Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 46 Issue 5

1 March 2008

Volume 46, Issue 5

Pages 1533–1923

  1. Original Articles

    1. Top of page
    2. Original Articles
    3. Articles
    4. Original Articles
    5. Articles
    6. Original Articles
    7. Articles
    8. Rapid Communications
    9. Notes
    1. Divergent synthesis and self-assembly of amphiphilic polymeric dendrons with selective degradable linkages (pages 1533–1547)

      Carl N. Urbani, Daria E. Lonsdale, Craig A. Bell, Michael R. Whittaker and Michael J. Monteiro

      Article first published online: 22 JAN 2008 | DOI: 10.1002/pola.22528

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      In this work, we demonstrate a strategy for the design and synthesis of complex macromolecular architectures. We use ATRP to produce well-defined polymers with telechelic end-group functionality, and “click” them together to form functional 3rd generation dendrons, and incorporated degradable linkages and certain functionality at the polymer chain-ends of each generation. The 3rd generation polymeric dendrons consisted of homopolymer polystyrene with either four solketals or eight alcohols, diblock polystyrene and poly(t-butyl acrylate), and amphiphilic diblock. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    2. Two novel oligomers based on fluorene and pyridine: Correlation between the structures and optoelectronic properties (pages 1548–1558)

      Hong-Ji Jiang, Hong-Yu Wang, Rui Zhu, Jun-Hua Wan, Feng Liu, Jia-Chun Feng, Wei Wei and Wei Huang

      Article first published online: 22 JAN 2008 | DOI: 10.1002/pola.22311

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      To investigate the fine optoelectronic difference of the target oligomers with or without peripheral fluorene moieties, two dumbbell-shaped oligomers (F0 and F1) were designed and convergently prepared via Suzuki coupling reaction. The molecular structures of the oligomers were fully characterized by 1H NMR, 13C NMR, and MALDI-TOF mass spectra, respectively. The absorption, photoluminescent behavior and energy band gaps of the oligomers were examined through UV-vis, photoluminescent spectra and cyclic voltammetry. The experimental results demonstrate that the absorption and photoluminescent properties are little affected by molecular architecture, while the absolute photoluminescence quantum efficiency of films and energy band gaps derived from cyclic voltammetry in solution are strongly correlated with the molecular frameworks. The observed energy band gaps of oligomers are further validated by the different molecular orbital contours of the HOMO energy levels from theoretical calculations. Preliminary electroluminescent investigations for F1 have also been conducted and discussed.

    3. Penultimate effect in radical copolymerization of 2-trifluoromethylacrylates (pages 1559–1565)

      Hiroshi Ito, Brian C. Trinque, Paul Kasai and C. Grant Willson

      Article first published online: 22 JAN 2008 | DOI: 10.1002/pola.22467

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      When the penultimate group R is methyl, t-butyl 2-trifluoromethylacrylate (TBTFMA) reacts with the radical generated by reducing n-butylmercuric chloride with sodium borohydride 24 times faster than t-butyl methacrylate (TBMA). The former is about 12 times more reactive than the latter toward the 4,4,4-trifluorobutyl radical. Thus, the reactivity of the propagating radical toward TBTFMA in comparison with TBMA is suppressed by a factor of two when the penultimate unit has the CF3 group. This result supports the penultimate effect observed in radical copolymerization of TBTFMA with norbornenes, vinyl ethers, and a substituted styrene.

    4. Synthesis, characterization, and electroluminescence of PPV copolymers containing electron and hole-transporting units (pages 1566–1576)

      Shidi Xun, Quanguo Zhou, Hongchao Li, Dongge Ma, Lixiang Wang, Xiabin Jing and Fosong Wang

      Article first published online: 22 JAN 2008 | DOI: 10.1002/pola.22489

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      Three series of PPV copolymers containing hole-transporting triphenylamine derivatives (donor) and electron-transporting oxadiazole unit (acceptor) were synthesized by improved Wittig polymerization. The intramolecular charge-transfer was observed in these D-A polymers. The balanced charge injection and transport could be achieved by tuning the content of oxadiazole moiety in the polymer. In comparison with corresponding polymers without oxadiazole unit, the single-layer devices based on the D-A polymers showed much improved electroluminescent (EL)properties.

    5. Nanometer-scale surface modification by polymerization of tetrafluoroethylene on polymer substrates in supercritical fluoroform (pages 1577–1585)

      Toshiaki Mori, Kanehira Imai, Mirei Hasegawa and Yoshio Okahata

      Article first published online: 22 JAN 2008 | DOI: 10.1002/pola.22494

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      Tetrafluoroethylene (TFE) was penetrated and photo-polymerized into polymer plates in supercritical fluoroform (scCHF3). [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    6. Synthesis and ion-sensing phenomena of two new helical conjugated oligomers containing 1,10-phenanthroline and oligo-alkylthiophene (pages 1586–1597)

      Chun-Guey Wu, Hung-Chieh Lu, Liang-Nien Chen and Yung-Chou Lin

      Article first published online: 22 JAN 2008 | DOI: 10.1002/pola.22495

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      1,10-phenanthroline (Phen)-containing conjugated molecules are good luminescence ion sensors. The distinguish responses toward metal ions of the monomers and their corresponding oligomers, suggested that the ionochromic responses were determined by not only the coordinating ability of Phen unit but also the conformation of the oligomer chains. The different ion sensing ability between thiophene-substituted and bisthiophene-substituted phenanthroline also indicated that the coordination ability of Phen moiety also depends on its substituents. These findings provide a new clue for designing (or fine-tuning) Phen-containing (or other luminescent conjugated polymer) ion-sensors for specified applications. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    7. Dimer effect on fractional polycondensation of poly(p-oxybenzoyl) (pages 1598–1606)

      Kunio Kimura, Yasuo Shimizu, Toshimitsu Ichimori, Shin-ichiro Kohama, Shinichi Yamazaki and Yuhiko Yamashita

      Article first published online: 22 JAN 2008 | DOI: 10.1002/pola.22496

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      Selective preparation of poly(p-oxybenzoyl) (POB) crystals was examined from the viewpoint of dimer effect on fractional polycondensation. The selectivity was enhanced by the fractional polycondensation of the dimer of p-acetoxybenzoic acid (p-ABA) and rn-acetoxybenzoic acid (m-ABA) compared with that of p-ABA and m-ABA. The precipitated crystals contained only about 3 mol % of m-oxybenzoyl moiety even at the content of rn-oxybenzoyl moiety in feed of 40 mol %. Dimer effect was clearly observed on the fractionability.

  2. Articles

    1. Top of page
    2. Original Articles
    3. Articles
    4. Original Articles
    5. Articles
    6. Original Articles
    7. Articles
    8. Rapid Communications
    9. Notes
    1. Poly(4-acryloylmorpholine) oligomers carrying a β-cyclodextrin residue at one terminus (pages 1607–1617)

      Marco Bencini, Elisabetta Ranucci, Paolo Ferruti, Amedea Manfredi, Francesco Trotta and Roberta Cavalli

      Article first published online: 24 JAN 2008 | DOI: 10.1002/pola.22497

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      4-Acryloylmorpholine oligomers carrying a β-cyclodextrin residue at one terminus were obtained by radical polymerization of 4-acryloylmorpholine in the presence of 6-deoxy-6-mercapto-β-cyclodextrin. These “tadpole-like” oligomers are highly soluble in water and in several organic solvents such as chloroform. They are capable of solubilizing in water 10-15 g/L of the poorly soluble antiviral drug Acyclovir slowly releasing it with a regular pattern.

  3. Original Articles

    1. Top of page
    2. Original Articles
    3. Articles
    4. Original Articles
    5. Articles
    6. Original Articles
    7. Articles
    8. Rapid Communications
    9. Notes
    1. Synthesis and characterization of a series of 2-aminopyridine nickel(II) complexes and their catalytic properties toward ethylene polymerization (pages 1618–1628)

      Zengfang Huang, Keming Song, Fengshou Liu, Jieming Long, Hao Hu, Haiyang Gao and Qing Wu

      Article first published online: 22 JAN 2008 | DOI: 10.1002/pola.22499

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      2-Aminopyridine nickel(II) complexes/MAO catalyzing ethylene polymerization produced the branched polymers with a quantity of oligomers. Enhancing the steric bulk of the ortho-aryl-substituent of the complex resulted in higher ratio of solid polymer to oligomer and higher molecular weight of the polymer. With ortho-haloid-substitution, the catalysts afforded a product with low polymer/oligomer ratio and even only oligomers.

    2. Living cationic polymerization of 2-adamantyl vinyl ether (pages 1629–1637)

      Tamotsu Hashimoto, Yusuke Makino, Michio Urushisaki and Toshikazu Sakaguchi

      Article first published online: 22 JAN 2008 | DOI: 10.1002/pola.22502

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      Living cationic polymerization of 2-adamantyl vinyl ether (2-vinyloxytricyclo[3.3.1.1]3,7decane; 2-AdVE) was achieved with the CH3CH(OiBu)OCOCH3/Et1.5AlCl1.5/CH3COOEt initiating system in toluene at 0°C to give the polymers with narrow molecular weight distributions (Mw/Mn = ∼1.1). The Poly(2-AdVE)s exhibited high grass transition temperature (Tg) and high thermal stability (decomposition temperature, Td).

    3. Palladium-mediated polymerization of cyclic diazoketones (pages 1638–1648)

      Eiji Ihara, Toshimitsu Hiraren, Tomomichi Itoh and Kenzo Inoue

      Article first published online: 22 JAN 2008 | DOI: 10.1002/pola.22504

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      Palladium-mediated polymerization of cyclic diazoketones was investigated. Although cyclic diazoketones 1a,b derived from cyclohexanone and 1-tetralone did not homopolymerize, they can be used as a comonomer for copolymerization with polymerizable acyclic diazoketones. On the other hand, an α,β-unsaturated cyclic diazoketone 2a prepared from 2-cyclohexen-1-one polymerized to give a polymer poly2a′ with Mn = 1400 in a 23.8% yield. Addition of some nucleophiles to C[DOUBLE BOND]C bond in poly2a′ was carried out. Copolymerization of 2a and its dimethyl-substituted analogues 2b,c with acyclic diazoketones was also investigated.

    4. Synthesis of poly(isobornyl acrylate) containing copolymers by atom transfer radical polymerization (pages 1649–1661)

      Bart Dervaux, Wim Van Camp, Lieven Van Renterghem and Filip E. Du Prez

      Article first published online: 22 JAN 2008 | DOI: 10.1002/pola.22505

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      Atom transfer radical polymerization has been used to prepare novel amphiphilic block and “block-like” copolymers containing poly(isobornyl acrylate) (PiBA) and poly(acrylic acid) (PAA) segments. The use of 1-ethoxyethyl acrylate (EEA) as the precursor monomer resulted in well-defined PiBA-PAA containing copolymers after thermolysis of the PEEA precursor segment.

    5. Synthesis of highly conductive EDOT copolymer films via oxidative chemical in situ polymerization (pages 1662–1673)

      Jui Hung Chen, Chi-An Dai and Wen-Yen Chiu

      Article first published online: 22 JAN 2008 | DOI: 10.1002/pola.22508

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      When TEBS/EDOT mole ratio was raised from 0 to 0.2, the conductivity was increased from 33.7 to 170 S/cm. When the molar ratio of TEBS to EDOT was further increased, the conductivities of the copolymer films start decreasing. The experimental results showed that TEBS monomer cannot dissolved in methanol completely when TEBS/EDOT molar ratio exceeded 0.67 which was disadvantageous for the copolymerization. It was observed that conductivity was highest when TEBS/EDOT molar ratio equals 0.2.

    6. Synthesis and properties of porous polyvinylamine microspheres from acrylonitrile (pages 1674–1682)

      Xin Hou, Dongge Huang, Xiaomin Chen, Zheguo Zhang and Kangde Yao

      Article first published online: 22 JAN 2008 | DOI: 10.1002/pola.22509

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      A novel route to synthesize crosslinked porous polyvinylamine (PVAm) microspheres from acrylonitrile (AN) was developed. In the first step, crosslinked porous polyacrylonitrile (PAN) spheres were prepared by copolymerization of AN and divinylbenzene (DVB). Then they were hydrolyzed to form polyacrylamide (PAM) spheres under acidic condition. And lastly, the porous PVAm spheres were successfully obtained via Hofmann degradation of PAM spheres.

    7. Functionalization and molecular dynamics study of carboxy-terminated poly(1-vinylpyrrolidin-2-one): A potential soluble carrier of biomolecules (pages 1683–1698)

      Clara Baldoli, Claudio Oldani, Stefano Maiorana, Paolo Ferruti, Elisabetta Ranucci, Marco Bencini and Alessandro Contini

      Article first published online: 22 JAN 2008 | DOI: 10.1002/pola.22510

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      The reactivity of carboxy-terminated poly(1-vinylpyrrolidin-2-one) (PVP-COOH) 40-mers with various small bi-functionalized molecules was investigated with the aim of widening the potential of end-carboxylated PVP as soluble carrier. A number of new differently functionalized PVP oligomers have been successfully obtained which proved amenable to coupling reactions with a number of model compounds, including for instance reduced glutathione. A molecular dynamics conformational study of PVP-COOH demonstrated that in solution the carboxyl group is not buried inside the coil, but well exposed to the solvent, thus explaining the good reactivity shown by experiments. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

  4. Articles

    1. Top of page
    2. Original Articles
    3. Articles
    4. Original Articles
    5. Articles
    6. Original Articles
    7. Articles
    8. Rapid Communications
    9. Notes
    1. Facile synthesis of core-shell organic–inorganic hybrid nanoparticles with amphiphilic polymer shell by one-step sol–gel reactions (pages 1699–1709)

      M. Marini, M. Toselli, S. Borsacchi, G. Mollica, M. Geppi and F. Pilati

      Article first published online: 24 JAN 2008 | DOI: 10.1002/pola.22511

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      Organic–inorganic hybrid core-shell nanoparticles with an inorganic-rich core and an external tapered shell composition, ranging from highly hydrophilic close to the silica surface to completely lipophilic in the very outer surface, were prepared by a one-step synthesis based on sol–gel reactions. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

  5. Original Articles

    1. Top of page
    2. Original Articles
    3. Articles
    4. Original Articles
    5. Articles
    6. Original Articles
    7. Articles
    8. Rapid Communications
    9. Notes
    1. Synthesis and dielectric properties of photoreactive polystyrene containing [1-(3-isopropenyl-phenyl)-1-methyl-ethyl]-carbamate in the side chain (pages 1710–1718)

      Ju Hee Kim, Kyung Hwan Kim, Min Ju Cho, Jung-Il Jin, Dong Hoon Choi, Gun Woo Hyung and Young Kwan Kim

      Article first published online: 22 JAN 2008 | DOI: 10.1002/pola.22512

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      Novel polystyrene derivatives comprising [1-(3-isopropenyl-phenyl)-1-methyl-ethyl]-carbamate in the side chain were synthesized as photoreactive copolymers. The copolymers are highly sensitive to the radical photoinitiators that can be activated by irradiation of UV light (λ = 300–365 nm). The dielectric constant was determined to be in the range of 4.2–6.0, which offers a potential for the application of these copolymers to OFET gate insulators. These soluble dielectrics exhibit good film uniformity and can also be patterned using a standard photolithographic technique. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    2. Sonochemical immobilization of silver nanoparticles on porous polypropylene (pages 1719–1729)

      Nina Perkas, Michael Shuster, Galina Amirian, Yuri Koltypin and Aharon Gedanken

      Article first published online: 22 JAN 2008 | DOI: 10.1002/pola.22513

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      Silver nanoparticles were deposited on solid-state porous polypropylene by a simple ultrasound-assisted method. Using water-soluble polymers, PEG, PVA, and PVP, as stabilizing agents, a highly homogeneous distribution of nanosilver on the propylene was achieved. The microjets formed as a result of sonochemical cavitation provide the strong adhesion of nanoparticles to the surface of the polymer. The Ag-PP composite demonstrated good stability and high antibacterial activity.

  6. Articles

    1. Top of page
    2. Original Articles
    3. Articles
    4. Original Articles
    5. Articles
    6. Original Articles
    7. Articles
    8. Rapid Communications
    9. Notes
    1. Confined space regulated polymerization (pages 1730–1737)

      Ye-Zi You and Cai-Yuan Pan

      Article first published online: 24 JAN 2008 | DOI: 10.1002/pola.22514

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      The condensation polymerization of A2+B3 in a confined space produced hyperbranched polymer because of which the reactions between two branched macromolecules are effectively suppressed. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    2. Precise control of microstructure of functionalized polypropylene synthesized by the ansa-zirconocene/ MAO catalysts (pages 1738–1748)

      Hideaki Hagihara, Takeshi Ishihara, Hoang The Ban and Takeshi Shiono

      Article first published online: 24 JAN 2008 | DOI: 10.1002/pola.22516

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      We investigated the polymerization behavior and the structure of copolymer obtained in the copolymerization of propylene and alkylaluminum-protected polar allyl derivatives. It was found that the location of polar group in the copolymer could be controlled by zirconocene catalyst and a kind of polar group. The indenyl or the 2-methylindenyl ligands of zirconocene were favored to produce end-functionalized polymers. On the other hand, the 2-methyl-4-phenylindenyl ligand produced the copolymers containing both the end-polar unit and inner-polar unit at the polymer chains. Terpolymerization of propylene, polar allyl monomer, and 5-hexen-1-ol was also conducted.

    3. Permeability control in electro-sensitive microcapsules with immobilized ferroelectric liquid crystalline segments (pages 1749–1757)

      Masahiro Yoshida, Tsutomu Matsui, Yasuo Hatate, Takayuki Takei, Koichiro Shiomori and Shiro Kiyoyama

      Article first published online: 24 JAN 2008 | DOI: 10.1002/pola.22517

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      Nylon-polystyrene microcapsules with immobilized ferroelectric liquid crystalline segments were prepared, and permeability control of an encapsulated core material was investigated under an external electric field. A ferroelectric liquid crystal monomer possessing both mesogenicity and chirality responded effectively to the external electrical field. Permeation of the material (oxprenolol) contained in the inner aqueous core of the microcapsules was enhanced under a weak electric field (2 V). Furthermore, the permeability of oxprenolol did not depend on the external electric field in the absence of the ferroelectric liquid crystal segments. To clarify the controlled release mechanism of the core material, the light transmittance of the polymer membranes was quantitatively evaluated under an external electric field using a handmade polarized light transmittance apparatus.

    4. Synthesis and characterization of sulfonated poly(phthalazinone ether phosphine oxide)s by direct polycondensation for proton exchange membranes (pages 1758–1769)

      Xuhui Ma, Chunjie Zhang, Guyu Xiao, Deyue Yan and Guoming Sun

      Article first published online: 24 JAN 2008 | DOI: 10.1002/pola.22519

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      A series of sulfonated poly(phthalazinone ether phosphine oxide)s (sPPEPO) were prepared via aromatic nucleophilic substitution polycondensation of 4-(4-hydroxyphenyl) phthalazinone with sulfonated bis(4-fluorophenyl)phenyl phosphine oxide and bis(4-fluorophenyl)phenyl phosphine oxide at various ratios. The properties such as molecular weight, ion exchange capacity (IEC), swelling, thermal stability, proton conductivity, and morphology were investigated. sPPEPO with high IEC exhibited high proton conductivity while they still showed low swelling. The low swelling was attributed to the strong intermolecular interaction including the electrostatic force and hydrogen bond. sPPEPO would be promising candidates used as proton exchange membranes.

    5. The synthesis and characterization of new thermoplastic poly(thiourethane-urethane)s (pages 1770–1782)

      Anna Kultys, Magdalena Rogulska and Stanisław Pikus

      Article first published online: 24 JAN 2008 | DOI: 10.1002/pola.22520

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      Two series of novel thermoplastic segmented poly(thiourethane-urethane)s (SPTUUs) were derived from bis[4-(mercaptomethyl)phenyl]methanone as a new aliphatic-aromatic dithiol chain extender, HDI, and 20–80 mol % polyether or polycarbonate diols as soft segments, i.e., poly(tetramethylene oxide) of Mn = 1000 or poly(hexamethylene carbonate) diol of Mn = 860, respectively. The structures of the SPTUUs were examined by FTIR, X-ray diffraction analysis, and scanning electron microscopy. The SPTUUs were also characterized by physicochemical, thermal, and tensile properties as well as Shore A/D hardness. Because the structure of the newly obtained SPTUUs incorporates sulfur atoms, they can exhibit improved biodegradability, adhesive properties, and refractive index.

    6. Synthesis and photorefractivity of poly[methyl-3-(7-dibenzo[a,g]carbazolyl)-propylsiloxane] (pages 1783–1791)

      In Kyu Moon, Chil-Sung Choi and Nakjoong Kim

      Article first published online: 24 JAN 2008 | DOI: 10.1002/pola.22521

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      The 7H-dibenzo[a,g]carbazole-substituted polysiloxane containing 30 wt % NLO chromophore showed a diffraction efficiency of 51% at 55 V/μm and a photorefractive response time constant of 0.42 s at 34 °C, which corresponded to the space-charge field of 12 V/μm under 70 V/μm.

    7. Preparation and characterization of branched and linear sulfonated poly(ether ketone sulfone) proton exchange membranes for fuel cell applications (pages 1792–1799)

      Hye Seok Park, Dong Wan Seo, Seung Woo Choi, Young Gi Jeong, Ju Ho Lee, Dong Il Kim and Whan-Gi Kim

      Article first published online: 25 JAN 2008 | DOI: 10.1002/pola.22522

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      Branched sulfonated poly(ether ketone sulfone)s (Br-SPEKS) were prepared with bisphenol A, bis(4-fluorophenyl)sulfone, 3,3′-disodiumsulfonyl-4,4′-difluorobenzophenone, and THPE (1,1,1-tris-p-hydroxyphenylethane), respectively using potassium carbonate in NMP (N-methylpyrrolidinone). THPE, as a branching agent, was used with 0.4 mol % of bisphenol A to synthesize branched copolymers. Copolymers containing 10–50 mol % disulfonated units were cast from dimethylsulfoxide solutions to form films. A series of copolymers were studied by FT-IR, 1H-NMR spectroscopy, differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). The synthesized Br-SPEKS and SPEKS membranes exhibit conductivities (25 °C) from 1.04 × 10−3 to 4.32 × 10−3 S/cm, water swell from 20.18 to 62.35%, IEC from 0.24 to 0.83 meq/g and methanol diffusion coefficients from 3.2 × 10−7 to 4.7 × 10−7 cm2/S at 25 °C.

    8. Studies on the conducting nanocomposite prepared by in situ polymerization of aniline monomers in a neat (aqueous) synthetic mica clay (pages 1800–1809)

      Chia-Sheng Wu, Ying-Jie Huang, Tar-Hwa Hsieh, Ping-Tsung Huang, Bi-Zen Hsieh, Yu-Kai Han and Ko-Shan Ho

      Article first published online: 25 JAN 2008 | DOI: 10.1002/pola.22523

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      The in situ polymerizing the anilinium-swollen synthetic mica clay spontaneously resulted in an intercalation of polyaniline inside the clay into a nanocomposite. The FT-IR spectra demonstrated a significant shift at 1292 cm−1 of the templated polymerized and intercalated polyaniline molecules. A red shift of λmax for polyaniline was found from UV–vis spectra. The intercalated polyaniline also expanded the clay basal spacing seen from WAXD patterns. The degradation rate and temperature were found to alleviate and increase compared to neat polyaniline, respectively. The microscopic examinations demonstrated an entirely different and more compatible morphology. Conductivity of nanocomposite gradually increased with polyaniline was found. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    9. Thermoreversible covalent crosslinking of maleated ethylene/propylene copolymers with diols (pages 1810–1825)

      M. A. J. van der Mee, J. G. P. Goossens and M. van Duin

      Article first published online: 25 JAN 2008 | DOI: 10.1002/pola.22524

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      The thermoreversible crosslinking of maleated ethylene/propylene copolymer (MAn-g-EPM) was studied using the equilibrium reaction with diols. Covalent hemi-ester crosslinks are formed via the reaction of anhydrides with alcohols, while an equilibrium shift at elevated temperatures may result in their removal. High conversions to hemi-ester are obtained at low temperatures, whereas conversions are low at high temperatures. The covalent crosslinks were only formed within aggregates. The properties were significantly improved upon increasing level of crosslinking. The reprocessability does not originate from an equilibrium shift, but from a dynamic exchange between crosslinked and non-crosslinked functional groups.

    10. Well-defined complex macromolecular architectures by anionic polymerization of styrenic single and double homo/miktoarm star-tailed macromonomers (pages 1826–1842)

      Paraskevi Driva, David J. Lohse and Nikos Hadjichristidis

      Article first published online: 25 JAN 2008 | DOI: 10.1002/pola.22527

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      Styrenic single and double star-tailed macromonomers were synthesized by selective reaction of living homo/miktoarm stars with the chlorosilane groups of 4-(chlorodimethylsilyl)- and 4-(dichloromethylsilyl)styrene, respectively. The in situ anionic homopolymerization of macromonomers with sec-BuLi and copolymerization with butadiene and styrene, led to single/double homo/miktoarm star-tailed molecular brushes and combs, as well as a block copolymer consisting of a linear polystyrene chain and a double miktoarm (PBd/PS) star-tailed brush-like block. These are only a few examples of the plethora of the possible complex architectures that one could imagine synthesizing using the above macromonomers. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    11. Single layer light-emitting diodes from copolymers comprised of mesogen-jacketed polymer containing oxadiazole units and PVK (pages 1843–1851)

      Ping Wang, Chunpeng Chai, Fuzhi Wang, Yutao Chuai, Xiaofang Chen, Xinghe Fan, Dechun Zou and Qifeng Zhou

      Article first published online: 25 JAN 2008 | DOI: 10.1002/pola.22529

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      A series of copolymers PCt-co-Poly(N-vinylcarbazole) were synthesized through common radical polymerization, in which P-Ct as a kind of mesogen-jacketed liquid crystalline polymer was introduced, and the effects of copolymers composing variation on the optical properties of the copolymers were studied. Single-layer LEDs with the configuration of ITO/PEDOT/PCt-nvk/Mg:Ag/Ag were fabricated, in which PCt-nvk8 emit a blue light of 443 and 492 nm with the maximum luminance of 703 cd/m2. The device performance varies with the device configurations, with device configuration (b) giving the best value of external quantum efficiency of 0.27%. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    12. Novel aliphatic poly(ester-carbonate) with pendant allyl ester groups and its folic acid functionalization (pages 1852–1861)

      Xiuli Hu, Xuesi Chen, Shi Liu, Quan Shi and Xiabin Jing

      Article first published online: 25 JAN 2008 | DOI: 10.1002/pola.22530

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      Ring-opening copolymerization of L-lactide (LA) and allylated cyclic carbonate, 5-methyl-5-allyloxycarbonyl-1,3-dioxan-2-one (MAC) led to a random copolymer P(LA-co-MAC). The allyl groups were further connected with folic acid via 2-aminoethanethiol. Incorporation of FA as side chains of the copolymer improved cell affinity, showing enhanced cell adhesion, spreading and proliferation, indicating the potential of the FA-grafted copolymer for drug delivery or tissue engineering.

    13. Multifunctional materials based on polyazomethines derived from 2,5-dihydroxy-1,4-benzoquinone and siloxane diamines (pages 1862–1872)

      Maria Cazacu, Angelica Vlad, Grigore Munteanu and Anton Airinei

      Article first published online: 25 JAN 2008 | DOI: 10.1002/pola.22531

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      New polyazomethines containing siloxane units and 2,5-dihydroxy-1,4-benzoquinoneimine alternating moieties along the chains have been synthesized and characterized. Some properties (spectral, thermal, redox) have been investigated. The polyazomethines proved also to be pH sensitive and having metal complexing ability. All these properties are in dependence on the siloxane sequence length.

    14. Living star polymer formation (RAFT) studied via electrospray ionization mass spectrometry (pages 1873–1892)

      Hugh Chaffey-Millar, Gene Hart-Smith and Christopher Barner-Kowollik

      Article first published online: 25 JAN 2008 | DOI: 10.1002/pola.22562

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      A mass spectrometry analysis has been performed on complex architecture polymeric material produced during reversibleaddition fragmentation chain transfer (RAFT) polymerizations yielding star polymers.

  7. Rapid Communications

    1. Top of page
    2. Original Articles
    3. Articles
    4. Original Articles
    5. Articles
    6. Original Articles
    7. Articles
    8. Rapid Communications
    9. Notes
    1. Poly(tetramethylene ether) glycol containing acetal linkages: New PTMG-based polyol for chemically recyclable polyurethane thermoplastic elastomer (pages 1893–1901)

      Tamotsu Hashimoto, Hiroaki Mori and Michio Urushisaki

      Article first published online: 28 JAN 2008 | DOI: 10.1002/pola.22501

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      To develop new chemically recyclable polyurethane elastomers, the poly(tetramethylene ether) glycol (PTMG) containing acetal linkages (PTMG-Acetal-OH) was prepared and subjected to the polyurethane synthesis with 4,4(-diphenylmethane diisocyanate (MDI) and 1,4-butanediol (BD; chain-extender). The obtained polyurethane (PTMG-Acetal-PU) shows very similar mechanical and thermal properties to those of the conventional PTMG-based thermoplastic polyurethane elastomers (PTMG-PU). The acid treatment of PTMG-Acetal-PU at room temperature caused hydrolysis reaction of their acetal units to regenerate PTMG as a degradation product.

    2. Synthesis and microphase-separated structure of poly(tricyclodecyl vinyl ether)-block-poly(n-butyl vinyl ether)-block-poly(tricyclodecyl vinyl ether): New triblock copolymer as thermoplastic elastomer composed solely of poly(vinyl ether) backbones (pages 1902–1906)

      Tamotsu Hashimoto, Takeshi Namikoshi, Satoshi Irie, Michio Urushisaki, Toshikazu Sakaguchi, Takashi Nemoto and Seiji Isoda

      Article first published online: 28 JAN 2008 | DOI: 10.1002/pola.22503

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      The sequential living cationic polymerization of 8-vinyloxytricyclo[5.2.1.02, 6]decane (TCDVE) and n-butyl vinyl ether (NBVE) afforded the A-B-A type triblock copolymer, poly(TCDVE)-block-poly(NBVE)-block-poly(TCDVE). Although composed solely of poly- (vinyl ether) main chains, the triblock copolymer formed a thermoplastic elastomer with microphase-separated structure. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    3. Syntheses of bisphenol-type oligomers having five-membered dithiocarbonate groups at the terminals and their application as accelerators to epoxy-amine curing system (pages 1907–1912)

      Yuan Zhang, Atsushi Sudo and Takeshi Endo

      Article first published online: 28 JAN 2008 | DOI: 10.1002/pola.22506

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      A series of oligo(bisphenol A-co-epichlorohydrin)-derivatives having dithiocarbonate moiety at terminals and substituted groups at side chains were synthesized and applied as additives in an epoxy-amine curing system to investigate their acceleration effects based on comparing the influences ascribed to substituted groups of the side chain. Good acceleration effects of these compounds were clarified as coming from the reactive group of dithiocarbonate primarily. The polar side chains such as hydroxyl group and phenyl urethane group of these oligomer-type additives also exhibited remarkable acceleration effects contrasting with the less polar side chains such as THP or cyclohexyl urethane groups. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    4. Facile metal-free living cationic polymerization of various vinyl ethers by hydrogen chloride with ether (pages 1913–1918)

      Shinji Sugihara, Yasuaki Tanabe, Masaru Kitagawa and Isao Ikeda

      Article first published online: 28 JAN 2008 | DOI: 10.1002/pola.22515

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      Useful metal-free living cationic polymerization of various vinyl ethers by hydrogen chloride with ether was found for the first time. This system is facile polymerization using not HCl/Lewis acid but HCl alone in ether (Et2O) without Lewis acid. The molecular weights of the obtained polymers can be controlled with the feed ratio of the monomer and HCl. Furthermore, after-treatment can be easily carried out, because the system is inherently free from contaminants from metal catalyst residues. The living polymerization also can be achieved at relatively higher temperature for cationic polymerization. The key to success of living cationic polymerization in the system is using HCl·Et2O and controlling the polymerization temperature.

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      Statistical copolymers of 2-(trimethylsilyloxy)ethyl methacrylate and methyl methacrylate synthesized by ATRP (pages 1919–1923)

      Pavel Ritz, Petra Látalová, Jaroslav Kříž, Jan Genzer and Petr Vlček

      Article first published online: 28 JAN 2008 | DOI: 10.1002/pola.22436

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      Monomer reactivity ratios of 2-(trimethylsiloxy)ethyl methacrylate and methyl methacrylate were established using extended Kelen-Tudos linear method and non-linear optimization method involved by COPOINT program. Copolymers of 2-(trimethylsiloxy)ethyl methacrylate and methyl methacrylate were synthesized by ATRP using methyl 2-bromo-2-methylpropionate/CuBr/CuBr2/bpy system.

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