Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Journal of Polymer Science Part A: Polymer Chemistry

15 April 2006

Volume 44, Issue 8

Pages 2363–2753

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      Formation of honeycomb-structured, porous films via breath figures with different polymer architectures (pages 2363–2375)

      Martina H. Stenzel, C. Barner-Kowollik and Thomas P. Davis

      Article first published online: 2 MAR 2006 | DOI: 10.1002/pola.21334

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      Honeycomb-structured, porous films with pore sizes ranging from 200 nm to 7 μm were prepared with breath figures. The regularity of the hexagonal array and the pore size was influenced by the polymer architecture and the casting conditions. A nanoscaled suborder next to the microarray was obtained with amphiphilic block copolymers. These films were shown to be suitable as surfaces for cell growth.

  2. Articles

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    1. Controlled radical copolymerization of β-pinene and acrylonitrile (pages 2376–2387)

      An-Long Li, Yi Wang, Hui Liang and Jiang Lu

      Article first published online: 1 MAR 2006 | DOI: 10.1002/pola.21316

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      The feasibility of the radical copolymerization of β-pinene and acrylonitrile was clarified for the first time. The Lewis acids were used for the sequence control of the copolymers, and almost perfectly alternating copolymers were obtained in the presence of Et2AlCl. Furthermore, the possibility of molecular weight control by reversible addition–fragmentation transfer copolymerization was also investigated.

    2. Electrochemical polymerization of aniline in the SDS/n-C5H11OH/H2SO4(aq) lyotropic liquid crystal (pages 2388–2394)

      Rong Guo, Zhong Chun Li and Tian Qing Liu

      Article first published online: 1 MAR 2006 | DOI: 10.1002/pola.21343

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      The electrochemical polymerization of aniline can be catalyzed by the SDS/n-C5H11OH/H2SO4(aq) lamellar liquid crystal and hexagonal liquid crystal because of the solubilization of aniline in the lyotropic liquid crystal. The hydrophobic surroundings of lyotropic liquid crystal are beneficial to the stability of aniline cationic radical, and so decrease the activity energy of polymerization of aniline. Moreover, the catalytic efficiency of the lamellar liquid crystal exceeds that of the hexagonal liquid crystal.

    3. Synthesis and characterization of novel red-emitting alternating copolymers based on fluorene and diketopyrrolopyrrole derivatives (pages 2395–2405)

      Derong Cao, Qilin Liu, Wenjing Zeng, Shaohu Han, Junbiao Peng and Shouping Liu

      Article first published online: 2 MAR 2006 | DOI: 10.1002/pola.21354

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      Two novel conjugated polymers (P1 and P2) based on fluorene and diketopyrrolopyrrole derivatives have been successfully synthesized through Suzuki polycondensation and well characterized. Both P1 and P2 exhibit red emission exclusively. P1 is superior to P2 for light emitting diodes (LED) applications, probably due to its much better conjugation.

    4. Polymerization of vinylidene fluoride with perfluoropolyether surfactants in supercritical carbon dioxide as a dispersing medium (pages 2406–2418)

      Alessandro Galia, Alberto Giaconia, Onofrio Scialdone, Marco Apostolo and Giuseppe Filardo

      Article first published online: 1 MAR 2006 | DOI: 10.1002/pola.21352

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      The heterogeneous free-radical polymerization of vinylidene fluoride (VDF) was investigated with supercritical carbon dioxide (scCO2) as a dispersing medium in the presence of different perfluoropolyether surfactants. When ammonium carboxylate salts were used, monomer conversions up to 63% were obtained, corresponding to a final solid content higher than 200 g/L, and the polymer was collected at the end of the process in the form of a white powder completely composed of microspheres. Collected experimental results suggest that ammonium perfluoropolyether carboxylic salts are the most effective surfactants yet tested in the heterogeneous polymerization of VDF in scCO2.

    5. Functionalized multi-walled carbon nanotubes with poly(N-(2-hydroxypropyl)methacrylamide) by RAFT polymerization (pages 2419–2427)

      Chun-Yan Hong, Ye-Zi You and Cai-Yuan Pan

      Article first published online: 2 MAR 2006 | DOI: 10.1002/pola.21341

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      Water-soluble and biocompatible polymer, poly(N-(2-hydroxypropyl) methacrylamide) (PHPMA), has been successfully attached to the surface of multi-walled carbon nanotubes (MWNTs) via RAFT polymerization using dithioesters immobilized on MWNTs as RAFT agent. MWNTs grafted with PHPMA chains have good solubility in distilled water, PBS buffer, and methanol. Thus they have potential applications in gene and drug delivery.

    6. In-line monitoring of UV photopolymerization with a quartz crystal resonator (pages 2428–2439)

      Hee Seok Choi, Young Han Kim and Shun Myung Shin

      Article first published online: 2 MAR 2006 | DOI: 10.1002/pola.21323

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      An in-line monitoring device using a quartz crystal resonator for thin film polymerization was developed and tested by implementing in the UV polymerization of 2-hydroxyethyl methacrylate with a photoinitiator of 1-chloroanthraquinone. The measurements of resonant resistance were compared with the outcome of instrumental analyses of polymerization degree using an FTIR spectrometer and a GPC. The experimental results showed that the resistance measurements were consistent with the experimental outcome of the instrumental analyses and indicate effectiveness of the proposed device. Due to the simplicity and availability of the resonator system, its wide utilization in the monitoring of a variety of film polymerization processes, including photoresistor application, is expected.

    7. Poly(arylene thioether) synthesis via nitro-displacement reaction (pages 2440–2447)

      Insik In and Sang Youl Kim

      Article first published online: 2 MAR 2006 | DOI: 10.1002/pola.21342

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      High molecular weight poly(arylene thioether)s containing trifluoromethyl groups were prepared through the aromatic nucleophilic nitro displacement reaction of a dinitro monomer with aromatic dithiols. The high reactivity of the monomer, 4,4′-dinitro-3,3′bis(trifluoromethyl)biphenyl, activated by ortho-trifluoromethyl groups and complete exclusion of oxygen were critical for the successful polymerization without any disulfide formation.

    8. Latent reactive polymers containing isocyanate moiety that show extreme stability under aerobic atmosphere (pages 2448–2453)

      Yasushi Kamimura, Osamu Haba and Takeshi Endo

      Article first published online: 2 MAR 2006 | DOI: 10.1002/pola.21325

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      This article deals with the latent reactive polymers having isocyanate moiety obtained from the radical copolymerization of 2-propenyl isocyanate (2PI) with styrene, 2PI with methyl methacrylate (MMA), and 2-methacryloyloxyethyl isocyanate (MOI) with styrene. The isocyanate moiety in each copolymer was stable at room temperature for more than six months under aerobic atmosphere. Isocyanate moiety of obtained copolymer (poly(2PI-co-St)) reacted with excess diamines or diols at 80 °C in THF solution to afford the crosslinked polymer quantitatively. These results could demonstrate that isocyanate moiety in the copolymers showed thermal and reactive latency.

    9. Well-defined thermosensitive, water-soluble polyacrylates and polystyrenics with short pendant oligo(ethylene glycol) groups synthesized by nitroxide-mediated radical polymerization (pages 2454–2467)

      Fengjun Hua, Xueguang Jiang, Dejin Li and Bin Zhao

      Article first published online: 1 MAR 2006 | DOI: 10.1002/pola.21357

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      Four new thermosensitive, water-soluble polymers with controlled molecular weights and narrow molecular weight distributions were synthesized by nitroxide-mediated radical polymerization with an α-hydrido alkoxyamine as an initiator in the presence of a free nitroxide radical. These polymers could be dissolved in water, forming transparent solutions, and undergo phase transitions from a soluble state to an insoluble state at elevated temperatures. The cloud points of poly[methoxydi(ethylene glycol) acrylate], poly[methoxytri(ethylene glycol) acrylate], poly[α-hydro-ω-(4-vinylbenzyl)tris(oxyethylene)], and poly[α-hydro-ω-(4-vinylbenzyl) tetrakis(oxyethylene)] were around 38, 58, 13, and 64 °C, respectively.

    10. Synthesis of diblock copolymers by combining stable free radical polymerization and atom transfer radical polymerization (pages 2468–2475)

      Yan Shi, Zhifeng Fu, Bingyi Li and Wantai Yang

      Article first published online: 1 MAR 2006 | DOI: 10.1002/pola.21321

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      Stable free- radical polymerization of styrene was carried out in the presence of a novel stable nitroxyl radical functionalized with an initiating group for atom transfer radical polymerization, 4-(2-bromo-2-methylpropionyloxy)-2,2,6,6-tetramethyl-1-piperidinyloxy. Using the obtained polystyrene as the macroinitiator for ATRP of methyl acrylate and ethyl acrylate, well-defined diblock copolymers were synthesized.

    11. Synthesis of PVC-g-PS through stereoselective nucleophilic substitution on PVC (pages 2476–2486)

      Gerardo Martínez

      Article first published online: 1 MAR 2006 | DOI: 10.1002/pola.21346

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      The nucleophilic substitution of poly(vinyl chloride) (PVC) with sodium azide was shown to proceed through the local configuration-driven mechanism found in a previous work for other nucleophiles. From this stereospecific chemical modification of PVC, the thermal decomposition of azide-modified PVC and the consequent reaction with styrene offer a method for the preparation of stereoselective graft copolymers. A correlation between the change in the mmr tetrad at the end of isotactic sequences and the evolution of density as a function of free-volume of the graft copolymers is obtained.

    12. Silole-containing poly(diphenylacetylene): Synthesis, characterization, and light emission (pages 2487–2498)

      Junwu Chen, Hoi Sing Kwok and Ben Zhong Tang

      Article first published online: 1 MAR 2006 | DOI: 10.1002/pola.21359

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      A soluble poly(diphenylacetylene) with a silole pendant was synthesized. The structure and properties of the polymer were characterized and evaluated by IR, UV, NMR, thermogravimetric analysis, differential scanning calorimetry, photoluminescence, and electroluminescence analyses. The polymer solution exhibited only a backbone emission at room temperature. The silole emission could be enhanced by cooling, and the solution displayed a pendant-dominant emission at lower temperatures.

    13. Synthesis and properties of polyacetylenes with directly attached bis(4-alkoxyphenyl)terephthalate mesogens as pendants (pages 2499–2509)

      Lie Chen, Yiwang Chen, Daijun Zha and Yan Yang

      Article first published online: 2 MAR 2006 | DOI: 10.1002/pola.21363

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      Liquid-crystalline, monosubstituted polyacetylenes containing lateral pendants of bis(4-alkoxyphenyl)terephthalate with no flexible spacers and alkoxy tails (RO, where R is CH3 or C6H13) were synthesized. The polymer with long tails (p-hexyloxy) formed a smectic mesophase upon heating above the melting temperature. The steric effect of bulky, liquid-crystalline mesogens and a direct connection with the main chain prevented the planar conformation of the polyene backbone.

    14. New reaction for the preparation of liquid rubber (pages 2510–2520)

      K. A. Dubkov, S. V. Semikolenov, D. E. Babushkin, L. G. Echevskaya, M. A. Matsko, D. P. Ivanov, V. A. Zakharov, V. N. Parmon and G. I. Panov

      Article first published online: 2 MAR 2006 | DOI: 10.1002/pola.21353

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      The reaction of nitrous oxide with C[DOUBLE BOND]C bonds of polybutadiene can lead to a smooth transformation of the material into a liquid rubber functionalized by C[DOUBLE BOND]O ketone groups in the polymer backbone. The image shows the effect of oxygen concentration (0.0–9.2 wt %) introduced into polybutadiene rubber by the reaction with N2O on the MWD of resulting material (GPC data).

    15. Synthesis and optical and electroluminescent properties of novel conjugated polyelectrolytes and their neutral precursors derived from fluorene and benzoselenadiazole (pages 2521–2532)

      Fei Huang, Lintao Hou, Huilin Shen, Renqiang Yang, Qiong Hou and Yong Cao

      Article first published online: 2 MAR 2006 | DOI: 10.1002/pola.21365

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      Novel polyelectrolytes and their neutral precursors were synthesized from amino-functionalized fluorene- and selenium-containing heterocycles by Suzuki coupling. Efficient energy transfer due to exciton trapping on the 2,1,3-benzoselenadiazole sites was observed. Devices from such copolymers emitted orange-red light around 600 nm, which was bathochromically shifted in comparison with the sulfur analogue. All the polymers showed good performance in devices with high-work-function metal Al as a cathode without the use of an additional electron-injection layer and are promising candidates for polymer light-emitting diode applications.

    16. Anionic/nonionic mixed surfactants templates preparation of hollow polymer spheres via emulsion polymerization (pages 2533–2541)

      Linyong Song, Xuewu Ge, Mozhen Wang, Zhicheng Zhang and Shicheng Li

      Article first published online: 2 MAR 2006 | DOI: 10.1002/pola.21322

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      A facile, convenient, and economical method has been reported to prepare hollow polymer spheres. By virtue of the phase transformation of nonionic surfactant at its cloud point, hollow spheres of polystyrene were prepared from vesicle templates formed by potassium oleate (KO) and alkyl-phenol polyoxyethylene (n) ether (n = 10, OP) at 70–80 °C. The hollow structure was characterized by TEM and FESEM. The diameter of the HSs varies from 200 to 800 nm, and the shell thickness is uniformly c.a. 30–50 nm.

    17. Preparation and characterization of mesoporous silica thin films from polyethoxysiloxanes (pages 2542–2550)

      Takahiro Gunji, Ryosuke Shimano, Koji Arimitsu and Yoshimoto Abe

      Article first published online: 3 MAR 2006 | DOI: 10.1002/pola.21344

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      Polyethoxysiloxanes were subjected to the sol–gel process in the presence of cetyltrimethylammonium bromide. The thin films, prepared by spin-coating, provided porous silica thin films on sintering. The structure of the thin films was dependent on the molecular weight of polymers: honeycomb structures were observed when the weight-average molecular weight is less than 5000.

    18. Minimally adhesive polymer surfaces prepared from star oligosiloxanes and star oligofluorosiloxanes (pages 2551–2566)

      Melissa A. Grunlan, Nam S. Lee, Florian Mansfeld, Esra Kus, John A. Finlay, James A. Callow, Maureen E. Callow and William P. Weber

      Article first published online: 3 MAR 2006 | DOI: 10.1002/pola.21362

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      Irregular epoxy-terminated tetrabranched star oligosiloxanes and fluorosiloxanes were prepared and subsequently crosslinked with α,ω-bis(3-aminopropyl)poly(dimethylsiloxane). The resulting films were characterized by goniometry and dynamic mechanical thermal analysis. Their hydrophobicity, storage modulus (G′), and glass-transition temperature (Tg) were related to their biofouling behavior. The corrosion protection of aluminum was evaluated by electrochemical impedance spectroscopy. Fluorosiloxane films displayed higher G′ and Tg values, decreased contact angles (with water), and more effectively released Ulva sporelings in comparison with siloxane films.

    19. Synthesis and characterization of polyimides from bis(3-aminophenyl)-4-(1-adamantyl)phenoxyphenyl phosphine oxide (pages 2567–2578)

      S. M. Kwak, J. H. Yeon and T. H. Yoon

      Article first published online: 6 MAR 2006 | DOI: 10.1002/pola.21364

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      A novel diamine, bis(3-aminophenyl)-4-(1-adamantyl)phenoxyphenyl-phosphine oxide (mDAATPPO), was synthesized via the Williamson ether reaction of 4-(1-adamantyl)phenol and bis(3-nitrophenyl)-4-fluorophenyl phosphine oxide, followed by reduction. The monomer was utilized to prepare polyimides with 6FDA, BTDA, ODPA, and PMDA by the conventional two-step synthesis, and the molecular weight was controlled to 20,000 g/mol by off-stoichiometry. In addition, solubility, intrinsic viscosity, dielectric constant, and birefringence of polyimides were also evaluated. Novel polyimides with mDAATPPO exhibited good solubility, high glass-transition temperatures (290–330 °C), excellent thermal stability (>500 °C), low dielectric constants (2.77–3.01), low refractive indices, and low birefringence values (0.0019–0.0030).

    20. Star polystyrenes by anionic star–star coupling reactions with divinylbenzene (pages 2579–2586)

      Hyung-Jae Lee, Kwanyoung Lee and Soo No Lee

      Article first published online: 6 MAR 2006 | DOI: 10.1002/pola.21356

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      The incremental addition of divinylbenzene to polystyryllithium provides a synthetic method for gradient-star polystyrenes effectively without the formation of gel content. This shows that their viscosity behavior greatly deviates from that of linear polystyrene.

    21. Synthesis and evaluation of photoluminescent and electrochemical properties of new aromatic polyamides and polyimides with a kink 1,2-phenylenediamine moiety (pages 2587–2603)

      Guey-Sheng Liou, Yi-Lung Yang and Yuhlong Oliver Su

      Article first published online: 6 MAR 2006 | DOI: 10.1002/pola.21358

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      A series of novel triphenylamine-containing aromatic polyamides and polyimides having crank and twisted noncoplanar structures were synthesized. These polymers had useful levels of thermal stability associated with relatively high glass-transition temperatures (174–311 °C). They exhibited strong ultraviolet–visible absorption bands around 300 nm in NMP solutions. The photoluminescence spectra of these polymers in NMP solutions (1 × 10−5 M) showed maximum peaks around 396–479 nm. Cyclic voltammetry of the polymer films cast onto an indium tin oxide coated glass substrate exhibited two reversible oxidation redox couples at potentials of 0.70–1.01 and 1.10–1.46 V, respectively, versus Ag/AgCl in acetonitrile solutions. The polymer films revealed electrochromic characteristics, with a color change from a neutral pale yellow to green and then to a blue oxidized form at applied potentials ranging from 0.00 to 1.75 V.

    22. Photocrosslinked poly(vinylbenzophenone)-core micelles via mild Friedel–Crafts benzoylation of polystyrene amphiphiles (pages 2604–2614)

      Ying Chen, Anita E. Tavakley, Tate M. Mathiason and T. Andrew Taton

      Article first published online: 6 MAR 2006 | DOI: 10.1002/pola.21367

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      Photocrosslinkable poly(vinylbenzophenone)-containing polymers were synthesized via a one-step, Friedel–Crafts benzoylation of polystyrene homopolymers and block copolymers [including polystyrene, polystyrene-block-poly(tert-butyl acrylate), polystyrene-block-poly(ethylene oxide), polystyrene-block-poly(methyl methacrylate), and polystyrene-block-poly(n-butyl acrylate)] with benzoyl trifluoromethanesulfonate as a mild benzoylation reagent. Micelles formed from one of the benzoylated products, [polystyrene0.25-co-poly-(vinylbenzophenone)0.75]115-block-poly(acrylic acid)14, were then irreversibly fixed by the irradiation of the micelle cores with UV light. Dynamic light scattering, transmission electron microscopy, spectrofluorimetry, and Fourier transform infrared spectroscopy were all used to verify the success and progress of the micelle photocrosslinking reaction.

    23. Nitro-substituted iron(II) tridentate bis(imino)pyridine complexes as high-temperature catalysts for the production of α-olefins (pages 2615–2635)

      Alex S. Ionkin, William J. Marshall, Douglas J. Adelman, Aaron L. Shoe, Rupert E. Spence and Tuyu Xie

      Article first published online: 6 MAR 2006 | DOI: 10.1002/pola.21360

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      Tridentate bis(imino)pyridine ligands containing nitro groups and their Fe(II) complexes were synthesized. An α-olefin catalyst prepared from 12 possessed exceptional temperature stability.

    24. Cationic polymerization of isobutyl vinyl ether initiated with transition-metal ate complexes (pages 2636–2641)

      Eiji Ihara, Naoki Yoshida, Jun-Ichi Ikeda, Tomomichi Itoh and Kenzo Inoue

      Article first published online: 9 MAR 2006 | DOI: 10.1002/pola.21383

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      The cationic polymerization of isobutyl vinyl ether was examined with transition-metal ate complexes with trityl cation as initiators. The initiators were generated by the reaction of triphenylmethyl chloride [trityl chloride (TrCl)] with ate complexes of Nb, Mo, and W with lithium cation, which were obtained in situ by the reaction of the transition-metal halides with anionic reagents (organolithium or lithium amide). When the polymerization was initiated with a mixture of TrCl and Li+[NbH5(NnBuPh)], the resulting poly(isobutyl vinyl ether)s had narrow molecular weight distributions (weight-average molecular weight/number-average molecular weight = 1.13–1.20). Although the polymerization was supposed to be initiated by the electrophilic attack of the trityl cation, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis of the resulting poly(isobutyl vinyl ether)s revealed the presence of H at the α-chain end.

    25. Highly magnetic latexes from submicrometer oil in water ferrofluid emulsions (pages 2642–2656)

      Franck Montagne, Olivier Mondain-Monval, Christian Pichot and Abdelhamid Elaïssari

      Article first published online: 13 MAR 2006 | DOI: 10.1002/pola.21391

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      The synthesis of submicronic highly magnetic latex particles exhibiting a core-shell morphology is reported. Seeded emulsion polymerization onto monomers swollen preformed oil-in-water ferrofluid emulsion droplets was carried out. The morphology of the final magnetic latex particles was found to be related to various parameters, such as the monomer composition, the initiator chemical nature, and finally, the used stabilizers.

    26. Preparation and ferromagnetic properties of Ni0.5Zn0.5Fe2O4/polyaniline core–shell nanocomposites (pages 2657–2664)

      K. H. Wu, Y. M. Shin, C. C. Yang, W. D. Ho and J. S. Hsu

      Article first published online: 9 MAR 2006 | DOI: 10.1002/pola.21384

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      A nanoparticle of Ni0.5Zn0.5Fe2O4/polyaniline with a core–shell structure exhibiting ferromagnetic properties was synthesized by in situ emulsion polymerization. Fourier transform infrared, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy studies established the formation of NiZn ferrite/polyaniline composites. The results of transmission electron microscopy experiments showed that the composites coexisted in both the conducting phase (polyaniline) and ferromagnetic phase (NiZn ferrite) in a single material. Measurements of the electron magnetic resonance in NiZn ferrite and NiZn ferrite/polyaniline composites exhibited the evolution of the resonance absorption from ferromagnetic resonance to electron paramagnetic resonance as the temperature went through the Curie point (420 K).

    27. Synthesis and characterization of novel fluorinated aromatic polyimides derived from 1,1-bis(4-amino-3,5-dimethylphenyl)-1-(3,5-ditrifluoromethylphenyl)-2,2,2-trifluoroethane and various aromatic dianhydrides (pages 2665–2674)

      Hong-Shen Li, Jin-Gang Liu, Jia-Ming Rui, Lin Fan and Shi-Yong Yang

      Article first published online: 9 MAR 2006 | DOI: 10.1002/pola.21395

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      A novel fluorinated aromatic diamine, 1,1-bis(4-amino-3,5-dimethylphenyl)-1-(3,5-ditrifluoromethylphenyl)-2,2,2-trifluoroethane, was synthesized and characterized, and it was employed to react with various aromatic dianhydrides to yield a series of fluorinated aromatic polyimides. The experimental results indicated that the polymers, with inherent viscosities of 0.37–0.74 dL/g, could easily be dissolved in many organic solvents to obtain homogeneous and stable polyimide solutions at room temperature. The high-quality freestanding polyimide films exhibited good thermal stability and outstanding mechanical properties. In addition, the fluorinated polyimide films had low dielectric constants of 2.70–3.09 and very low moisture absorption (<0.58%). The polymer films showed good optical transparency. One poly imide [1,1-bis(4-amino-3,5-dimethylphenyl)-1-(3,5-ditrifluoromethylphenyl)-2,2,2-trifluoroethane/benzophenone tetracarboxylic dianhydride] also exhibited an intrinsic photosensitivity to the i-line (365 nm), and a fine pattern could be obtained via a standard lithography procedure.

    28. Synthesis and characterization of novel photoactive polymer poly(vinyl alcohol)-graft-poly(vinyl naphthalene) (pages 2675–2683)

      Monika Rymarczyk-Machał, Szczepan Zapotoczny and Maria Nowakowska

      Article first published online: 14 MAR 2006 | DOI: 10.1002/pola.21396

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      A copolymer of poly(vinyl naphthalene) grafted onto poly(vinyl alcohol) has been synthesized by controlled radical polymerization. The electronic absorption spectrum of the copolymer in water displays absorption bands characteristic of naphthalene (ca. 280 and 320 nm) but is also extended to much longer wavelengths. This indicates strong interactions between the chromophores, which lead to the formation of aggregates absorbing at longer wavelengths. This conclusion is also supported by the fluorescence spectra: in an aqueous solution, the polymeric chromophores can be excited at wavelengths as long as 450 nm and fluoresce up to 650 nm.

    29. Hydroxyl chain-end functionalization of polymeric organolithium compounds with oxetane (pages 2684–2693)

      Roderic P. Quirk, Young J. Kim, Ya Guo, Chrys Wesdemiotis and Mark A. Arnould

      Article first published online: 9 MAR 2006 | DOI: 10.1002/pola.21345

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      The oxetane functionalization of poly(styryl)lithium, polystyrene-oligobutadienyllithium, and 4-(1-lithio-1,1-diphenylethyl)polystyrene forms the corresponding 4-hydroxypropyl-functionalized polymers in 98, 97 and 86% yields, respectively, as determined by 13C and 1H NMR, MALDI-TOF MS and quantitative silica gel chromatography. This provides a useful alternative to hydroxyl functionalization with ethylene oxide.

    30. Lithographic design of photosensitive polyarylates based on reaction development patterning (pages 2694–2706)

      Toshiyuki Oyama, Akira Kitamura, Eiichi Sato and Masao Tomoi

      Article first published online: 10 MAR 2006 | DOI: 10.1002/pola.21386

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      The factors affecting pattern-forming properties in reaction development patterning were examined with polyarylates with various bisphenol moieties. The developability of the photosensitive polyarylates was dependent on the properties of R. The development time decreased in the following order: C(CH3)2 > fluorenyl unit ≫ phenolphthalein unit > C(CF3)2 > SO2. This order agreed with that of the reactivity between the polyarylates and ethanolamine, and these orders can be explained by pKa of the bisphenol moieties in the polyarylates. The development with NH2[BOND]R′[BOND]OH resulted in successful positive-tone pattern formation. However, pattern formation with the developers containing NH2[BOND]R′[BOND]OCH3 was unsuccessful.

    31. Synthesis and characterization of new type molecular wires with tetrathiafulvalene as redox center (pages 2707–2713)

      Erjing Wang, Hongxiang Li, Wenping Hu and Daoben Zhu

      Article first published online: 10 MAR 2006 | DOI: 10.1002/pola.21390

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      A new type of molecular wires 1ac with tetrathiafulvalene units was synthesized and characterized. The UV–vis spectra and electrochemistry results showed that comparing with PPE, these polymers had smaller HOMO–LUMO band gap, and the HOMO level of polymer 1a (−5.05 eV) was closer to the work function energy of Au electrode. Thermal stability analyses indicated that these polymers had good thermal stability. All of the results showed that the introduction of TTF units made polymers 1ac better candidates for molecular wires than PPE. [Color figure can be viewed in the online issue, which is available at]

    32. Synthesis and radical polymerization behavior of bifunctional vinyl monomer derived from N-vinylacetamide and p-chloromethylstyrene (pages 2714–2723)

      Takeru Iwamura, Tomoyuki Nakagawa and Takeshi Endo

      Article first published online: 14 MAR 2006 | DOI: 10.1002/pola.21381

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      The radical polymerization of N-(p-vinylbenzyl)-N-vinylacetamide (1) prepared by the reaction of N-vinylacetamide with p-chloromethylstyrene was carried out by using radical initiators such as AIBN or BPO in benzene, chlorobenzene, or bulk. As a result, poly 1 was successfully isolated by dialysis (yield, 10–36 %). The crosslinking reaction of poly 1 was carried out at 60–100 °C for 8 h. By using a radical initiator such as AIBN or BPO (3 mol %), the crosslinking proceeded (yield, 63–79 %). Moreover, the crosslinking reaction of poly 1 proceeded at 100°C without the use of a radical initiator in 50% yield.

    33. Characteristics of polypyrrole electrodeposited onto roughened substrates composed of gold–silver bimetallic nanoparticles (pages 2724–2731)

      Hsun-Tsing Lee, Yu-Chuan Liu and Li-Huei Lin

      Article first published online: 9 MAR 2006 | DOI: 10.1002/pola.21385

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      Because surfaces with bimetallic nanoparticles of different deposition domain sizes provide more possibilities for molecules to deposit on the boundaries of gold and silver nanoparticles, a polypyrrole spectrum, as shown in spectrum a, obtained on a roughened gold substrate with the modification of silver nanoparticles exhibits a higher intensity, more than eight times in magnitude, than that, as shown in spectrum b, on an unmodified roughened gold substrate.

    34. Selective preparation of poly(p-oxybenzoyl) by using fractional polycondensation (pages 2732–2743)

      Kunio Kimura, Shin-Ichiro Kohama, Junya Kuroda, Yasuo Shimizu, Toshimitsu Ichimori and Yuhiko Yamashita

      Article first published online: 9 MAR 2006 | DOI: 10.1002/pola.21375

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      Fractional polycondensation was achieved by polymerization of p-acetoxybenzoic acid (p-ABA) and m-acetoxybenzoic acid m-(ABA) in poor solvents at high temperature. Polymer crystals mainly composed of p-oxybenzoyl moiety were precipitated when the content of m-ABA in the feed was 30 mol %. Homo-oligomers were more rapidly formed in solution than do co-oligomers at the early stage in polymerization because of twice higher reactivity of p-ABA, and they were preferentially precipitated by crystallization to form crystals because of lower miscibility. The solid-state polymerization occurred in the precipitated crystal and, finally, the crystals containing few m-oxybenzoyl moiety were formed.

  3. Rapid Communications

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    1. Sulfonated block polyimide copolymers as a proton-conductive membrane (pages 2744–2748)

      Naoki Asano, Kenji Miyatake and Masahiro Watanabe

      Article first published online: 9 MAR 2006 | DOI: 10.1002/pola.21361

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      A series of sulfonated block copolyimide (SPI-B) ionomers were synthesized, and the effect of the block length was investigated. The new block SPI-B ionomer membranes showed chemical stability comparable to that of the random sulfonated polyimide equivalent. Among the SPI-B copolymers examined, the block/block copolymer SPI-B150/150 membrane, containing long block segments in both the hydrophilic and hydrophobic components, showed the highest proton conductivity of 2 × 10−2 S cm−1 at 48% relative humidity, which was comparable to that of a conventional perfluorinated ionomer membrane. Widespread and well-connected hydrophilic domains were confirmed by scanning transmission electron microscopy, proving the high proton-transporting properties of the SPI- B150/150 membrane. These results proved its potential availability as an electrolyte for high-temperature polymer electrolyte fuel cells.

    2. Cp2VCl2-catalyzed aqueous polymerization using oxygen as a cocatalyst: The remarkable effect of oxygen on the molecular weights and yields of the polymers (pages 2749–2753)

      Braja N. Patra and Manish Bhattacharjee

      Article first published online: 10 MAR 2006 | DOI: 10.1002/pola.21378

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      The activation of oxygen by an early-transition-metal compound, Cp2VCl2, has been used to generate an initiator for aqueous emulsion polymerization under aerobic conditions.