Journal of Polymer Science Part A: Polymer Chemistry

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

15 August 2009

Volume 47, Issue 16

Pages 3957–4213

  1. Highlights

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid Communications
    5. Notes
    1. You have free access to this content
      Production and processing of spider silk proteins (pages 3957–3963)

      John G. Hardy and Thomas R. Scheibel

      Version of Record online: 6 JUL 2009 | DOI: 10.1002/pola.23484

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      We produce Spider silk-like proteins using biotechnology, and subsequently utilize biomimetic processes to prepare useful materials morphologies that have a variety of technical and biomedical applications. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

  2. Articles

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid Communications
    5. Notes
    1. Random and sequential radical cotelomerizations of 3,3,3-trifluoropropene (H2C[DOUBLE BOND]CHCF3) with vinylidene fluoride (F2C[DOUBLE BOND]CH2) (pages 3964–3981)

      Georgi Kostov, Frédéric Boschet, Stephan Brandstadter and Bruno Ameduri

      Version of Record online: 6 JUL 2009 | DOI: 10.1002/pola.23455

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      The sequential and random cotelomerizations of vinylidene fluoride (VDF) and 3,3,3-trifluoropropene (TFP) with (CF3)2CFI led to polyadducts with molecular weights ranging from 700 to 66,000 g mol−1 in high yields. Both paths showed that TFP is more reactive than VDF, and the random cotelomerization allowed the assessment of the reactivity ratios (rVDF = 0.28 ± 0.07 and rTFP = 2.35 ± 0.26 at 75 °C) as well as the Q and e parameters for TFP (QTFP = 0.037–0.279, and eTFP = 1.007–1.847).

    2. Synthesis and palladium-catalyzed addition polymerization of norbornene carrying epoxy moiety (pages 3982–3989)

      Hidetada Morishita, Atsushi Sudo and Takeshi Endo

      Version of Record online: 6 JUL 2009 | DOI: 10.1002/pola.23459

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      A norbornene monomer carrying epoxy moiety 1 was successfully synthesized from 5-norbornene-2-carbardehyde by treating it with thioylide in ambient temperature. With using a catalytic system consisted of Pd(II)(OAc)2/P(C6H11)3/[Ph3C+][B(C6F5)4], copolymerization of the obtained monomer 1 and 5-butyl-2-norbornene (BNB) was examined to give poly(norbornene)s carrying epoxy moiety in the side chains, of which composition ratios corresponded to initial feed ratios [1]0:[BNB]0. Influence of the epoxy moiety of 1 on its Pd-catalyzed addition polymerization was elucidated by detail investigation of the homopolymerizations and copolymerization behaviors of 1 and BNB.

    3. Copolymerization of norbornene and 5-norbornene-2-yl acetate using novel bis(β-ketonaphthylamino)Ni(II)/B(C6F5)3/AlEt3 catalytic system (pages 3990–4000)

      Fuping He, Yiwang Chen, Xiaohui He, Muqing Chen, Weihua Zhou and Qing Wu

      Version of Record online: 6 JUL 2009 | DOI: 10.1002/pola.23460

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      Copolymerization of NBE and NBE-OCOMe in toluene undergoes vinyl polymerization by simple bis(β-ketonaphthylamino)Ni(II) complex activated with a combination of B(C6F5)3/AlEt3. For copolymerization of nobornene and their polar derivatives, involvement of AlEt3 in catalyst is necessary. Slight addition of NBE-OCOMe in copolymerization of NBE and NBE-OCOMe gives rise to significant increase of catalyst activity for catalytic system bis(β-ketonaphthylamino)Ni(II)/B(C6F5)3/AlEt3.

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      Synthesis of amphiphilic and thermoresponsive ABC miktoarm star terpolymer via a combination of consecutive click reactions and atom transfer radical polymerization (pages 4001–4013)

      Changhua Li, Zhishen Ge, Hewen Liu and Shiyong Liu

      Version of Record online: 6 JUL 2009 | DOI: 10.1002/pola.23461

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      We report on the synthesis of well-defined amphiphilic and thermoresponsive ABC miktoarm star terpolymer consisting of poly(ethylene glycol) (PEG), poly(t-butyl methacrylate) (PtBMA), and poly(N-isopropylacrylamide) (PNIPAM) arms via a combination of consecutive click reactions and ATRP, starting from a trifunctional core molecule, bis(2-azidoethyl)amine. The obtained PEG(-b-PtBMA)-b-PNIPAM miktoarm star terpolymer self-assembles in aqueous solution into PtBMA-core micelles stabilized with hybrid PEG/PNIPAM coronas, which undergo further structural rearrangement and fuse into much larger aggregates solely stabilized by PEG coronas. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    5. Nanostructured polymer composite nanoparticles synthesized in a single step via simultaneous ROMP and ATRP under microemulsion conditions (pages 4014–4027)

      Cédric Airaud, Emmanuel Ibarboure, Cédric Gaillard and Valérie Héroguez

      Version of Record online: 6 JUL 2009 | DOI: 10.1002/pola.23462

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      A straightforward one-pot, one-step, one-catalyst route is proposed to synthesize polymer hybrid particles based on the simultaneous combination of two mechanistically distinct polymerizations in microemulsion. Norbornene and methyl metacrylate were converted via Ring-Opening Metathesis Polymerization and Atom Transfer Radical Polymerization, respectively. Depending on the combination fashion, the prepared particles exhibited various original morphologies as imaged by AFM. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    6. Poly(thienylene-vinylene-thienylene) with cyano substituent: Synthesis and application in field-effect transistor and polymer solar cell (pages 4028–4036)

      Meixiu Wan, Weiping Wu, Guangyi Sang, Yingping Zou, Yunqi Liu and Yongfang Li

      Version of Record online: 8 JUL 2009 | DOI: 10.1002/pola.23464

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      A novel conjugated polymer, poly(thienylene-vinylene-thienylene) bearing cyano substituent (CN-PTVT), was synthesized by Stille coupling. The corporation of cyano group effectively decreased the HOMO energy level of the polymer. The FET device based on CN-PTVT possesses excellent air-stability as well as a higher hole mobility of 5.9 × 10−3 cm2 V−1 s−1 with Ion/Ioff ratio of 4.9 × 104. The PSC device with CN-PTVT as donor and PCBM as acceptor shows a relatively high open-circuit voltage of 0.82 V and a power conversion efficiency of 0.3% under the illumination of AM1.5, 100 mW/cm2. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    7. New P-type of poly(4-methoxy-triphenylamine)s derived by coupling reactions: Synthesis, electrochromic behaviors, and hole mobility (pages 4037–4050)

      Hui-Wen Chang, Kai-Han Lin, Chu-Chen Chueh, Guey-Sheng Liou and Wen-Chang Chen

      Version of Record online: 8 JUL 2009 | DOI: 10.1002/pola.23465

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      Poly(triphenylamine)s with 4-methoxy-substituted were synthesized from the nickel-catalyzed Yamamoto and oxidative coupling reaction with FeCl3. These polymers were amorphous with high glass-transition temperatures (Tgs) in the range of 152–273 °C and bluish green light (430–487 nm) fluorescence quantum efficiency up to 45–62% in NMP solution. All polymers exhibited reversible oxidation redox peaks with electrochromic and p-type characteristics, the hole-mobility of O-PMOTPA and Y-PMOPD was up to 1.5 × 10−4 and 5.6 × 10−5 cm2 V−1 s−1, respectively. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    8. A straightforward strategy for the efficient synthesis of acrylate and phosphine oxide-containing vegetable oils and their crosslinked materials (pages 4051–4063)

      L. Montero De Espinosa, J. C. Ronda, M. GaliÀ and V. Cádiz

      Version of Record online: 8 JUL 2009 | DOI: 10.1002/pola.23466

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      Phosphorus-containing triglycerides were prepared from a straightforward route that involves firstly the preparation of secondary allylic alcohols from the unsaturated oil. These allylic alcohols in presence of chlorodiphenylphosphine give allylic phosphinites capable to undergo a [2,3]-sigmatropic rearrangement leading to tertiary phosphine oxides directly linked to triglyceride in a one pot two step reaction. The obtained phosphorus and hydroxyl-containing triglycerides have been esterified to acrylate esters that can radically crosslink providing a promising route to obtain phosphorus-containing polymeric networks. The thermal, dinamomechanical, and flame retardancy properties of the final materials were evaluated and thermal and thermooxidative degradation was studied. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    9. Synthesis and characterization of high molecular weight hexafluoroisopropylidene-containing polybenzimidazole for high-temperature polymer electrolyte membrane fuel cells (pages 4064–4073)

      Guoqing Qian and Brian C. Benicewicz

      Version of Record online: 8 JUL 2009 | DOI: 10.1002/pola.23467

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      The high molecular weight hexafluoroisopropylidene containing polybenzimidazole (6F-PBI) was synthesized from 3,3′-diaminobenzidine (TAB) and 2,2-bis(4-carboxyphenyl) hexafluoropropane (6F-diacid), using polyphosphoric acid (PPA) as both the polycondensation agent and the polymerization solvent. Investigation of polymerization conditions to achieve high molecular weight polymers was explored via stepwise temperature control, monomer concentration in PPA, and final polymerization temperature.

    10. Reducible polyethylenimine hydrogels with disulfide crosslinkers prepared by michael addition chemistry as drug delivery carriers: Synthesis, properties, and in vitro release (pages 4074–4082)

      Shou-Chen Han, Wei-Dong He, Jian Li, Li-Ying Li, Xiao-Li Sun, Bo-Yu Zhang and Ting-Ting Pan

      Version of Record online: 8 JUL 2009 | DOI: 10.1002/pola.23468

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      Disulfide crosslinked PEI hydrogels with disulfide crosslinks (SS-PEI hydrogels) were synthesized via Michael addition reaction. The hydrogels had a uniformly crosslinked network, which can improve control over the release of encapsulated drug, and the hydrogels degraded into water-soluble polymers in the presence of the dithiothreitol. In addition, the degradation of hydrogels can trigger the release of encapsulated drug molecules, as well as facilitate the removal of empty vehicles.

    11. Self-assembly of π-conjugated bis(terpyridine) ligands with zinc(II) ions: New metallosupramolecular materials for optoelectronic applications (pages 4083–4098)

      Andreas Winter, Christian Friebe, Manuela Chiper, Martin D. Hager and Ulrich S. Schubert

      Version of Record online: 8 JUL 2009 | DOI: 10.1002/pola.23469

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      A series of main-chain metallopolymers (P1P10) based on rigid-linear π-conjugated bis(terpyridine)s and ZnII ions was prepared and characterized. The electrochemical and photophysical properties of the monomers and polymers in solution were investigated. Bright purple to green PL emission was observed for P1P10 with the emission color strongly depending on the nature of the π-conjugated bis(terpyridine) system. For a representative example the processability and the film-forming ability as well as the electro-optical behavior in the solid state were investigated. Utilizing metallo-polymer P6 as emitter, yellow PL as well as orange EL emission were found. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    12. Morphological transitions in aggregates of thermosensitive poly(ethylene oxide)-b-poly(N-isopropylacrylamide) block copolymers prepared via RAFT polymerization (pages 4099–4110)

      Junpeng Zhao, Guangzhao Zhang and Stergios Pispas

      Version of Record online: 8 JUL 2009 | DOI: 10.1002/pola.23470

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      Highly asymmetric thermosensitive PEO-b-PNIPAM double hydrophilic block copolymers were prepared by RAFT polymerization using a PEO-based CTA. Above LCST, the copolymers form aggregates with morphologies depending greatly on copolymer composition, concentration, temperature, and heating rate, which is ascribed to both thermodynamics and different kinetics during the temperature induced aggregation processes. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    13. Photoreactive particle prepared from natural rubber and 1,9-nonandioldimethacrylate (pages 4111–4118)

      Nanthaporn Pukkate, Tatsuya Horimai, Osamu Wakisaka, Yoshimasa Yamamoto and Seiichi Kawahara

      Version of Record online: 10 JUL 2009 | DOI: 10.1002/pola.23471

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      Photoreactive particle was prepared by graft copolymerization of 1,9-nonandioldimethacrylate (NDMA) onto deproteinized natural rubber (DPNR) particles in latex stage. First, NDMA was mixed with α-cyclodextrin (α-CD) as a coupling agent to form an inclusion complex stabilize a carbon-carbon double bond of NDMA as a bifunctional monomer. Second, the inclusion complex was graft-copolymerized DPNR in latex stage with potassium persulfate (KPS) as an initiator.

    14. Unusually highly efficient, singlet state, visible light photoinitiators based on styrylbenzimidazolium phenyltributylborate photoredox pairs for vinyl monomers free radical polymerization (pages 4119–4129)

      Marek Pietrzak, Beata Jędrzejewska and Jerzy Pączkowski

      Version of Record online: 8 JUL 2009 | DOI: 10.1002/pola.23472

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      1,3-Dimethyl-2-[4-(N,N-dialkylamino)styryl]benzimidazolium phenyl-tri-n-butylborates were employed as the novel, very effective, singlet state photoinitiators operating in the visible light region. The tested photoredox couples exhibit unexpectedly high photoinitiation efficiency of vinyl monomers free radical polymerization with a double bond conversion of about 45% and quantum yield of polymerization reaching value of about 67. They are the example of the system that generates more than one radical after one photon absorption. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    15. SET-LRP of vinyl chloride initiated with CHBr3 in DMSO at 25 °C (pages 4130–4140)

      Monika J. Sienkowska, Brad M. Rosen and Virgil Percec

      Version of Record online: 8 JUL 2009 | DOI: 10.1002/pola.23536

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      The development of Cu(0)/TREN/CuBr2-catalyzed SET-LRP of VC initiated with CHBr3 in DMSO at 25 °C is described. Employment of CuBr2 as an additive allows for the first LRP of low molecular weight VC (target DP = 100), as well as lower Cu powder loading levels, improved Ieff, and control in the synthesis of higher molecular VC. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    16. Alternated π-conjugated polymers based on a 1,2-diiminocyclohexane chiral unit for nitroaromatics sensing (pages 4141–4149)

      Simon Clavaguera, Olivier J. Dautel, Lionel Hairault, Christophe Méthivier, Pierre Montméat, Eric Pasquinet, Claire-Marie Pradier, Françoise Serein-Spirau, Salem Wakim, Florian Veignal, Joël J. E. Moreau and Jean-Pierre Lère-Porte

      Version of Record online: 8 JUL 2009 | DOI: 10.1002/pola.23474

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      A new class of polyimines consisting of alternating conjugated segments and chiral units exhibiting high sensitivity towards nitroaromatics vapors (NACs) detecting has been developed. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    17. Water soluble azido polyisocyanopeptides as functional β-sheet mimics (pages 4150–4164)

      Erik Schwartz, Matthieu Koepf, Heather J. Kitto, Mónica Espelt, Vicent J. Nebot-Carda, Rene De Gelder, Roeland J. M. Nolte, Jeroen J. L. M. Cornelissen and Alan E. Rowan

      Version of Record online: 8 JUL 2009 | DOI: 10.1002/pola.23477

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      The design and synthesis of functional biomimetic water soluble polymers with a defined secondary structure has been developed using beta-sheet polyisocyanopeptide scaffolds. Water soluble isocyanopolymers were prepared by random copolymerization of the azido functionalized isocyanopeptides with nonfunctionalized methyl ester isocyanides derived from alanine. Upon saponification of the latter function a rigid rod water soluble polymer was obtained with an accessible azide for post-functionalization. The potential of these biomimetic polymers was successfully demonstrated by using the click chemistry reaction of these polymers with an acetylene functionalized rhodamine dye. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    18. Dendronized supramolecular polymers self-assembled from dendritic ionic liquids (pages 4165–4193)

      Mohammad R. Imam, Mihai Peterca, Ulrica Edlund, Venkatachalapathy S. K. Balagurusamy and Virgil Percec

      Version of Record online: 8 JUL 2009 | DOI: 10.1002/pola.23523

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      Self-assembling dendritic ionic liquids containing triethyl and tripropyl ammonium, pyridinium, and 3-methylimidazolium chloride, tetrafluoroborate and hexafluorophosphate at their apex were synthesized. Their structural analysis has demonstrated the ionic liquid mediated self-assembly of columnar and spherical supramolecular assemblies that represent a new class of dendronized supramolecular polymers. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    19. Antithetic function of alcohol in living cationic polymerization: From terminator/inhibitor to useful initiator (pages 4194–4201)

      Kazuhiro Nakatani, Makoto Ouchi and Mitsuo Sawamoto

      Version of Record online: 8 JUL 2009 | DOI: 10.1002/pola.23488

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      Various alcohols and water were used as new initiators for living cationic polymerization of vinyl ethers and p-methoxystyrene. While they were conventionally terminators or chain-transfer agents, they worked as effective initiators with borontrifluoride etherate (BF3OEt2) as a catalyst and dimethyl sulfide (Me2S) as a basic additive. The molecular weights of the produced polymers were increased in direct proportion to the monomer conversion with narrow molecular weight distributions (Mw/Mn ∼ 1.2). The system would be easily accessible to obtain the well-defined polymers, and possibly contribute to stereospecific control via counteranion design with a wide variety of ubiquitously available alcohols. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

  3. Rapid Communications

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid Communications
    5. Notes
    1. You have free access to this content
      HPMC-salicylate conjugates as macromolecular prodrugs: Design, characterization, and nano-rods formation (pages 4202–4208)

      Muhammad A. Hussain, Munair Badshah, Mohammad S. Iqbal, Muhammad N. Tahir, Wolfgang Tremel, Sheshanath V. Bhosale, Muhammad Sher and Muhammad T. Haseeb

      Version of Record online: 8 JUL 2009 | DOI: 10.1002/pola.23463

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      Hydroxypropylmethylcellulose (HPMC) is a neutral, nonionic, acid resistant, and hydrolysable in basic medium. Keeping in view these properties, HPMC-salicylic acid conjugates, that is, macromolecular prodrugs were successfully synthesized, purified, and characterized by gel permeation chromatography, thermal analysis (TGA/DTA/DSC) and UV, FTIR, 1H NMR spectroscopic techniques. Chemical attachment (covalent) of the salicylic acid on HPMC and purity of products was verified by spectroscopic analyses. UV spectroscopy has indicated the incorporation of the drug in the conjugates after in vitro release in basic medium. Transmission electron microscopy has shown formation of nano-rods because of amphiphilic nature of products (HPMC-salicylate). All the samples synthesized were found thermally as stable as native HPMC. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

  4. Notes

    1. Top of page
    2. Highlights
    3. Articles
    4. Rapid Communications
    5. Notes
    1. You have free access to this content
      A latent s-chelated ruthenium benzylidene initiator for ring-opening metathesis polymerization (pages 4209–4213)

      Charles E. Diesendruck, Yuval Vidavsky, Amos Ben-Asuly and N. Gabriel Lemcoff

      Version of Record online: 8 JUL 2009 | DOI: 10.1002/pola.23476

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      Herein, we present the first results on the use of sulfur chelated ruthenium olefin metathesis catalysts in ring-opening metathesis polymerization (ROMP). By the use of these slow initiators, monomer consumption, undetectable at room temperature, could be reversibly turned on and off as desired by heating and cooling cycles, respectively. Significantly, polymer size essentially remained constant throughout reaction progress, irrespective of catalyst loading. The polymers produced presented monomodal high molecular weights (>105 g/mol) with relatively low polydispersities (<1.4). [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

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