in 30 w/w % aqueous KOH at 100 °C for 1 h. The unusually high-temperature subglass relaxation (285 °C) apparently occur in the rigid polyimides. In addition, this novel polyimide also exhibited a low dielectric constant (2.65–2.77), low moisture absorption (<0.67 %), good solubility, high Tg, and unusually high thermal stability.

    19. Azine bridge formation during the electrografting of acrylonitrile (pages 1685–1695)

      Penelope A. Easter and D. Martin Taylor

      Version of Record online: 10 FEB 2009 | DOI: 10.1002/pola.23266

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      The AFM image shows a 30-nm-thick film of polyacrylonitrile electrografted onto a gold electrode. FTIR spectra show the film to be identical to those reported by other groups. However, Raman spectroscopy reveals the presence of previously unreported structural features. These we attribute to the formation of azine-linked polyacrylonitrile chains which form close to the electrode surface during the early part of film growth. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    20. RAFT polymerization of activated 4-vinylbenzoates (pages 1696–1705)

      Katja Nilles and Patrick Theato

      Version of Record online: 10 FEB 2009 | DOI: 10.1002/pola.23270

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      RAFT polymerization of five active ester monomers based on 4-vinylbenzoic acid had been performed. Pentafluorophenyl 4-vinylbenzoate could be polymerized under RAFT conditions yielding polymers with very good control over molecular weight and narrow molecular weight distributions. Further, the synthesis of diblock copolymers consisting of an inert block and poly(pentafluorophenyl 4-vinylbenzoate) as a reactive block was successfully performed. The diblock copolymer poly(pentafluoro styrene)-block-poly(pentafluorophenyl 4-vinylbenzoate) had been analyzed by 19F-NMR spectroscopy in solution, demonstrating the synthetic potential of pentafluorophenyl 4-vinylbenzoate as an extremely valuable monomer for the synthesis of highly functionalized polymeric architectures. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    21. Core-shell particles with glycopolymer shell and polynucleoside core via RAFT: From micelles to rods (pages 1706–1723)

      Samuel Pearson, Nathan Allen and Martina H. Stenzel

      Version of Record online: 10 FEB 2009 | DOI: 10.1002/pola.23275

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      An amphiphilic block copolymer with a glucose-based hydrophilic block and a uridine-based hydrophobic block was synthesised via RAFT polymerisation and the kinetics investigated. TEM images of the self-assembled structures in water show a transition from spherical micelles to rods as the length of the hydrophobic block increases. DSC measurements indicate that the uridine-containing block interacts strongly with its complementary base adenosine.

  2. Rapid Communication

    1. Top of page
    2. Articles
    3. Rapid Communication
    1. You have free access to this content
      Fluorous miniemulsions: A powerful tool to control morphology in metallocene-catalyzed propene polymerization (pages 1724–1730)

      Svetlin Nenov, Michael S. Hoffmann, Werner Steffen, Markus Klapper and Klaus Müllen

      Version of Record online: 10 FEB 2009 | DOI: 10.1002/pola.23242

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      The nonaqueous miniemulsion polymerization of liquid propene using highly water sensitive metallocene catalysts is presented. In the emulsion perfluoromethylcyclohexane is applied as continuous phase in which the monomer is polymerized to high molecular weights. The droplets are stabilized by specially designed of hydrocarbon/perfluorinated block copolymers. This technique offers the possibility to generate polyolefin nanoparticles with a narrow size distribution and diameters below 100 nm. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

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