Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 49 Issue 12

15 June 2011

Volume 49, Issue 12

Pages 2529–2760

  1. Articles

    1. Top of page
    2. Articles
    3. Notes
    1. Nanocomposite prepared from in situ grafting of polypyrrole to aminobenzoyl-functionalized multiwalled carbon nanotube and its electrochemical properties (pages 2529–2537)

      In-Yup Jeon, Hyun-Jung Choi, Loon-Seng Tan and Jong-Beom Baek

      Version of Record online: 14 APR 2011 | DOI: 10.1002/pola.24684

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      Polypyrrole grafted multiwalled carbon nanotube (PPy-g-MWCNT) was prepared from in situ polymerization of pyrrole in the presence of aminobenzoyl-functionalized MWCNT. Without conventional acid doping, the conductivity of PPy-g-MWCNT was 20 times higher than that of PPy. The improved electron conductivity should be because MWCNT served as nonvolatile dopant and conducting bridge. The electrochemical and electrocatalytic performances of PPy-g-MWCNT were also significantly enhanced.

    2. Synthesis and two-photon absorption properties of conjugated polymers with N-arylpyrrole as conjugated bridge and isolation moieties (pages 2538–2545)

      Qianqian Li, Jing Huang, Zhiguo Pei, Aoshu Zhong, Ming Peng, Jun Liu, Zhenli Huang, Jingui Qin and Zhen Li

      Version of Record online: 14 APR 2011 | DOI: 10.1002/pola.24685

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      The two-photon absorption moieties (blue part in the structure), which contained pyrrole ring as the π-conjugated bridge, were linked together through an isolation group (the purple part) to construct new kind of conjugated polymers, for the application as two-photon absorption materials.

    3. Dendritic surface functionalization of biodegradable polymer assemblies (pages 2546–2559)

      Ali Nazemi, Ryan C. Amos, Colin V. Bonduelle and Elizabeth R. Gillies

      Version of Record online: 14 APR 2011 | DOI: 10.1002/pola.24686

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      Poly(ethylene oxide)-polycaprolactone block copolymers with terminal azide groups were synthesized and assembled to form micelles and vesicles with surface azides. These azide groups were used to conjugate dendrons to the surfaces of the assemblies. The effect of the dendron's peripheral groups on the conjugation yields and stabilities of the assemblies was studied and interesting differences between the micelles and vesicles, as well as different dendritic groups were observed. Functionalization with a dendritic guanidine was found to enhance the uptake of micelles into HeLa cells, demonstrating the promise of this approach for readily modulating the biological properties of the assemblies.

    4. Nitroxide-mediated polymerization of 1,3-butadiene in the presence of diphenylamine with hydrogen peroxide as initiator (pages 2560–2565)

      Hassan Rezaei Haghighat, Mehdi Barikani and Jalil Morshedian

      Version of Record online: 21 APR 2011 | DOI: 10.1002/pola.24687

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      Living behavior of a nitroxide-mediated polymerization of 1,3-butadiene in the presence of diphenyl nitroxide (DPN) as counter radical and hydrogen peroxide (H2O2) as initiator has been studied to elucidate the bimodal molar mass distribution of the product by four approaches such as hydrolyzation of the oligomeric product, peak separation technique, which defines the oligobutadiene molar mass dependency in relation to α as a ratio of [nitroxide] to [H2O2], variation of hydroxyl value with respect to α, and para-substituted DPN.

    5. Single chain self-assembly of well-defined heterotelechelic polymers generated by ATRP and click chemistry revisited (pages 2566–2576)

      Ozcan Altintas, Tobias Rudolph and Christopher Barner-Kowollik

      Version of Record online: 25 APR 2011 | DOI: 10.1002/pola.24688

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      Well-defined heterotelechelic hydrogen donor/acceptor functional polymers are prepared via a combination of atom transfer radical polymerization and copper catalyzed azide–alkyne cycloaddition. The α,ω-functional donor/acceptor chains are subsequently self-assembled as single cyclic chains to emulate—on a simple level—the self-folding behavior of natural biomacromolecules. Besides the structural characterization of the heterotelechelic polymers via dynamic light scattering, the circular self-assembly of these polymers is demonstrated using 1H NMR in deuterated dichloromethane.

    6. Synthesis of all-conjugated poly(3-hexylthiophene)-block- poly(3-(4′-(3″,7″-dimethyloctyloxy)-3′-pyridinyl)thiophene) and its blend for photovoltaic applications (pages 2577–2587)

      Yi-Cang Lai, Kaoru Ohshimizu, Ayumi Takahashi, Jung-Ching Hsu, Tomoya Higashihara, Mitsuru Ueda and Wen-Chang Chen

      Version of Record online: 21 APR 2011 | DOI: 10.1002/pola.24689

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      New all-conjugated regioregular block copolythiophene, P3HT-b-P3PyT was successfully synthesized by quasi-living Grignard metathesis polymerization for photovoltaic applications. The photvoltaic devices based on P3HT-b-P3PyT/PCBM blend showed a comparable solar cell performance to that of the P3HT/PCBM. P3HT-b-P3PyT could also be used as a surfactant to enhance the long-term thermal stability of P3HT/PCBM-based solar cells, through the supramolecular interaction between the pyridine ring of P3PyT and PCBM. This study represents a new supramolecular approach to design all-conjugated block copolymers for high-performance photovoltaic devices.

    7. Cu powder-catalyzed single electron transfer-living radical polymerization of acrylonitrile (pages 2588–2593)

      Jing Ma, Hou Chen, Min Zhang and Lingfang Chen

      Version of Record online: 21 APR 2011 | DOI: 10.1002/pola.24690

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      Single electron transfer living radical polymerization (SET-LRP) has been used for synthesis of polyacrylonitrile (PAN) catalyzed by Cu(0) powder with carbon tetrachloride (CCl4) as the initiator and hexamethylenetetramine (HMTA) as the ligand in N,N-dimethylformamide (DMF) or mixed solvent. Kinetics data of the polymerizations at both ambient temperature and elevated temperature demonstrate living/controlled feature. An increase of ligand yields a higher monomer conversion and almost no polymerization occurs in the absence of ligand. The reaction rate exhibits an increase with the increase of catalyst Cu(0)/HMTA. Better control on the molecular weight distribution has been produced with addition of CuCl2.

    8. Copper(0)-catalyzed one-pot synthesis of ABC triblock copolymers via the combination of single electron transfer nitroxide radical coupling reaction and “click” chemistry (pages 2594–2600)

      Rongkuan Jing, Wencheng Lin, Guowei Wang and Junlian Huang

      Version of Record online: 25 APR 2011 | DOI: 10.1002/pola.24691

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      ABC triblock copolymers were prepared via the combination of SET-NRC reaction and “click” chemistry, in which Cu(I) generated from Cu(0) in SET-NRC reaction was used to catalyze “click” chemistry. It was found that increasing active surface area of Cu(0) could accelerate the one-pot reaction remarkably.

    9. Synthesis of aromatic oxazolyl- and carboxyl-functionalized polymers: Atom transfer radical polymerization of styrene initiated by 2-[(4-bromomethyl)phenyl]-4,5-dihydro-4,4-dimethyloxazole (pages 2601–2614)

      Gabriel J. Summers, Rejoice B. Maseko, B. M. Parveen Beebeejaun and Carol A. Summers

      Version of Record online: 27 APR 2011 | DOI: 10.1002/pola.24692

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      The synthesis of a new compound 2-[(4-bromomethyl)phenyl]-4,5-dihydro-4,4-dimethyloxazole (1) and its utility as an oxazolyl-functionalized initiator for the preparation of aromatic oxazolyl-functionalized polymers by atom transfer radical polymerization (ATRP) are reported. The ATRP of styrene, initiated by 2-[(4-bromomethyl)phenyl]-4,5-dihydro-4,4-dimethyloxazole (1) in the presence of a copper(I) bromide/2,2′-bipyridyl catalyst system, affords well-defined α-oxazolyl-functionalized polystyrene (2) via a controlled free radical polymerization process. Post-ATRP chain end modification of α-oxazolyl-functionalized polystyrene (2) to form the corresponding α-carboxyl-functionalized polystyrene (3) was achieved by successive acid catalyzed hydrolysis, saponification, and acidification reactions.

    10. Synthesis and properties of liquid crystalline urethane methacrylates for dental composite applications (pages 2615–2626)

      Tinca Buruiana, Violeta Melinte, George Costin and Emil C. Buruiana

      Version of Record online: 25 APR 2011 | DOI: 10.1002/pola.24693

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      Novel LC photopolymerizable methacrylates with alkylammonium or cholesteryl moieties are designed and proposed for use in dental formulations with reduced polymerization shrinkage and good properties. Their ability to preserve the LC nature when are incorporated into a formulation was demonstrated through DSC and polarizing optical microscopy analysis. All monomers showed reduced volumetric shrinkage, and their photobehavior depends on structural and compositional factors. For the resin composites containing around 4.5 wt % cationic groups, the bacteriostatic activity of against S. mutans was evidenced.

    11. Amphiphilic block glycopolymers via atom transfer radical polymerization: Synthesis, self-assembly and biomolecular recognition (pages 2627–2635)

      Orietta León, Alexandra Muñoz-Bonilla, Vanesa Bordegé, Manuel Sánchez-Chaves and Marta Fernández-García

      Version of Record online: 21 APR 2011 | DOI: 10.1002/pola.24694

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      Diblock and triblock glycopolymers based on poly(butyl acrylate) and poly(2-{[(D-glucosamin-2-N-yl)carbonyl]oxy}ethyl methacrylate) were synthesized by atom transfer radical polymerization. The self-assembly of these glycopolymers showed the coexistence of spherical micelles and polymeric vesicles. In addition, all the water-soluble glycopolymers present the ability to bind Concanavalin A, which is dependent on the HEMAGl copolymer composition.

    12. Synthesis, characterization, and rheological properties of hybrid titanium star-shaped poly(n-butyl acrylate) (pages 2636–2644)

      Fabien Périneau, Guangjun Hu, Laurence Rozes, François Ribot, Clément Sanchez, Costantino Creton, Laurent Bouteiller and Sandrine Pensec

      Version of Record online: 25 APR 2011 | DOI: 10.1002/pola.24695

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      We described the synthesis and characterization of inorganic/organic hybrid star like architectures composed of a titanium oxo-cluster core and a poly(n-butyl acrylate) shell. Starting from a well-defined multifunctional titanium oxo-cluster initiator, a “grafting from” approach based on atom transfer radical polymerization has been developed. Its successful development paves the way to incorporate and disperse homogeneously these Ti nano-objects into a PnBA elastomeric matrix. In addition to the kinetics of polymerization and the molecular architecture, we characterized the rheological properties of the hybrid stars and showed conclusively that the presence of the Ti core significantly slows the dynamics at low frequency relative to identical stars with an organic core.

    13. Annealing effect on performance and morphology of photovoltaic devices based on poly(3-hexylthiophene)-b-poly(ethylene oxide) (pages 2645–2652)

      Zhijie Gu, Tatsuya Kanto, Kousuke Tsuchiya, Takeshi Shimomura and Kenji Ogino

      Version of Record online: 25 APR 2011 | DOI: 10.1002/pola.24696

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      To control the morphology in polymer photovoltaic devices, a series of block copolymers poly(3-hexylthiophene)-block-poly(ethylene oxide) (P3HT-b-PEO) with different PEO contents were prepared via Suzuki coupling reaction between P3HT and PEO homopolymers. The surface morphology of the P3HT/PCBM and P3HT-b-PEO/PCBM blend films was studied by AFM measurement after thermal or solvent annealing. The blend films using the block copolymer showed the partially aligned lamellar phase-separated structure with smaller domain size compared with the homopolymer blend. The effect of annealing processes on the performance of photovoltaic devices based on the block copolymers was also investigated, and the device of P3HT-b-PEO/PCBM showed higher efficiency than that of P3HT/PCBM after thermal annealing.

    14. Synthesis and self-assembly of thermotropic block copolymer with long alkyl tethered cage silsesquioxane in the side chain (pages 2653–2664)

      Yoshihito Ishida, Tomoyasu Hirai, Raita Goseki, Masatoshi Tokita, Masa-Aki Kakimoto and Teruaki Hayakawa

      Version of Record online: 25 APR 2011 | DOI: 10.1002/pola.24697

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      Thermotropic POSS-containing poly(methacrylate) with long alkyl chain tethered polyhedral oligomeric silsesquioxane (POSS) in the side chain and the block copolymers were synthesized by living anionic polymerization. Polymers obtained show a phase transition from spherocrystal to isotropic phase at 112 °C because of the crystalline nature of long alkyl chain tethered POSS. Thermal annealing of block copolymer thin film led to form dot and line-like structure with thermally equilibrium state based on each volume fraction of the block copolymers obtained.

    15. Poly(L-glutamic acid) grafted with oligo(2-(2-(2-methoxyethoxy)ethoxy)ethyl methacrylate): Thermal phase transition, secondary structure, and self-assembly (pages 2665–2676)

      Jianxun Ding, Chunsheng Xiao, Li Zhao, Yilong Cheng, Lili Ma, Zhaohui Tang, Xiuli Zhuang and Xuesi Chen

      Version of Record online: 27 APR 2011 | DOI: 10.1002/pola.24698

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      Thermoresponsive and pH-responsive graft copolymers, poly(L-glutamate)-g-oligo(2-(2-(2-methoxyethoxy)ethoxy)ethyl methacrylate) and poly(L-glutamic acid-co-(L-glutamate-g-oligo(2-(2-(2-methoxyethoxy)ethoxy)ethyl methacrylate))), are synthesized by ring-opening polymerization and subsequent atom transfer radical polymerization. The thermal phase transition, secondary structure and self-assembly of graft copolymers can be tuned by the molecular weight of OMEO3MA, composition of PLGA backbone, temperature and pH. In vitro MTT assay reveals that the graft copolymers are biocompatible to HeLa cells. Therefore, with good biocompatibility, well-defined secondary structure, and mono-, dual-responsiveness, these graft copolymers are promising stimuli-responsive materials for biomedical applications.

    16. Controlled synthesis of polyepichlorohydrin with pendant cyclic carbonate functions for isocyanate-free polyurethane networks (pages 2677–2684)

      Anne-Laure Brocas, Gabriel Cendejas, Sylvain Caillol, Alain Deffieux and Stephane Carlotti

      Version of Record online: 27 APR 2011 | DOI: 10.1002/pola.24699

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      A series of well-defined gradient poly(epichlorhydrin-co-allyl glycidyl ether) were synthesized by monomer-activated anionic polymerization with molar masses from 3,000 to 29,000 g mol−1. Pendant allyl groups were then chemically modified into cyclic carbonates. These polyethers were used as precursors for isocyanate-free polyurethane networks by reaction with diamines. Various materials with glass transition temperatures ranging from −24 to 90 °C were obtained according to the number of pendant reactive functions.

    17. Low band gap copolymers consisting of porphyrins, thiophenes, and 2,1,3-benzothiadiazole moieties for bulk heterojunction solar cells (pages 2685–2692)

      Weiping Zhou, Ping Shen, Bin Zhao, Peng Jiang, Lijun Deng and Songting Tan

      Version of Record online: 27 APR 2011 | DOI: 10.1002/pola.24700

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      Two low band gap conjugated copolymers containing porphyrins, thiophenes, and 2,1,3-benzothiadiazole moieties were synthesized and applied in bulk heterojunction solar cells.

    18. Synthesis and optical and transport properties of a phenyl-substituted polythiophene (pages 2693–2699)

      Siraye E. Debebe, Desta A. Gedefaw, Wendimagegn Mammo, Teketel Yohannes, Francesca Tinti, Alberto Zanelli, Valeria Fattori and Nadia Camaioni

      Version of Record online: 27 APR 2011 | DOI: 10.1002/pola.24701

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      A novel polythiophene substituted with a 2′-pentyloxy-5′-(1″′-oxooctyl) phenyl group (PPOPT) is synthesized and characterized. The bulk transport properties of thin films of PPOPT are investigated by admittance spectroscopy. The dramatic effect of the phenyl side chain on the mobility of positive carriers in films of PPOPT is described.

    19. Ethylene homopolymerizaton and copolymerizaton by vanadium(III) complexes containing tridentate or tetradentate iminopyrrolyl ligands (pages 2700–2708)

      Jing-Shan Mu, Xin-Cui Shi and Yue-Sheng Li

      Version of Record online: 27 APR 2011 | DOI: 10.1002/pola.24702

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      A series of vanadium(III) complexes bearing [NNX] (X = S, P) tridentate and [NNNN] tetradentate iminopyrrolyl ligands have been synthesized, characterized and investigated as catalyst precursors for ethylene polymerization and ethylene/1-hexene copolymerization. The chain transfer mechanism was proposed by investigating the microstructure of ethylene/1-hexene copolymers.

    20. Synthesis of poly(m-phenylene) and poly(m-phenylene)-block- poly(3-hexylthiophene) with low polydispersities (pages 2709–2714)

      Kaoru Ohshimizu, Ayumi Takahashi, Tomoya Higashihara and Mitsuru Ueda

      Version of Record online: 27 APR 2011 | DOI: 10.1002/pola.24703

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      The synthesis of well-defined poly(m-phenylene), poly(m-phenylene)-block-poly(3-hexylthiophene) and their characterization, such as 1H NMR spectra, SEC profiles, DSC profiles, AFM, and UV–vis spectra have been investigated.

    21. Synthesis and photovoltaic properties of low-bandgap 4,7-dithien-2-yl-2,1,3-benzothiadiazole-based poly(heteroarylenevinylene)s (pages 2715–2724)

      Shanpeng Wen, Jianing Pei, Pengfei Li, Yinhua Zhou, Weidong Cheng, Qingfeng Dong, Zaifang Li and Wenjing Tian

      Version of Record online: 27 APR 2011 | DOI: 10.1002/pola.24704

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      A series of novel low-bandgap 4,7-dithien-2-yl-2,1,3-benzothiadiazole-based conjugated polymers (PFV-HBT, PPV-HBT, and PTV-HBT) consisting of different electron-rich donors in main-chains were synthesized. The PSC device containing blend of donor PTV-HBT and acceptor PCBM in 1:4 weight ratio showed the highest PCE value of 1.05% with Voc = 0.52 V, Jsc = 3.98 mA/cm2, and FF = 0.51.

    22. Hydrophilic dual-responsive magnetite/PMAA core/shell microspheres with high magnetic susceptibility and ph sensitivity via distillation-precipitation polymerization (pages 2725–2733)

      Wanfu Ma, Shuai Xu, Jumei Li, Jia Guo, Yao Lin and Changchun Wang

      Version of Record online: 27 APR 2011 | DOI: 10.1002/pola.24705

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      Hydrophilic dual-responsive magnetite/PMAA core/shell microspheres were directly fabricated through encapsulating MPS-modified magnetite colloid nanocrystal clusters (MCNCs) with crosslinked poly(methacrylic acid) (PMAA) shell via distillation-precipitation polymerization. The experimental results indicated that the obtained composite microspheres had well-defined core/shell structure, high saturation magnetization value, and abundant surface carboxyl groups. These core/shell composite microspheres possess fairly good magnetic susceptibility and pH sensitivity. 108:

    23. Synthesis and crystallization behavior study of syndiotactic polystyrene-g-isotactic polypropylene (sPS-g-iPP) graft copolymers (pages 2734–2745)

      HuaHua Huang, Hui Niu and Jin-Yong Dong

      Version of Record online: 27 APR 2011 | DOI: 10.1002/pola.24706

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      We synthesized all-crystalline graft copolymers of sPS-g-iPP and studied their melting and crystallization behavior. The graft copolymer synthesis was based on macromonomer incorporation with coordination polymerization mechanism using mono-titanocene/MAO catalyst that generates syndiotactic polystyrene (sPS), with a proprietary styryl-capped iPP macromonomer (iPP-t-St). The graft copolymers were generally found with dual melting and crystallization temperatures, which were ascribable, respectively, to the sPS backbone and iPP graft. However, it was revealed that the two segments displayed largely different melting and crystallization behaviors than sPS homopolymer and the precursory iPP-t-St macromonomer.

    24. Synthesis and photovoltaic properties of copolymers based on bithiophene and bithiazole (pages 2746–2754)

      Maojie Zhang, Haijun Fan, Xia Guo, Yang Yang, Shanshan Wang, Zhi-Guo Zhang, Jing Zhang, Xiaowei Zhan and Yongfang Li

      Version of Record online: 2 MAY 2011 | DOI: 10.1002/pola.24708

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      Three simple structured D-A copolymers with different alkyl chain length, PBTBTz-1, PBTBTz-2, and PBTBTz-3 were synthesized for the application as donor materials in polymer solar cells (PSCs). The power conversion efficiency of the PSC based on PBTBTz-2:PC70BM = 1:1(w/w) reached 2.58% with a open circuit voltage of 0.77 V and a short circuit current of 8.70 mA/cm2, under the illumination of AM1.5, 100 mW/cm2.

  2. Notes

    1. Top of page
    2. Articles
    3. Notes
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      Functionalization of polymeric surfaces by simple photoactivation of C[BOND]H bonds (pages 2755–2760)

      Jing Xu, Yuhong Ma, Jingyi Xie, F.J. Xu and Wantai Yang

      Version of Record online: 25 APR 2011 | DOI: 10.1002/pola.24707

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      Excited acetone acted as a pair of scissors cutting both the C[BOND]H bond of the substrate and the O[BOND]H bond of the penol, thereby generating confined carbon-centered chain radicals and mobile oxygen-centered phenoxy radicals. By a coupling, various functionalities as substituents of phenols, such as [BOND]OH, [BOND]COOH, [BOND]NH2, [BOND]SO3H, and [BOND]SH, were bonded to the polymer surface.