Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 45 Issue 8

15 April 2007

Volume 45, Issue 8

Pages 1377–1574

  1. Articles

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    2. Articles
    3. Rapid Communications
    1. Electrochemical polymerization of pyrrole in cholesteric liquid crystals: Morphology and optical properties (pages 1377–1387)

      Hiromasa Goto

      Version of Record online: 28 FEB 2007 | DOI: 10.1002/pola.21900

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      The electrochemical polymerization of pyrrole in a cholesteric liquid-crystal electrolyte was performed. Polypyrrole grew in the cholesteric liquid-crystal medium as a structural chiral collective during the electrochemical polymerization process. Various textures of the liquid-crystal electrolyte provided the formation of Schlieren-texture, globular, Nazca-line, wire-loop, and sea-anemone structures for polypyrrole. The polypyrrole film exhibited a chiroptical property.

    2. Infrared thermographic analysis on copolymerization of spiroorthoester with oxetane (pages 1388–1393)

      Tomomi Nagasawa, Bungo Ochiai and Takeshi Endo

      Version of Record online: 28 FEB 2007 | DOI: 10.1002/pola.21884

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      The temperature changes in the copolymerization of a spiroorthoester (SOE) and an oxetane were monitored by infrared thermography. The SOE monomer effectively suppressed the heat of polymerization as well as the volume shrinkage.

    3. Synthesis and photovoltaic properties of a low-band-gap polymer consisting of alternating thiophene and benzothiadiazole derivatives for bulk-heterojunction and dye-sensitized solar cells (pages 1394–1402)

      Won Suk Shin, Sung Chul Kim, Seung-Joon Lee, Han-Su Jeon, Mi-Kyoung Kim, B. Vijaya Kumar Naidu, Sung-Ho Jin, Jin-Kook Lee, Jae Wook Lee and Yeong-Soon Gal

      Version of Record online: 28 FEB 2007 | DOI: 10.1002/pola.21909

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      We synthesized a novel low-band-gap, conjugated polymer, poly[4,7-bis(3′,3′-diheptyl-3,4-propylenedioxythienyl)-2,1,3-benzothiadiazole], consisting of alternating electron-rich, diheptyl-substituted propylene dioxythiophene and electron-deficient 2,1,3-benzothiadiazole units, and its photovoltaic properties were investigated.

    4. Induced helix formation and stabilization of a meta-linked polymer containing pyridine units (pages 1403–1412)

      Cuihong Li, Yanbing Guo, Jing Lv, Jialiang Xu, Yuliang Li, Shu Wang, Huibiao Liu and Daoben Zhu

      Version of Record online: 28 FEB 2007 | DOI: 10.1002/pola.21910

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      A new amphiphilic, meta-linked polymer containing pyridine units, poly(m-ethynylpyridine) (m-PPY) was synthesized. Polar solvents drove it to undergo a cooperative conformational transition from an extended coil structure to a helical structure. A metal ion or H+ could stabilize the ordered structure. Moreover, the solvophobically induced helical structure was stable to environmental stimuli.

    5. Preparation of gradient copolymers via ATRP in miniemulsion. II. Forced gradient (pages 1413–1423)

      Ke Min, Jung Kwon Oh and Krzysztof Matyjaszewski

      Version of Record online: 1 MAR 2007 | DOI: 10.1002/pola.21911

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      A series of forced gradient copolymers with different controlled distribution of monomers units along the copolymer backbone were successfully prepared by atom transfer radical polymerization in miniemulsion. The newly developed initiation technique, known as activators generated by electron transfer, was beneficial for forced gradient copolymers preparation in miniemulsion. Various monomer pairs with different reactivity ratios were examined in this study. The shape of the gradient along the backbone of the copolymers was influenced by the molar ratio of the monomers, the reactivity ratio of the comonomers, the feeding rate and the relative hydrophobicities of the comonomers.

    6. Water-resistant conducting hybrids from electrostatic interactions (pages 1424–1431)

      Jing Luo, Qiguan Wang, Xianhong Wang, Ji Li, Xiaojiang Zhao and Fosong Wang

      Version of Record online: 5 MAR 2007 | DOI: 10.1002/pola.21912

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      A novel electrostatic-interaction conductive hybrid with good water stability was prepared in a water/ethanol solution by a sol–gel process from an inorganic sol containing carboxyl groups and water-borne conductive polyaniline (cPANI). The introduced electrostatic interaction greatly enhanced the compatibility between the organic and inorganic components and contributed to the homogeneous distribution of cPANI in the inorganic phase. The obtained electrostatic-interaction hybrid films displayed 1–2 orders of magnitude higher electrical conductivity and a lower conductivity percolation threshold (1.1 wt % polyaniline) in comparison with hybrids without electrostatic interactions.

    7. Facile synthesis of dumbbell-shaped dendritic-linear-dendritic triblock copolymer via reversible addition-fragmentation chain transfer polymerization (pages 1432–1445)

      Zhishen Ge, Daoyong Chen, Jingyan Zhang, Jingyi Rao, Jun Yin, Di Wang, Xuejuan Wan, Wenfang Shi and Shiyong Liu

      Version of Record online: 5 MAR 2007 | DOI: 10.1002/pola.21914

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      We report the first instance of facile synthesis of dumbbell-shaped dendritic-linear- dendritic triblock copolymer, [G-3]-PNIPAM-[G-3], consisting of third generation poly(benzyl ether) monodendrons ([G-3]) and linear poly(N-isopropylacrylamide) (PNIPAM), via reversible addition-fragmentation chain transfer (RAFT) polymerization. The key step was the preparation of novel [G-3]-based RAFT agent, [G-3]-CH2SCSSCH2-[G-3] (1), from third-generation dendritic poly(benzyl ether) bromide, [G-3]-CH2Br. The micellar properties of dumbbell-shaped [G-3]-PNIPAM-[G-3] were then characterized in detail.

    8. Syntheses and micellar properties of well-defined amphiphilic AB2 and A2B Y-shaped miktoarm star copolymers of ε-caprolactone and 2-(dimethylamino)ethyl methacrylate (pages 1446–1462)

      Hao Liu, Jian Xu, Jiali Jiang, Jun Yin, Ravin Narain, Yuanli Cai and Shiyong Liu

      Version of Record online: 5 MAR 2007 | DOI: 10.1002/pola.21915

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      Well-defined amphiphilic PCL-b-(PDMA)2 and (PCL)2-b-PDMA Y-shaped miktoarm star copolymers and PCL-b-PDMA linear diblock copolymer were synthesized via a combination of ring-opening polymerization and atom transfer radical polymerization, where PCL is poly (ε-caprolactone) and PDMA is poly(2-(dimethylamino)ethyl methacrylate). All three types of copolymers have comparable composition and overall molecular weights. The chain architectural effects on the micellization properties, including the aggregation number, size, polydispersity, and micelle densities of the amphiphilic nonlinear and linear copolymers were explored by a combination of dynamic and static laser light scattering.

    9. Semicontinuous heterophase polymerization under monomer starved conditions to prepare nanoparticles with narrow size distribution (pages 1463–1473)

      Raquel Ledezma, M. Esther Treviño, Luis E. Elizalde, Lourdes A. Pérez-Carrillo, Eduardo Mendizábal, Jorge E. Puig and Raúl G. López

      Version of Record online: 5 MAR 2007 | DOI: 10.1002/pola.21916

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      High-solid content nanolatexes of poly(methyl methacrylate) were prepared by semicontinuous polymerization in heterophase under monomer-starved conditions. Particle size and molar masses decrease with the decreasing of monomer addition rate. Nanoparticles with average diameter from 20 to 35 nm and polydispersity index (Dw/Dn) close to 1.04 were obtained when monomer addition rate was varied. Molar masses obtained in all polymerizations carried out in this work are much lower than those reported for the polymerization of methyl methacrylate in emulsion and other microemulsion sytems. Possible explanations for the results obtained here are provided.

    10. Dramatic effect of solvent on the NMR spectral resolution of hyperbranched polyethers (pages 1474–1480)

      Girish Ch. Behera and S. Ramakrishnan

      Version of Record online: 5 MAR 2007 | DOI: 10.1002/pola.21917

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      Proton NMR spectra of hyperbranched polyethers containing aromatic rings exhibit dramatically improved resolution when recorded in benzene-d6. This lead to the identification of well-resolved peaks belonging to three types of segments in such polymers, namely dendritic (D), linear (L), and terminal (T) units, which in turn permitted the determination of the degree of branching (DB) without the need to resort to the use of any model compounds.

    11. New highly luminescent cationic polyelectrolytes based on poly(phenylenevinylene-alt-fluorenevinylene) or poly(fluorenevinylene) derivatives and their neutral precursors (pages 1481–1491)

      John A. Mikroyannidis and Vasilis P. Barberis

      Version of Record online: 6 MAR 2007 | DOI: 10.1002/pola.21918

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      Two conjugated neutral polymers PF and F were synthesized via Heck coupling and they were postquaternized by reacting with bromoethane to the corresponding cationic polyelectrolytes PFQ and FQ. The quaternized polymer PFQ is dissolved in water and alcohol whereas all other polymers are dissolved only in common organic solvents. The polymers emitted intense blue-greenish light in both solution with relatively high PL quantum yields (up to 0.57) and thin films. The water soluble cationic polyelectrolyte PFQ could find potential applications as chemo or biosensor.

    12. Synthesis and properties of novel electrophosphorescent polymers from quinoline- and pyridine-end-capped polyfluorenes with rhenium(I) chromophores (pages 1492–1498)

      Po-I Lee and Steve Lien-Chung Hsu

      Version of Record online: 6 MAR 2007 | DOI: 10.1002/pola.21919

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      Novel electrophosphorescent polymers were prepared from quinoline- and pyridine-end-capped polyfluorenes reacted with 4,4′-dimethyl-2,2′-bipyridyl (tricarbonyl)rhenium(I) chloride. Fourier transform infrared and photoluminescence spectroscopy confirmed that the rhenium complex was successfully incorporated into the polymer backbones. The energy transfer could be reached by an efficient intramolecular process. The emission contributions of the polyfluorene and organic complex were found from the electroluminescence spectra.

    13. Controlled synthesis of carboxylic acid end-capped poly(heptadecafluorodecyl acrylate) and copolymers with 2-hydroxyethyl acrylate (pages 1499–1506)

      Bruno Grignard, Christine Jérôme, Cédric Calberg, Christophe Detrembleur and Robert Jérôme

      Version of Record online: 6 MAR 2007 | DOI: 10.1002/pola.21920

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      1H,1H,2H,2H-Heptadecafluorodecyl acrylate was successfully polymerized [poly(1H,1H,2H,2H-heptadecafluorodecyl acrylate) (PAC8)] and copolymerized with 2-hydroxyethyl acrylate [poly(1H,1H,2H,2H-heptadecafluorodecyl acrylate)-b-poly(2-hydroxyethyl acrylate) (PAC8-b-PHEA)] by reversible addition–fragmentation chain transfer in the presence of S-1-dodecyl-S-(α,α′-dimethyl-α″-acetic acid)trithiocarbonate as a chain-transfer agent. The control of the (co)polymerization was emphasized by the linear dependence of both ln([M]0/[M]) on time and Mn on the (co)monomer conversion and by the carboxylic acid end capping of the chains. The randomness of the copolymerization was assessed by the constant 1H,1H,2H,2H-heptadecafluorodecyl acrylate/2-hydroxyethyl acrylate composition versus the conversion. Finally, PAC8 was successfully used as a macroinitiator for the synthesis of the PAC8-b-PHEA diblock copolymers, which were typically amphiphilic compounds.

    14. π-conjugated polymers having diaza[12]annulene rings and aminopenta-2,4-dienylidene groups generated by the ring opening of pyridinium rings (pages 1507–1514)

      Isao Yamaguchi, Yoshiaki Gobara and Moriyuki Sato

      Version of Record online: 6 MAR 2007 | DOI: 10.1002/pola.21921

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      Reactions of N-(2,4-dinitrophenyl)pyridinium chloride with 2,5-dimethyl-1,4-phenylenediamine gave π-conjugated polymers consisting of 5-(2,5-dimethyl-1,4-phenylene)penta-2,4-dienylideneammonium chloride (unit A) and N-2,5-dimethyl-1,4-phenylene diaza[12]annulenium dichloride (unit B). The composition ratios of unit A to unit B of the polymers varied, depending on the monomer ratios. Pellets molded from polymers with a higher unit B content exhibited a metallic luster, which was ascribed to the ordered structures of the polymers in the solid state.

    15. Synthesis and helicity of optically active poly(N-propargylphosphonamidates) having chiral phosphorus center (pages 1515–1524)

      Dongmei Yue, Toru Fujii, Kayo Terada, Junichi Tabei, Masashi Shiotsuki, Fumio Sanda and Toshio Masuda

      Version of Record online: 6 MAR 2007 | DOI: 10.1002/pola.21922

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      A series of novel poly(N-propargylamides) [poly(1)–poly(4)] with chiral-P and C centers were synthesized by the polymerization of the corresponding monomers using an Rh catalyst. Poly(1)–poly(4) took one-hand helical conformation in CHCl3, THF, toluene, chlorobenzene, and Et2O, which was confirmed by polarimetric and CD spectroscopic analyses. The polymers with different P-chirality showed CD signals with opposite sign each other. It seems that P-chirality plays an important role in forming a helical conformation. The polymers decreased the helicity upon addition of CH3OH and raising temperature.

    16. Novel heterocyclic poly(arylene ether ketone)s: Synthesis and polymerization of 4-(4′-hydroxyaryl)(2H)phthalazin-1-ones with methyl groups (pages 1525–1535)

      Lin Cheng, Lei Ying, Juan Feng, Chen Yi Wang, Jian Ling Li and Zhen Xu

      Version of Record online: 15 MAR 2007 | DOI: 10.1002/pola.21880

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      A simple and efficient direct synthesis of 4-(4′-hydroxyaryl)(2H)phthalazin-1-ones (2a–2f) has been developed using a two-step reaction in which the Friedel–Crafts acylation reaction is carried out and then followed by cyclization with hydrazine hydrate. A number of novel heterocyclic poly(arylene ether ketone)s were prepared from several unsymmetrical, twist, and noncoplanar phthalazinone-containing monomers and an activated difluoro monomer via a N[BOND]C coupling reaction. The obtained monomers and polymers exhibited diverse properties with the variation of the number and location of substituted methyl groups. All these polymers were of high molecular weight with Mn and ηinh in the range of 44,960–169,000 Da and 0.38–0.79 dL/g, respectively. The polymers display excellent thermal properties with Tg's ranging from 222 to 248 °C and 5% weight loss temperatures in nitrogen higher than 430 °C. The polymers were also readily soluble in common organic solvents and could be cast into flexible and colorless, or nearly colorless, films by spin-coating or casting processes.

    17. Palladium-mediated copolymerization of diazocarbonyl compounds with phenyldiazomethane (pages 1536–1545)

      Eiji Ihara, Masami Kida, Masayasu Fujioka, Nobuyuki Haida, Tomomichi Itoh and Kenzo Inoue

      Version of Record online: 8 MAR 2007 | DOI: 10.1002/pola.21881

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      Phenyldiazomethane was found to be polymerized by the reaction with palladium-based initiating systems. Homopolymerization of phenyldiazomethane afforded a polymer, whose main chain consists of phenylmethylene framework (–CHPh–) and azo groups (–N[DOUBLE BOND]N–). The incorporation of the azo group was suggested from the results of elemental analyses, and confirmed by Raman spectroscopy. Palladium-mediated copolymerization of phenyldiazomethane with (E)-1-diazo-3-nonen-2-one or ethyl diazoacetate proceeded to give copolymers having phenylmethylene framework, azo group, and acylmethylene or ethoxycarbonylmethylene framework in the main chain, with a variety of their compositions.

    18. Synthesis of chromo- and fluorogenic poly(ortho-diaminophenylene) chemosensors for fluoride anion (pages 1546–1556)

      Hyung Jun Kim, Jung hyo Lee, Tae Hoon Kim, Won Seok Lyoo, Dong Wook Kim, Changjin Lee and Taek Seung Lee

      Version of Record online: 8 MAR 2007 | DOI: 10.1002/pola.21923

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      We are presenting the conjugated polymers as a chromogenic and fluorogenic sensor toward fluoride anion that utilizes intramolecular hydrogen bonding as a sensing module. The polymer solution showed changes in color and fluorescence quenching upon addition of fluoride anion. [A color version of the adjacent figure can be viewed in the online issue, which is available at]

    19. Amine-blocked polyisocyanates. I. Synthesis of novel N-methylaniline-blocked polyisocyanates and deblocking studies using hot-stage fourier transform infrared spectroscopy (pages 1557–1570)

      Govindarajan Sankar and A. Sultan Nasar

      Version of Record online: 8 MAR 2007 | DOI: 10.1002/pola.21924

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      A series of novel N-methylaniline-blocked polyisocyanates based on 4,4′-methylenebis(phenyl isocyanate), poly(tetrahydrofuran), and a series of substituted N-methylanilines were prepared. The study of the cure behavior of these blocked polyisocyanates with hydroxyl-terminated polybutadiene and their deblocking studies, including the determination of the deblocking temperatures and deblocking kinetic parameters, were performed with hot-stage FTIR spectroscopy.

  2. Rapid Communications

    1. Top of page
    2. Articles
    3. Rapid Communications
    1. You have free access to this content
      Solvent-free synthesis of pseudopolyrotaxane and polyrotaxane: Efficient threading complexation of a cyclodextrin wheel and a linear polymer axle to yield pseudopolyrotaxane and its fixation to polyrotaxane by the direct grinding of a solid mixture (pages 1571–1574)

      Runtao Liu, Takeshi Maeda, Nobuhiro Kihara, Akira Harada and Toshikazu Takata

      Version of Record online: 8 MAR 2007 | DOI: 10.1002/pola.21913

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      Pseudopolyrotaxane was obtained through the grinding of a mixture of O-trimethyl-α-cyclodextrin and polytetrahydrofuran in a mortar by solvent-free synthesis, and it was fixed to stable polyrotaxane by a successive end-capping reaction with a bulky isocyanate by solid-state grinding in a mortar. Higher molecular weight polytetrahydrofurans (Mn > 1000) successfully produced corresponding polyrotaxanes in moderate yields and with moderate coverage ratios. O-Trimethyl-β-cyclodextrin and poly(ethylene glycol) also formed corresponding pseudopolyrotaxanes and polyrotaxanes by the grinding method.