Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 44 Issue 12

15 June 2006

Volume 44, Issue 12

Pages xi–xi, 3729–3946

  1. Editorial Announcement

    1. Top of page
    2. Editorial Announcement
    3. Highlight
    4. Articles
    5. Rapid Communication
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      Editorial announcement (page xi)

      Craig J. Hawker, Virgil Percec, Mitsuo Sawamoto and Karen L. Wooley

      Version of Record online: 8 MAY 2006 | DOI: 10.1002/pola.21507

  2. Highlight

    1. Top of page
    2. Editorial Announcement
    3. Highlight
    4. Articles
    5. Rapid Communication
    1. You have free access to this content
      Electroluminescent copolymers based on dihexylfluorene and 2-{2,6-bis[2-(4-diphenylaminophenyl)vinyl]pyran-4-ylidene}malononitrile units (pages 3729–3737)

      Joo Hyun Kim, Nam-Ho You and Hoosung Lee

      Version of Record online: 25 APR 2006 | DOI: 10.1002/pola.21435

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      A series of polyfluorene derivatives with red-emitting 2-[2,6-bis(2-{4-[(4-bromophenyl)phenylamino]phenyl}vinyl)pyran-4-ylidene]malononitrile (DDCM) units were synthesized. Although the composition of DDCM varied little in the copolymers, the emission color redshifted dramatically. From the energy levels of DDCM, it was concluded that energy transfer took place from the high-energy oligofluorene block to the low-energy segment containing DDCM. The Commission Internationale de l'Eclairage (CIE) chromaticity coordinates of the copolymer (x = 0.63, y = 0.37) including 10 mol % DDCM were very close to the chromaticity coordinates (x = 0.67, y = 0.33) for National Television System Committee (NTSC) red with a maximum photometric power efficiency of 0.27 cd/A.

  3. Articles

    1. Top of page
    2. Editorial Announcement
    3. Highlight
    4. Articles
    5. Rapid Communication
    1. Highly efficient, polymerizable, sulfur-containing photoinitiator comprising a structure of planar N-phenylmaleimide and benzophenone for photopolymerization (pages 3738–3750)

      Hongyu Wang, Jun Wei, Xuesong Jiang and Jie Yin

      Version of Record online: 25 APR 2006 | DOI: 10.1002/pola.21476

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      A novel, polymerizable, sulfur-containing photoinitiator, 4-[(4-maleimido)thiophenyl]benzophenone (MTPBP), comprising a structure of planar N-phenylmaleimide (NPMI) and benzophenone (BP) was synthesized. The results showed that MTPBP possessed a greatly redshifted UV maximal absorption in contrast to BP and a very weak fluorescence emission. Electron spin resonance spectra indicated that MTPBP underwent photolysis reactions at its C[BOND]S bond. A photopolymerization study indicated surprisingly high efficiency of MTPBP due to the mutual influence between NPMI and BP as in their physical mixtures and photolysis reactions at the C[BOND]S bond. Both 4-[(4-maleimido)phenoxy]benzophenone (MPBP) and MTPBP behaved with similar regularity toward different monomers, which initiated the photopolymerization more efficiently than the BP system.

    2. Chemically modified proton-conducting membranes based on sulfonated polyimides: Improved water stability and fuel-cell performance (pages 3751–3762)

      Yan Yin, Otoo Yamada, Shunsuke Hayashi, Kazuhiro Tanaka, Hidetoshi Kita and Ken-Ichi Okamoto

      Version of Record online: 25 APR 2006 | DOI: 10.1002/pola.21477

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      Sulfonated polyimide (SPI) oligomers branched/crosslinked by 1,3,5-tris(4-aminophenoxy)benzene (TAPB) have a network structure and exhibit high proton conductivity, low membrane swelling and superior mechanical properties before and after aging in water at 130 °C. High fuel-cell performances in both polymer electrolyte fuel cells and direct methanol fuel cells have been achieved for these branched/crosslinked SPI membranes.

    3. Synthesis and comparison of the structure–property relationships of symmetric and asymmetric water-soluble poly(p-phenylene)s (pages 3763–3777)

      Muthalagu Vetrichelvan, Li Hairong, Renu Ravindranath and Suresh Valiyaveettil

      Version of Record online: 26 APR 2006 | DOI: 10.1002/pola.21464

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      Water-soluble, conjugated poly(p-phenylene)s in symmetric and asymmetric forms were synthesized and investigated with respect to their structural, optical, and aggregation behavior. Significant fluorescence quenching was observed in the presence of positively charged viologen derivatives and cytochrome-C.

    4. Anionic grafting polymerization of propylene sulfide onto human hair in water (pages 3778–3786)

      Hisatoyo Morinaga, Bungo Ochiai, Hideharu Mori and Takeshi Endo

      Version of Record online: 26 APR 2006 | DOI: 10.1002/pola.21478

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      Natural human hair was modified by the graft polymerization of propylene sulfide in aqueous media. The grafted polymer was isolated by the hydrolysis of the polymer-grafted hair under basic conditions and confirmed to be poly(propylene sulfide).

    5. Synthesis of poly(2-hydroxyethyl methacrylate) in protic media through atom transfer radical polymerization using activators generated by electron transfer (pages 3787–3796)

      Jung Kwon Oh and Krzysztof Matyjaszewski

      Version of Record online: 26 APR 2006 | DOI: 10.1002/pola.21482

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      Atom transfer radical polymerization (ATRP) using activators generated by electron transfer (AGET) allowed the synthesis of well-defined poly(2-hydroxyethyl methacrylate) homopolymers and a poly(methyl methacrylate)-b-poly(2-hydroxyethyl methacrylate) block copolymer in protic media. With an additional benefit from the use of a more air-stable Cu(II) complex, AGET ATRP retained a level of control similar to that of normal ATRP, and this resulted in a linear increase in the molecular weight with the conversion and a narrow molecular weight distribution.

    6. New π-conjugated polyaryleneethynylenes containing a 1,3,5-triazine unit in the main chain: Synthesis and optical and electrochemical properties (pages 3797–3806)

      Qiang Fang, Shijie Ren, Bing Xu, Junping Du and Amin Cao

      Version of Record online: 26 APR 2006 | DOI: 10.1002/pola.21485

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      A series of new π-conjugated poly(aryleneethynylene)s possessing an s-triazine unit in the main chain (P1P4) were synthesized in yields higher than 70%. They had a number-average molecular weight in the range of 5000–10,000 and showed good solubility in common organic solvents. The polymers were photoluminescent both in solutions and in the solid state. Powder X-ray diffraction patterns revealed that the polymers were semicrystalline. Electrochemically, the polymers appeared to be reversible under reduction.

    7. Preparation of SiO2/PMMA composite particles via conventional emulsion polymerization (pages 3807–3816)

      Xinjian Cheng, Min Chen, Shuxue Zhou and Limin Wu

      Version of Record online: 27 APR 2006 | DOI: 10.1002/pola.21472

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      A series of SiO2/PMMA composite particles with multicore-shell, raspberry-like and conventional core-shell morphologies were prepared via conventional emulsion polymerization by the aid of acid-base interaction between the silanol groups of unmodified silica particles and the amino groups of 4-vinylpyridine. No surface treatment for nanosilica particles was required. The morphologies of composite particles could be controlled by modulating emulsifier content, monomer/silica ratio, silica size and monomer feed method.

    8. Poly(dimethylsiloxane)-based polymer organogelators with L-lysine derivatives as a organogelation-causing segment (pages 3817–3824)

      Masahiro Suzuki, Sanae Owa, Hirofusa Shirai and Kenji Hanabusa

      Version of Record online: 27 APR 2006 | DOI: 10.1002/pola.21473

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      New poly(dimethylsiloxane)-based polymer organogelators with L-lysine derivatives were prepared from the isocyanate-terminated L-lysine derivatives and poly(dimethylsiloxane) with amino groups. These polymer organogelators form organogels in many organic solvents through the construction of a mesoporous structure with a pore size of ca. 1 micrometer formed by entanglement of supramolecular polymers. The L-lysine derivatives in the polymer gelators function as a gelation-causing segment and the organogelation is induced by the self-assembly of the L-lysine segments through a hydrogen bonding interaction.

    9. Epoxy/polyhedral oligomeric silsesquioxane nanocomposites from octakis(glycidyldimethylsiloxy)octasilsesquioxane and small-molecule curing agents (pages 3825–3835)

      Ying-Ling Liu, Gung-Pei Chang, Keh-Ying Hsu and Feng-Chih Chang

      Version of Record online: 28 APR 2006 | DOI: 10.1002/pola.21484

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      The use of small molecules of diethylphosphite and dicyandiamide as curing agents promoted the homogeneity of nanocomposites made from octakis(glycidyldimethylsiloxy)octasilsesquioxane. The addition of octakis(glycidyldimethylsiloxy)octasilsesquioxane to diglycidyl ether of bisphenol A/diethylphosphite and diglycidyl ether of bisphenol A/dicyandiamide curing compositions resulted in epoxy/polyhedral oligometric silsesquioxane nanocomposites with a high octakis(glycidyldimethylsiloxy)octasilsesquioxane loading of 54 wt %. The nanocomposites possessing high octakis(glycidyldimethylsiloxy)octasilsesquioxane contents exhibited good thermal stability, improved flammability, and high storage moduli.

    10. Synthesis of poly(ethylene oxide) with pending 2,2,6,6-tetramethylpiperidine-1-oxyl groups and its further initiation of the grafting polymerization of styrene (pages 3836–3842)

      Zhongfan Jia, Qiang Fu and Junlian Huang

      Version of Record online: 28 APR 2006 | DOI: 10.1002/pola.21488

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      Novel amphiphilic graft copolymers of poly(ethylene oxide) as the main chain and polystyrene as the side chains were prepared by the combination of anionic ring-opening polymerization and 2,2,6,6-tetramethylpiperidine-1-oxyl-mediated controlled radical polymerization. The graft copolymerization of styrene could be controlled by the variation of the polymerization time and feed ratio of 4-glycidyloxy-2,2,6,6-tetramethylpiperidine-1-oxyl and ethylene oxide in the ring-opening copolymerization.

    11. Simultaneous synthesis of silver nanoparticles and poly(2,5-dimethoxyaniline) in poly(styrene sulfonic acid) (pages 3843–3852)

      Li-Ming Huang, Ching-Chun Tsai, Ten-Chin Wen and A. Gopalan

      Version of Record online: 28 APR 2006 | DOI: 10.1002/pola.21479

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      The simultaneous synthesis of conductive poly(2,5-dimethoxyaniline) and silver nanoparticles was achieved in the presence of poly(styrene sulfonic acid). Transmission electron microscopy and particle size analysis revealed that spherical silver nanoparticles with sizes ranging from 4 to 22 nm were distributed in the matrix of the conducting polymer.

    12. Novel, well-defined polystyrene with a fluorine cluster end-capped group: Synthesis, characterization, and surface properties (pages 3853–3858)

      Hong Li, Yong Ming Zhang, Heng Zhang, Min Zhao Xue and Yan Gang Liu

      Version of Record online: 28 APR 2006 | DOI: 10.1002/pola.21486

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      Novel, well-defined fluorinated polystyrene, which was synthesized for the first time via the controlled/living radical polymerization of styrene with a fluorinated initiator with a fluorine cluster structure, showed fantastic surface properties in the surface treatment of polymer films.

    13. Synthesis and characterization of new radiopaque microspheres by the dispersion polymerization of an iodinated acrylate monomer for X-ray imaging applications (pages 3859–3868)

      Anna Galperin and Shlomo Margel

      Version of Record online: 2 MAY 2006 | DOI: 10.1002/pola.21487

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      Radiopaque microspheres of sizes ranging from 0.2 to 1.4 μm were formed by the dispersion polymerization of the monomer 2-methacryloyloxyethyl(2,3,5-triiodobenzoate) in the presence of polyvinylpyrrolidone as the stabilizer and 2-methoxyethanol as the continuous phase. The radiopacity of these poly[2-methacryloyloxyethyl(2,3,5-triiodobenzoate)] microspheres was demonstrated with a computed tomography (CT) scanner.

    14. Synthesis and self-assembly of polystyrene-grafted multiwalled carbon nanotubes with a hairy-rod nanostructure (pages 3869–3881)

      Yingkui Yang, Xiaolin Xie, Jingao Wu and Yiu-Wing Mai

      Version of Record online: 2 MAY 2006 | DOI: 10.1002/pola.21491

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      A polystyrene-grafted multiwalled carbon nanotube (PS-g-MWNT) was synthesized by the in situ free-radical polymerization of styrene in the presence of multiwalled carbon nanotubes (MWNTs) terminated with vinyl groups. Hairy-rod, nanostructural PS-g-MWNT was generated, in which the rigid MWNTs acted as rodlike backbones and large amounts of flexible polystyrene (PS) macromolecules acted as side chains like hairs. A uniform and thin layer of a PS shell covered the outer wall of every MWNT and formed some novel assembly patterns, including nanopins and circlelike and starlike structures.

    15. Synthesis and optical and electrochemical properties of copolymers containing 9,9-dihexylfluorene and 9-dimethylaminopropylcarbazole chromophores (pages 3882–3895)

      Chien-Hsin Liu, Shinn-Horng Chen and Yun Chen

      Version of Record online: 2 MAY 2006 | DOI: 10.1002/pola.21492

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      Soluble and well-defined 9,9-dihexylfluorene and 9-dimethylaminopropylcarbazole based copolymers PFCN and 5PFCN have been prepared by Suzuki coupling polymerization. For comparison, alternate copolymer of 9,9-dihexylfluorene and 9-hexylcarbazole (PFC) was also prepared by the same method. Furthermore, alternate copolymer of 9,9-dihexylfluorene and 9-dimethylethylammoniumpropylcarbazole (PFCNE) was prepared from PFCN by ethylating its dimethylaminopropyl groups with bromoethane. The optimized architecture of PFCN from a simulation was a spiral, which was different from the linear structure of poly(9,9-dihexylfluorene) (PFO). Both the absorption and photoluminescence emission peaks of these copolymers showed blueshifts after the introduction of the carbazole units because of reduced conjugation. Moreover, the introduction of carbazole moieties effectively prevented the excimer formation of PFO. According to cyclic voltammetry results, PFCNE exhibited the most stable reduction–oxidation cycles. The turn-on electric fields of their electroluminescence devices decreased with increasing carbazole content.

    16. Original crosslinking of poly(vinylidene fluoride) via trialkoxysilane-containing cure-site monomers (pages 3896–3910)

      J. Guiot, B. Ameduri, B. Boutevin and T. Lannuzel

      Version of Record online: 8 MAY 2006 | DOI: 10.1002/pola.21489

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      The synthesis and copolymerizations of silicon-containing fluoromonomers with vinylidene fluoride (VDF) led to original PVDF which were crosslinked in the presence of moisture at 200 °C leading to insoluble materials stable in solvents, oils, water, and to acids.

    17. Synthesis of TiO2–SiO2/polymer core–shell microspheres with a microphase-inversion method (pages 3911–3920)

      Peng Xu, Haitao Wang, Rui Lv, Qiangguo Du, Wei Zhong and Yuliang Yang

      Version of Record online: 8 MAY 2006 | DOI: 10.1002/pola.21490

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      A novel microphase-inversion method was proposed for the preparation of inorganic–polymer core–shell nanocomposite particles such as silica, titania, and TiO2–SiO2/poly(methyl methacrylate) ones. The inorganic–polymer nanocomposites were first synthesized via a free-radical copolymerization in a tetrahydrofuran solution, and the poor solvent was mixed slowly to induce the microphase separation of the nanocomposite and result in the formation of nanoparticles.

    18. Dimethacrylate derivatives of dimer acid (pages 3921–3929)

      Marianela Trujillo-Lemon, Junhao Ge, Hui Lu, Jiro Tanaka and Jeffrey W. Stansbury

      Version of Record online: 8 MAY 2006 | DOI: 10.1002/pola.21493

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      Novel dimer acid dimethacrylate monomers with low double-bond concentrations and different linking group functionalities were readily synthesized in moderate-to-high yields with commercially available starting materials. In crosslinking photopolymerizations, these monomers rapidly achieved very high conversions coupled with low polymerization shrinkage and nearly negligible water sorption values in comparison with conventional dimethacrylate monomers.

    19. Hyperbranched polycarbosiloxane with dendritic boron cores: Synthesis, characterization, and structure regulation (pages 3930–3941)

      Jie Kong, Xiaodong Fan, Qingfa Si, Guobin Zhang, Shengjie Wang and Xin Wang

      Version of Record online: 8 MAY 2006 | DOI: 10.1002/pola.21474

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      The synthesis, characterization and structure regulation of hyperbranched polycarbosiloxane with dendritic boron cores were realized in this paper. The hyperbranched polycarbosiloxanes with dendritic boron cores of bis(allyloxy)dimethylsilane were synthesized via hydrosilylation with AB2 type monomer of bis(allyloxy)methylsilane and dendritic boron cores as presented as in the scheme. SEC/MALLS analysis reveals that the structures of hyperbranched polycarbosiloxane could be regulated effectively by incorporation of functional dendritic cores. TGA analysis indicates that both the decomposition temperature and ceramic yields are increased as the results of the incorporation of dendritic boron cores cooperation into hyperbranched polycarbosiloxane.

  4. Rapid Communication

    1. Top of page
    2. Editorial Announcement
    3. Highlight
    4. Articles
    5. Rapid Communication
    1. Synthesis of a novel centipede-like copolymer of styrene, isoprene, and methyl methacrylate (pages 3942–3946)

      Aixiang Li, Zaijun Lu, Qifeng Zhou, Feng Qiu and Yuliang Yang

      Version of Record online: 8 MAY 2006 | DOI: 10.1002/pola.21481

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      A well-defined, ABC-type, centipede-like copolymer of styrene, isoprene, and methyl methacrylate (MMA) was synthesized by the combination of living anionic polymerization and atom transfer radical polymerization (ATRP). The synthetic approach involved the coupling reaction of a polystyrene (PS) backbone bearing 1,1-diphenylethene pendant groups, produced by ATRP and Wittig reactions, with living polyisoprenyllithium (PILi) and the subsequent polymerization of the resulting 1,1-diphenylmethyl anions with MMA. The centipede-like copolymer was characterized with 1H NMR, IR, size exclusion chromatography, static light scattering, and differential scanning calorimetry measurements.

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