Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 49 Issue 2

15 January 2011

Volume 49, Issue 2

Pages 301–549

  1. Articles

    1. Top of page
    2. Articles
    3. Rapid Communications
    1. Preparation of polyurethane elastomers (PUEs) in a high-throughput workflow (pages 301–313)

      László I. Majoros, Bernard Dekeyser, Nancy Haucourt, Pieter Castelein, Johan Paul, Johannes M. Kranenburg, Erik Rettler, Richard Hoogenboom and Ulrich S. Schubert

      Version of Record online: 29 NOV 2010 | DOI: 10.1002/pola.24397

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      In this contribution, a concept is reported for the high-throughput preparation and screening of polyurethane elastomer (PUE) samples that are mainly applied within the automotive industry as covering materials. The raw materials for the preparation of PUEs are very viscous and reactive; therefore, their handling requires a highly flexible and fast high-throughput tool. Nowadays, these non-cellular PU materials are mainly processed in a manual way enabling the preparation of a maximum of 20 elastomer samples per day and per person which does not allow fast innovation. The growing markets and demands for new PU materials are pushing companies towards the use of high-throughput technologies as the key approach to discover and develop new polymer products faster and more energy efficient than before.

    2. Automated batch emulsion copolymerization of styrene and butyl acrylate (pages 314–326)

      Monique A. Mballa Mballa, Ulrich S. Schubert, Johan P. A. Heuts and Alex M. van Herk

      Version of Record online: 29 NOV 2010 | DOI: 10.1002/pola.24403

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      For the first time, challenges for carrying out automated batch emulsion copolymerization with a stirred tank robotic platform are explored. The automated system used meets the requirements for successfully carrying out emulsion copolymerizations revealing a high reproducibility and yielding comparable results with conventional experiments.

    3. Syndiospecific polymerization of styrene in the presence of cyclic olefins: A new approach for molecular weight, molecular weight distribution, and stereoregularity controls for syndiotactic polystyrene (pages 327–336)

      Fu-Yuan Tzeng and Jing-Cherng Tsai

      Version of Record online: 29 NOV 2010 | DOI: 10.1002/pola.24412

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      A new approach for regulating the chin reaction pathway during syndiospecific polymerization of styrene can be accomplished by conducting the styrene polymerization in the presence of cyclic olefins. The new approach offers an exciting opportunity for microstructural modification (e.g., stereoregulaity, molecular weight, and molecular weight distribution) of syndiotactic polystyrene through a controlled chain reaction pathway.

    4. Enhanced redox stability and electrochromic properties of aromatic polyamides based on N,N-bis(4-carboxyphenyl)-N′,N′-bis(4-tert-butylphenyl)-1,4-phenylenediamine (pages 337–351)

      Hui-Min Wang and Sheng-Huei Hsiao

      Version of Record online: 18 NOV 2010 | DOI: 10.1002/pola.24421

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      A new series of redox-active polyamides with di-tert-butyl-substituted N,N,N′,N′-tetraphenylphenylenediamine (TPPA) units were prepared via the phosphorylation polyamidation reactions from a new dicarboxylic acid monomer, namely N,N-bis(4-carboxyphenyl)-N′,N′-bis(4-tert-butylphenyl)-1,4-phenylenediamine, with various aromatic diamines. Most of these polyamides could be solution cast into tough and flexible films with high thermal stability. They exhibited enhanced redox stability and electrochromic performance when compared with the corresponding analogues without tert-butyl substituents on the TPPA unit. The polyamide with the TPPA unit in both the diacid and diamine components shows multicolored electrochromic behavior. A polyamide containing both the cathodic coloring anthraquinone group and the anodic coloring TPPA group has the ability to show red, green, and blue states, the additive colors for RGB-based display devices.

    5. Thermally crosslinkable hole-transporting poly(fluorene-co-triphenylamine) for multilayer polymer light-emitting diodes (pages 352–360)

      Wen-Fen Su, Ruei-Tang Chen and Yun Chen

      Version of Record online: 18 NOV 2010 | DOI: 10.1002/pola.24432

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      A new thermally crosslinkable hole-transporting copolymer (PFO-TPA) with reactive pedant styryl groups was synthesized and applied in fabrication of multilayer polymer light-emitting diodes (PLEDs). Multilayer device using crosslinked PFO-TPA as hole-injection layer, ITO/PEDOT:PSS/PFO-TPA/PFO/LiF/Ca/Al, was successfully fabricated by successive spin-coating processes. Its maximum luminance and maximum luminance efficiency were 6140 cd/m2 and 3.16 cd/A, respectively, in which the efficiency was about six times higher than that without PFO-TPA layer.

    6. A single-layer approach to electrochromic materials (pages 361–368)

      Simona Percec and Susan Tilford

      Version of Record online: 18 NOV 2010 | DOI: 10.1002/pola.24433

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      Electrochromic structures consisting of carbazole equipped with alkyl or alkyl oxide linkers were synthesized using different chemistries. They were used in chemical modification reactions of poly(epichlorohydrin-co-ethylene oxide), polyvinyl butyral, and Na neutralized poly(ethylene-co-methacrylic acid), with the purpose of inducing electrochromic properties. A proof of concept of a single layer all solid electrochromic device was demonstrated in the case of carbazole-modified poly(epichlorohydrin-co-ethylene oxide) assembled between ITO electrodes. This changed color when the potential was switched from 0 V (OFF state) to 1 V (ON state).

    7. Syntheses and characterization of carbazole based new low-band gap copolymers containing highly soluble benzimidazole derivatives for solar cell application (pages 369–380)

      Jaehong Kim, Sung Heum Park, Jinwoo Kim, Shinuk Cho, Youngeup Jin, Joo Young Shim, Hyunmin Shin, Sooncheol Kwon, Il Kim, Kwanghee Lee, Alan J. Heeger and Hongsuk Suh

      Version of Record online: 23 NOV 2010 | DOI: 10.1002/pola.24435

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      Newly designed 2H-benzimidazole derivatives, which substituted the sulfur of the BT unit of PCDTBT with alkylated carbon to improve the solubility of the polymers, were synthesized as the electron-deficient moiety for ICT copolymers. By this new approach, two highly soluble low-band gap polymers for OPVs were synthesized and characterized.

    8. New polymers derived from 4-vinylsilylbenzocyclobutene monomer with good thermal stability, excellent film-forming property, and low-dielectric constant (pages 381–391)

      Junxiao Yang, Shangchun Liu, Fanghua Zhu, Yawen Huang, Bo Li and Lin Zhang

      Version of Record online: 23 NOV 2010 | DOI: 10.1002/pola.24437

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      The new polymers derived from 4-(1′,1′-dimethyl-1′-vinyl) silylbenzocyclobutene have good film-forming property and lower dielectric constant compared with most matrix materials.

    9. Arylamino-functionalized fluorene- and carbazole-based copolymers: Color-tuning their CdTe nanocrystal composites from red to white (pages 392–402)

      Ioannis Kanelidis, Yi Ren, Vladimir Lesnyak, Jan-Christoph Gasse, Ronald Frahm, Alexander Eychmüller and Elisabeth Holder

      Version of Record online: 29 NOV 2010 | DOI: 10.1002/pola.24438

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      The Suzuki-mediated synthesis of blue-light emitting, amino-functionalized fluorene, and carbazole-based copolymers is shown. Facile condensation reactions and Ullmann couplings allowed introducing of amino- and diphenylamino-functionalities in the C9-position of the fluorene and carbazole building blocks. Subsequent copolymerization according to Suzuki resulted in copolymers, which were fully characterized and their wide optical bandgaps revealed suitability for hosting nanocrystals such as CdTe and to moreover provide a simple system for color-tuning on demand within these novel composite materials.

    10. Ring-opening polymerization of cyclic esters promoted by phosphido-diphosphine pincer group 3 complexes (pages 403–413)

      Ilaria D'auria, Mina Mazzeo, Daniela Pappalardo, Marina Lamberti and Claudio Pellecchia

      Version of Record online: 18 NOV 2010 | DOI: 10.1002/pola.24447

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      The phosphido-diphosphine pincer yttrium and scandium complexes 1–4 are very active initiators for the ring-opening polymerization of ε-caprolactone, L-lactide and δ-valerolactone under mild polymerization conditions. In the presence of alcohol, living immortal polymerizations were achieved allowing the production of large quantities of microstructurally controlled polymers with small amounts of catalyst, thus optimizing the productivity and minimizing the contamination of polymer with metal residues.

    11. Fluorine-containing linear block terpolymers: Synthesis and self-assembly in solution (pages 414–422)

      Lihong He, Juan Pablo Hinestrosa, Joseph M. Pickel, Shanju Zhang, David G. Bucknall, S. Michael Kilbey II, Jimmy W. Mays and Kunlun Hong

      Version of Record online: 23 NOV 2010 | DOI: 10.1002/pola.24453

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      The polymerization of 2-fluoroethyl methacrylate (2FEMA) was studied by reversible addition fragmentation chain transfer technique. Linear triblock terpolymers of PnBMA-PMMA-P2FEMA were also synthesized by sequential RAFT polymerizations and characterized by NMR and gel permeation chromatography. These polymers formed complex micellar aggregates in a tetrahydrofuran/methanol mixture with structures and diameters controlled by polymer compositions, as revealed by scanning electron microscopy and dynamic light scattering.

    12. Synthesis of cationic N-[3-(dimethylamino)propyl]methacrylamide brushes on silicon wafer via surface-initiated RAFT polymerization (pages 423–431)

      Nergiz Gurbuz, Serkan Demirci, Serkan Yavuz and Tuncer Caykara

      Version of Record online: 18 NOV 2010 | DOI: 10.1002/pola.24454

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      Well-defined cationic poly(N-[3-(dimethylamino)propyl]methacrylamide) [poly(DMAPMA)] brushes were synthesized by surface-initiated RAFT polymerization using the dithioester-immobilized silicon surface as a RAFT agent. Moreover, the calculation of grafting parameters, including grafting density, σ (chain per nm2), and average distance between grafting sites, D (nm) from the number-average molecular weight, Mn (g/mol) and ellipsometric thickness, h (nm) values indicated the formation of densely and uniform poly(DMAPMA) films and allowed us to predict a “brush-like” conformation.

    13. Synthesis of zwitterionic polymer by SET-LRP at room temperature in aqueous (pages 432–440)

      Wei Ding, Chongfu Lv, Ying Sun, Xiaojun Liu, Tao Yu, Guangmiao Qu and Huoxin Luan

      Version of Record online: 18 NOV 2010 | DOI: 10.1002/pola.24455

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      The SET-LRP of acrylamide in aqueous solution using CPA as initiator and Cu0 powder/Me6-TREN/CuCl2 as catalytic system, the kinetic plots showed first order and the initiator efficiency was high as well as the apparent prorogation rate, kpapp = 0.2118 min−1. The zwitterionic polymers with narrow distribution were obtained and in salts aqueous solutions, it showed the properties of antipolyelectrolyte well.

    14. The N[DOUBLE BOND]S[DOUBLE BOND]N link as electron accepting moiety for stable, solution-processable conjugated oligomers (pages 441–451)

      Mingfeng Wang, Yanming Sun, Minghong Tong, Eneida S. Chesnut, Jung Hua Seo, Rajeev Kumar and Fred Wudl

      Version of Record online: 23 NOV 2010 | DOI: 10.1002/pola.24456

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      New conjugated oligomers, oligo(9,9-didodecylfluorene-bis-sulphurdiimide), consisting of 9,9-didodecylfluorene separated by [BOND]N[DOUBLE BOND]=S[DOUBLE BOND]=N[BOND] moieties are reported. These oligomers are stable purple solids under ambient conditions with absorption covering a broad spectral window in the UV-vis range and a main broad peak centered at 555 nm with onset extending to 700 nm. These oligomers show an obviously longer conjugation length than its dimeric analogue, bis-9,9-didodecyl-fluorene-2-sulfurdiimide that shows a band-edge absorption centered at 484 nm with onset at 590 nm. Moreover, photoinduced charge transfer was observed in composites of these oligomers blended with an electronic partner that either donates or accepts electrons.

    15. Synthesis and properties of multiblock copoly(arylene ether)s containing superacid groups for fuel cell membranes (pages 452–464)

      Takefumi Mikami, Kenji Miyatake and Masahiro Watanabe

      Version of Record online: 23 NOV 2010 | DOI: 10.1002/pola.24458

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      A series of block copoly(arylene ether)s containing pendant superacid groups were synthesized, and their properties were investigated. The ionomer membranes exhibited higher water uptake and proton conductivity than those of our previous random copolymer, and well-developed hydrophilic/hydrophobic phase separation with large hydrophilic clusters was observed.

    16. Photopolymerization behavior in nanocomposites formed with thiol–acrylate and polymerizable organoclays (pages 465–475)

      Soon Ki Kim and C. Allan Guymon

      Version of Record online: 29 NOV 2010 | DOI: 10.1002/pola.24460

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      This study investigates the influence of monomer composition and the type of polymerizable organoclay on thiol–acrylate photopolymerization behavior in preparation of photocurable clay nanocomposite systems. To this end, two types of polymerizable organoclays with acrylate or thiol functional group on the clay surfaces were compared in monomer compositions with different polarity and functionality. Higher chemical compatibility of components induced enhanced clay exfoliation resulting in increases in photopolymerization rate. By affecting the stoichiometric ratio of functional groups in the clay gallery, thiolated organoclays enhance thiol–ene reaction, whereas acrylated organoclays encourage acrylate homopolymerization.

    17. Fast switching immobilized photochromic dyes (pages 476–486)

      Nino Malic, Jonathan A. Campbell, Abdelselam S. Ali, Craig L. Francis and Richard A. Evans

      Version of Record online: 29 NOV 2010 | DOI: 10.1002/pola.24461

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      A hetero Y-branching architecture incorporating a photochromic dye, soft poly(dimethylsiloxane) oligomer, and a polymerizable methacrylate moiety allows both tethering to a radically polymerized polymer matrix and fast photochromic switching performance. Faster switching kinetics compared with a conventional unbound dye in a rigid polymeric matrix has been achieved with this new concept dye–polymer conjugate.

    18. Syntheses and characterization of block copolymers of poly(aliphatic ester) with clickable polyphosphoester (pages 487–494)

      Yu-Cai Wang, You-Yong Yuan, Feng Wang and Jun Wang

      Version of Record online: 29 NOV 2010 | DOI: 10.1002/pola.24462

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      We report a series of biocompatible and biodegradable block copolymers of poly(ε-caprolactone) with “clickable” polyphosphoester through controlled ring-opening polymerization of five-membered cyclic phosphoester monomer. The polymerization reveals living characteristics, and the molecular weight and composition are controllable. Azide-functionalized poly(ethylene glycol) has been grafted to the copolymer to demonstrate the reactive feasibility by Cu(I)-catalyzed “click” chemistry of azides and alkynes, generating “brush-coil” polymers. The mild conditions associated with the “click” reaction are shown to be compatible with poly(ε-caprolactone) and polyphosphoester backbones, rendering the “click” reaction a generally useful method for grafting numerous types of functionality onto the block copolymers.

    19. Synthesis, characterization and properties of N-maleimide side-chain liquid crystalline copolymers (pages 495–510)

      J. M. Bautista de Ojeda, I. Quijada-Garrido and J. M. Barrales-Rienda

      Version of Record online: 29 NOV 2010 | DOI: 10.1002/pola.24463

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      A new series of side chain liquid crystalline copolymers with poly(N-maleimide) backbone, a mesogen based on phenyl benzoate moieties with n-alkyloxy pendant groups and n-octadecyl side chain comonomer has been investigated. Due to the stiffness and regularity of the poly(N-maleimide) backbone, the smectic mesophase is retained for high content of the non-mesogenic comonomer. In addition this system presents a high thermal stability and a smectic-isotropic temperature can be modulated by changing the content of the non-mesogenic comonomer.

    20. Well-defined polyolefin/poly(ε-caprolactone) diblock copolymers: New synthetic strategy and application (pages 511–517)

      Qi-Zheng Li, Guo-Yi Zhang, Jian-Zhuang Chen, Qiao-Ling Zhao, Hui-Chao Lu, Jin Huang, Liu-He Wei, Franck D'agosto, Christophe Boisson and Zhi Ma

      Version of Record online: 29 NOV 2010 | DOI: 10.1002/pola.24464

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      Well-defined polymethylene-b-poly(ε-caprolactone) (PM-b-PCL) diblock copolymers were synthesized via the combination of living polymerization of ylides and ring-opening polymerization of ε-caprolactone. The cryofractured surface of LDPE/PCL or LDPE/polycarbonate PC blends with and without PM-b-PCL were observed by SEM, revealing that such PM-b-PCL diblock copolymers are an effective compatibilizer for the considered blends. A highly ordered porous film with the average pore size of 2.8μm in diameter was successfully fabricated via breath-figure method using PM1-b-PCL3 (3.0 wt %) in CH2Cl2 at 25 °C under a static humid condition (RH = 95%).

    21. Polyurethanes from polyols obtained by ADMET polymerization of a castor oil-based diene: Characterization and shape memory properties (pages 518–525)

      E. Del Rio, G. Lligadas, J. C. Ronda, M. Galià, M. A. R. Meier and V. Cádiz

      Version of Record online: 29 NOV 2010 | DOI: 10.1002/pola.24466

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      Novel biobased poly(ether urethane)s with good thermal and mechanical properties, as well as shape memory properties have been obtained. The starting polyether polyols have been synthesized by ADMET polymerization of 1,3-di-10-undecenoxy-2-propanol, a castor oil based diene, and using 10-undecenol as renewable comonomer to end-cap polymer chains and limit the molecular weight. The polyols obtained in this way were reacted with 4,4′-methylenebis(phenylisocyanate) (MDI) to yield a series of amorphous and semicrystalline polyurethane networks.

    22. Gluconolactone-derivated polymers: Copolymerization, thermal properties, and their potential use as polymeric surfactants (pages 526–536)

      Vanesa Bordegé, Alexandra Muñoz-bonilla, Orietta León, Rocío Cuervo-rodríguez, Manuel Sánchez-chaves and Marta Fernández-García

      Version of Record online: 29 NOV 2010 | DOI: 10.1002/pola.24467

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      Amphiphilic statistical glycopolymers bearing gluconolactone moieties were synthesized by conventional radical polymerization, one of the most widely used in industry. The composition of the glycopolymer was varied in a wide range of delivering copolymers with different grades of amphiphilicity. The obtained glycopolymers were used as stabilizer in the emulsion polymerization of methyl acrylate, exhibiting relatively good surfactant properties, which depend on the glycopolymer composition. Furthermore, incorporation of these glycopolymers (containing carbohydrate in the open-chain form) on the poly(methyl acrylate) latex particles imparts antifouling properties to the polymer particles and hence to the polymer coatings.

    23. Dicarbonyl pentaphenylcyclopentadienyl iron complex for living radical polymerization: Smooth generation of real active catalysts collaborating with phosphine ligand (pages 537–544)

      Muneki Ishio, Makoto Ouchi and Mitsuo Sawamoto

      Version of Record online: 29 NOV 2010 | DOI: 10.1002/pola.24468

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      Dicarbonyl pentaphenylcyclopentadienyl iron complex [(CpPh)Fe(CO)2Br; CpPh = η-C5Ph5] was used for living radical polymerization. In the presence of triphenylphosphine (PPh3), MMA was smoothly polymerized to give controlled polymers with narrow molecular weight distributions (Mn ∼ 100,000; Mw/Mn ∼ 1.2). The carbonyl ligands were efficiently exchanged with the phosphine for the inactive complex to transform into real active catalyst via an activation of the initiator (R[BOND]Br), supported by FTIR and 31P NMR for the model reactions. The ligand exchange was much faster than with other cyclopentadienyl complexes [i.e., CpFe(CO)2Br, Cp = C5H5; Cp*Fe(CO)2Br, Cp* = C5Me5], which led to the superiority in the catalytic activity.

  2. Rapid Communications

    1. Top of page
    2. Articles
    3. Rapid Communications
    1. Synthesis of a methacrylic monomer having pendant cyclohexene cyclic carbonate—Easy CO2 fixation and radical polymerization (pages 545–549)

      Balaka Barkakaty, Kazuhide Morino, Atsushi Sudo and Takeshi Endo

      Version of Record online: 29 NOV 2010 | DOI: 10.1002/pola.24471

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      We present here the key-effect of using CO2 catching agent N-methyltetrahydropyrimidine (MTHP) on the facile transformation of sterically hindered cyclohexene oxide methacrylate to its corresponding cyclic carbonate methacrylate under mild conditions in contrast to the usual-highly improbable and high energy consuming (high temperature-high pressure) reactions when carried out in its absence. Detailed investigations of reaction conditions were also carried out with respect to the influence of different types of tetra-alkyl halide salts as cocatalyst (Bu4MX) and at various temperatures. Furthermore, the free radical polymerization of the obtained di-substituted cyclohexyl-cyclic-carbonate-methacrylate monomer along with the characterization of the resulting homopolymer is also reported.

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