Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 47 Issue 12

15 June 2009

Volume 47, Issue 12

Pages 2959–3207

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      Green polymer chemistry using nature's catalysts, enzymes (pages 2959–2976)

      Judit E. Puskas, Mustafa Y. Sen and Kwang Su Seo

      Version of Record online: 7 MAY 2009 | DOI: 10.1002/pola.23351

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      This article highlights “green polymer chemistry,” that is, precision functionalization of polymers using enzymatic catalysis. In the example shown, quantitative functionalization of poly(ethylene glycol) (PEG) with thymine using enzymatic catalysis was achieved by Candida antarctica lipase B-catalyzed transesterification of vinyl acrylate with PEG followed by Amano lipase M-catalyzed Michael addition of thymine onto the resulting acrylated PEG chain-ends. 1H NMR spectroscopy confirmed the expected chain-end structure.

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    1. Monomer/polymer Schiff base copper(II) complexes for catalytic oxidative polymerization of 2,2′-dihydroxybiphenyl (pages 2977–2984)

      Ali̇ Bi̇li̇ci̇, İsmet Kaya and Fati̇h Doğan

      Version of Record online: 7 MAY 2009 | DOI: 10.1002/pola.23370

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      The synthesis of poly-2,2′-dihydroxybiphenyl (PDHBP) with high molecular weights by oxidative coupling polymerization of 2,2′-dihydroxybiphenyl (DHBP) has been developed. Polymerizations were conducted in acetonitrile in the presence of Schiff base monomer/polymer-Cu(II) complexes as the catalysts and hydrogen peroxide as oxidant. To determine the optimum conditions, the effects of the amounts of the catalysts and the oxidant as well as the reaction times, temperatures were investigated. We assume that Schiff base polymer metal complex compounds will be attractive and acceptable catalysts for many catalytic reactions.

    2. Synthesis, characterization, and electroluminescent performance of a novel copolyfluorene containing pendant crown ether groups (pages 2985–2995)

      Juin-Meng Yu and Yun Chen

      Version of Record online: 7 MAY 2009 | DOI: 10.1002/pola.23380

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      Copolyfluorene PFC containing pendant crown ethers was prepared by the Suzuki coupling reaction. Pendant polar crown ethers improved electron injection and device performance. Double-layer electroluminescent device using PFC as emitting layer (ITO/PEDOT:PSS/PFC/Ca/Al) revealed maximum luminance (7910 cd/m2) and maximum luminance efficiency (2.3 cd/A) superior to those of polyfluorene device (860 cd/m2, 0.29 cd/A). Using thin PFC film as electron injection layer also enhanced the performance of polyfluorene device.

    3. Solvent-induced self-assembly in cardanol-based urethane methacrylate comb polymers (pages 2996–3009)

      N. Rekha and S. K. Asha

      Version of Record online: 7 MAY 2009 | DOI: 10.1002/pola.23383

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      Three-dimensional honeycomb pattern formation by breathe figure mechanism was observed from chloroform; whereas in tetrahydrofuran, self-assembly into multiple morphologies such as spheres and tubes was observed for cardanol-based urethane methacrylate comb polymers.

    4. Electrochemical synthesis of PEDOT derivatives bearing imidazolium-ionic liquid moieties (pages 3010–3021)

      Markus Döbbelin, Cristina Pozo-Gonzalo, Rebeca Marcilla, Raúl Blanco, José L. Segura, Jose A. Pomposo and David Mecerreyes

      Version of Record online: 7 MAY 2009 | DOI: 10.1002/pola.23384

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      Novel poly(3,4-ethylenedioxythiophene) (PEDOT) polymers bearing imidazolium-ionic liquid moieties were synthesized by electrochemical polymerization. The polymers could be dissolved in a range of polar organic solvents such as dimethylformamide, propylene carbonate, and dimethyl sulfoxide making them interesting candidates for wet processing methods. Interestingly, the hydrophobic character of electropolymerized films could be modified depending on the anion type. The hydrophobicity followed the trend PFmath image > (CF3SO2)2N > BFmath image > pure PEDOT as determined by water contact angle measurements. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.].

    5. Cyclic poly(ε-caprolactone) synthesized by combination of ring-opening polymerization with ring-closing metathesis, ring closing enyne metathesis, or “click” reaction (pages 3022–3033)

      Meiran Xie, Jiaxin Shi, Liang Ding, Jinxin Li, Huijing Han and Yiqun Zhang

      Version of Record online: 7 MAY 2009 | DOI: 10.1002/pola.23390

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      Cyclic poly(ε-caprolactone) was synthesized by ring-closing metathesis (RCM), ring closing enyne metathesis (RCEM), and “click” reaction of different difunctional linear poly(ε-caprolactone), which was prepared by ring-opening polymerization (ROP) of ε-caprolactone in bulk using 10-undecen-1-ol or propargyl alcohol as the initiator, followed by reacting with corresponding acyl chloride containing vinyl or azido end group.

    6. Polymerization of branched thiophene monomers and optoelectronic properties of materials (pages 3034–3044)

      Koji Takagi, Chikako Torii and Yusuke Yamashita

      Version of Record online: 7 MAY 2009 | DOI: 10.1002/pola.23399

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      We have investigated the synthesis and polymerization of branched thiophene monomers. The introduction of thiophene-1,1-dioxide as the side group had a negative influence on the expansion of conjugation system, whereas the polymerization of branched terthiophene monomers effectively increase the conjugation length along main chain. The presence and position of n-hexyl chain in terthiophene monomers gave a significant influence on the monomer polymerizability and optoelectronic properties of resulting materials. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    7. RAFT copolymerization of methacrylic acid and poly(ethylene glycol) methyl ether methacrylate in the presence of a hydrophobic chain transfer agent in organic solution and in water (pages 3045–3055)

      David Rinaldi, Thierry Hamaide, Christian Graillat, Franck D'Agosto, Roger Spitz, Sébastien Georges, Martin Mosquet and Philippe Maitrasse

      Version of Record online: 7 MAY 2009 | DOI: 10.1002/pola.23374

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      RAFT copolymerization of poly(ethylene glycol) methyl ether methacrylate (PEGMA, 1100 g mol−1) with methacrylic acid (MAA) ([PEGMA]/[MAA] = 40/60) mediated by cyanoisopropyl dithiobenzoate (CPDB) was performed in dioxane and in water at 85 °C. A strong increase in polymerization rate was observed in water with almost quantitative conversion (98%) in 2 h without affecting the level of control of the final copolymers (PDI ∼ 1.30). This was tentatively explained by the formation of hydrophobic domains in which the polymerization occurred as in bulk. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    8. Conjugated polyelectrolyte with pendant carboxylate groups: Synthesis, photophysics, and pH responses in the presence of surfactants (pages 3056–3065)

      Tao Zhang, Hongliang Fan, Jianguang Zhou and Qinhan Jin

      Version of Record online: 7 MAY 2009 | DOI: 10.1002/pola.23387

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      A water-soluble poly(phenylene ethynylene) with pendant carboxylate groups was successfully synthesized via a facile synthetic route and fully characterized on the optical properties. Further studies on the interaction and stabilization of PPE-OBS with various surfactants were performed to improve the fluorescence stability. It was also found that the PPE-OBS/surfactant complex exhibited a sensitive response over a relatively wide pH-range, which was believed to facilitate the continuous monitoring of small fluctuations in [H+], and certain physiological processes that involve proton release/consumption might be sensed indirectly. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    9. One-pot synthesis of ABC miktoarm star terpolymers by coupling ATRP, ROP, and click chemistry techniques (pages 3066–3077)

      Yanfeng Zhang, Changhua Li and Shiyong Liu

      Version of Record online: 7 MAY 2009 | DOI: 10.1002/pola.23388

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      We report on the one-pot synthesis of well-defined ABC miktoarm star terpolymers consisting of poly(2-(dimethylamino)ethyl methacrylate), poly(ε-caprolactone), and polystyrene or poly(ethylene oxide) arms, PS(-b-PCL)-b-PDMA and PEO (-b-PCL)-b-PDMA, by simultaneously conducting atom transfer radical polymerization (ATRP), ring-opening polymerization (ROP), and click chemistry, taking advantage of the compatibility and mutual tolerability of reaction conditions (catalysts and monomers) employed for these three types reactions. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    10. Synthesis and characterization of amphiphilic poly(N-vinyl pyrrolidone)-b-poly(ε-caprolactone) copolymers by a combination of cobalt-mediated radical polymerization and ring-opening polymerization (pages 3078–3085)

      Hyun Jeong Jeon, Young Chang You and Ji Ho Youk

      Version of Record online: 7 MAY 2009 | DOI: 10.1002/pola.23396

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      An amphiphilic block copolymer of poly(N-vinyl pyrrolidone)-b-poly(ε-caprolactone) (PVP-b-PCL) was synthesized by a combination of cobalt-mediated radical polymerization (CMRP) and ring-opening polymerization (ROP). The PVP-b-PCL micelles were spherical in shape with an average diameter of 105 nm. The nanosized PVP-b-PCL micelles show promise as novel drug carriers in biomedical and pharmaceutical applications.

    11. Grafting of montmorillonite nano-clay with butyl acrylate and methyl methacrylate by atom transfer radical polymerization: Blends with poly(BuA-co-MMA) (pages 3086–3097)

      Mikko Karesoja, Harri Jokinen, Erno Karjalainen, Petri Pulkkinen, Mika Torkkeli, Antti Soininen, Janne Ruokolainen and Heikki Tenhu

      Version of Record online: 8 MAY 2009 | DOI: 10.1002/pola.23400

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      An atom transfer radical polymerization (ATRP) initiator was covalently bound on montmorillonite clay platelets via silylation and used to polymerize butyl acrylate (BuA) and methyl methacrylate (MMA) on the clay surface. The polymer-modified clay was mixed with a poly(BuA-co-MMA) matrix. Well exfoliated composites were obtained. Mechanical properties of the composites were studied by dynamic mechanical thermal analysis. Mechanical properties clearly improved with small additions of the clay, as well as with increasing homogeneity of the nanocomposites. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    12. Fabrication of well-developed nano-ribbons composed of hierarchically grown isotactic poly(methyl methacrylate) crystals on substrates (pages 3098–3110)

      Kun Zhang and Takeshi Serizawa

      Version of Record online: 8 MAY 2009 | DOI: 10.1002/pola.23409

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      Well-developed nano-ribbons composed of isotactic poly(methyl methacrylate) were successfully prepared on mica via a simple solution-casting method. Nano-ribbons with about 0.6 nm thickness and 30–40 nm widths were composed of two-dimensional folded chain crystals. Nano-ribbons were developed by incubating tetrahydrofuran solutions, more than equi-amounts of water were added to incubated THF solutions, and solutions were cast onto mica. Interestingly, a modulation of the method succeeded in the development of epitaxially grown nano-ribbons. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    13. Substituent effects in ethene/styrene copolymerization: Dormant state destabilization? (pages 3111–3117)

      Giles W. Theaker, Colin Morton and Peter Scott

      Version of Record online: 8 MAY 2009 | DOI: 10.1002/pola.23417

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      Copolymerizations of ethene (E) and p-tert-butylstyrene (TBS) catalyzed by metallocene and constrained geometry systems occur with dramatically higher degrees of incorporation and overall productivity than with styrene. The σ-donating effect of the tert-butyl substituent destabilizes an otherwise dormant benzylic species following 2,1-insertion of the styrene. As a result, TBS-alt-E (44% TBS with no sequential TBS units) was synthesized at impressively high productivity and unusually low concentration of comonomer. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    14. Versatile ω-end group functionalization of RAFT polymers using functional methane thiosulfonates (pages 3118–3130)

      Peter J. Roth, Daniel Kessler, Rudolf Zentel and Patrick Theato

      Version of Record online: 8 MAY 2009 | DOI: 10.1002/pola.23392

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      The high and selective reactivity of methane thiosulfonates toward thiols can be used to intercept terminal thiols generated in situ from polymers prepared by the RAFT process through aminolysis. Thereby, side reactions such as oxidation forming polymer-polymer disulfides or backbiting forming terminal thiolactons on poly[(meth)acrylates] are avoided. By employing a functionalized methane thiosulfonate, we could introduce a terminal triple bond connected with a disulfide bridge with near quantitative yields into various polymethacrylates, polystyrene and poly[N-isopropylacrylamide]. The acetylene-terminated polymers were clicked onto an azide functionalized surface and were removed again by selective reduction of the disulfides. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    15. A photo-oxidizable kinetic pathway of three-component photoinitiator systems containing porphrin dye (Zn-tpp), an electron donor and diphenyl iodonium salt (pages 3131–3141)

      Dongkwan Kim and Jeffrey W. Stansbury

      Version of Record online: 8 MAY 2009 | DOI: 10.1002/pola.23401

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      Three-component photoinitiator systems generally include a light-absorbing photosensitizer (PS), an electron donor, and an electron acceptor. Using the thermodynamic feasibility, we suggest two different kinetic mechanisms, which are (i) photo-reducible series mechanism of camphorquinone (CQ) and (ii) photo-oxidizable series mechanism of 5,10,15,20-tetraphenyl-21H,23H-porphyrin zinc (Zn-tpp). It was concluded from the kinetic results that the photo-oxidizable series mechanism efficiently retards back electron transfer and the recombination reaction step as well provides an efficient secondary reaction step that involves consumption of the dye-based radical and regeneration of the original PS.

    16. PPEGMEA-g-PDEAEMA: Double hydrophilic double-grafted copolymer stimuli-responsive to both pH and salinity (pages 3142–3153)

      Lina Gu, Chun Feng, Dong Yang, Yaogong Li, Jianhua Hu, Guolin Lu and Xiaoyu Huang

      Version of Record online: 8 MAY 2009 | DOI: 10.1002/pola.23405

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      Well-defined stimuli-responsive double hydrophilic graft copolymers, consisting of polyacrylate backbone, hydrophilic poly(2-(diethylamino)ethyl methacrylate) and poly(ethylene glycol) side chains, were synthesized by successive ATRP, they can aggregate to form reversible micelles in basic surroundings which can be conveniently dissociated with the addition of salt at room temperature. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    17. N-(2-benzimidazolylquinolin-8-yl)benzamidate half-titanocene chlorides: Synthesis, characterization and their catalytic behavior toward ethylene polymerization (pages 3154–3169)

      Shaofeng Liu, Jianjun Yi, Weiwei Zuo, Kefeng Wang, Deligeer Wang and Wen-Hua Sun

      Version of Record online: 8 MAY 2009 | DOI: 10.1002/pola.23413

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      N-(2-Benzimidazolyquinolin-8-yl)benzamidate half-titanocene chlorides, Cp′TiLCl exhibited good to high catalytic activities towards ethylene polymerization and ethylene/α-olefin copolymerization in the presence of methylaluminoxane (MAO) cocatalyst. The polymerization productivities were enhanced with either elevating reaction temperature or increasing the ratio of MAO to titanium precursor. In general, it was observed that the higher the catalytic activity of the catalytic system showed, the lower the molecular weight of polyethylene was observed.

    18. Facile synthesis of polymers bearing cyclic carbonate structure through radical solution and precipitation polymerizations accompanied by concurrent carbon dioxide fixation (pages 3170–3176)

      Bungo Ochiai, Yugo Hatano and Takeshi Endo

      Version of Record online: 8 MAY 2009 | DOI: 10.1002/pola.23415

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      The radical polymerization of glycidyl methacrylate (GMA) under a carbon dioxide atmosphere (1 atm) in the presence of catalysts for carbon dioxide fixation afforded (co)polymers bearing five-membered cyclic carbonate and oxirane groups. The degrees of the carbon dioxide fixation depended on catalysts, concentration, and solvents. When the polymerization was conducted in 1,4-dioxane, polymers were precipitated out as the progress of the polymerization and the carbon dioxide fixation. As a result, polymers could be obtained by simple filtration and rinsing with methanol.

    19. Functional syndiotactic poly(β-hydroxyalkanoate)s via stereoselective ring-opening copolymerization of rac-β-butyrolactone and rac-allyl-β-butyrolactone (pages 3177–3189)

      Noureddine Ajellal, Christophe M. Thomas and Jean-François Carpentier

      Version of Record online: 8 MAY 2009 | DOI: 10.1002/pola.23418

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      The copolymerization of racemic β-butyrolactone with racemic “allyl-β-butyrolactone”, catalyzed by a discrete amino-alkoxy-bis(phenolate) yttrium-amido complex, gave new poly(β-hydroxyalkanoate)s with unsaturated side chains. The copolymers produced have a highly syndiotactic backbone structure (Pr = 0.80–0.84) with a random enchainment of monomer units, and high molecular weight (Mn up to 58,000 g.mol−1) with a narrow polydispersity (Mw/Mn = 1.07–1.37). The pendant vinyl bond of the side-chains in those copolymers allowed the effective introduction of hydroxy or epoxy groups via dihydroxylation, hydroboration-oxidation or epoxidation reactions. Some thermal properties (Tm, ΔHm, Tg) of the prepared polymers have been also evaluated.

    20. New tetrafunctional monomer 1,3-di(2-hydroxy-3-methacryloyloxypropoxy)benzene in the synthesis of porous microspheres (pages 3190–3201)

      Marta Grochowicz, Barbara Gawdzik and Andrzej Bartnicki

      Version of Record online: 8 MAY 2009 | DOI: 10.1002/pola.23398

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      This article presented the synthesis of porous microspheres obtained from new aromatic tetrafunctional methacrylate monomer 1,3-di(2-hydroxy-3-methacryloyloxypropoxy)benzene and trimethylolpropane trimethacrylate. Copolymerization was carried out in the presence of pore-forming diluents, decan-1-ol and chlorobenzene. Influence of diluents composition on microspheres porous structures was studied. Thermal resistance and tendency to swell in different organic diluents for a chosen sample were also determined.

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      ARGET ATRP of acrylonitrile catalyzed by FeCl3/isophthalic acid in the presence of air (pages 3202–3207)

      Hou Chen, Lixia Yang, Ying Liang, Zhihai Hao and Zixuan Lu

      Version of Record online: 8 MAY 2009 | DOI: 10.1002/pola.23406

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      ARGET ATRP of acrylonitrile initiated by ethyl 2-bromoisobutyrate was approached for the first time in the presence of air, using a novel catalyst system based on FeCl3/isophthalic acid complexes and using ascorbic acid as a reducing agent. The polymerization in the presence of air provided rather slow reaction rate and showed better control of molecular weight and its distribution with the molar ratio of [AN]:[EBiB]:[FeCl3]:[IA]:[VC] at 3000:1:0.09:1:0.99. Polyacrylonitrile obtained was successfully used as a macroinitiator to proceed the chain extension polymerization of styrene via ARGET ATRP in the presence of air.

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