Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 48 Issue 2

15 January 2010

Volume 48, Issue 2

Pages 251–492

  1. Highlight

    1. Top of page
    2. Highlight
    3. Articles
    4. Rapid Communication
    5. Corrigendum
    1. You have free access to this content
      Cyclic polymers: Synthetic strategies and physical properties (pages 251–284)

      Hans R. Kricheldorf

      Version of Record online: 7 DEC 2009 | DOI: 10.1002/pola.23755

      Thumbnail image of graphical abstract

      Numerous synthetic strategies and polymerization methods are compared with regard to their usefulness for the preparation of cyclic polymers.

  2. Articles

    1. Top of page
    2. Highlight
    3. Articles
    4. Rapid Communication
    5. Corrigendum
    1. Synthesis and characterization of perfluorinated arylenevinylene polymers (pages 285–291)

      Antonio Cardone, Carmela Martinelli, Vita Pinto, Francesco Babudri, Maria Losurdo, Giovanni Bruno, Pinalysa Cosma, Francesco Naso and Gianluca M. Farinola

      Version of Record online: 7 DEC 2009 | DOI: 10.1002/pola.23782

      Thumbnail image of graphical abstract

      Perfluorinated poly(phenylenevinylene) and poly(thienylenevinylene) were synthesized via the Stille reaction and characterized by FT-IR spectroscopy and MALDI-TOF mass spectrometry. Thin films were obtained by thermal evaporation and their electrochemical and optical properties were investigated revealing wide band gap values compared to the nonfluorinated counterparts.

    2. Conjugated copolymers comprised cyanophenyl-substituted spirobifluorene and tricarbazole-triphenylamine repeat units for blue-light-emitting diodes (pages 292–301)

      Ying Lin, Zhi-Kuan Chen, Teng-Ling Ye, Yan-Feng Dai, Dong-Ge Ma, Zhun Ma, Qin-De Liu and Yu Chen

      Version of Record online: 7 DEC 2009 | DOI: 10.1002/pola.23783

      Thumbnail image of graphical abstract

      Blue-light-emitting copolymers, comprised different ratios of spirobifluorene substituted with cyanophenyl groups as electron-withdrawing segments and tricarbazole-triphenylamines as electron-donating segments, have been developed. Compared with the reference homopolymers, the copolymers showed improved device performance due to balanced charge transporting property. Pure blue emission with CIE coordinates of (0.15, 0.14) and maximum current efficiency of 1.76 cd/A has been demonstrated based on the new developed copolymers.

    3. A highly controllable latent ruthenium Schiff base olefin metathesis catalyst: Catalyst activation and mechanistic studies (pages 302–310)

      Stijn Monsaert, Nele Ledoux, Renata Drozdzak and Francis Verpoort

      Version of Record online: 7 DEC 2009 | DOI: 10.1002/pola.23784

      Thumbnail image of graphical abstract

      The depicted ruthenium Schiff base catalyst 5 exhibits latency toward the Ring-Opening Metathesis Polymerization of cis,cis-1,5-cyclooctadiene and dicyclopentadiene. However, on addition of hydrochloric acid as a cocatalyst, the catalyst turns highly active. This concept proved applicable in a Reaction Injection Molding process and allowed for monomer-to-catalyst ratios up to 60,000/1. Control on the activation of the latent catalyst was afforded when the cocatalyst was formed in situ from the reaction of an alcohol with the appropriate Lewis acid. An in-depth 1H NMR study revealed the observation of the activated catalyst 10. On addition of cyclic olefins, the propagating specie 11 can be observed as well.

    4. Ethylene polymerization by the chromium catalysts based on bidentate [O, P[DOUBLE BOND]O] or [S, P] ligands (pages 311–319)

      Li-Peng He, Hong-Liang Mu, Bai-Xiang Li and Yue-Sheng Li

      Version of Record online: 7 DEC 2009 | DOI: 10.1002/pola.23785

      Thumbnail image of graphical abstract

      Novel bidentate phenoxy-phosphinoyl [O, P[DOUBLE BOND]O] and thiophenol-phosphine [S, P] were found to be effective ligands of chromium catalysts for ethylene polymerization. Both the coordinated donor and the ortho-substituent of the ligands play an important role in determining catalytic activity. Thiophenol-phosphine based chromium catalysts displayed higher catalytic activities and better temperature tolerance for ethylene polymerization than phenoxy-phosphinoyl based ones.

    5. Facile one-step synthesis of electromagnetic functionalized polypyrrole/Fe3O4 nanotubes via a self-assembly process (pages 320–326)

      Wei-Dong Zhang, Hong-Mei Xiao, Lu-Ping Zhu, Shao-Yun Fu and Mei-Xiang Wan

      Version of Record online: 7 DEC 2009 | DOI: 10.1002/pola.23787

      Thumbnail image of graphical abstract

      This article reports a simple self-assembly process for facile one-step synthesis of novel electromagnetic functionalized polypyrrole/Fe3O4 composite nanotubes with a diameter of 400–800 nm and a length of 20–50 μm using p-toluenesulfonic acid (p-TSA) as the dopant and FeCl3 as the oxidant. The novel composite nanotubes show relatively high conductivity and display interesting ferromagnetic behavior.

    6. Multistimuli responsive amphiphilic graft poly(ether amine): Synthesis, characterization, and self-assembly in aqueous solution (pages 327–335)

      Yanrong Ren, Xuesong Jiang, Guilin Yin and Jie Yin

      Version of Record online: 7 DEC 2009 | DOI: 10.1002/pola.23788

      Thumbnail image of graphical abstract

      Multiresponsive amphiphilic graft poly(ether amine)s (agPEAs) comprised of hydrophilic poly(ethylene oxide) (PEO) and hydrophobic octadecyl alkyl chain as side-chain were prepared through one-post synthesis. In aqueous solution, these obtained agPEAs can self-assemble into stable nanomicelles, whose aggregation can be controlled by temperature, pH, and ionic strength with tunable cloud point (CP). The obtained agPEAs are expected to be potential in application such as encapsulation and controlled release of drugs, due to their simple synthesis.

    7. Study on incomplete fluorescence quenching of cationic poly(p-phenylenevinylene)s with different contents of cis- and trans-vinylic linkages (pages 336–341)

      Guang-Wei Zhang, Xiao-Mei Lu, Qu-Li Fan, Yan-Qin Huang and Wei Huang

      Version of Record online: 7 DEC 2009 | DOI: 10.1002/pola.23789

      Thumbnail image of graphical abstract

      Fluorescence quenching of a series of cationic poly(p-phenylenevinylene) derivatives with different contents of cis- and trans-vinylic linkages are intensively investigated. Downward Stern-Volmer curves are found in PPVs with cis-/trans-vinylic linkages while upward Stern-Volmer curves in PPVs with all trans-vinylic linkages. This result shows that the presence of cis-vinylic linkages would most probably cause inaccessible fluorophore and thus the incomplete quenching.

    8. Effect of solvent on the dehydrogenation of poly(1,3-cyclohexadiene): Formation and characteristics of benzoquinone–aromatic hydrocarbon charge-transfer complexes (pages 342–350)

      Itaru Natori, Shizue Natori, Hiroyuki Sekikawa and Kenji Ogino

      Version of Record online: 8 DEC 2009 | DOI: 10.1002/pola.23790

      Thumbnail image of graphical abstract

      The effect of solvent on the dehydrogenation of poly(1,3-cyclohexadiene) (PCHD) with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) [or 2,3,5,6-tetrachloro-1,4-(p-)-benzoquinone (TCQ)] was examined to improve the reactivity of benzoquinones for this dehydrogenation reaction. The dehydrogenation of PCHD with DDQ (or TCQ) was strongly affected by the type of solvent, and aromatic hydrocarbon based solvents were appropriate for this dehydrogenation reaction. A charge transfer complex between DDQ (or TCQ) and aromatic hydrocarbons was formed in the reaction mixture, and the reactivity of the complex was much higher than that of free DDQ (or TCQ). The formation of a DDQ-aromatic hydrocarbon complex, which has a large diamagnetic shift of the 13C NMR signals with respect to DDQ, was the primary factor for improvement of the reactivity of DDQ. For the TCQ-aromatic hydrocarbon complex, the existence of an electron-withdrawing group on the aromatic hydrocarbon was the major factor for improvement of the reactivity of TCQ.

    9. Effects of external donors and hydrogen concentration on oligomer formation and chain end distribution in propylene polymerization with Ziegler-Natta catalysts (pages 351–358)

      Torvald Vestberg, Peter Denifl, Matthew Parkinson and Carl-Eric WilÉN

      Version of Record online: 7 DEC 2009 | DOI: 10.1002/pola.23791

      Thumbnail image of graphical abstract

      In this article oligomer formation and chain end distribution of the oligomer fraction in polypropylenes produced with two Ziegler-Natta catalysts was studied. One of the Zeigler-Natter catalysts (Cat A) was produced using the novel emulsion Sirius technology, which gives very compact catalyst particles without internal pore volume. The results showed that this type of catalyst produced polypropylene with 50% less oligomers than a conventional Ziegler-Natta catalyst (Cat B). Cat A also resulted in a higher amount of regioirregular 2,1 insertions, causing n-butyl terminated oligomers.

    10. Alternating copolymerization of carbon dioxide and propylene oxide under bifunctional cobalt salen complexes: Role of Lewis base substituent covalent bonded on salen ligand (pages 359–365)

      Binyuan Liu, Yanhao Gao, Xin Zhao, Weidong Yan and Xianhong Wang

      Version of Record online: 7 DEC 2009 | DOI: 10.1002/pola.23792

      Thumbnail image of graphical abstract

      Bifunctional cobalt salen complexes containing a Lewis acidic metal center and a Lewis base unit in one molecule have been identified as effective catalysts for the CO2/PO copolymerization with no assistance of cocatalyst, which show high polymeric/cyclic carbonate selectivity. The tethered Lewis basic group on the complexes catalyst activity of cobalt salen complexes can tailor the catalytic activity, molecular weight, and refined micro-structure of the resultant copolymer. This work might shed new lights on designing new metal salen complex-based catalysts for the copolymerization of epoxide and CO2.

    11. Synthesis and characterization of cross-linkable ruthenium complex dye and its application on dye-sensitized solar cells (pages 366–372)

      Ken-Yen Liu, Chiao-Ling Hsu, Shun-Hsing Chang, Jian-Ging Chen, Kuo-Chuan Ho and King-Fu Lin

      Version of Record online: 8 DEC 2009 | DOI: 10.1002/pola.23793

      Thumbnail image of graphical abstract

      The DSSCs with crosslinked Ru-C and Ru-C-co-MAA, respectively adsorbing on TiO2 mesoporous layer have been assessed to have long storage life.

    12. Thermoregulated phase-transfer catalysis via PEG-armed Ru(II)-bearing microgel core star polymers: Efficient and reusable Ru(II) catalysts for aqueous transfer hydrogenation of ketones (pages 373–379)

      Takaya Terashima, Makoto Ouchi, Tsuyoshi Ando and Mitsuo Sawamoto

      Version of Record online: 7 DEC 2009 | DOI: 10.1002/pola.23794

      Thumbnail image of graphical abstract

      PEG-armed Ru(II)-bearing microgel star catalyst (1), which was directly prepared by ruthenium-catalyzed living radical polymerization and subsequent linking reaction in the presence of a phosphine ligand monomer, performed a thermoregulated phase-transfer catalysis for transfer hydrogenation of 2-octanone in 2-propanol/H2O biphasic media. It was superior to the original Ru(II) catalyst and a block-type catalyst with similar structure in terms of activity as well as recovery/recycle. Additionally, the star catalyst efficiently induced aqueous transfer hydrogenation of other ketones (less hydrophobic alkyl ketones and aromatic ketone).

    13. Cleavable multiblock copolymer synthesized by ring-opening metathesis copolymerization of cyclooctene and macrocyclic olefin and its hydrolysis to give carboxyl-telechelic polymer (pages 380–388)

      Meiran Xie, Weizhen Wang, Liang Ding, Jingwei Liu, Dan Yang, Ling Wei and Yiqun Zhang

      Version of Record online: 7 DEC 2009 | DOI: 10.1002/pola.23795

      Thumbnail image of graphical abstract

      Cleavable multiblock copolymer was synthesized by ring-opening metathesis copolymerization of cyclooctene (COE) and a 27-membered macrocyclic olefin (2). Each multiblock copolymer [Poly(COE)-2]m chain consisting of Poly(COE) blocks and ring-opened 2 segments can be cleaved under alkali condition to afford a number of (m = 7–16) carboxyl-telechelic Poly(COE) blocks.

    14. Investigation of spacer influences in phosphorescent-emitting nonconjugated PLED systems (pages 389–402)

      Manuel W. Thesen, Hartmut Krueger, Silvia Janietz, Armin Wedel and Marion Graf

      Version of Record online: 8 DEC 2009 | DOI: 10.1002/pola.23796

      Thumbnail image of graphical abstract

      RGB-colored phosphorescent polymers are synthesized and polymer light emitting diodes (PLEDs) are built of these materials. Therefore, the hole- (HT) and electron-transporting (ET) molecules as well as the phosphorescent Ir-complex (TE) were covalently linked to a nonconjugated poly-(styrene) backbone. The influence of a hexyl spacer between the charge transporting molecules and the polymer backbone compared with the nonspacered analog was studied in respect to the PLED performance. In all cases the nonspacered polymer system showed better device properties than the hexyl spacer variants.

    15. Mimicking “nascent” Cu(0) mediated SET-LRP of methyl acrylate in DMSO leads to complete conversion in several minutes (pages 403–409)

      Xuan Jiang, Brad M. Rosen and Virgil Percec

      Version of Record online: 7 DEC 2009 | DOI: 10.1002/pola.23797

      Thumbnail image of graphical abstract

      Cu(0) nanopowders prepared via disproportionation of CuBr were used as mimics of “nascent” Cu(0) in the single-electron transfer living radical polymerization (SET-LRP) of methyl acrylate (MA), providing faster polymerization than any commercial Cu(0) powder, Cu(0) wire, or CuBr and achieving 80% conversion in <5 min reaction time. Despite the high rate, a living polymerization was observed with linear evolution of molecular weight, narrow polydispersity, no induction period, and high retention of chain-end functionality. Besides providing an unprecedentedly fast, yet controlled, LRP of MA, these studies suggest that “nascent” Cu(0) species formed via disproportionation in SET-LRP are the most active catalysts.

    16. Dendronized polymers via Diels–Alder “click” reaction (pages 410–416)

      Murat Tonga, Nergiz Cengiz, Meliha Merve Kose, Tuna Dede and Amitav Sanyal

      Version of Record online: 8 DEC 2009 | DOI: 10.1002/pola.23799

      Thumbnail image of graphical abstract

      A modular approach toward the synthesis of dendronized polymers is developed using the Diels–Alder “click” reaction. First through third-generation dendrons containing furan-protected maleimide groups at their focal point can be appended onto polymers containing reactive dienes as side-chain functionality. Facile, reagent-free, thermal Diels–Alder cycloaddition between the anthracene-containing polymer and latent-reactive dendrons leads to quantitative functionalization of the polymer chains to afford dendronized polymers.

    17. Copolymerization of ethylene with 1-hexene promoted by novel multi-chelated non-metallocene complexes with imine bridged imidazole ligand (pages 417–424)

      Lifu Ma, Hongli Wang, Jianjun Yi, Qigu Huang, Kejing Gao and Wantai Yang

      Version of Record online: 7 DEC 2009 | DOI: 10.1002/pola.23800

      Thumbnail image of graphical abstract

      A series of novel bridged multi-chelated non-metallocene catalysts, MAO as cocatalyst, are favorable for copolymerization of ethylene with 1-hexene and homopolymerization of ethylene. The copolymer feature high content of 1-hexene incorporation.

    18. Thermosensitive graphene nanocomposites formed using pyrene-terminal polymers made by RAFT polymerization (pages 425–433)

      Jingquan Liu, Wenrong Yang, Lei Tao, Dan Li, Cyrille Boyer and Thomas P. Davis

      Version of Record online: 7 DEC 2009 | DOI: 10.1002/pola.23802

      Thumbnail image of graphical abstract

      Thermosensitive graphene-polymer composites have been prepared by attaching poly(N-isopropylacrylamide) (PNIPAAm) onto the basal plane of graphene sheets via π-π stacking. Pyrene-terminated PNIPAAm was synthesized using reversible addition fragmentation chain transfer (RAFT) polymerization via a pyrene-functional RAFT agent. Aqueous solutions of the graphene-polymer composites were stable and thermosensitive. The lower critical solution temperature (LCST) of pyrene-terminated PNIPAAm was measured to be 33 °C. When the pyrene-functional polymer was attached to graphene the resultant composites were also thermosensitive in aqueous solutions exhibiting a reversible suspension behavior at 24 °C.

    19. Photoluminescent, liquid-crystalline, and electrochemical properties of para-phenylene-based alternating conjugated copolymers (pages 434–442)

      Kai Yao, Yiwang Chen, Lie Chen, Huanling Kong, Weihua Zhou, Fan Li, Xiaohui He and Yen Wei

      Version of Record online: 7 DEC 2009 | DOI: 10.1002/pola.23803

      Thumbnail image of graphical abstract

      Novel liquid-crystalline alternating conjugated copolymers [P(P(n)CN-alt-Cz) and P(P(6)CN-alt-MeP)] with phenylene and carbazolylene or phenylene with methyl substitution onto the main chain have been synthesized through palladium-catalyzed Suzuki coupling reactions. The conjugated copolymers possess strong electronic absorption, high photoluminescence, and exhibit enantiotropic smecticity mesogenic phase. The mixed aromatic rings onto the polyphenylene main chain exert great influence on the electrochemical properties of the copolymers. The band gaps of copolymers (2.3–2.4 eV) are much lower than the band gap of poly(p-phenylene) without substitution.

    20. Macromolecular brushes synthesized by “grafting from” approach based on “click chemistry” and RAFT polymerization (pages 443–453)

      Dongxia Wu, Xiaohui Song, Tao Tang and Hanying Zhao

      Version of Record online: 7 DEC 2009 | DOI: 10.1002/pola.23804

      Thumbnail image of graphical abstract

      Well-defined macromolecular brushes with PNIPAM side chains on random copolymer backbones were synthesized by “grafting from” approach based on click chemistry and reversible addition-fragmentation chain transfer polymerization.

    21. Synthesis and characterization of hyperbranched polystyrene via click reaction of AB2 macromonomer (pages 454–462)

      Li-Zhi Kong, Miao Sun, Hua-Ming Qiao and Cai-Yuan Pan

      Version of Record online: 7 DEC 2009 | DOI: 10.1002/pola.23806

      Thumbnail image of graphical abstract

      Step polymerization of macromonomer PS with two alkynyl groups at one end and an azide group at another end via click reaction produces “HyperMacs” PS with controlled molecular weight and moderately narrow polydispersity. With the molecular weight increase of the macromonomer, the molecular weights of HyperMacs PS obtained increase significantly, and the highly reactivity of click reaction is responsible for complete disappearance of macromonomer and low x-mers in the product and formation of up to 8 × 105 g/mol of HyperMacs PS.

    22. Synthesis, one- and two-photon properties of poly[9,10-bis(3,4-bis(2-ethylhexyl-oxy)phenyl)-2,6-anthracenevinylene-alt-N-octyl-3,6-/2,7-carbazolevinylene] (pages 463–470)

      Haichang Zhang, Erqian Guo, Xueheng Zhang and Wenjun Yang

      Version of Record online: 7 DEC 2009 | DOI: 10.1002/pola.23807

      Thumbnail image of graphical abstract

      2,6-Anthracenevinylene-based polymers are synthesized and their one- and two-photon properties are investigated. They show large two-photon absorption cross-sections (δ) and strong one- and two-photon excitation fluorescence under femtosecond laser pulses. The increased δ of the polymers with the strength of the electron-donating moieties indicates that, at least in this system, the incorporation of the strong electron-donating moieties into the polymer backbone to form D–π–D motif is more effective in enhancing δ than the extension of conjugation length.

    23. Vanadium complex with tetradentate [O,N,N,O] ligand supported on magnesium type carrier for ethylene homopolymerization and copolymerization (pages 471–478)

      Marzena Białek and Ozanna Liboska

      Version of Record online: 8 DEC 2009 | DOI: 10.1002/pola.23808

      Thumbnail image of graphical abstract

      The vanadium complex (1,2-cyclohexylenebis(5-chlorosalicylideneiminato)vanadium dichloride) immobilized on the magnesium support obtained in the reaction of MgCl2·3.4EtOH with Et2AlCl was used in ethylene homopolymerization and copolymerization with 1-octene. This catalyst exhibits the highest activity in conjunction with MAO, and also it is very active with common trialkylaluminium compounds. Though the supported vanadium catalyst is less active then its titanium counterpart, it gives copolymers with significantly higher comonomer contents, as may be seen in the picture which presents comonomer incorporation versus comonomer concentration in the feed (1-vanadium catalyst/MAO; 2-titanium catalyst/Me3Al).

    24. Highly efficient catalysts-acetylacetonato complexes of transition metals in the 4th period for ring-opening polymerization of 1,3-benzoxazine (pages 479–484)

      Atsushi Sudo, Shoji Hirayama and Takeshi Endo

      Version of Record online: 8 DEC 2009 | DOI: 10.1002/pola.23810

      Thumbnail image of graphical abstract

      Hexafluoroacetylacetonato (F6-acac) complexes of manganese, iron, and cobalt were employed as moisture-tolerant Lewis acidic catalysts for the ring-opening polymerization of benzoxazine. Their activity was higher than that of p-toluenesulfonic acid, one of the strong acids.

  3. Rapid Communication

    1. Top of page
    2. Highlight
    3. Articles
    4. Rapid Communication
    5. Corrigendum
    1. You have free access to this content
      Enantioseparation of doubly functionalized polar norbornenes by HPLC and their ruthenium-catalyzed ring-opening metathesis polymerization (pages 485–491)

      Yasushi Nishihara, Yukiko Doi, Seisuke Izawa, Horng-Yi Li, Yoshiaki Inoue, Masaaki Kojima, Jwu-Ting Chen and Kentaro Takagi

      Version of Record online: 7 DEC 2009 | DOI: 10.1002/pola.23781

      Thumbnail image of graphical abstract

      Doubly fuctionalized polar norbornene monomers bearing the cyano and ester groups are synthesized and enantiomers are separated by high performance liquid chromatography (HPLC). These optically active monomers are polymerized by a ruthenium carbene catalyst in a living fashion. The chiral monomer gave an optically active polymer of lower, but opposite sign of optical rotation (monomer [α]D = +61.0°, polymer [α]D = −3.1°).

  4. Corrigendum

    1. Top of page
    2. Highlight
    3. Articles
    4. Rapid Communication
    5. Corrigendum
    1. You have free access to this content
      Corrigendum (page 492)

      Leena Nebhani and Christopher Barner-Kowollik

      Version of Record online: 7 DEC 2009 | DOI: 10.1002/pola.23798