Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 49 Issue 6

15 March 2011

Volume 49, Issue 6

Pages 1299–1516

  1. Highlights

    1. Top of page
    2. Highlights
    3. Articles
    4. Articles
    5. Original Article
    6. Articles
    7. Rapid Communications
    8. Notes
    1. You have free access to this content
      Chiral crystallization and the origin of chiral life on earth (pages 1299–1308)

      Otto Vogl

      Article first published online: 11 JAN 2011 | DOI: 10.1002/pola.24548

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      Evidence of chiral emergence by a combination of chiral crystallization, formation of helical polymers with preferred structure based on macromolecular asymmetry inspired ideas and rules for the origin of chiral life. These investigations needed the understanding of the requirements for chiral crystallization, for the stereochemistry of the initial formation of helical polymers, the measurements of optical activity of solids, and their coordination with the fundamentals of chirality. Spacial modeling of the “oligo-crystallization” of NaClO3 led to “isotactic” linear crystallization involving helical propagation that requires unequal sizes of the cations and anions, which by branching propagation leads to 3D chiral crystallization.

  2. Articles

    1. Top of page
    2. Highlights
    3. Articles
    4. Articles
    5. Original Article
    6. Articles
    7. Rapid Communications
    8. Notes
    1. Generation of well-defined clickable glycopolymers from aqueous RAFT polymerization of isomaltulose-derived acrylamides (pages 1309–1318)

      Ouaiss Abdelkader, Sylvie Moebs-Sanchez, Yves Queneau, Julien Bernard and Etienne Fleury

      Article first published online: 2 FEB 2011 | DOI: 10.1002/pola.24549

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      The preparation of well-defined clickable glycopolymers by reversible addition fragmentation chain transfer (RAFT) polymerization was investigated. The polymerization behaviour of C-2 or C-6 azide-functionalized acrylamide-based glycomonomers and their azide-free analogue was compared. Examining the parameters affording a controlled/”living” status of the polymerization process provided an insight into the influence of the azide group and of the polymerization temperature.

    2. Photoactive liquid crystalline polymers: A comprehensive study of linear and hyperbranched polymers synthesized by A2B2, A2B3, A3B2, and A3B3 approaches (pages 1319–1330)

      V. Srinivasa Rao and A. B. Samui

      Article first published online: 18 JAN 2011 | DOI: 10.1002/pola.24550

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      The effect of different architectures on their thermal and photoresponsive properties were studied. All the polymers showed nematic droplets over a broad temperature range. The effect of architecture nature is highly considerable for both thermal and photoresponsive properties. The findings in photoresponsive properties were further supported by molecular modeling studies. Substantial variation of refractive index (0.015–0.024) indicates that these polymers could be used for optical recording.

    3. Soluble high-Tg polyetherimides with good flame retardancy based on an asymmetric phosphinated etherdiamine (pages 1331–1340)

      Ching Hsuan Lin, Sheng Lung Chang and Po Wen Cheng

      Article first published online: 20 JAN 2011 | DOI: 10.1002/pola.24552

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      An asymmetric phosphinated etherdiamine (3) was prepared. Based on (3), light colored, tough, and foldable polyetherimides (PEIs) with good thermal stability, good organo-solubility, and flame retardancy were prepared. Properties of the resulting PEIs were evaluated and compared with those of symmetric PEIs and polyimides. The structure–property relationship was discussed.

    4. Elaboration of densely functionalized polylactide nanoparticles from N-acryloxysuccinimide-based block copolymers (pages 1341–1350)

      Nadège Handké, Thomas Trimaille, Elsa Luciani, Marion Rollet, Thierry Delair, Bernard Verrier, Denis Bertin and Didier Gigmes

      Article first published online: 18 JAN 2011 | DOI: 10.1002/pola.24553

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      Well-defined poly(N-acryloxysuccinimide) (PNAS) and poly(N-acryloxysuccinimide-co-N-vinylpyrrolidone) (P(NAS-co-NVP)) were prepared by nitroxide-mediated polymerization in N,N-dimethylformamide in the presence of free SG1 with MAMA-SG1 alkoxyamine (BlocBuilder) as initiator. The reactivity ratios of NAS and NVP were determined to be rNAS = 0.12 and rNVP = 0, indicating a strong alternating tendency for the obtained copolymer. Then, poly(D,L-lactide)-b-P(NAS-co-NVP) was synthesized by NMP of NAS/NVP from a PLA-SG1 macro-alkoxyamine as initiator and used as surface modifier in the PLA nanoprecipitation or diafiltration process to achieve surface-functionalized and hydrophilic PLA nanoparticles of potential interest in drug delivery applications.

    5. Radical-induced oxidation of RAFT agents—A kinetic study (pages 1351–1360)

      Changxi Li, Junpo He, Yanwu Zhou, Yuankai Gu and Yuliang Yang

      Article first published online: 18 JAN 2011 | DOI: 10.1002/pola.24554

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      Thiocarbonylthio moieties are readily oxidized to carbonylthio groups in the presence of oxygen and a radical source.

    6. Synthesis of macrocyclic molecular brushes with amphiphilic block copolymers as side chains (pages 1361–1367)

      Xiaoshan Fan, Guowei Wang and Junlian Huang

      Article first published online: 2 FEB 2011 | DOI: 10.1002/pola.24555

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      Macrocyclic molecular brushes c-PHEMA-g-(PS-b-PEO) consisting of macrocyclic poly(2-hydroxylethyl methacrylate) as backbone and polystyrene-b-poly(ethylene oxide) amphiphilic block copolymers as side chains were synthesized by the combination of atom transfer radical polymerization, click chemistry, and single-electron transfer nitroxide radical coupling.

    7. Synthesis of dendronized polymers through bergman cyclization of enediyne-containing Frechet-type dendrimers (pages 1368–1375)

      Jianguo Ma, Xiaowei Ma, Sheng Deng, Fei Li and Aiguo Hu

      Article first published online: 18 JAN 2011 | DOI: 10.1002/pola.24556

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      Dendronized polymers with conjugated backbones were synthesized through Bergman cyclization of conically functionalized Frechet type dendrimers. The occurrence of Bergman cyclization and formation of conjugated backbone was confirmed via a variety of techniques including IR, NMR, UV-vis spectroscopy, and AFM.

    8. Synthesis and characterization of ABA-type amphiphilic tri-block copolymers through anionic polymerization using end functionalized poly(ethylene oxide) oligomers (pages 1376–1386)

      Palash Jyoti Das, Anil Barak, Yusuke Kawakami and Tharanikkarasu Kannan

      Article first published online: 2 FEB 2011 | DOI: 10.1002/pola.24558

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      As poly(ethylene oxide) anion cannot initiate hydrocarbon monomers, such as styrene, ABA-type amphiphilic tri-block copolymers like poly(styrene)-b-poly(ethylene oxide)-b-poly(styrene) tri-block copolymers cannot be synthesized through anionic polymerization. To overcome this, telechelic bromo terminated poly(ethylene oxide) was prepared and reacted with polystyrene anion, as a result, poly(styrene)-b-poly-(ethylene oxide)-b-poly(styrene) (PS-b-PEO-b-PS) tri-block copolymers were successfully prepared. Similarly, telechelic diphenylethylene terminated poly(ethylene oxide) was also prepared and used to synthesize PS-b-PEO-b-PS and poly(methyl methacrylate)-b-poly(ethylene oxide)-b-poly(methyl methacrylate) tri-block copolymers.

    9. Synthesis and helical properties of N-substituted p-benzamide random copolymers possessing chiral/achiral and (S)/(R) side chains (pages 1387–1395)

      Akihiro Yokoyama, Yuko Inagaki, Tomomi Ono and Tsutomu Yokozawa

      Article first published online: 18 JAN 2011 | DOI: 10.1002/pola.24559

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      Random copolymers with a poly(p-benzamide) backbone 13 were synthesized. Addition of a mixture of the two monomers and an initiator to a solution of LiHMDS all at once gave 1 and 3. On the other hand, synthesis of 2 required dropwise addition of the achiral monomer to a mixture of the chiral monomer, an initiator, and LiHMDS. The relationships between the CD signal intensity of 13 in chloroform and the monomer unit composition indicated the absence of cooperativity between the monomer units along these copolymers.

    10. Synthesis, characterization, and micellization studies of coil-rod-coil and ABA ruthenium(II) terpyridine assemblies with π-conjugated electron acceptor systems (pages 1396–1408)

      Florian Schlütter, Georges M. Pavlov, Jean-François Gohy, Andreas Winter, Andreas Wild, Martin D. Hager, Stephanie Hoeppener and Ulrich S. Schubert

      Article first published online: 18 JAN 2011 | DOI: 10.1002/pola.24560

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      The micellization of an amphiphilic metallo-supramolecular RuII triblock copolymer in aqueous solution was studied by dynamic light scattering, transmission electron microscopy, and analytical ultracentrifugation: good correlation of the hydrodynamic radii determined by these three independent techniques was observed. Applying velocity sedimentation experiments, the number of amphiphilic RuII ABA triblock copolymer molecules within individual micelles could be estimated.

    11. Side-chain ferrocene-containing (meth)acrylate polymers: Synthesis and properties (pages 1409–1420)

      Christopher G. Hardy, Lixia Ren, Tuedjo C. Tamboue and Chuanbing Tang

      Article first published online: 18 JAN 2011 | DOI: 10.1002/pola.24561

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      A series of ferrocene-containing (meth)acrylate monomers were prepared and polymerized via ATRP. The kinetic studies indicated that polymerization of most monomers followed a “controlled”/living manner. The polymerization rates were affected by the vinyl monomer structures and decreased with an increase of the linker length. The optical absorption, thermal properties, and electrochemical properties of polymers were characterized.

    1. Synthesis of main-chain poly(carbazole)s via CuAAC (pages 1421–1426)

      Zheng Chen, Daniel R. Dreyer, Zong-quan Wu, Kelly M. Wiggins, Zhenhua Jiang and Christopher W. Bielawski

      Article first published online: 24 JAN 2011 | DOI: 10.1002/pola.24563

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      The synthesis and characterization of a family of novel main-chain carbazole-containing polymers using copper-catalyzed azide-alkyne cycloaddition (CuAAC) chemistry is reported. The reactions were performed under mild conditions using readily available copper catalysts and ligands, which afforded polymeric products with Mws up to 18 kDa. The materials produced using this method were found to be thermally stable and highly emissive, suggesting they may find use in various organic-based emissive materials. The approach described offers practical advantages over other synthetic methods typically used to prepare main-chain carbazole-containing polymers, especially with regard to the lack of need for rigorously inert conditions and the absence of byproducts generated during polymerization.

  3. Articles

    1. Top of page
    2. Highlights
    3. Articles
    4. Articles
    5. Original Article
    6. Articles
    7. Rapid Communications
    8. Notes
    1. Synthesis and photovoltaic behaviors of narrow-band-gap π-conjugated polymers composed of dialkoxybenzodithiophene- and thiophene-based fused aromatic rings (pages 1427–1433)

      Kwang-hoi Lee, Ho-Jin Lee, Kazuhide Morino, Atsushi Sudo and Takeshi Endo

      Article first published online: 20 JAN 2011 | DOI: 10.1002/pola.24564

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      π-Conjugated polymers, PBDT-CNETT and PBDT-CNECPDT, were prepared by the Stille cross-coupling polymerization. The polymers exhibited very narrow band gaps of 1.39 and 1.13 eV for PBDT-CNETT and PBDT-CNECPDT, respectively. HOMO energy levels estimated by surface analyzer were −5.17 and −5.11 eV for PBDT-CNETT and PBDT-CNECPDT, respectively. The solar cells based on the new polymers were evaluated with the cell configuration of ITO/PEDOT-PSS/polymer:PC61BH/LiF/Al. The power conversion efficiencies of the solar cells based on the polymers were 1.57 and 0.161% for PBDT-CNETT and PBDT-CNECPDT, respectively.

    2. Synthesis of poly(2-furyloxirane) with high molecular weight and improved regioregularity using macrocyclic ether as a cocatalyst to potassium tert-butoxide (pages 1434–1442)

      Riting Su, Yusheng Qin, Lijun Qiao, Ji Li, Xiaojiang Zhao, Pixin Wang, Xianhong Wang and Fosong Wang

      Article first published online: 20 JAN 2011 | DOI: 10.1002/pola.24565

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      2-Furyloxirane (FO), a monomer from nonpetroleum route, was polymerized rapidly catalyzed by potassium tert-butoxide in the presence of macrocyclic ether, receiving PFO with raising molecular weight of 39.2 kg/mol and more regular regioregularity as H-T structure content of 70.6%. The resulted PFO has improved thermal performances.

  4. Original Article

    1. Top of page
    2. Highlights
    3. Articles
    4. Articles
    5. Original Article
    6. Articles
    7. Rapid Communications
    8. Notes
    1. Influence of electronic effects from bridging groups on synthetic reaction and thermally activated polymerization of bisphenol-based benzoxazines (pages 1443–1452)

      Xiaoying Wang, Feng Chen and Yi Gu

      Article first published online: 24 JAN 2011 | DOI: 10.1002/pola.24566

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      Six bis-benzoxazines based on bisphenols with different bridging groups, [BOND]C(CH3)2[BOND], [BOND]CH2[BOND], [BOND]O[BOND], [BOND]CO[BOND], [BOND]SO2[BOND], and single bond, were synthesized in toluene. Electron-withdrawing groups and electron-donating groups acted an opposite role both in the two reactions. Electron-withdrawing groups decreased the charge density of α-C of bisphenols, which increased the reaction energy barrier between [BOND]N[BOND](CH2[BOND]OH)2 and α-C resulting in lower monomer yield. In the stage of thermally activated polymerization, electron-withdrawing groups weakened C[BOND]O bond of benzoxazine, which was availed for initiation of polymerization and lowered the energy barrier and cure temperature.

  5. Articles

    1. Top of page
    2. Highlights
    3. Articles
    4. Articles
    5. Original Article
    6. Articles
    7. Rapid Communications
    8. Notes
    1. Design and synthesis of dithieno[3,2-b:2′3′-d]pyrrole-based conjugated polymers for photovoltaic applications: consensus between low bandgap and low HOMO energy level (pages 1453–1461)

      Min-Min Shi, Dan Deng, Lin Chen, Jun Ling, Lei Fu, Xiao-Lian Hu and Hong-Zheng Chen

      Article first published online: 2 FEB 2011 | DOI: 10.1002/pola.24567

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      Three conjugated polymers P1, P2, and P3 were designed for photovoltaic applications. Through the molecular modification of the electron-accepting (A) units, the extents of intrachain charge transfer from the electron-donating dithieno[3,2-b:2′3′-d]pyrrole (D) to different A moieties and aromaticity in the polymer backbone were finely tuned to obtain the most appropriate energy levels (both low bandgap and low-lying HOMO). The effectiveness of the above bandgap engineering was proved by the further photovoltaic study of the blends of P1P3 and PCBM.

    2. Copolymers of fluorene and thiophene with conjugated side chain for polymer solar cells: Effect of pendant acceptors (pages 1462–1470)

      Haijun Fan, Zhiguo Zhang, Yongfang Li and Xiaowei Zhan

      Article first published online: 24 JAN 2011 | DOI: 10.1002/pola.24568

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      Two new conjugated fluorene–thiophene copolymers with pendant acceptor cyanoacetate (P2) and malononitrile (P3) were synthesized. In comparison with P2, P3 exhibits stronger UV–vis absorption and higher hole mobility. Polymer solar cells based on P3:PC71BM exhibit a power conversion efficiency of 1.33% under AM 1.5, 100 mW cm−2, which is three times of that based on P2:PC71BM. The higher efficiency is attributed to the reduced phase separation scale in P3:PC71BM blend. The aggregate domain size in P3:PC71BM blend is 50 nm, much smaller than that in P2:PC71BM blend (200 nm).

    3. Synthesis of polynorbornene-poly(tert-butyl acrylate) nanoparticles with original morphologies by tandem ROMP and ATRP in microemulsion (pages 1471–1482)

      Minh Ngoc Nguyen, Sébastien-Jun Mougnier, Emmanuel Ibarboure and Valérie Heroguez

      Article first published online: 2 FEB 2011 | DOI: 10.1002/pola.24569

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      The tandem polymerizations of ROMP and ATRP have been successfully performed in microemulsion for preparing in situ polymer composite nanoparticles composed of PNB and PtBA. Homopolymer blend and graft-copolymer nanoparticles with different compositions were synthesized. DLS and TEM characterizations showed that spherical particles with size smaller than 50 nm have been prepared. The homopolymer blend particles had core-shell morphology (PNB core and PtBA shell). However, this morphology was only obtained for the graft-copolymer particles with high proportion of PtBA. Otherwise, a partial covering of the PNB core by PtBA shell was adopted at low proportion of PtBA.

    4. Synthesis of poly(tert-butyl methacrylate)-graft-poly(dimethylsiloxane) graft copolymers via reversible addition-fragmentation chain transfer polymerization (pages 1483–1493)

      Jiawei Li, Lingmin Yi, Heming Lin and Ruigang Hou

      Article first published online: 24 JAN 2011 | DOI: 10.1002/pola.24571

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      Well-defined poly(tert-butyl methacrylate)-graft-poly(dimethylsiloxane) (PtBuMA-g-PDMS) graft copolymers with homogeneous, gradient, or blocky branch spacing were synthesized via the RAFT copolymerization of methacryloyl-terminated poly(dimethylsiloxane) (PDMS-MA) with tert-butyl methacrylate (tBuMA) in ethyl acetate, using 2,2″-azobis(isobutyronitrile) (AIBN) as the initiator and 2-cyanoprop-2-yl dithiobenzoate (CPDB) as the RAFT agent. The arrangement of monomer units in copolymer chains could be controlled by the way of RAFT statistical or block copolymerization.

    5. Narrow disperse polymers using amine functionalized dithiobenzoate RAFT agent and easy removal of thiocarbonyl end group from the resultant polymers (pages 1494–1502)

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

      Article first published online: 24 JAN 2011 | DOI: 10.1002/pola.24572

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      A novel amine functionalized dithiobenzoate RAFT agent has been synthesized and utilized to control the polymerization of vinyl monomers. This amine functionalized RAFT agent controls the polymerization of MMA and St very well and simplifies the removal procedure of the thiocarbonyl end group from the polymer produced.

  6. Rapid Communications

    1. Top of page
    2. Highlights
    3. Articles
    4. Articles
    5. Original Article
    6. Articles
    7. Rapid Communications
    8. Notes
    1. A solid homogeneous zirconocene catalyst from Cp2ZrCl2 supported on porous polymer particles (pages 1503–1507)

      Jinhua Lei, Dongliang Li, Honghua Wang, Zhuqian Wang and Guangyuan Zhou

      Article first published online: 24 JAN 2011 | DOI: 10.1002/pola.24570

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      We have successfully prepared a porous polymer supported zirconocene. Such catalyst system disintergrated gradually as the polymerization proceed and performed as a solid homogeneous zirconocene. The potential value of this result is great, on the one hand, the porous polymer supported metallocene meets the requirements of polymerization process; on the other hand, it preserves the homogeneous characteristic of the Zr active sites and maintains the advantages of a homogeneous zirconocene.

  7. Notes

    1. Top of page
    2. Highlights
    3. Articles
    4. Articles
    5. Original Article
    6. Articles
    7. Rapid Communications
    8. Notes
    1. You have free access to this content
      Bithiophene–bithiazole alternating copolymers with thiophene side chains: Synthesis by organometallic polycondensation and chemical properties of the copolymers (pages 1508–1512)

      Takakazu Yamamoto, Syun-Ichi Otsuka, Hiroki Fukumoto, Yoshimasa Sakai, Shinji Aramaki, Takashi Fukuda, Akira Emoto and Hirobumi Ushijima

      Article first published online: 18 JAN 2011 | DOI: 10.1002/pola.24557

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      New bithiophene–bithiazole alternating copolymers with thiophene side chains at the bithiazole unit have been prepared. The copolymers show a strong tendency to self-assemble and align on the surface of substrates, similarly to related copolymers with alkyl side chains at the bithiazole unit.

    2. You have free access to this content
      A new end group structure of poly(ethylene glycol) for hydrolysis-resistant biomaterials (pages 1513–1516)

      Xinming Tong, Jingjing Lai, Bao-Hua Guo and Yanbin Huang

      Article first published online: 20 JAN 2011 | DOI: 10.1002/pola.24562

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      A new PEG end-group structure (α-PEG-MA) was designed and synthesized. When compared with the conventionally used PEG-acrylate structure, the vinyl group in the new structure showed comparable reactivity in thiol-ene reactions, but the formed materials were hydrolysis resistant because there is no ester linkage in the backbone chains.

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