Journal of Polymer Science Part A: Polymer Chemistry

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

15 May 2009

Volume 47, Issue 10

Pages 2463–2712

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      Advances in liquid crystalline conjugated polymers (pages 2463–2485)

      Kazuo Akagi

      Version of Record online: 8 APR 2009 | DOI: 10.1002/pola.23277

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      The ferroelectric liquid crystalline poly(para-phenylene) and poly(meta-phenylene) derivatives newly synthesized showed quick response to electric field to give a reversible switching in macroscopic alignment through polarization inversion, and the latter showed a potential memory function owing to a large residual polarization. Next, the multifunctional conjugated polymers bearing fluorescent, liquid crystalline and photoresponsive functions were synthesized by introducing the dithienylethene moieties into side chains of poly(para-phenylenevinylene) and poly(bithienylene-phenylene). Dynamic quenching and emitting in fluorescence were observed through the photoisomerization between open and closed forms of side chains. Liquid crystallinity-enforced macroscopic alignment enabled the polymers to exhibit the linearly polarized fluorescence with reversible photoswitching behavior. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

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    1. Facile and efficient preparation of phosphinate-functionalized aromatic diamines and their high-Tg polyimides (pages 2486–2499)

      Chia Wei Chang, Ching Hsuan Lin, Po Wen Cheng, Hann Jang Hwang and Shenghong A. Dai

      Version of Record online: 8 APR 2009 | DOI: 10.1002/pola.23320

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      Two novel phosphorus-functionalized aromatic diamines (1–2) were prepared via an efficient, one-pot procedure. Based on diamines (1) and (2), a series of new polyimides, (5a–5d) and (6a–6d), were prepared, respectively. The reaction mechanism for the synthesis of (1–2), and the thermal and dimensional properties of polyimides (5–6) were discussed in detail. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    2. Poly-(p-phenylene vinylenes) with pendent 2,4-difluorophenyl and fluorenyl moieties: Synthesis, characterization, and device performance (pages 2500–2508)

      Shengbiao Li, Ping Zhao, Yanqin Huang, Tingcheng Li, Chao Tang, Rui Zhu, Lei Zhao, Quli Fan, Shiqiang Huang, Zushun Xu and Wei Huang

      Version of Record online: 8 APR 2009 | DOI: 10.1002/pola.23322

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      To improve efficiency, processibility and stability, three novel poly-(p-phenylene vinylenes) (PPV) derivatives (Pa,Pb, and Pc) with pendent 2,4-difluorophenyl and fluorenyl moieties were synthesized via Gilch reaction. Compared with those of PPV and MEH-PPV, the absolute quantum efficiencies of these polymers showed remarkable improvement (measured at 38.7, 37.2, and 20.3%, respectively), which can be attributed to the presence of twisted multi-aryl segments and fluorine atoms. TGA revealed that the inflexion temperatures of their thermal decomposition curves were above 400 °C. Double-layered electroluminescent (EL) devices with these polymers as light-emiting layers [ITO/PEDOT:PSS/Polymer/Ba/Al] showed peak emissions at 493/515, 503, 600 nm and maximum luminance of 2700, 450, and 4700 cd/m2 for Pa, Pb, and Pc, respectively, with onset voltages of about 4 V.

    3. (Meth)acrylate vinyl ester hybrid polymerizations (pages 2509–2517)

      Tai Yeon Lee, Neil B. Cramer, Charles E. Hoyle, Jeffrey W. Stansbury and Christopher N. Bowman

      Version of Record online: 8 APR 2009 | DOI: 10.1002/pola.23327

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      Copolymerization of methacrylate and vinyl ester monomers results in two distinct polymerization regimes. With the appropriate choice of vinyl ester and methacrylate monomers, the two distinct polymerization regimes can be designed for polymerization-induced phase separation between the two reactive species. The phase separation morphology is controlled by both the monomer components and the polymerization kinetics. The phase separated domains become larger and more distinct with slower polymerization and correspondingly increased time for diffusion.

    4. Ferrocenyl-functionalized long chain branched polydienes (pages 2518–2529)

      Frederik Wurm, Francisco Javier López Villanueva and Holger Frey

      Version of Record online: 8 APR 2009 | DOI: 10.1002/pola.23334

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      Branched, functionalized polydienes (polybutadiene and polyisoprene) were obtained by a concurrent ABn + AR type of copolymerization with mono- and difunctional ferrocenyl silanes (fcSiMe2H or fc2SiMeH). Classical living anionic polymerization was used to synthesize different ABn type poly (diene) macromonomers. Quantitative end-capping with chlorodimethylsilane resulted in the desired ABn macromonomer structures. In the ensuing Pt-catalyzed hydrosilylation polyaddition, branched polymers were obtained (Mn = 10,000 to 44,000 g/mol, SEC/MALLS). High loading with ferrocene units up to 63 wt % of ferrocene was achieved. Detailed studies show full conversion of the functional silanes and incorporation in the polymers. Electrochemical studies demonstrated different electrochemical properties for fcSiMe2- or fc2SiMe-units. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    5. Chiral polyamides consisting of N-α-benzoyl-L-glutamic acid as a diacid component (pages 2530–2538)

      Yoshimi Ikeuchi, Maiko Nakagawa, Masakazu Yoshikawa, Hidekazu Yoshida and Shinichi Sakurai

      Version of Record online: 8 APR 2009 | DOI: 10.1002/pola.23335

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      Chiral polyamide was prepared from 4,4′-diaminodiphenyl methane and N-α-benzoyl-L-glutamic acid by means of triphenyl phosphite. The polyamide showed optical rotation, implying that optically active polyamide was successfully prepared. The polyamide thus obtained gave a durable self-standing membrane. The membrane showed chiral separation ability by using potential difference as a driving force for membrane transport. Permselctivity was greatly dependent on potential difference. The L-isomer of N-α-acetyl-L-tryptophan was selectively transported at the applied potential difference of 2.0 V from the racemic mixtures of N-α-acetyltryptophan, whereas the D-isomer was preferentially transported at that of 3.0 V.

    6. Heterotactic-specific radical polymerization of N-isopropylacrylamide and phase transition behavior of aqueous solution of heterotactic poly(N-isopropylacrylamide) (pages 2539–2550)

      Tomohiro Hirano, Takahiro Kamikubo, Yuya Okumura, Yoichi Bando, Ryosuke Yamaoka, Takeshi Mori and Koichi Ute

      Version of Record online: 8 APR 2009 | DOI: 10.1002/pola.23338

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      Radical polymerization of N-isopropylacrylamide (NIPAAm) in toluene at low-temperatures was carried out in the presence of fluorinated-alcohols. It was found that heterotactic polymer, comprising an alternating sequence of meso and racemo dyads, was obtained. Formation of the 1:1 complex of NIPAAm and fluorinated alcohols through C[DOUBLE BOND]O···H[BOND]O hydrogen bonding is responsible for the induction of the heterotactic specificity. The phase transition behavior of heterotactic poly(NIPAAm) in aqueous solution was examined. It appeared that the hysteresis of the phase transition between heating and cooling cycles depended on the average length of meso dyad. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    7. Carbon nanotubes decorated with terpyridine-ruthenium complexes (pages 2551–2559)

      Andreas A. Stefopoulos, Eleftherios K. Pefkianakis, Konstantinos Papagelis, Aikaterini K. Andreopoulou and Joannis K. Kallitsis

      Version of Record online: 8 APR 2009 | DOI: 10.1002/pola.23339

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      Immobilization of metallocomplexes onto the CNTs' surface using three different methodologies afforded soluble hybrid CNT composites with direct proof of the tpy-Ru(II)-tpy moieties attachment via various techniques. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    8. Vinyl addition polymerization of norbornene with cationic (allyl)Ni catalysts: Mechanistic insights and characterization of first insertion products (pages 2560–2573)

      Marc D. Walter, Rebecca A. Moorhouse, Peter S. White and Maurice Brookhart

      Version of Record online: 8 APR 2009 | DOI: 10.1002/pola.23340

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      A series of highly active cationic Ni catalyst for the (2,3)-vinyl addition polymerization of norbonene has been investigated and first insertion product of norbornene into the allyl group has been characterized. Despite the low MWD value these system suffer from slow initiation followed by rapid propagation.

    9. Incorporating glycidyl methacrylate into block copolymers using poly(methacrylate-ran-styrene) macroinitiators synthesized by nitroxide-mediated polymerization (pages 2574–2588)

      Benoît Lessard and Milan Marić

      Version of Record online: 8 APR 2009 | DOI: 10.1002/pola.23343

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      Methyl methacrylate (MMA), ethyl methacrylate (EMA) and n-butyl methacrylate (BMA) were copolymerized with styrene (S) comonomer (∼5–10 mol % S) using BlocBuilder unimolecular initiator and 10 mol % added SG1 free nitroxide relative to BlocBuilder. Methacrylate rich copolymers (81–87 mol % methacrylate) with low polydispersities = 1.23–1.46 and glass transition temperatures comparable to the pure poly(methacrylates) resulted. MMA/S, EMA/S and BMA/S random copolymers were effective macroinitiators for subsequent chain extensions of mixtures of glycidyl methacrylate (GMA), methacrylate (MMA, EMA or BMA) and ∼5–10 mol % S provided necessary precautions (low conversion and low target molecular weight, fractionation) were taken to ensure macroinitiator “livingness”. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    10. Synthesis and characterization of novel PDMS nanocomposites using POSS derivatives as cross-linking filler (pages 2589–2596)

      Theodore F. Baumann, Ticora V. Jones, Thomas Wilson, Andrew P. Saab and Robert S. Maxwell

      Version of Record online: 8 APR 2009 | DOI: 10.1002/pola.23344

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      We report the synthesis and characterization of novel elastomeric nanocomposites containing polyhedral oligomeric silsesquioxanes (POSS) as both the cross-linker and filler within a polydimethylsiloxane (PDMS) polymer matrix. These polymer composites were prepared through hydrosilylation of vinyl-terminated PDMS chains with either octasilane-POSS or larger super-POSS cross-linkers, consisting of multiple POSS molecules attached to a central octasilane-POSS core. The PDMS nanocomposites prepared from these POSS cross-linkers exhibited enhanced mechanical properties relative to polymers synthesized with the tetrafunctional TDSS cross-linker at equivalent loading levels, due to the size and increased dimensionality of POSS cross-linkers. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    11. Synthesis of exact comb polybutadienes with two and three branches (pages 2597–2607)

      Anastasia Nikopoulou, Hermis Iatrou, David J. Lohse and Nikos Hadjichristidis

      Version of Record online: 9 APR 2009 | DOI: 10.1002/pola.23345

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      Two methodologies, on the basis of living star polymers and anionic polymerizations high vacuum techniques, were used for the synthesis of exact comb polybutadienes (PBds) with two (C-2) and three identical branches (symmetric, sC-3 and asymmetric, aC-3). Both methodologies are general and can be extended to combs/grafts with two or three different branches at controllable positions along the backbone. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    12. Synthesis of amphiphilic copolymer brushes possessing alternating poly(methyl methacrylate) and poly(N-isopropylacrylamide) grafts via a combination of ATRP and click chemistry (pages 2608–2619)

      Jun Yin, Zhishen Ge, Hao Liu and Shiyong Liu

      Version of Record online: 9 APR 2009 | DOI: 10.1002/pola.23346

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      Well-defined amphiphilic copolymer brushes possessing alternating poly(methyl methacrylate) and poly(N-isopropylacrylamide) grafts, poly(PMMA-alt-PNIPAM) were synthesized via a combination of atom transfer radical polymerization (ATRP) and click reaction. In aqueous solution, the obtained alternating copolymer brushes supramolecularly self-assemble into spherical micelles consisting of PMMA cores and thermoresponsive PNIPAM coronas. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    13. An efficient synthetic route to well-defined theta-shaped copolymers (pages 2620–2630)

      Gang-Yin Shi and Cai-Yuan Pan

      Version of Record online: 9 APR 2009 | DOI: 10.1002/pola.23347

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      A convenient approach for the preparation of well-defined theta-shaped copolymers composed of PS and PCL with controlled molecular weight and narrow molecular weight distribution were reported. The synthetic procedure involves preparation of AB2 miktoarm star copolymers, which contain one PCL chain terminated with two acetylene groups and two PS chains with two azido groups at their one end via ATRP and ROP and intramolecular cyclization of the star precursors under high dilution through “click” chemistry. The mobility decrease of PCL chain across PS ring in the theta-shaped copolymers reduced its crystallization ability of PCL segment. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    14. Control of molecular aggregation in symmetrically substituted π-conjugated bulky poly(p-phenylenevinylene)s and their copolymers (pages 2631–2646)

      R. Resmi, S. R. Amrutha and M. Jayakannan

      Version of Record online: 9 APR 2009 | DOI: 10.1002/pola.23348

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      A new series of symmetrically substituted bulky PPV-copolymers bearing tricyclodecane (TCD) pendants were synthesized to trace the origin of the molecular aggregates in π-conjugated polymer chains. The aggregation behaviour of the polymer chains were analyzed in different solvent combinations and temperature using absorption, photoluminescence, and time-resolved fluorescence decay techniques. TCD-incorporation hinders the perfect stacking of the polymer chains via steric hindrance and improves the luminescent properties almost twice compared with that of normal PPV. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    15. Studies on sulfonic acid functionalized hollow silica spheres/Nafion® composite proton exchange membranes (pages 2647–2655)

      Junjie Yuan, Hongting Pu and Zhenglong Yang

      Version of Record online: 9 APR 2009 | DOI: 10.1002/pola.23349

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      It was found that the boundary between SAFHSS and Nafion® membrane became blurry, indicating the good compatibility between them. This was of critical importance to the integration for the composite membrane. The proton conductivity of SAFHSS/Nafion® composite membranes was always higher than that of the recast Nafion®112 at all temperatures (50∼130 °C). The maximum conductivity reached 0.1 S cm−1 at 100% relative humidity and 100 °C.

    16. Catalyst-free synthesis of polyorganosiloxanes by high temperature and pressure water. II. Understanding of the reaction process (pages 2656–2663)

      Takuya Ogawa, Jun Watanabe and Yoshito Oshima

      Version of Record online: 9 APR 2009 | DOI: 10.1002/pola.23350

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      The catalyst-free synthesis of poly(phenylsilsesquioxane) by hydrolysis and subsequent condensation of phenyltrimethoxy-silane was carried out focusing on impacts of the elemental reactions on the polymer properties. In-depth understanding of the elemental reactions suggests that the synthesis can be regarded as a two-stage reaction. A reaction system with a volatile material trap and a stop-valve proved to be very effective to yield a polymer with the molecular weight greater than 10,000. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    17. (Meth)acrylate-based photoelastomers as tailored biomaterials for artificial vascular grafts (pages 2664–2676)

      Stefan Baudis, Christian Heller, Robert Liska, Juergen Stampfl, Helga Bergmeister and Guenter Weigel

      Version of Record online: 9 APR 2009 | DOI: 10.1002/pola.23352

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      By means of microstereolithography, the developed resin formulation consisting of cyanoethyl acrylate as base monomer, polyethylene glycol diacrylate as crosslinker, and polyethylene glycol as solvent was successfully structured giving a mechanically tailored and biocompatible photopolymer material designated for artificial blood vessel substitutes. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    18. High quantum yield photoluminescence of new polyamides containing oligo-PPV amino derivatives and related oligomers (pages 2677–2689)

      Antonio Roviello, Fabio Borbone, Antonio Carella, Rosita Diana, Giuseppina Roviello, Barbara Panunzi, Antonio Ambrosio and Pasqualino Maddalena

      Version of Record online: 9 APR 2009 | DOI: 10.1002/pola.23353

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      New polyamides containing oligo-derivatives of PPV have been prepared and their fluorescence properties measured. All the polymers are strong blue emitters in solution. Interestingly, oligomers (o-PDMAS) of one of the prepared polymers (PDMAS) are instead white emitters when excited in polar solvents. This behavior is related to a different emission wavelength shown by the fluorophores depending on they are terminal groups of the polymeric chain (orange emission) or they are in the inner part of the backbone (blue emission). As the chain length is reduced the chain terminations emission become comparable to the inner chromophores emission and an overall white emission is observed. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

    19. Synthesis and characterization of side-chain liquid crystalline polymers bearing cholesterol mesogen (pages 2690–2701)

      Suk-Kyun Ahn, Long T. Nguyen Le and Rajeswari M. Kasi

      Version of Record online: 9 APR 2009 | DOI: 10.1002/pola.23354

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      New side-chain liquid crystalline polymers, poly(norbornene carboxylic cholesteryl ester), were prepared by ring opening metathesis polymerization. The thermal, mesomorphic, and morphological properties of these new homopolymers were investigated.

    20. Well-defined poly[(dimethylamimo)ethyl methacrylate]-b-poly(fluoroalkyl methacrylate) diblock copolymers: Effects of different fluoroalkyl groups on the solution properties (pages 2702–2712)

      Cuicui Liu, Jinlin He, Qun Zhao, Mingzu Zhang and Peihong Ni

      Version of Record online: 9 APR 2009 | DOI: 10.1002/pola.23355

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      We have investigated the effect of different fluoroalkyl groups on the solution properties of a series of fluorinated copolymers by turbidimetric measurement. The typical temperature-sensitive property of copolymers is herein described. The increasing temperature to a critical value can cause the polymer solution from transparency to opacity. The reason may be that the copolymer appears an expansible chain configuration at lower temperature, whereas the chains can shrink into a globular configuration for the weak hydrophobic-interaction between (N,N-dimethylamino)ethyl groups as temperature raises to the critical value. These results indicate that the fluorinated copolymer possesses well temperature-responsive property. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

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