Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 49 Issue 23

1 December 2011

Volume 49, Issue 23

Pages i–iv, 4927–5131

  1. Cover Image

    1. Top of page
    2. Cover Image
    3. Articles
    4. Notes
    1. You have free access to this content
      Cover Image, Volume 49, Issue 23 (pages i–ii)

      Article first published online: 21 OCT 2011 | DOI: 10.1002/pola.25051

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      The fabrication of biocompatible and biodegradable 3D scaffolds by lithography-based additive manufacturing technology represents an appealing approach in tissue engineering. The cover image shows a 3D scaffold mimicking the structure of cancellous bone, made of a photopolymerizable hybrid resin based on vinyl esters shaped by a digital light-processing technique. Emphasis is given on high photoreactivity and low cytotoxicity of the resin as well as on the mechanical properties and controlled degradability of the final polymer. More information can be found in the article on page 4927 by Robert Liska and colleagues.

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      Inside Cover, Volume 49, Issue 23 (pages iii–iv)

      Article first published online: 21 OCT 2011 | DOI: 10.1002/pola.25052

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      A novel, ladder-like silsesquioxane with pendant methacryl moieties is synthesized, and pristine micropatterns are obtained through a simple spin-coating method, as presented by Seung-Sock Choi, Albert S. Lee, He Seung Lee, Hyeon Yeol Jeon, Kyung-Youl Baek, Dong Hoon Choi, and Seung Sang Hwang on page 5012. Without the need for any photoinitiators, ladder-like structured silsesquioxanes are photocured to give high surface modulus values exceeding 8 Gpa. The use of these ladder-like structured materials is shown to vastly simplify the processing of thermally stable, high-modulus micropatterned films.

  2. Articles

    1. Top of page
    2. Cover Image
    3. Articles
    4. Notes
    1. Biomaterials based on low cytotoxic vinyl esters for bone replacement application (pages 4927–4934)

      Branislav Husár, Christian Heller, Martin Schwentenwein, Andreas Mautner, Franz Varga, Thomas Koch, Jürgen Stampfl and Robert Liska

      Article first published online: 7 SEP 2011 | DOI: 10.1002/pola.24933

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      For the printing of biocompatible and biodegradable scaffolds by additive manufacturing technology, (meth)acrylate-based monomers were replaced by sufficiently reactive vinyl esters with exceptional low cytotoxicity. Mechanical properties similar to poly(lactic acid) could be obtained by adding suitable fillers such as hydroxylapatite. The right ratio of hydrophobic and hydrophilic monomers allows the tuning of the degradation behavior over a broad range.

    2. Synthesis and chemosensing behavior of fluorene-based alternating copolymers containing ether side chains and Si–vinylene units in the main chain (pages 4935–4940)

      Naofumi Naga, Yoshikazu Ohkura, Nanae Tagaya and Haruhiko Tomoda

      Article first published online: 9 SEP 2011 | DOI: 10.1002/pola.24943

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      Alternating copolymerization of 9,9-bis(3,6,9-trioxadecyl)-2,7-dibromofluorene (ODFl) with Si containing divinyl compounds, divinyldiphenylsilane (VPS) is investigated using the Mizoroki-Heck reaction with palladium(II) acetate. The photo luminescence spectroscopy of ODFl-VPS copolymer is investigated in the presence of Li+, Na+, and K+, and the intensity of emission peak is decreased by those metal cations, especially by Na+. The Stern-Volumer plots show curved relationship, which can be explained by the two capture models, inter-chain and intra-chain capture models.

    3. Synthesis and properties of a deuterated phenolic resin (pages 4941–4947)

      Atsushi Izumi, Toshio Nakao and Mitsuhiro Shibayama

      Article first published online: 9 SEP 2011 | DOI: 10.1002/pola.24948

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      A highly deuterated novolac-type phenolic resin was prepared by the polycondensation of deuterated phenol and formaldehyde using oxalic acid as an acid catalyst. The exponents of the Mark–Houwink–Sakurada equation suggest that phenolic resins behave like a compact sphere in THF irrespective of deuteration. The curing behavior with hexamethylenetetramine was confirmed by DSC, and the cured resin exhibits a low incoherent neutron scattering background.

    4. Cationation of dimethylallyl alcohols by B(C6F5)3 as models of the (Re)initiation reaction in the bio-inspired cationic polymerization of isoprene (pages 4948–4954)

      Samira Ouardad, Sergei V. Kostjuk, François Ganachaud, Judit E. Puskas, Alain Deffieux and Frederic Peruch

      Article first published online: 9 SEP 2011 | DOI: 10.1002/pola.24949

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      We report on model studies of cationic reactions that could occur both in cationic polymerizations of isoprene and analogs and in natural rubber biosynthesis within enzymes.

    5. Preparation of reactive block copolymers and their transformation to hollowed nanostructures (pages 4955–4963)

      Meiran Xie, Liya Zhang, Yang Liao, Liang Ding, Chi Zeng and Zewang You

      Article first published online: 20 SEP 2011 | DOI: 10.1002/pola.24951

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      Polymeric hollow nanostructure was generated using micellar template method through a three-step procedure, including preparation of block copolymer precursors via ring-opening metathesis polymerization and atom transfer radical polymerization, the shell-crosslinked micelles by RCM, and the hollowed spherical nanoparticles by removing the micellar copolymer backbone from the crosslinked network of branches.

    6. Synthesis of diblock methylcellulose derivatives with regioselective functionalization patterns (pages 4964–4976)

      Atsushi Nakagawa, Dominik Fenn, Andreas Koschella, Thomas Heinze and Hiroshi Kamitakahara

      Article first published online: 8 SEP 2011 | DOI: 10.1002/pola.24952

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      This article describes a new synthetic method consisting of the glycosyl trichloroacetimidate method and the acid-catalyzed methanolysis method for diblock copolymers of regioselectively methylated celluloses and unmodified cello-oligosaccharides. These diblock copolymers are of importance as model compounds for investigations on thermoreversible gelation of aqueous solution of methylcellulose.

    7. Covalent polymeric modification of graphene nanosheets via surface-initiated single-electron-transfer living radical polymerization (pages 4977–4986)

      Xiaoyi Chen, Li Yuan, Pengyuan Yang, Jianhua Hu and Dong Yang

      Article first published online: 9 SEP 2011 | DOI: 10.1002/pola.24953

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      Poly(tert-butyl methacrylate) (PtBMA) chains (71.7 wt % grafting efficiency) was successfully grown in stiu from the surface of reduced graphene oxide, and the resulting G-PtBMA still maintained the separated single layers, and the dispersibility in organic solvents was significantly improved

    8. Synthesis, characterization, and properties of poly(ester-phosphoester)s by lanthanum triphenolate-catalyzed ring-opening copolymerization (pages 4987–4992)

      Weipu Zhu, Shuai Sun, Ning Xu and Zhiquan Shen

      Article first published online: 9 SEP 2011 | DOI: 10.1002/pola.24956

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      PCL-based copolymers with reduced crystallinity and enhanced hydrophilicity were prepared facilely via ring-opening copolymerization using MEP as hydrophilic comonomer and La(DBMP)3 as high efficient catalyst. The properties of the copolymers were characterized by XRD, DSC, DMA, and SWCA.

    9. Synthesis and isomerization of conjugated oligomers containing azoimidazole unit (pages 4993–5000)

      Koji Takagi, Takato Isomura, Yohei Ito, Masanori Sakaida, Shusaku Nagano and Takahiro Seki

      Article first published online: 9 SEP 2011 | DOI: 10.1002/pola.24958

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      The conjugated oligomers and model compound containing the azoimidazole unit were synthesized by the Suzuki and Stille coupling reactions. The UV spectra were measured in the solution and film states. The trans-to-cis photoisomerization and cis-to-trans thermal isomerization were investigated for the neutral conjugated oligomer and the cationic conjugated oligomer that was obtained by the quaternization of imidazole in the main chain.

    10. Photovoltaic response to structural modifications on a series of conjugated polymers based on 2-aryl-2H-benzotriazoles (pages 5001–5011)

      Felix M. Pasker, Michael F. G. Klein, Monamie Sanyal, Esther Barrena, Uli Lemmer, Alexander Colsmann and Sigurd Höger

      Article first published online: 9 SEP 2011 | DOI: 10.1002/pola.24959

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      Four conjugated polymers containing 2-aryl-2H-benzotriazoles and “bis(thiopheno)dialkylfluorenes” were obtained via Suzuki-polycondensation. The impact of systematical structural changes on the electronic and morphological properties and device efficiencies was studied. Organic solar cells using PCBM derivatives as electron accepting materials and the polymers as light-harvesting and electron-donating materials exhibit power conversion efficiencies up to 1.8%.

    11. Synthesis and characterization of UV-curable ladder-like polysilsesquioxane (pages 5012–5018)

      Seung–Sock Choi, Albert S. Lee, He Seung Lee, Hyeon Yeol Jeon, Kyung–Youl Baek, Dong Hoon Choi and Seung Sang Hwang

      Article first published online: 12 SEP 2011 | DOI: 10.1002/pola.24942

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      Various ladder-like structured poly(phenyl-co-methacryl silsesquioxane)s (LPMSQ)s with high molecular weight (Mw = 13,000 ∼ 40,000) were synthesized by direct hydrolysis and polymerization in the presence of base catalyst at 25 °C. Synthesized LPMSQs showed closed ladder-like polysilsesquioxane structures. After photocuring, LPMSQs were demonstrated excellent surface modulus in thin film state. Furthermore, obtained LPMSQ showed very cleanly micro-pattern.

    12. Water-based inorganic/polymer hybrid particles prepared via a multiple miniemulsion process (pages 5019–5029)

      Nermeen Nabih, Katharina Landfester and Andreas Taden

      Article first published online: 20 SEP 2011 | DOI: 10.1002/pola.24963

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      A multiple miniemulsion route was developed providing a versatile method to prepare hybrid inorganic/polymer particles in aqueous dispersion. Inorganic particle synthesis and polymerization reactions were carried out in separate steps, offering additional flexibility to the process. Zinc phosphate, barium sulfate, and calcium carbonate were synthesized as examples in an epoxy-acrylic styrene polymer matrix.

    13. Enhanced photopolymerization of dimethacrylates with ketones, amines, and iodonium salts: The CQ system (pages 5030–5041)

      Wayne D. Cook and Fei Chen

      Article first published online: 20 SEP 2011 | DOI: 10.1002/pola.24964

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      Photo-DSC and spectroscopy studies showed that photopolymerization of dimethacrylate monomers (e.g., TEGDMA) with a three-component initiator system consisting of camphorquinone (CQ), amine (e.g., TMA) and iodonium salt (Ph2IPF6) significantly enhanced the polymerization rate due to irreversible oxidation of the amine radical by the iodonium salt which results in more efficient and a faster rate of initiation of the polymerization but also a slower consumption of the CQ.

    14. Synthesis and polymerizations of six aminophosphonate-containing methacrylates (pages 5042–5048)

      Zeynep Sarayli Bilgici, Oznur Demir Ordu, Mehtap Isik and Duygu Avci

      Article first published online: 9 SEP 2011 | DOI: 10.1002/pola.24965

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      Two groups of novel aminophosphonate-containing methacrylates were synthesized and their polymerization behavior was investigated. The first group involves reactions of alkyl α-bromomethacryates with diethyl aminomethylphosphonate and diethyl 2-aminoethylphosphonate. The second group involves the Michael addition reaction between diethyl aminomethylphosphonate and diethyl 2-aminoethylphosphonate with 3-(acryloyloxy)-2-hydroxypropyl methacrylate.

    15. Effects of hydration and hydrophilicity on Na-Clay-supported aqueous-phase catalysis for atom transfer radical polymerization (pages 5049–5056)

      Ravi Aggarwal and Durairaj Baskaran

      Article first published online: 19 SEP 2011 | DOI: 10.1002/pola.24968

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      Supported aqueous-phase catalysis for AGET ATRP of benzyl methacrylate has been performed using hydrated Na-clay-CuBr2/L system in the presence of sodium ascorbate as reducing agent in anisole at ambient temperature. The effects of hydration, reducing agent, [CuII]0/[I]0, and hydrophobicity on Na-clay are investigated using a series of batch and kinetics experiments.

    16. Synthesis of copolyamides based on PA 66 bearing lithium sulfonate groups and having unique thermal properties (pages 5057–5062)

      Geoffroy Cammage, Roger Spitz, Christophe Boisson, René Rossin, Stéphane Jéol and Franck Touraud

      Article first published online: 12 SEP 2011 | DOI: 10.1002/pola.24971

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      Copolyamides of PA 66/6LiSIPA containing up to 40 mol % of lithium 5-sulfoisophthalic acid (LiSIPA) were prepared. The Tg increased from 59 °C for PA 66 to 155 °C for a copolymer containing about 40 mol % of LiSIPA. A study of interactions between amide functions and lithium sulfonate moieties by infrared spectroscopy strongly suggests the presence in the copolyamides of crosslinking points centered on lithium cations, which decreases the chain mobility of the polymers.

    17. Photoresponsive soft materials: Synthesis and photophysical studies of a stilbene-based diblock copolymer (pages 5063–5073)

      Sajith Menon, Remyamol Thekkayil, Shinto Varghese and Suresh Das

      Article first published online: 15 SEP 2011 | DOI: 10.1002/pola.24973

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      Here, we report a light responsive amphiphilic diblock copolymer synthesized via atom transfer radical polymerization. The block copolymer (BCP) consisted of hydrophilic polyethylene oxide and photoisomerizable stilbene units. The BCP forms well defined aggregates which can act as carriers of hydrophobic curcumin molecules in aqueous environment. The aggregation properties of the BCP and the release kinetics of the encapsulated guest molecule in response to light have been evaluated.

    18. Star macromolecules with hyperbranched poly(arylene oxindole) cores and polyacid arms: Synthesis and solution behavior (pages 5074–5086)

      Agnieszka Kowalczuk, Barbara Trzebicka, Stanislav Rangelov, Mario Smet and Andrzej Dworak

      Article first published online: 12 SEP 2011 | DOI: 10.1002/pola.24974

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      Stars consisting of poly(arylene oxindole) core and poly(tert-butyl methacrylate) arms were synthesized by ATRP and precisely characterized by variety of techniques. By acidic hydrolysis of present copolymers as well as a series of previously prepared poly(tert-butyl acrylate) stars, a library of amphiphilic stars with polyacrylic or polymethacrylic acid arms was prepared. Their solubility in water was strongly depending on pH, for poly(methacrylic acid) stars the solubility was limited significantly to narrower pH range than for reflecting poly(acrylic acid) stars. The aqueous solution properties of selected copolymers from the two series as a function of pH were studied by LS.

    19. Surface modification of poly(butylene terephthalate) nonwoven by photochemistry and biofunctionalization with peptides for blood filtration (pages 5087–5099)

      Estelle Gérard, Emilie Bessy, Gregory Hénard, Laurent Ducoroy, Thierry Verpoort and Jacqueline Marchand-Brynaert

      Article first published online: 14 SEP 2011 | DOI: 10.1002/pola.24975

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      Poly(butylene terephthalate) nonwoven has been surface functionalized by UV irradiation with a photolinker and coupling to molecular probes or peptides. This two-step protocol gave high grafting yield (assayed by liquid scintillation counting and X-ray photoelectron spectroscopy). The irradiation also led to the formation of oxygenated functions and enabled the fixation of molecules via aminolysis reactions. The treatments induce neither morphological modifications of the poly(butylene terephthalate) non-woven nor cytotoxicity. The derivatizations were stable under steam-sterilization conditions and the modified materials with the peptides have been evaluated for the retention of leukocytes during a whole blood filtration experiment.

    20. Synthesis of ω-sulfonated polystyrene via reversible addition fragmentation chain transfer polymerization and postpolymerization modification (pages 5100–5108)

      Lei Feng, Kevin A. Cavicchi, Bryan C. Katzenmeyer and Chrys Wesdemiotis

      Article first published online: 15 SEP 2011 | DOI: 10.1002/pola.24976

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      ω-Sulfonated polystyrene has been synthesized through a combination of RAFT polymerization and postpolymerization modification.

    21. Single electron transfer-living radical polymerization of methyl methacrylate catalyzed by ytterbium powder (pages 5109–5115)

      Delong Liu, Jing Ma, Hou Chen, Ping Yin, Naiyi Ji and Guangxi Zong

      Article first published online: 15 SEP 2011 | DOI: 10.1002/pola.24978

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      Well-defined poly(methyl methacrylate) (PMMA) using Yb(0) as a novel catalyst of SET-LRP initiated by carbon tetrachloride (CCl4) in N, N-dimethylformamide (DMF) and dimethyl sulfoxide (DMSO), respectively. The polymerizations proceed in the features of “living”/controlled free-radical polymerization, as evidenced by first-order kinetic plots of polymerization, the linear increase of molecular weight values with monomer conversions, and narrow PDI values of the polymers. The apparent activation energy of polymerization is accounted to be 36.2 kJ/mol, and the energy of equilibrium state is calculated to be 13.9 kJ/mol. The effect of Yb(0) powder content, solvent, different ligands and concentration of initiator on the polymerization are also investigated.

    22. Synthesis of poly(N-isopropylacrylamide) with a low molecular weight and a low polydispersity index by single-electron transfer living radical polymerization (pages 5116–5123)

      Eylem Turan, Adem Zengi̇n and Tuncer Caykara

      Article first published online: 15 SEP 2011 | DOI: 10.1002/pola.24979

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      Single electron transfer-living radical polymerization (SET-LRP) of N-isopropylacrylamide in the presence of 2-mercaptoethylamine chain transfer agent (TH) was carried out by Cu(0) generated in situ from the disproportionation of CuBr/2,2′-bipyridine in N,N-dimethylformamide at 90 °C. Analysis of polymerization kinetics in the presence of TH showed that the premature termination of growing polymer chains leads to retardation.

  3. Notes

    1. Top of page
    2. Cover Image
    3. Articles
    4. Notes
    1. You have free access to this content
      Synthesis of poly(oxyethylene phosphate)-g-poly(ethylene oxide) via the “grafting onto” approach by “click” chemistry (pages 5124–5128)

      Karima Oussadi, Véronique Montembault and Laurent Fontaine

      Article first published online: 7 SEP 2011 | DOI: 10.1002/pola.24950

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      A general method for the synthesis of grafted poly(alkylene phosphate)s is presented by combination of Atherton–Todd reaction and “click” chemistry. In the first step, the proposed method uses in a first step the Atherton-–Todd reaction to yield poly(tetraoxyethylene phosphate) with pendant acetylenic groups from poly(tetraoxyethylene H-phosphonate). In a the second step, “click” functionalization of the acetylene-containing poly(tetraoxyethylene phosphate) with azido-terminated poly(ethylene oxide)PEO leads to poly(tetraoxyethylene phosphate)-g-poly(ethylene oxide).

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      Synthesis and polymerization of novel fluoroalkyl 2-trifluoromethylacrylate possessing tetrahydrofuran moiety (pages 5129–5131)

      Akihiro Hosoya, Hiroshi Hamana, Atsushi Takani and Tadashi Narita

      Article first published online: 14 SEP 2011 | DOI: 10.1002/pola.24955

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      Synthesis and polymerization of novel 2-trifluoromethyl-3-(2-tetrahydrofuranyl)-1-propyl 2-trifluoromethylacrylate [CH2=C(CF3)COOCH2CH(CF3)CH2(C4H7O)] were developed. The fluorinated ester alkyl moiety was synthesized by reduction of the compound from the radical addition of tert-butyl 2-trifluoromethylacrylate [CH2=C(CF3)COOC4H9] with tetrahydrofuran. The fluoroalkyl 2-trifluoromethylacrylate was synthesized by the reaction of 2-trifluoromethylacryloyl chloride with the fluorinated alcohol. Radical and anionic polymerizations of the monomer were examined to afford a polymer of 1.0 × 104 as the highest molecular weight initiated by 2,2′-azobisisobutyronitrile at 60 °C in spite of the low yield of the polymer, though ethyl 2-trifluoromethylacrylate showed poor polymerization reactivity under radical conditions.