Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 54 Issue 6

Early View (Online Version of Record published before inclusion in an issue)

Impact Factor: 3.113

ISI Journal Citation Reports © Ranking: 2014: 18/82 (Polymer Science)

Online ISSN: 1099-0518

Associated Title(s): Journal of Polymer Science Part B: Polymer Physics

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  1. 1 - 100
  2. 101
  1. Articles

    1. Copolymerization of carbon dioxide and cyclohexene oxide catalyzed by chromium complexes bearing semirigid [ONSO]-type ligands

      Bing Han, Li Zhang, Samuel J. Kyran, Binyuan Liu, Zhongyu Duan and Donald J. Darensbourg

      Article first published online: 8 FEB 2016 | DOI: 10.1002/pola.28052

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      Imine-thioether-bridged bis(phenolate) chromium complexes, the softer analogs to (salalen)CrIII catalysts, were employed in the copolymerization of CO2 and cyclohexene oxide to produce poly(cyclohexene carbonate). Their activity can be enhanced by the use of electron-withdrawing groups on the ligand.

    2. The synthesis and photoactive properties of cyclic amphiphilic polymers with azobenzene in main chain

      Ganquan Jiang, Lishan Li, Xiaofei Xu, Jinjie Lu, Xing Zhu, Zhengbiao Zhang, Nianchen Zhou and Xiulin Zhu

      Article first published online: 8 FEB 2016 | DOI: 10.1002/pola.28045

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      Cyclic amphiphilic polymers with azobenzene in main chain, cyclic-Azo-TEG-PS were successfully prepared by ATRP and CuAAC “click” cyclization from α-TMS-alkyne-ω-azido linear precursors. The cyclic polymers displayed a higher Tg than that of the linear ones. The trans-to-cis and cis-to-trans photoisomerization of cyclic polymers was both slower than that of their respective linear counterparts with the azobenzene moiety at chain end.

    3. Fluorinated star-shaped block copolymers: Synthesis and optical properties

      Jing Qu, Xinran Luo and Zhonggang Wang

      Article first published online: 8 FEB 2016 | DOI: 10.1002/pola.28056

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      Wholly aromatic ATRP initiator tetrakis(4-(1-bromoethyl)phenyl)silane is synthesized, which successively initiates the atom transfer radical polymerizations of MMA and fluorinated monomer (FGOA) to create fluorinated star-shaped block copolymers PMMA-b-poly(FGOA)s in controlled manner with the polydispersity indices less than 1.30. The fluorinated films exhibit excellent hydrophobicity, tunable refractive indices and extremely low birefringence coefficients, showing potential application in optical waveguide devices.

    4. 2,2,2-trifluoroacetophenone-based D-π-A type photoinitiators for radical and cationic photopolymerizations under near-UV and visible LEDs

      Ming Jin, Man Yu, Yuan Zhang, Decheng Wan and Hongting Pu

      Article first published online: 5 FEB 2016 | DOI: 10.1002/pola.28053

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      Two novel D-π-A type trifluoroacetophenone-based photoinitiators having a biphenyl or fluorenyl conjugated systems were synthesized by Suzuki reactions. The obtained photoinitiators exhibited high UV-Visible light sensitivity. Furthermore, two photoinitiators were soluble in common monomers of acrylate and epoxides. These results improved their applications in the radical and cationic photopolymerizations at 365 to 450 nm LEDs light sources even in low concentration initiators and weak exposure intensity, e.g., 1 to 2 mW cm−2.

    5. Synthesis of well-defined polyacrylonitrile by ICAR ATRP with low concentrations of catalyst

      Melissa Lamson, Maciej Kopeć, Hangjun Ding, Mingjiang Zhong and Krzysztof Matyjaszewski

      Article first published online: 4 FEB 2016 | DOI: 10.1002/pola.28055

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      The polymerization of acrylonitrile by ICAR ATRP with copper catalyst loadings between 1 and 50 ppm was investigated. Polyacrylonitrile (PAN) with predefined molecular weights and low dispersities were obtained. Efficient chain extension of PAN with n-butyl acrylate (BA) was demonstrated to yield well-defined PAN-b-PBA block copolymers and confirmed high chain-end functionality of the PAN macroinitiators synthesized by ICAR ATRP.

  2. Reviews

    1. Recent progress on cyclic polymers: Synthesis, bioproperties, and biomedical applications

      Xiao-Yan Tu, Ming-Zhu Liu and Hua Wei

      Article first published online: 3 FEB 2016 | DOI: 10.1002/pola.28051

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      Polymer topologies exert a significant effect on its properties, and polymer nanostructures with advanced architectures are a promising class of materials with advantages over conventional linear counterparts. The current review focuses on the recent progress in the design and development of cyclic polymers with an emphasis on its synthesis and bio-related properties and applications.

  3. Articles

    1. Determination of methylene bridge crosslinking in chloromethylated PS-DVB resins

      G. Leslie Burnett, John C. Rohanna, Steve Rosenberg, Alfred K. Schultz and Javier Read de Alaniz

      Article first published online: 3 FEB 2016 | DOI: 10.1002/pola.28054

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      New conditions for the room temperature reduction of chloromethylated PS-DVB resins are established, which enables the ratio of the newly formed reduced methyls to the methylene bridge crosslinker to be determined. Utilizing this ratio, the amount of methylene bridging resulting from the chloromethylation of PS-DVB is determined in the chloromethylated resin.

    2. Designing semiencapsulation based covalently self-healable poly(methyl methacrylate) composites by Atom Transfer Radical Polymerization

      Bhaskar Jyoti Saikia and Swapan Kumar Dolui

      Article first published online: 2 FEB 2016 | DOI: 10.1002/pola.28046

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      Self-healing poly(methyl methacrylate) composites with embedded glycidyl methacrylate encapsulated poly(melamine-formaldehyde) microcapsules were fabricated. One linear and one star shaped living PMMA matrix were synthesized by ATRP. Both were able to restore 100% of their fracture toughness after healing, although the star shaped polymer matrix was able to recover the crack much faster than the previous one.

    3. Chitosan/Ce(IV) redox polymerization-based amplification for detection of DNA point mutation

      Dequan Zhuang, Fei Wen, Yanjun Cui, Tianwei Tan and Jing Yang

      Article first published online: 2 FEB 2016 | DOI: 10.1002/pola.28050

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      Feasible and visual detection of DNA mutation was developed using redox polymerization with high-molecular weight chitosan and Ce4+ as an effective redox couple.

    4. Comprehensive study of pyrido[3,4-b]pyrazine-based D–π–a copolymer for efficient polymer solar cells

      Yu-Qi Wu, Hsieh-Chih Chen, Yun-Siou Yang, Sheng Hsiung Chang, Pin-Jiun Wu, Yen-Yi Chu and Chun-Guey Wu

      Article first published online: 29 JAN 2016 | DOI: 10.1002/pola.28044

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      A D-π-A copolymer containing a strong electron acceptor unit of pyrido-quinoxaline (PQ) in comparison with the benzo-quinoxaline (BQ)-based analog was proved to be an efficient p-type polymer for solution-processed organic photovoltaics

    5. Biocompatible stimuli-responsive nanogels for controlled antitumor drug delivery

      Garbiñe Aguirre, Eva Villar-Alvarez, Adrián González, Jose Ramos, Pablo Taboada and Jacqueline Forcada

      Article first published online: 20 JAN 2016 | DOI: 10.1002/pola.28025

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      Thermo-responsive poly(N-vinylcaprolactam)-based, pH-responsive poly(2-(diethylamino)ethyl) methacrylate-based, and thermo- and pH-responsive PDEAEMA/PVCL-based core-shell nanogels are reported, and their suitability for potential nanocarriers for drug delivery are analyzed. Doxorubicin hydrochloride was effectively loaded into the nanogels, the drug release profiles were studied at various pHs, and the cytocompatibility was assessed in vitro using cervical cancer and breast cancer cell lines.

    6. Poly(3-hexyl thiophene)-b-poly(N-isopropyl acrylamide): Synthesis and its composition dependent structural, solubility, thermoresponsive, electrochemical, and electronic properties

      Pallavi Kumari, Koomkoom Khawas, Sunit Hazra and Biplab Kumar Kuila

      Article first published online: 19 JAN 2016 | DOI: 10.1002/pola.28040

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      P3HT-b-PNIPAMs of varying compositions were synthesized by a facile click reaction. The composition-dependent solubility, thermoresponsive property in water, phase behavior, and electrochemical and electronic properties of these block copolymers were investigated. In aqueous solution, block copolymers with higher volume fraction of PNIPAM self-assemble into thermosensitive spherical micelles with P3HT-rich crystalline cores and PNIPAM coronas. The block copolymers show improved or similar charge carrier mobility compared with pure P3HT depending on the composition of the block copolymer.

    7. Synthesis, characterization, and thin-film properties of 6-oxoverdazyl polymers prepared by ring-opening metathesis polymerization

      Joseph A. Paquette, Sabastine Ezugwu, Vishal Yadav, Giovanni Fanchini and Joe B. Gilroy

      Article first published online: 18 JAN 2016 | DOI: 10.1002/pola.28042

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      Ring-opening metathesis polymerization was used to prepare polymers bearing pendant 6-oxoverdazyl radicals. Detailed characterization, including FT-IR, UV-vis absorption, and electron paramagnetic resonance spectroscopy quantitatively and qualitatively confirmed the high radical content within the polymer backbone. The polymers exhibited ambipolar redox properties in solution, and the resistivity of thin-films varied drastically before and after an external potential of 5 V was applied (1010 Ω m [RIGHTWARDS ARROW]104 Ω m).

    8. Synthesis of polymerizable poly(alkenoic acid)s via reversible addition fragmentation transfer polymerization for dental applications

      Yohann Catel, Lucie Maissiat and Norbert Moszner

      Article first published online: 18 JAN 2016 | DOI: 10.1002/pola.28043

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      Three new polymerizable poly(alkenoic acid)s were synthesized via RAFT polymerization. Self-etch adhesives based on these acidic polymers were able to mediate a strong bond between the dental hard tissues (dentin and enamel) and a restorative material. The addition of these poly(alkenoic acid)s to an adhesive containing 10-methacryloyloxydecyl dihydrogen phosphate resulted in a significant improvement of the dentin adhesion.

    9. Solution polymerization of polybenzimidazole

      Kayley J. Fishel, Alexander L. Gulledge, Andrew T. Pingitore, Jason P. Hoffman, Warren P. Steckle Jr. and Brian C. Benicewicz

      Article first published online: 15 JAN 2016 | DOI: 10.1002/pola.28041

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      Polybenzimidazoles (PBI) are an important class of heterocyclic high-performance polymers particularly known for their flame resistance. The current methods for synthesizing high inherent viscosity PBI include a two-stage melt/solid polymerization or a polymerization performed in polyphosphoric acid at high temperatures. In this article, a novel, direct polymerization of PBI in N,N-dimethyl acetamide to obtain high molecular weight polymer is reported.

    10. Cationic polymerization of vinyl ethers with alkyl or ionic side groups in ionic liquids

      Hayato Yoshimitsu, Arihiro Kanazawa, Shokyoku Kanaoka and Sadahito Aoshima

      Article first published online: 13 JAN 2016 | DOI: 10.1002/pola.28039

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      Ionic liquids (ILs) are employed as a polymerization solvent for cationic polymerization of vinyl ethers with pendant alkyl or ionic groups. The polymerization of isobutyl vinyl ether proceeds in a controlled manner in an imidazolium-based IL using TiCl4 as a catalyst. A vinyl ether with pendant imidazolium salt is also directly polymerized in the IL. The obtained polymers exhibit solubilities that are readily tuned by counteranion exchange.

    11. Tuning the adsorption and fluorescence properties of aminal-linked porous organic polymers through N-heterocyclic group decoration

      Jun-Ying Weng, Yue-Ling Xu, Wei-Chao Song and Ying-Hui Zhang

      Article first published online: 11 JAN 2016 | DOI: 10.1002/pola.28028

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      Four new aminal-linked porous organic polymers (NAPOPs), synthesized through the polycondensation reaction of four aldehydes decorated with different N-heterocyclic groups with 1,4-Bis(4,6-diamino-s-triazin-2-yl) benzene, exhibit good CO2/N2 adsorption selectivity (34–77 at 273 K and 100 kPa), excellent I2 sorption capacity (>200 wt %), and versatile fluorescence emission varying from 526 to 633 nm.

    12. Sulfonated polyaniline-graphene oxide hybrids: Synthesis and effect of monomer composition on the electrochemical signal for direct DNA detection

      Le Meng, Huaiyin Chen, Tong Ge, Tao Yang and Kui Jiao

      Article first published online: 9 JAN 2016 | DOI: 10.1002/pola.28032

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      A variety of sulfonated polyaniline-graphene oxide nanocomposites (SPAN-GNO) are prepared via changing the mole ratio of aniline (ANI) to m-aminobenzenesulfonic acid (ABSA). Self-signals of SPAN-GNO are employed for the comparison of DNA sensing behavior. The effects of preparation conditions (component, monomer composition, and reaction time) on DNA immobilization and hybridization are estimated. The mole ratio plays a lead role over other factors on hybridization efficiency.

    13. Rotaxane-type hyperbranched polymers from a crown ether host and paraquat guests containing blocking groups

      Minjae Lee and Harry W. Gibson

      Article first published online: 8 JAN 2016 | DOI: 10.1002/pola.28022

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      Supramolecular rotaxane-type hyperbranched polymers are synthesized from A2B type semi-rotaxane monomers formed in situ via complexation of difunctional bis(m-phenylene)-32-crown-10 dimethanol and two monofunctional paraquat ω-n-alkylenecarboxylic acid derivatives with tris(p-t-butylphenyl)methylphenylalkylene stoppers. The polymers possess hyperbranched structures and properties, which are confirmed by NMR, dynamic light scattering and viscosity studies.

    14. Detrimental Ni(0) transfer in Kumada catalyst transfer polycondensation of benzo[2,1-b:3,4-b']dithiophene

      Anjan Bedi, Julien De Winter, Pascal Gerbaux and Guy Koeckelberghs

      Article first published online: 8 JAN 2016 | DOI: 10.1002/pola.28026

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      An in-depth study of Kumada catalyst transfer polycondensation (KCTP) of a fused monomer unravels that after few initial steps of correct polymerization the Ni(0) species interacts with the “non-aromatic double bond” in the π-system neither very strongly nor too weak to undergo a catalyst transfer to a fresh monomer (which starts polymerizing then individually) thus terminating the correctly initiated polymerization abruptly.

    15. Toward large tubular helices based on the polymerization of tri(benzamide)s

      Maren Schulze and Andreas F. M. Kilbinger

      Article first published online: 8 JAN 2016 | DOI: 10.1002/pola.28029

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      The polycondensation of tri(p-benzamide)s could allow the synthesis of helical polymers with inner diameters defined only be the monomer sequence. We report initial synthetic efforts toward this goal and provide GPC and circular dichroism spectroscopy data that support our hypothesis.

    16. Architecture-controlled synthesis of redox-degradable hyperbranched polyglycerol block copolymers and the structural implications of their degradation

      Suhyun Son, Haeree Park, Eeseul Shin, Yuji Shibasaki and Byeong-Su Kim

      Article first published online: 8 JAN 2016 | DOI: 10.1002/pola.28031

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      The two types of redox-degradable polyglycerols, P(G-b-SSG) and P(SSG-b-G), are newly designed and synthesized with controlled architectures. The degradation of two types of hyperbranched block copolymers is studied and the degradation mechanism is suggested, depending on the structure of polymers. The proposed idea was confirmed by a series of 1H NMR spectroscopy and GPC experiments, revealing different degradation products from P(G-b-SSG) and P(SSG-b-G). This study will aid understanding of the structure of degradable hyperbranched polyglycerol.

    17. Synthesis of bisphenol A-free oligomeric phthalonitrile resins with sulfone and sulfone-ketone containing backbones

      Matthew Laskoski, Jadah S. Clarke, Arianna Neal, Holly L. Ricks-Laskoski, W. Judson Hervey and Teddy M. Keller

      Article first published online: 8 JAN 2016 | DOI: 10.1002/pola.28020

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      Two new oligomeric sulfone and sulfone-ketone containing phthalonitrile resins with excellent processability have been developed. These phthalonitrile resins exhibited good viscosities and cure times for molding into various shapes. The crosslinked polymers demonstrated superb mechanical properties and thermo-oxidative stability, and good dielectric properties.

    18. Pd-initiated polymerization of diazo compounds bearing dialkoxyphosphinyl group and hydrolysis of the resulting polymers and oligomers to afford phosphonic acid-containing products

      Hiroaki Shimomoto, Akira Oda, Motoki Kanayama, Tomoya Sako, Tomomichi Itoh, Eiji Ihara, Naohiro Hoshikawa, Akihiko Koiwai and Naoki Hasegawa

      Article first published online: 8 JAN 2016 | DOI: 10.1002/pola.28030

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      Pd-initiated polymerization of diazo compounds, containing a dialkoxyphosphinyl group and subsequent hydrolysis of the products, were conducted to prepare C-C main chain polymers or oligomers bearing phosphonic acid on each main chain carbon atom, which were expected to form effective pathways for proton transfer around the main chain.

    19. Synthesis of new Azo-based liquid crystalline polymers and their selective sensing behaviors to alkali metal ions

      In-Joon Byun, Minjae Lee and Yang-Kyoo Han

      Article first published online: 7 JAN 2016 | DOI: 10.1002/pola.28027

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      Novel liquid crystalline polymers containing pendant azobenzene moieties with ethyleneoxy spacer ligands of different length and n-dodecyl substituent show selective sensing behaviors for Li+ and Na+ cations in solutions. UV-Vis and 1H NMR studies confirm that both the ethyleneoxy spacer and azobenzene units participate in binding to Li+ and Na+ cations. Such findings suggest a great potential of the new azopolymers as either selective metallic sensors or separation membranes for alkali metal cations.

    20. One-pot fabrication of robust interpenetrating hydrogels via orthogonal click reactions

      Takuya Murakami, Hugh R. Brown and Craig J. Hawker

      Article first published online: 5 JAN 2016 | DOI: 10.1002/pola.28021

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      Interpenetrating polymer network (IPN) hydrogels have been fabricated through a facile one-pot approach by orthogonal double click reactions: epoxy-amine reaction and copper catalyzed azide-alkyne cycloaddition. Compared to corresponding single network gels, the IPN gels containing both tightly and loosely crosslinked networks exhibit superior mechanical properties with fracture stresses over 40 MPa. The synthetic versatility of this one-pot approach will further establish design principles for the next generation of robust hydrogel materials.

    21. Synthesis of pH- and thermoresponsive poly(2-n-propyl-2-oxazoline) based copolymers

      Marcel A. Boerman, Harry L. Van der Laan, Johan C. M. E. Bender, Richard Hoogenboom, John A. Jansen, Sander C. Leeuwenburgh and Jan C. M. Van Hest

      Article first published online: 5 JAN 2016 | DOI: 10.1002/pola.28011

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      In this work, we present a systematic study after the aqueous solution behavior of thermoresponsive poly(2-n-propyl-2-oxazoline) based copolymers at various biologically relevant conditions. By introduction of carboxylic acid and amine groups into the polymer chain, they become both pH and thermoresponsive, making them stimulus-responsive around body temperature, which increases their potential for biomedical applications.

    22. Triple hydrogen-bonding block copolymers via RAFT polymerization: Synthesis, vesicle formation, and molecule-recognition behavior

      Shixue Wang, Maosheng Li, Hang Zhang, Xinxiao Yang, Xiaojie Zhang, Youhua Tao and Xianhong Wang

      Article first published online: 5 JAN 2016 | DOI: 10.1002/pola.28019

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      RAFT polymerization afforded triple hydrogen-bonding block copolymers with well-controlled molecular weight and molecular weight distributions (1.2-1.4). The complexation via specific hydrogen bonding between these block copolymers in CHCl3 provided an unprecedented approach for the formation of spherical vesicles. AFM and DLS measurements revealed that the resultant polymeric vesicles were about 100 nm in radius. These results indicated that these vesicles of triple hydrogen-bonding block copolymer could be a potential new vehicle for molecular recognition.

    23. Emulsion copolymerization of substituted acetylenes for constructing optically active helical polymer nanoparticles. Synergistic effects and helicity inversion

      Biao Zhao, Jianping Deng and Wantai Yang

      Article first published online: 5 JAN 2016 | DOI: 10.1002/pola.28023

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      Copolymerization can provide polymers with desirable properties which cannot be performed by homopolymers. Chiral substituted acetylene monomers, containing cholic acid groups, successfully undergo emulsion copolymerization with an achiral acetylenic monomer. Synergistic effects and helicity inversion simultaneously occur in the helical copolymer emulsions. The emulsion copolymerizations directly provide optically active helical polymer nanoparticles.

    24. Conjugated polymer nanoparticles with aggregation induced emission characteristics for intracellular Fe3+ sensing

      Dongliang Yang, Fei Li, Zhimin Luo, Biqing Bao, Yanling Hu, Lixing Weng, Yixiang Cheng and Lianhui Wang

      Article first published online: 5 JAN 2016 | DOI: 10.1002/pola.28024

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      Conjugated polymer nanoparticles (CPNs) with aggregation induced emission characteristics were synthesized. The obtained nanoparticles exhibited a selective fluorescence response for Fe3+ ions compared with other metal ions. Applications of the TPE-contained CPNs for in vitro bioimaging are successfully demonstrated using A549 cells. The AIE-active CNPs show an excellent Fe3+ detection ability in vitro due to low cytotoxicity, high photostability and the enhanced cell permeability.

    25. Hyperbranched polybenzoxazoles incorporated polybenzoxazoles for high-performance and low-K materials

      Yan Wang, Junrong Yu, Jing Zhu and Zuming Hu

      Article first published online: 28 DEC 2015 | DOI: 10.1002/pola.28018

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      This work describes an effective approach to reduce the k value while preserve the good mechanical and thermal properties of aromatic polymers. This approach involves the covalent incorporation of hyperbranched polybenzoxazole (HBPBO) into linear PBO matrix. The obtained polymers show good mechanical and thermal properties because of the same chemical compositions and the covalent linking effect of HBPBO to linear PBO, coupled with greatly reduced k values due to the increased free volume resulted from the disturbed chain packing of PBO by the globular HBPBO, and the intrinsic cavities in HBPBO.

    26. Polymerization-induced self-assembly of block copolymer through dispersion RAFT polymerization in ionic liquid

      Heng Zhou, Chonggao Liu, Chengqiang Gao, Yaqing Qu, Keyu Shi and Wangqing Zhang

      Article first published online: 28 DEC 2015 | DOI: 10.1002/pola.28002

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      In situ synthesis of block copolymer nano-objects through the macro-RAFT agent mediated dispersion polymerization in the ionic liquid of 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIN][PF6]) is investigated. This dispersion RAFT polymerization in ionic liquid affords three advantages including (1) the fast polymerization kinetics, (2) good control on the polymer molecular weight and molecular weight distribution and (3) the tunable morphology of the block copolymer nano-objects.

    27. Thiophene π bridge effect on bulky side-chained benzodithiophene-based photovoltaic polymers

      Ruiying Sheng, Qian Liu, Weiye Chen, Mingliang Sun, Huilin Zheng, Jing Ren and Renqiang Yang

      Article first published online: 24 DEC 2015 | DOI: 10.1002/pola.28017

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      In this article, the polymers P1 and P3 form by copolymerizing benzo[1,2-b:4,5-b′]dithiophene (BDT) with a terthiophene side chain and thieno[3,4-c]pyrrole-4,6-dione (TPD) and thieno[3,4-b]thiophene (TT), separately, exhibit relatively low power conversion efficiencies (PCEs). After inserting the thiophene bridge, the polymers P2 and P4 show higher JSC and FF and finally increase the PCEs of polymer solar cells (PSCs) greatly. The preliminary conclusion is that, for bulky side-chained benzodithiophene polymers, introducing a thiophene π bridge on the main chain may be helpful to PSCs performances.

    28. Synthesis and characterizations of new isotactic homopolyesters, statistical and block copolyesters derived of poly((S)-3,3-dimethylmalic acid) via the lactone route

      Rima Belibel, Imadeddine Azzouz and Christel Barbaud

      Article first published online: 23 DEC 2015 | DOI: 10.1002/pola.27997

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      For temporary therapeutic applications, it will be innovative to use biodegradable and bioassimilable stereopolymers. In this study, a series of new isotactic and semicrystalline stereopolyesters derived from malic acid was synthesized by anionic polymerization from optically active β-lactones as monomers. Therefore, this article describes in detail the total synthesis and characterization by NMR, DSC, TGA, and SEC.

    29. Electrosynthesis and electrochromic properties of free-standing copolymer based on oligo(oxyethylene) cross-linked 2,2’-bithiophene and 3,4-ethylenedioxythiophene

      Yongjing Hu, Zhipeng Wang, Kaiwen Lin, Jingkun Xu, Xuemin Duan, Feng Zhao, Jian Hou and Fengxing Jiang

      Article first published online: 22 DEC 2015 | DOI: 10.1002/pola.28012

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      The electrochemical copolymerization of oligo(oxyethylene) cross-linked 2,2’-bithiophene and EDOT has been completed successfully to produce favorable optical property and free-standing copolymers in a neutral medium. This approach in the present work will bring new prospect for the development of novel free-standing organic electrochromic devices and optical displays.

    30. Polymers for application in organic solar cells: Bithiophene can work better than thienothiophene when coupled to benzodithiophene

      Francesca Parenti, Rosa Ricciardi, Rosita Diana, Pasquale Morvillo, Claudio Fontanesi, Francesco Tassinari, Luisa Schenetti, Carla Minarini and Adele Mucci

      Article first published online: 22 DEC 2015 | DOI: 10.1002/pola.28014

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      Thienothienyl and bithienyl units were copolymerized with a benzodithiophene substituted with alkylsulfanylthienyl groups and the obtained copolymers were tested in combination with [70]PCBM as photoactive layers in bulk-heterojunction polymer solar cells, with the aim to compare the efficiency of the final devices.

  4. Original Articles

    1. Synthesis and characterization of PDEAEMA-based magneto-nanogels: Preliminary results on the biocompatibility with cells of human peripheral blood

      Aintzane Pikabea, Jose Ramos, Nikos Papachristos, Dimosthenis Stamopoulos and Jacqueline Forcada

      Article first published online: 19 DEC 2015 | DOI: 10.1002/pola.27996

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      Magneto-nanogels synthesized reveal multistimuli (pH, temperature, magnetic field) responsive behavior together with tolerable biocompatibility with blood cells, suggesting potential use in magnetically driven biomedical applications.

  5. Articles

    1. Random poly(3-hexylthiophene-co-3-cyanothiophene-co-3-(2-ethylhexyl)thiophene) copolymers with high open-circuit voltage in polymer solar cells

      Andrey E. Rudenko, Petr P. Khlyabich and Barry C. Thompson

      Article first published online: 17 DEC 2015 | DOI: 10.1002/pola.28007

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      In this work we explored a combined approach of random incorporation of 3-cyanothiophene and 3-(2-ethylhexyl)thiophene units into the polymer backbone for the purpose of developing poly(3-hexylthiophene) based copolymers with deep-lying highest occupied molecular orbital (HOMO) levels for polymer solar cells with high open-circuit voltage (Voc). Lower HOMO levels result in higher Voc and higher power conversion efficiencies compared to the previously reported P3HT-CNT copolymers containing only 3-hexylthiophene and CNT units.

    2. Vinyl phenylboronic acid controlling co-monomer for nitroxide mediated synthesis of thermoresponsive poly(2-N morpholinoethyl methacrylate)

      Xeniya Savelyeva, David Chondon and Milan Marić

      Article first published online: 17 DEC 2015 | DOI: 10.1002/pola.28010

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      Nitroxide mediated polymerization of N-morpholinoethyl methacrylate (MEMA) was accomplished with small concentrations of vinylphenylboronic acid (VPBA) as a controlling co-monomer. Resulting poly(MEMA-ran-VPBA) copolymers were thermoresponsive and the VPBA imparted glucose-sensing functionality. Cloud point temperatures (CPT) varied from about 31 to 33 °C to 88 °C as pH was altered from 7 to 4. Rheological tests with small angle light scattering (SALS) confirmed CPTs measured by UV-Vis and DLS. Chain extensions with a second batch of VPBA resulted in monomodal shifts (SEC) to higher molecular weights, indicating block copolymer formation.

    3. The influence of vinyl activating groups on β-allyl sulfone-based chain transfer agents for tough methacrylate networks

      Paul Gauss, Samuel Clark Ligon-Auer, Markus Griesser, Christian Gorsche, Helena Svajdlenkova, Thomas Koch, Norbert Moszner and Robert Liska

      Article first published online: 17 DEC 2015 | DOI: 10.1002/pola.27993

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      Additive manufacturing technologies using methacrylates as photo-curable resins find increased application in industry and academia. While photo-curing allows rapid production of well-defined free-standing objects, inhomogenous polymer architecture and shrinkage stress during bulk polymerization leads to brittle materials with low impact resistance. In this study β-ally sulfones with different vinyl activating groups were coreacted with methacrylate monomers to determine the effect on polymerization and to improve the impact resistance of resultant materials.

    4. Amphiphilic diblock copolymers bearing pendant aromatic acetal groups: Synthesis and tunable pH-triggered assembly/disassembly transition behavior

      Wanbin Zhang, Xiaodong Fan, Haitao Zhang, Xiuzhong Zhu and Wei Tian

      Article first published online: 17 DEC 2015 | DOI: 10.1002/pola.28008

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      Amphiphilic diblock copolymers (PDAEP-b-PEG) bearing pendant acid-labile acetal groups were synthesized by combining RAFT polymerization with click reaction. The diblock copolymers can self-assemble into spherical micelles in aqueous solution. The micelles are stable in a neutral environment, however, in an acidic environment, acetal groups hydrolyzed gradually, and led to the swelling of the micelles. When the acetals hydrolysis was carried out for a sufficiently long time, the micelles disassembled and were converted to water soluble unimers.

    5. Kinetic study of low-temperature imidization of poly(amic acid)s and preparation of colorless, transparent polyimide films

      Hwan-Chul Yu, Jae-Woo Jung, Ju-Young Choi and Chan-Moon Chung

      Article first published online: 17 DEC 2015 | DOI: 10.1002/pola.28013

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      Chemical imidization of poly(amic acid)s is carried out at low temperatures of 40–160 °C. A kinetic study is conducted to determine the imidization activation energies. As the imidization temperature decreases, optical transparency and colorlessness of the resultant polyimides are improved. Films of a partially aliphatic polyimide prepared at 40 °C show 94% imidization, up to 97% transmittance in the visible region, a considerably short cutoff wavelength (253 nm), and colorlessness.

    6. Dynamic cross-links to facilitate recyclable polybutadiene elastomer with excellent toughness and stretchability

      Dong Wang, Huan Zhang, Beichen Cheng, Zhenchao Qian, Wenxing Liu, Ning Zhao and Jian Xu

      Article first published online: 17 DEC 2015 | DOI: 10.1002/pola.27983

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      A facile method to fabricate PB elastomers crosslinked by dynamic ionic hydrogen bonds is demonstrated. Compared to conventional chemical cross-linking, the prepared PB elastomers show excellent toughness, superior stretchability, good self-recovery and enhanced damping capacity. More importantly, the cross-linked elastomers can be thermally reprocessed and recycled due to the thermal reversibility of ionic hydrogen bonds.

    7. Tailor-made and chemically designed synthesis of coumarin-containing benzoxazines and their reactivity study toward their thermosets

      Pablo Froimowicz, Carlos Rodriguez Arza, Seishi Ohashi and Hatsuo Ishida

      Article first published online: 17 DEC 2015 | DOI: 10.1002/pola.27994

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      Coumarins are used as a natural renewable resource to synthesize coumarin-containing benzoxazines. These resins have been chemically designed to exhibit different, predictable, and programmable polymerization temperatures without affecting the thermal properties of their respective polybenzoxazines. Importantly, the resulting thermosets have also been proven to be competitive monomers when compared to petroleum-based benzoxazines toward the generation of thermoset materials.

    8. Poly(2-oxazoline) hydrogels crosslinked with aliphatic bis(2-oxazoline)s: Properties, cytotoxicity, and cell cultivation

      Anna Zahoranová, Zuzana Kroneková, Miroslav Zahoran, Dušan Chorvát Jr., Ivica Janigová and Juraj Kronek

      Article first published online: 17 DEC 2015 | DOI: 10.1002/pola.28009

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      Three bis(2-oxazoline) crosslinkers with different aliphatic chain lengths were used for the preparation of hydrogels. The influence of the type and the percentage of the crosslinker on swelling, mechanical properties, and water content in hydrogels was studied. The prepared hydrogels with low crosslinking percentage exhibited a good biocompatibility toward fibroblast cells.

    9. Influence of actinic wavelength on properties of light-cured interpenetrating polymer networks

      Feyza Karasu, Caroline Rocco, Maxime Lecompère, Céline Croutxé-Barghorn, Xavier Allonas, Yujing Zhang, A. Catarina C. Esteves, Leendert G. J. van der Ven, Rolf A. T. M. van Benthem and Gijsbertus de With

      Article first published online: 11 DEC 2015 | DOI: 10.1002/pola.27988

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      Interpenetrating polymer networks (IPNs) exhibit advanced features, such as high mechanical strength, good thermal stability, and chemical resistance, that allow the ability to overcome the limitations of stand-alone polymer networks. Photocured acrylate/epoxide IPNs representing the most suitable photoinitiating systems were studied using UV and visible-LED irradiation. Characterizations of the mechanical and morphological properties of the coatings were also performed. The investigations showed high interpenetration of different networks and homogeneous morphologies.

    10. Phosphonated homopolymers and copolymers via ring opening metathesis polymerization: Tg tuning, flame resistance, and photolithography

      Xiaojuan Zhang, Qian Zhang, Chao Xie, Aiting Gao, Zheng Chang, Jung Kwon Oh, Peng Yang and Pengfei Li

      Article first published online: 2 DEC 2015 | DOI: 10.1002/pola.27990

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      Phosphonated polymers prepared via ROMP were Tg-tunable spanning more than 100 °C by conveniently using comonomers with varying flexibility. They were very promising in flame-retarding and photolithography applications.

    11. Random styrenic copolymers with pendant pyrene moieties: Synthesis and applications in organic field-effect transistor memory

      Fei-Jan Chung, Hsin-Yu Liu, Bo-Yi Jiang, Guan-Yu He, Shi-Hao Wang, Wen-Chung Wu and Cheng-Liang Liu

      Article first published online: 2 DEC 2015 | DOI: 10.1002/pola.27995

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      Random copolymers comprised of pendant styrene and 4-(1-pyrenyl)-styrene (PyS) moieties in different molar ratios (21.4:1 (P1), 3.9:1 (P2) and 1.4:1 (P3)) were prepared. The resulting pendant copolymers were characterized by thermal analysis, optical and photoluminescence spectroscopy, and electrochemistry, and further used as electret layer in organic field-effect transistor memory device. The differences in molar ratio of the polymer electret were shown to influence the memory properties.

    12. Attapulgite grafted with polystyrene via a simultaneous reverse and normal initiation atom transfer radical polymerization

      Haicun Yang, Hongting Pu and Fanghong Gong

      Article first published online: 2 DEC 2015 | DOI: 10.1002/pola.27998

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      Simultaneous reverse and normal initiation atom transfer radical polymerization (SR&NI ATRP) initiated by a dual initiator system consisting of conventional radical initiator and attapulgite-supported ATRP initiator was used to synthesize polymer-nanoclay hybrids. The obtained hybrids were characterized by FTIR spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction and thermogravimetric analysis. The kinetics of the SR&NI ATRP of styrene from the surface of attapulgite was studied in detail.

    13. Synthesis of thermally stable aromatic poly(spiroorthocarbonate)s having a Cardo or bent structure

      Masaki Moritsugu, Ryota Seto, Kozo Matsumoto and Takeshi Endo

      Article first published online: 28 NOV 2015 | DOI: 10.1002/pola.27991

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      Novel poly(spiroorthocarbonate)s [poly(SOC)]s having a Cardo or bent structure were synthesized by polycondensation of several bis-catechols with tetrachlorobenzobisdioxole. The obtained poly(SOC)s exhibited high thermal stability. Furthermore, several poly(SOC)s were soluble in common organic solvents and exhibited high transparency in the optical wavelength range. These results suggested that the SOC structure is thermally stable with solubility improved and transparency increased by the Cardo or bent structure which kept the main-chain from becoming packed.

    14. Highly redox-stable and electrochromic aramids with morpholinyl-substituted triphenylamine units

      Sheng-Huei Hsiao, Ying-Hsiu Hsiao and Yu-Ruei Kung

      Article first published online: 27 NOV 2015 | DOI: 10.1002/pola.27972

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      A series of new redox-active aromatic polyamides bearing (4-morpholinyl)triphenylamine units were readily prepared from 4,4′-diamino-4″-(4-morpholinyl)triphenylamine and various aromatic dicarboxylic acids by the phosphorylation polyamidation technique. The polyamides exhibit good solubility in many organic solvents and can be solution-cast into flexible and strong films with high thermal stability. The materials show well-defined and reversible redox waves during oxidative scanning, with a strong color change from the colorless neutral form to the green and deep blue oxidized forms.

    15. Rapid living cationic polymerization of vinyl ethers by a single-molecular initiating system

      Junzhe Song, Jinbao Xu and Donglin Tang

      Article first published online: 27 NOV 2015 | DOI: 10.1002/pola.27986

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      Initiated by a single organic molecule, trifluoromethanesulfonimide (HNTf2), vinyl ethers polymerize rapidly in a “living” manner. The addition of Lewis base (such as THF) has no effect on the polymerizations. HNTf2 is considered to be playing multiple roles in the polymerization, such as initiator, activator, and stabilizer.

  6. Rapid Communication

    1. You have free access to this content
      Design and synthesis of biodegradable grafted cationic polycarbonates as broad spectrum antimicrobial agents

      Zhan Yuin Ong, Daniel J. Coady, Jeremy P. K. Tan, Yan Li, Julian M. W. Chan, Yi Yan Yang and James L. Hedrick

      Article first published online: 27 NOV 2015 | DOI: 10.1002/pola.27987

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      Several biodegradable grafted cationic polycarbonates prepared via metal-free organocatalytic ring-opening polymerization are investigated for their antimicrobial activity, mechanism of action, and biocompatibility.

  7. Articles

    1. Autonomous conveyer gel driven by frontal polymerization

      Xiao-Qiao Wang, Nian Liu, Cai-Feng Wang and Su Chen

      Article first published online: 26 NOV 2015 | DOI: 10.1002/pola.27965

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      A series of autonomous conveyer gels were fabricated by frontal polymerization (FP), and exhibited a powerful capability for transporting gel microballoons. The transportation speed can be efficiently controlled by adjusting initiation temperature of the FP reaction. The autonomous transportation was further applied for the targeted synthesis of CdS nanocrystals.

    2. Catalysts and temperature driven melt polycondensation reaction for helical poly(ester-urethane)s based on natural L-amino acids

      Santhanaraj Anantharaj and Manickam Jayakannan

      Article first published online: 26 NOV 2015 | DOI: 10.1002/pola.27970

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      A temperature- and catalyst-driven, chemoselective polymerization route was developed for the first time to form natural l-amino acids for producing diverse macromolecular structures that are self-assembled as well-defined nanofibrous morphologies for thermoplastic applications.

    3. Regular conjugated terpolymers comprising two different acceptors and bithiophene donor in repeating group: Effect of strong and weak acceptors on semiconducting properties

      Mai Ha Hoang, Jong-Soo Ahn, Duc Nghia Nguyen, Trinh Tung Ngo, Dae Hee Lee, Min Ju Cho and Dong Hoon Choi

      Article first published online: 26 NOV 2015 | DOI: 10.1002/pola.27979

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      Two regular terpolymers, P(DPP-TPyT) and P(DPP-T3MTT), were successfully synthesized to investigate the electronic and optoelectronic performance. P(DPP-T3MTT)-bearing methyl thiophene-3-carboxylate (3MT) showed high carrier mobility and power conversion efficiency compared to P(DPP-TPyT)-bearing pyridine (Py) unit.

    4. Synthesis and UCST-type phase behavior of OEGylated poly(γ-benzyl-l-glutamate) in organic media

      Mengxiang Zhu, Yanzhi Xu, Chenglong Ge, Ying Ling and Haoyu Tang

      Article first published online: 24 NOV 2015 | DOI: 10.1002/pola.27982

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      A series of OEGylated poly(γ-benzyl-l-glutamate) with different molecular weight and narrow molecular weight distribution were prepared from triethylamine initiated ring-opening polymerization (ROP) of OEGylated γ-benzyl-l-glutamic acid based N-carboxyanhydride. They exhibited a reversible UCST-type phase behavior in various alcoholic organic solvents with a UCST-type transition temperature (Tpt) in the range of 16.0–66.3 °C, which was highly depended on the solvent, polymer concentration, side- and main-chain length.

    5. Breathable rubbery skin protectors: Design, synthesis, characterization, and properties of cyanoacrylated silicone rubber networks

      Amalia Szanka, Istvan Szanka and Joseph P. Kennedy

      Article first published online: 24 NOV 2015 | DOI: 10.1002/pola.27984

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      A method was developed for the synthesis of cyanoacrylated polydimethylsiloxane (PDMS-CA) by the use of various molecular weight PDMS carrying SiH functions. Homonetworks of PDMS-CA and conetworks of PDMS-CA/2-octyl cyanoacrylate were prepared by polymerizing the cyanoacrylate groups. The chemical attachment between PDMS-CA and porcine skin was tested. A dry conformal coating was formed on the skin which could not be removed without damaging the tissue.

    6. Photo-triggered microgel aggregation using o-nitrobenzaldehyde as aggregating power source

      Shingo Tamesue, Shinji Abe, Tetsu Mitsumata, Norio Tsubokawa and Takeshi Yamauchi

      Article first published online: 24 NOV 2015 | DOI: 10.1002/pola.27985

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      The photo responsive microgel aggregating system is constructed utilizing cationic and anionic gels, and o-nitrobenzaldehyde, which reacts and releases protons in response to UV light. Also, the shapes of the resultant microgel aggregations are regulated due to masking. Additionally, the difference of the thermal responsive property between the resultant microgel aggregation and bulk gel is evaluated.

    7. Polytriacetylenes bearing directly attached functional groups with tunable physical and electronic properties

      Keda Hu and Yang Qin

      Article first published online: 24 NOV 2015 | DOI: 10.1002/pola.27989

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      Polytriacetylenes (PTAs) having aromatic substituents directed attached to the main-chain double bonds were prepared, for the first time, by a palladium catalyzed oxidative coupling reaction, which displays tunability in polymer electronic and physical properties.

    8. Degradable precision polynorbornenes via ring-opening metathesis polymerization

      Dafni Moatsou, Amit Nagarkar, Andreas F. M. Kilbinger and Rachel K. O'Reilly

      Article first published online: 22 NOV 2015 | DOI: 10.1002/pola.27964

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      The potential use of dioxepins in ring-opening metathesis polymerization (ROMP) as building blocks of sequence-controlled polymers is evaluated. It is shown that as a result of their low reactivity, dioxepins cannot undergo homopolymerization; however, in the presence of norbornenes they can copolymerize. Therefore, when an excess of dioxepins is present in the ROMP of norbornenes, some sequence control is achieved. Additionally, the copolymers are partially degradable due to the labile dioxepin acetal, resulting in lower molecular weight polynorbornenes.

    9. Efficient synthesis of ionic triblock copolyesters and facile access to charge-reversal hybrid micells

      Shaohua Wu, Liuchun Zheng, Wen Zhou, Chuncheng Li, Yaonan Xiao and Wenxiang Zhu

      Article first published online: 22 NOV 2015 | DOI: 10.1002/pola.27968

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      Well-defined carboxyl- and amino-functionalized triblock copolyesters were designed and synthesized for the efficient construction of pH-responsive charge-reversal hybrid micelles. The hybrid micelles showed apparent pH-triggered Nile red-release behavior in acidic condition resembling tumor intracellular environment, which is fairly desirable for drug delivery.

    10. Preparation and properties of thermoresponsive and conductive composite fibers with core-sheath structure

      Mei-Fei Lin, Trong-Ming Don, Fang-Tzu Chang, Shih-Ru Huang and Wen-Yen Chiu

      Article first published online: 22 NOV 2015 | DOI: 10.1002/pola.27976

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      Thermo-responsive and conductive fibers with core-sheath (PBS/PDPNN) structures were fabricated by co-axial electrospinning. After co-axial electrospinning, the morphology, thermo-responsive properties, flexibility, and conductivity of the core-sheath fibers were evaluated. The surface conductivity of the fiber mats reached 29.4 S/cm when the weight ratio of PEDOT:PSS/PNN was 0.20 in the sheath. The fiber mats exhibited improved flexibility as determined via bending tests.

    11. Pressure-sensitive adhesive utilizing molecular interactions between thymine and adenine

      Nobuhiro Ishikawa, Masahiro Furutani and Koji Arimitsu

      Article first published online: 22 NOV 2015 | DOI: 10.1002/pola.27977

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      A simple pressure-sensitive adhesion (PSA) system consisting of a copolymer having thymine moieties and a low-molecular-weight bifunctional adenine cross-linker is presented. The thymine and adenine units demonstrate hydrogen bonding, and both Young's modulus and the glass transition temperature increase by adding the adenine cross-linker.

    12. Kinetics and mechanistic investigation of epoxy–anhydride compositions cured with quaternary phosphonium salts as accelerators

      Lyaysan R. Amirova, Alexander R. Burilov, Liliya M. Amirova, Ingmar Bauer and Wolf D. Habicher

      Article first published online: 20 NOV 2015 | DOI: 10.1002/pola.27946

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      The mechanism and curing kinetics of an epoxy/anhydride system using phosphonium salts as accelerators was investigated by differential scanning calorimetry (DSC) and electrospray ionization mass-spectrometry (ESI-MS). The apparent activation energy values for the overall curing process were determined using DSC. The mechanism of curing initiated by either phosphonium compounds or 2-methylimidazole was suggested using the model reaction of epichlorohydrin (E) with phthalic anhydride (PA).

    13. A new class of stereoregular vinylene-arylene copolymers with double-decker silsesquioxane in the main chain

      Patrycja Żak, Beata Dudziec, Michał Dutkiewicz, Monika Ludwiczak, Bogdan Marciniec and Marek Nowicki

      Article first published online: 12 NOV 2015 | DOI: 10.1002/pola.27957

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      A new class of stereoregular DDSQ-silylene-vinylene-arylene copolymers with double-decker silsesquioxane in the main chain was synthesized via complementary SCC and ADMET copolymerization reactions. The impact of reaction type, its duration, type of DDSQ-2SiVi and diolefin on structure, thermal, and mechanical properties are studied.

    14. Aminothiazonaphthalic anhydride derivatives as photoinitiators for violet/blue LED-Induced cationic and radical photopolymerizations and 3D-Printing resins

      Jing Zhang, Frédéric Dumur, Pu Xiao, Bernadette Graff, Didier Gigmes, Jean Pierre Fouassier and Jacques Lalevée

      Article first published online: 12 NOV 2015 | DOI: 10.1002/pola.27958

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      Aminothiazonaphthalic anhydride derivatives (ATNAs) along with iodonium salt, N-vinylcarbazole, amine, or chloro triazine can act as photoinitiating systems to initiate the ring-opening cationic polymerization of epoxides and the free radical polymerization of acrylates under LEDs at 405 or 455 nm. The optimized ATNA-based photoinitiating system with high reactivity can also work in resins for 3D-printing using a LED projector at 405 nm.

    15. Synthesis of versatile poly(PMMA-b-VI) macromonomer-based hydrogels via infrared laser ignited frontal polymerization

      Ting Chen, Yang Li, Sheng-Yang Yang, Cai-Feng Wang and Su Chen

      Article first published online: 12 NOV 2015 | DOI: 10.1002/pola.27961

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      A series of poly((PMMA-b-VI)-co-AA) hydrogels with outstanding electric bending properties were successfully fabricated via infrared laser ignited frontal polymerization using poly(methyl methacrylate-b−1-vinylimidazole) macromonomers and acrylic acid (AA) monomers. The poly((PMMA-b-VI)-co-AA) hydrogels are sensitive towards substances of different flavors, including sourness (citric acid or gluconic acid), umami (sodium glutamate), saltiness (sodium chloride), and sweetness (glucose), enabling their potential as artificial tongue-like sensing materials.

    16. Preparation of hybrid triple-stimuli responsive nanogels based on poly(L-histidine)

      Panayiotis Bilalis, Spyridon Varlas, Aikaterini Kiafa, Athanassios Velentzas, Dimitrios Stravopodis and Hermis Iatrou

      Article first published online: 12 NOV 2015 | DOI: 10.1002/pola.27971

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      Novel hybrid multi-stimuli responsive nanogels consisting of a PEO corona and a disulfide cross-linked PHis core were synthesized in order to be used as promising drug delivery systems. The dependence between the cross-linker's ratio and pH-sensitivity was evaluated and also the GSH responsiveness proving that these polymeric structures could be disrupted under intracellular-mimicking conditions.

    17. Well-defined epoxide-containing styrenic polymers and their functionalization with alcohols

      David C. McLeod and Nicolay V. Tsarevsky

      Article first published online: 12 NOV 2015 | DOI: 10.1002/pola.27952

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      4-Vinylphenyloxirane (4VPO) was polymerized in a controlled manner under reversible addition-fragmentation chain-transfer (RAFT) polymerization conditions. A successful chain extension reaction was carried out with styrene, which proved the high degree of chain-end functionalization of the poly4VPO-based macro-chain transfer agent. Poly4VPO was also efficiently converted to β-hydroxy ether-functionalized polymers by CBr4- or BF3-catalyzed reactions with a library of alcohols and phenols, some of which contained reactive functional groups.

    18. Amphiphilic liquid-crystalline 4-miktoarm star copolymers with a siloxane junction leading to cylindrically nanostructured templates for a siloxane-based nanodot array

      Md Asadul Hoque, Hideaki Komiyama, Hiroki Nishiyama, Keiji Nagai, Takehiro Kawauchi and Tomokazu Iyoda

      Article first published online: 12 NOV 2015 | DOI: 10.1002/pola.27960

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      Well-defined A3B-, A2B2-, and AB3-type 4-miktoarm star copolymers consisting of PEO and polymethacrylate bearing azobenzene mesogen as the arms and cyclotetrasiloxane as the core unit were synthesized. The A3B-type star-(PEO)3[PMA(Az)]1 copolymer formed a nanostructured thin film with a more highly ordered PEO cylinder array in the PMA(Az) matrix than that of the corresponding linear-type block copolymer. We also succeeded in preparing a siloxane-based nanodot array via the oxygen reactive ion etching of the nanostructured film.

    19. New π-Conjugated polymers containing 4H,4H-[1,1-Bithieno [3,4-C]Pyrrole]-4,4,6,6(5H,5H)-Tetraone (biTPD) units and their application to thin-Film transistors and photovoltaic cells

      Dae Hee Lee, Kyung Hwan Kim, Jicheol Shin, Min Ju Cho and Dong Hoon Choi

      Article first published online: 12 NOV 2015 | DOI: 10.1002/pola.27963

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      New donor-acceptor copolymers that employ 1,10-bithienopyrrolodione (biTPD), thiophene, and selenophene-based donor monomeric units were successfully synthesized. Among the thin-film transistor devices made of PBTPDEBT and PBTPDEBS, the annealed PBTPDEBS device displayed relatively high hole mobility, which was twice that of the PBTPDEBT-based device. In addition, an organic photovoltaic device based on a PBTPDEBS:PC71BM blend displayed a maximum power conversion efficiency of 3.85%.

    20. Bifunctional benzoxazines: Synthesis and polymerization of resorcinol based single isomers

      Hannes Schäfer, André Arnebold, Johannes Stelten, Jordi Marquet, Rosa María Sebastián, Andreas Hartwig and Katharina Koschek

      Article first published online: 12 NOV 2015 | DOI: 10.1002/pola.27966

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      The polymerization of reactive bifunctional benzoxazine monomers based on resorcinol is presented. The new monomers were synthesized as pure isomers differing in their constitution and altered substitution pattern at the aniline component. The functionalized symmetric and asymmetric benzoxazines influence the polymerization, yielding the lowest curing temperatures for asymmetric monomers bearing no or electron-donating groups in the meta position of the aniline moiety.

    21. Energy transfer in poly(3-hexylthiophene)-g-Polyfluorene graft copolymers

      Joost Steverlynck, Amaury De Cattelle, Julien De Winter, Pascal Gerbaux and Guy Koeckelberghs

      Article first published online: 12 NOV 2015 | DOI: 10.1002/pola.27967

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      A series of all-conjugated graft copolymers with an increasing degree of grafting were prepared. By comparing the experimental UV-Vis spectra with spectra simulated on basis of the homopolymers the influence on the self assembly of these materials was investigated. Using fluorescence spectra energy funneling from the PF side chains to the P3AT “core” was demonstrated.

    22. Well-controlled ATRP of 2-(2-(2-azidoethyoxy)ethoxy)ethyl methacrylate for high-density click functionalization of polymers and metallic substrates

      Pingsheng Liu and Jie Song

      Article first published online: 12 NOV 2015 | DOI: 10.1002/pola.27969

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      We demonstrated the poor controllability of atom transfer radical polymerization (ATRP) of an azido-bearing methacrylate under commonly adopted conditions, and identified more suitable polymerization temperature and monomer concentration to optimize the polymerization outcome in solution and on metallic surfaces. The well-controlled ATRP of azido-bearing methacrylates provides high-quality precursor polymers for subsequent high-density click functionalization of the azido-bearing side chains for macromolecular engineering and surface functionalization.

    23. Blue to light gray electrochromic polymers from dodecyl-derivatized thiophene Bis-substituted dibenzothiophene/dibenzofuran

      Kaiwen Lin, Yao Zhao, Shouli Ming, Hongtao Liu, Shijie Zhen, Jingkun Xu and Baoyang Lu

      Article first published online: 12 NOV 2015 | DOI: 10.1002/pola.27973

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      Two novel DBT/DBF-heterocycle hybrid polymers were electropolymerized and their electrochemical and electrochromic properties were explored.

    24. Thermo- and pH-induced self-assembly of P(AA-b-NIPAAm-b-AA) triblock copolymers synthesized via RAFT polymerization

      Chih-Yu Kuo, Trong-Ming Don, Shih-Chi Hsu, Chia-Fen Lee, Wen-Yen Chiu and Chih-Yuan Huang

      Article first published online: 3 NOV 2015 | DOI: 10.1002/pola.27950

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      A series of thermo- and pH-responsive ABA triblock copolymers, P(AA-b-NIPAAm-b-AA) with various compositions, were synthesized by RAFT copolymerization. Either physically crosslinked nanogels or core-shell nanoparticles were observed depending on the pH value, temperature, and copolymer composition. In addition, various nanoparticles with their sizes ranging from hundreds nanometer to several micrometer could also be obtained. With these properties, it is believed that the P(AA-b-NIPAAm-b-AA) triblock copolymers have a great potential to be utilized as biomedical nanocapsules for drug encapsulation, smart delivery, triggered release, and targeting therapy.

    25. Adding magnetic ionic liquid monomers to the emulsion polymerization tool-box: Towards polymer latexes and coatings with new properties

      Audrey Bonnefond, Miren Ibarra, David Mecerreyes and Jose R. Leiza

      Article first published online: 3 NOV 2015 | DOI: 10.1002/pola.27953

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      An innovative, rapid, and efficient strategy is developed to synthesize magnetic polymer particles by using magnetic ionic liquids as surfmers in the emulsion polymerization of methyl methacrylate/n-butyl acrylate.

    26. Synthesis and characterization of polycyanurates as dismantlable adhesives

      Tomoya Higashihara, Mao-Chun Fu, Takaaki Uno and Mitsuru Ueda

      Article first published online: 3 NOV 2015 | DOI: 10.1002/pola.27955

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      Random copolycyanurates with a low number of amide or propylene thioether units in the main chain have been developed as candidates for dismantlable adhesives based on the rapid decrease in molecular weight during rearrangement to polyisocyanurates upon thermal treatment.

    27. Structured poly(divinylbenzene-co-chloromethylstyrene) microspheres by thermal imprinting precipitation polymerization

      Yuqing Zhao, Nicholas A. D. Burke and Harald D. H. Stöver

      Article first published online: 3 NOV 2015 | DOI: 10.1002/pola.27956

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      Varying the temperature during the growth phase of crosslinking precipitation polymerizations near the theta-condition, can lead to different types of core-shell structures. This is attributed to temperature-dependent crosslink densities of the growing surface gel layer being deposited, resulting in differential swellabilities of core versus shell domains. This article illustrates the process, and introduces model experiments that may help screen for suitable solvents.

    28. PEG–PLGA copolymers bearing carboxylated side chains: Novel hydrogels with enhanced crosslinking via ionic interactions

      Sytze J. Buwalda, Abderrahmane Amgoune and Didier Bourissou

      Article first published online: 3 NOV 2015 | DOI: 10.1002/pola.27962

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      Novel water-soluble amphiphilic poly(ethylene glycol)-poly(lactide-co-glycolide) block copolymers with pendant carboxylic acid groups are synthesized and used for the preparation of noncovalently crosslinked hydrogels. The introduction of COOH groups in the hydrophobic block significantly enhances the water solubility of the PEG–polyester copolymer and allows additional crosslinking via ionic interactions between metal ions and carboxylic acid groups to form functionalized hydrogels with improved physical properties.

    29. Thioxanthonation of fluorenone: Visible photoinitiator for radical polymerization

      Nurcan Karaca, Demet Karaca Balta, Nuket Ocal and Nergis Arsu

      Article first published online: 30 OCT 2015 | DOI: 10.1002/pola.27938

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      Synthesis and characterization of thioxanthone–fluorenone (TX–FN) was achieved and compared with photoinitiator parameters of camphorquinone. Excellent absorption in the visible region was observed. Photophysical properties, fluorescence and phosphorescence emission spectra, and fluorescence quantum yield (φf = 0.127) in addition to photopolymerization experiments of several monomers were performed. The transient absorption spectra of TX–FN was monitored via laser flash photolysis. It was concluded that TX–FN shows typical Type II photoinitiator behavior.

    30. Twisted olefinic building blocks for low bandgap polymers in solar cells and ambipolar field-effect transistors

      Chien-Yang Chiu, Hengbin Wang, Hung Phan, Kazuya Shiratori, Thuc-Quyen Nguyen and Craig J. Hawker

      Article first published online: 28 OCT 2015 | DOI: 10.1002/pola.27944

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      A series of conjugated polymers based on structurally twisted building blocks are reported. These 8,8′-biindeno[2,1-b]thiophenylidene-based polymers exhibit low bandgap properties and lead to good performances in solar cells and ambipolar field-effect transistors.

    31. Thermoresponsive conductive polymer composite thin film and fiber mat: Crosslinked PEDOT:PSS and P(NIPAAm-co-NMA) composite

      Shih-Ru Huang, King-Fu Lin, Trong-Ming Don, Chai-Fen Lee, Man-Sheng Wang and Wen-Yen Chiu

      Article first published online: 28 OCT 2015 | DOI: 10.1002/pola.27945

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      Conductive polymer composite fibers have been investigated intensively by researchers in recent years; however, few researchers have focused on the combination of thermoresponsive and conductive polymers that might have potential in sensor applications. The thermal stimuli were found to cause a structural response in the polymer composite, which changed the conductive properties. During heating from 25 to 50 °C, the difference in surface resistance reached 800 Ω/□.

    32. Polyisobutylene-based polyurethanes. VIII. Polyurethanes with -O-S-PIB-S-O- soft segments

      Kalman Toth, Nur Cicek Kekec, Nihan Nugay and Joseph. P. Kennedy

      Article first published online: 28 OCT 2015 | DOI: 10.1002/pola.27951

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      A novel thermoplastic elastomer polyurethane was prepared by the use of a new polyisobutylene diol, HO-CH2CH2-S-PIB-S-CH2CH2-OH, soft segment, and conventional hard segments. The soft segment is obtained by efficient low-cost click chemistry. Products were characterized by a battery of techniques and structure–property relationships were investigated. The polyurethane exhibits outstanding oxidative–hydrolytic resistance and permanent set, together with good mechanical properties.

    33. Soluble and transparent polyimides with high Tg from a new diamine containing tert-butyl and fluorene units

      Lang Yi, Congyan Li, Wei Huang and Deyue Yan

      Article first published online: 26 OCT 2015 | DOI: 10.1002/pola.27933

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      A series of soluble polyimides (PIs) containing large pendant groups with tert-butyl and fluorene units were synthesized through a one-pot method. The introduction of tert-butyl and fluorene units evidently enhanced the transparency of the PI films and lightened their color. All the resulting PIs exhibited high Tg, excellent thermal stability, low dielectric constants, and low water absorption rates.

    34. Anion conductive aromatic polymers containing fluorenyl groups: Effect of the position and number of ammonium groups

      Manai Shimada, Shigefumi Shimada, Junpei Miyake, Makoto Uchida and Kenji Miyatake

      Article first published online: 23 OCT 2015 | DOI: 10.1002/pola.27928

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      Three series of anion conductive aromatic block copolymers containing fluorenylidene biphenylene groups as scaffold for ammonium groups were synthesized and their properties were compared. The polymer membrane containing two ammonium groups on a fluorenyl group exhibited highest anion conductivity. The membrane showed good alkaline fuel cell performance with high open circuit voltage and power density with humidified hydrogen and oxygen.

    35. Fundamental investigations into the free-radical copolymerization of N-phenylmaleimide and norbornene

      Kevin R. Gmernicki, Matthew Cameron and Brian K. Long

      Article first published online: 22 OCT 2015 | DOI: 10.1002/pola.27934

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      Polymers containing more than one structural unit are often found to possess many desirable traits. In this report, a fundamental investigation into the copolymerization of N-phenylmaleimide and norbornene is presented. The polymerization conditions are optimized and the resultant polymers are analyzed to gain mechanistic insight into their polymerization. It is shown that these copolymers deviate from strictly alternating copolymerization behavior.

    36. Dual stimuli-responsive polyamines derived from modified N-vinylpyrrolidones through CuAAC click chemistry

      Anselmo del Prado, Rodrigo Navarro, Pavel Levkin, Alberto Gallardo, Carlos Elvira and Helmut Reinecke

      Article first published online: 22 OCT 2015 | DOI: 10.1002/pola.27949

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      Novel dual stimuli-responsive polymers with a true polyvinylpyrrolidone backbone have been synthesized for the first time using a conventional radical copolymerization of N-vinylpyrrolidone (VP) and three aminated VP-derivatives obtained through copper(I)-catalyzed azide alkyne cycloaddition. These polymers exhibit thermo-sensitiveness which depends on the nature and the amount of the amine in the polymer, as well as the pH of the media.

    37. Cyclic peptide–polymer conjugates: Grafting-to vs grafting-from

      Sophie C. Larnaudie, Johannes C. Brendel, Katrina A. Jolliffe and Sébastien Perrier

      Article first published online: 20 OCT 2015 | DOI: 10.1002/pola.27937

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      Peptide–polymer conjugates achieve remarkable properties by combining the precise structure and function of biomolecules with the tunable nature of polymers. Such materials can be synthesized by a convergent or a divergent approach. Here, the two routes are studied and compared for the synthesis of a wide range of cyclic peptide–polymer conjugates. In most cases, both pathways led to similar products, while some exceptions highlighted the advantages of each method, thereby demonstrating their complementarity.

    38. Synthesis, self-assembly, and formation of photo-crosslinking-stabilized fluorescent micelles covalently containing zinc(II)-bis(8-hydroxyquinoline) for ABC triblock copolymer bearing cinnamoyl and 8-hydroxyquinoline side groups

      Wenjuan Wang, Ling Lin, Jiang Lu, Hui Liang, Hao Feng and Lifen Hu

      Article first published online: 20 OCT 2015 | DOI: 10.1002/pola.27941

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      Triblock copolymer MPEG-b-PCEMA-b-PHQHEMA was synthesized via a two-step RAFT polymerization. The triblock copolymer could self-assemble into micelles in mixture solvent of THF and ethanol. The self-assembly micelles were stabilized by photo-crosslinking of the PCEMA inner shell under UV irradiation. Fluorescent Znq2-containing stabilized micelles were obtained by complex reaction of stabilized micelles with zinc acetate in mixture solvent of THF/ethanol or THF/toluene, exhibiting intensive green emission with λmax at 520 nm.

    39. Arborescent micelles: Dendritic poly(γ-benzyl l-glutamate) cores grafted with hydrophilic chain segments

      Greg Whitton and Mario Gauthier

      Article first published online: 20 OCT 2015 | DOI: 10.1002/pola.27943

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      Dendritic graft (arborescent) copolymers with a hydrophobic poly(γ-benzyl l-glutamate) core and a hydrophilic corona of either polyglycidol, polyethylene oxide, or poly(l-glutamic acid) were obtained by both random and terminal grafting onto the polypeptide chains forming the core.

    40. In situ synthesis of nano-assemblies of the high molecular weight ferrocene-containing block copolymer via dispersion RAFT polymerization

      Chengqiang Gao, Chonggao Liu, Heng Zhou, Shuang Wang and Wangqing Zhang

      Article first published online: 20 OCT 2015 | DOI: 10.1002/pola.27947

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      High molecular weight ferrocene-containing block copolymer of poly(ethylene glycol)-block-poly(4-vinylbenzyl ferrocenecarboxylate) are prepared through dispersion RAFT polymerization, and block copolymer nano-objects with interesting morphologies are formed.

    41. Synthesis and functionalization of dendron-polymer conjugate based hydrogels via sequential thiol-ene “click” reactions

      Sadik Kaga, Tugce N. Gevrek, Amitav Sanyal and Rana Sanyal

      Article first published online: 20 OCT 2015 | DOI: 10.1002/pola.27926

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      Dendron-polymer conjugates are used to fabricate and functionalize “clickable” hydrogels. Bulk and micropatterned hydrogels are obtained using photoinitiated radical thiol-ene reaction. Hydrogels containing varying amounts of residual alkene groups are obtained ready to functionalize with thiol-containing molecules.

    42. Thermoresponsive poly(ionic liquid): Controllable RAFT synthesis, thermoresponse, and application in dispersion RAFT polymerization

      Chonggao Liu, Shuang Wang, Heng Zhou, Chengqiang Gao and Wangqing Zhang

      Article first published online: 20 OCT 2015 | DOI: 10.1002/pola.27929

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      A thermoresponsive poly(ionic liquid) of poly[1-(4-vinylbenzyl)-3-methylimidozolium tetrafluoroborate] trithiocarbonate was synthesized by RAFT polymerization, and this poly(ionic liquid) shows an upper critical solution temperature (UCST)-type phase transition in a methanol/water mixture. The polymerization degree, the polymer concentration, and the weight ratio of methanol/water in the solvent are found to exert influence on the UCST.

    43. Synthesis and self-assembly of thermoresponsive block-graft fluoropolymer as well as its tunable wettability surface

      Bingyan Jiang and Hao Pang

      Article first published online: 20 OCT 2015 | DOI: 10.1002/pola.27936

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      Amphiphilic thermal-responsive block-graft fluoropolymer is investigated the self-assemble morphology and its application on the tunable wettability surface for cotton fabric by dip-coating into its micelle with different temperatures. The fiber's surface processed in cold micelle with uniform spheres is smooth and hydrophobic by fluorinated parts on the outmost layer of fibers; the one dipped in hot micelle is rough and hydrophilic by the outmost layer of hydrophilic PNIPAM segments on fibers layers.

    44. α-exomethylene lactone possessing acetal–ester linkage: Polymerization and postpolymerization modification for water-soluble polymer

      Yasuhiro Kohsaka, Yusuke Matsumoto, Tianyi Zhang, Yosuke Matsuhashi and Tatsuki Kitayama

      Article first published online: 16 OCT 2015 | DOI: 10.1002/pola.27931

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      2,6-Dimethyl-5-methylene-1,3-dioxa-4-one, a novel trifunctional monomer with acrylate, ester, and acetal moieties in a 6-membered ring, was prepared from the Baylis–Hillman reaction of an aryl acrylate. The radical and anionic polymerization with azo and ester enolate initiators, respectively, afforded the corresponding vinyl polymers, which were converted to water-soluble polymers bearing hydroxyl and carboxy pendants via the acid hydrolysis of the acetal–ester linkage. The polymerization characteristics are also discussed through the comparison with respective acyclic monomers.

    45. Raft polymerization of N,N-dimethylacrylamide from magnetic poly(2-hydroxyethyl methacrylate) microspheres to suppress nonspecific protein adsorption

      Xueteng Cao, Daniel Horák, Zesheng An and Zdeněk Plichta

      Article first published online: 16 OCT 2015 | DOI: 10.1002/pola.27939

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      4 μm monodisperse magnetic poly(2-hydroxyethyl methacrylate) microspheres grafted with poly(N,N-dimethylacrylamide) are shown to resist nonspecific protein adsorption. While the microspheres are obtained by a multiple swelling polymerization, the hydrophilic shell is prepared by RAFT polymerization.

    46. Temperature and pH dual-sensitive polyaspartamide derivatives for antitumor drug delivery

      Yingying Ma, Guangyan Zhang, Lingjuan Li, Huan Yu, Jia Liu, Chaoqun Wang, Yanfeng Chu, Renxi Zhuo and Xulin Jiang

      Article first published online: 13 OCT 2015 | DOI: 10.1002/pola.27930

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      Temperature and pH dual-sensitive polyaspartamide derivatives containing pendant aromatic structures, ionizable tertiary amino groups and hydrophilic long PEG chains were designed, synthesized and characterized. These facile nontoxic thermo/pH-sensitive polymeric micelles as anticancer drug carriers for intracellular delivery show easy drug-loading processes, faster release at pH 5 than at pH 7.4 and enhancement of drug cytotoxicity.

    47. Ethylene/1-heptene copolymers as interesting alternatives to 1-octene-based LLDPE: Molecular structure and physical properties

      Anthony Ndiripo, Dawid Joubert and Harald Pasch

      Article first published online: 13 OCT 2015 | DOI: 10.1002/pola.27932

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      The microstructure of Ziegler–Natta linear low density polyethylene is revealed through the use of several advanced analytical techniques and related to the mechanical and physical properties. Two types of LLDPE made from two different comonomers (1-heptene and 1-octene) perform similarly both in terms of microstructure and mechanical properties at low comonomer contents. However, this is not the case at higher comonomer contents. These findings are supported by several techniques which use different concepts in analysis.

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