Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 52 Issue 15

1 August 2014

Volume 52, Issue 15

Pages i–iv, 2083–2238

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      Cover Image, Volume 52, Issue 15 (pages i–ii)

      Version of Record online: 24 JUN 2014 | DOI: 10.1002/pola.27284

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      Kinetic insight into the ATRP (atom transfer radical polymerization) rate controlling ability of micro-molecular, macromolecular, and immobilized initiators for the synthesis of fluorinated homopolymers, gradient, block copolymer, and nanocomposite polymers is presented by Yin-Ning Zhou and Zheng-Hong Luo on page 2228 (DOI: 10.1002/pola.27249). The activity of the copper(I) chloride/1,1,4,7,7-pentamethyldiethylenetriamine heterogeneous catalytic complex is highest for ethyl 2-bromoisobutyrate, lower for bromo-poly(styrene), and lowest for bromo-aminopropyl functionalized SiO2. Additionally, the initiation system of ethyl 2-bromoisobutyrate with CuCl/4,4′-dinonyl-2,2′-bipyridyl has relatively lower activating ability, but the polymerization remains controllable by its higher deactivation ability.

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      Cover Image, Volume 52, Issue 15 (pages iii–iv)

      Version of Record online: 24 JUN 2014 | DOI: 10.1002/pola.27285

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      On page 2139 (DOI: 10.1002/pola.27250), Nicholas Stanley, Georgiana Bucataru, Yong Miao, Audrey Favrelle, Marc Bria, Francois Stoffelbach, Patrice Woisel, and Philippe Zinck report the graft copolymerization of ε-caprolactone with water-soluble polysaccharides conducted in aqueous media using Brønsted acids as catalysts. This allows a mild and one-step access to graft copolymers, some of which self-assemble into nanoparticles after dissolution in water.

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      Synthesis of complex macromolecules using iterative copper(0)-mediated radical polymerization (pages 2083–2098)

      Cyrille Boyer, Per B. Zetterlund and Michael R. Whittaker

      Version of Record online: 12 MAY 2014 | DOI: 10.1002/pola.27220

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      The use of copper(0) mediated radical polymerization for the synthesis of complex macromolecules in a one-pot polymerization is reported. This polymerization is an efficient and versatile polymerization technique which allows the control of acrylates and methacrylates with an unprecedented maintenance of end group fidelity (∼100%).

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      Organic nitrate functional nanoparticles for the glutathione-triggered slow-release of nitric oxide (pages 2099–2103)

      Hien T. T. Duong, Amy Ho, Thomas P. Davis and Cyrille Boyer

      Version of Record online: 4 MAY 2014 | DOI: 10.1002/pola.27221

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      Nitrate-containing amphiphilic block copolymer chains were self-assembled into micellar nanostructures as a reservoir for the slow-release delivery of nitric oxide (NO). Poly(oligo(ethylene glycol) methyl ether methacrylate)-block-poly(vinyl benzyl chloride-co-styrene) was prepared by reversible addition fragmentation chain transfer (RAFT) polymerization. Pendant chloro- groups in the polymer backbone were reacted with silver nitrate (AgNO3) to introduce nitrate functionality. The nitrate-containing micelles proved to be stable in water, with no detectableNOrelease. The release ofNOwas then triggered by exposure to glutathione, and it was found that 36 and 99% of NO was released at 37 and 60° C, respectively, after 21 h.

  4. Articles

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    1. Low glass transition temperature polymer electrolyte prepared from ionic liquid grafted polyethylene oxide (pages 2104–2110)

      Heyi Hu, Wen Yuan, Lanshuo Lu, Hui Zhao, Zhe Jia and Gregory L. Baker

      Version of Record online: 28 APR 2014 | DOI: 10.1002/pola.27217

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      Polymer electrolytes were prepared from tethering ionic liquids side chain onto polyethylene oxide backbone with different molecular weights, exhibit low Tg and high conductivity up to 10−3 S cm−1. Also a high viscosity of 4000 Pa s obtains from this type of polymer electrolyte.

    2. Olefin polymerization and copolymerization by complexes bearing [ONNO]-Type salan ligands: Effect of ligand structure and metal type (titanium, zirconium, and vanadium) (pages 2111–2123)

      Marzena Białek, Monika Pochwała and Grzegorz Spaleniak

      Version of Record online: 6 MAY 2014 | DOI: 10.1002/pola.27218

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      Polymerization and copolymerization processes of olefins are catalyzed by new salan complexes of transition metals, resulting in products with different properties depending on the ligand structure, transition metal, and cocatalyst type.

    3. Plasticization of a polymer layer harnessed to a silicon microcantilever as a highly sensitive and selective means to detect nitroaromatic derivatives (pages 2124–2130)

      Ariel Shemesh, Tanya Blank, Shai Meltzman, Sara Stolyarova, Rachel Edrei, Elena Borzin, Yael Nemirovsky and Yoav Eichen

      Version of Record online: 20 MAY 2014 | DOI: 10.1002/pola.27219

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      While most guest molecules interact reversibly with 3-aminopropyl silane modified silicon microcantilevers by amplifying their thermally activated bending, nitroaromatic systems react with this layer to induce its plasticization. Using this approach, it was possible to detect a sample of 100 pg TNT even in the presence of a ∼109 fold excess of a background material such as acetonitrile, all under ambient atmosphere.

    4. Triple stimuli-responsive amphiphilic glycopolymer (pages 2131–2138)

      Wenjuan Guo, Tieshi Wang, Xinde Tang, Qun Zhang, Faqi Yu and Meishan Pei

      Version of Record online: 4 MAY 2014 | DOI: 10.1002/pola.27222

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      Temperature/pH/photo triple stimuli-responsive amphiphilic block copolymer poly(2-(dimethylamino)ethyl methacrylate-co-6-O-methacryloyl-1,2,3,4-di-O-isopropylidene-Dgalactopyranose)-b-poly(4-(4-methoxyphenylazo)phenoxy methacrylate) was prepared by ATRP, and its aqueous micellar bahavior was investigated.

    5. Brønsted acid-catalyzed polymerization of ε-caprolactone in water: A mild and straightforward route to poly(ε-caprolactone)-graft-water-soluble polysaccharides (pages 2139–2145)

      Nicholas Stanley, Georgiana Bucataru, Yong Miao, Audrey Favrelle, Marc Bria, Francois Stoffelbach, Patrice Woisel and Philippe Zinck

      Version of Record online: 6 JUN 2014 | DOI: 10.1002/pola.27250

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      The graft polymerization of ε-caprolactone with water-soluble polysaccharides is conducted in water using Brønsted acids as catalysts. This straightforward one-step access to poly(ε-caprolactone)-graft-dextran and poly(ε-caprolactone)-graft-methylcellulose operates in mild conditions (i.e., low temperatures), using readily available metal-free catalysts and water as a solvent. For low degree of substitution, the dextran hydroxyester self-assembles in water to form nanoparticles.

    6. Synthesis of amphiphilic linear-hyperbranched graft-copolymers via grafting based on linear polyethylene backbone (pages 2146–2154)

      Jingshan Mu, Fei Yang, Wei Li, Dirong Gong, Zhongsu Liu, Feng Jiang and Zhongren Chen

      Version of Record online: 10 MAY 2014 | DOI: 10.1002/pola.27224

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      The amphiphilic linear-hyperbranched graft-copolymers were successfully synthesized in a grafting approach, confirmed by 1H/13C NMR, GPC, and TGA. The complicated microstructures caused by the unsymmetric glycidol structure were analyzed by DEPT and 2D HSQC spectra. The degrees of branching were calculated to be 0.63–0.66, indicating the extent of branching is close to theoretical values. The thermal analysis of linear-hyperbranched copolymers via TGA and DSC is also presented.

    7. Thermoresponsive diblock copolymer micellar macro-RAFT agent-mediated dispersion RAFT polymerization and synthesis of temperature-sensitive ABC triblock copolymer nanoparticles (pages 2155–2165)

      Chengqiang Gao, Quanlong Li, Yongliang Cui, Fei Huo, Shentong Li, Yang Su and Wangqing Zhang

      Version of Record online: 14 MAY 2014 | DOI: 10.1002/pola.27227

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      A thermoresponsive micellar macro-RAFT agent is employed to accelerate the dispersion RAFT polymerization. The reaction provides the in situ synthesis of temperaturesensitive ABC triblock copolymer nanoparticles.

    8. Spotlight Article

      Synthesis and characterization of polythiophene derivatives with nitrogen heterocycles on the side chain (pages 2166–2174)

      Koji Takagi, Eiki Kawagita and Ryo Kouchi

      Version of Record online: 14 MAY 2014 | DOI: 10.1002/pola.27228

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      Three polythiophene derivatives bearing nitrogen heterocycles on the side chain were synthesized by the Grignard metathesis (GRIM) reaction and Kumada coupling polymerization. The products were investigated by GC, NMR, GPC, and MALDI-TOF mass spectrometry. The polymers were characterized by NMR, UV-VIS, DFT calculations, and CV measurements.

    9. Atom transfer radical polymerization of ionic liquid monomer: The influence of salt/counterion on polymerization (pages 2175–2184)

      Hongkun He, Mingjiang Zhong, David Luebke, Hunaid Nulwala and Krzysztof Matyjaszewski

      Version of Record online: 14 MAY 2014 | DOI: 10.1002/pola.27229

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      The effect of salt/counterion on atom transfer radical polymerization is studied. The different types and amounts of salts, solvents, ligands, and monomers have distinct influence on polymerization.

    10. Preparation of zwitterionic sulfobetaine end-functionalized poly(ethylene glycol)-b-poly(caprolactone) diblock copolymers and examination of their thermogelling properties (pages 2185–2191)

      Sun Woo Shim, Doo Yeon Kwon, Ji Hoon Park, Jae Ho Kim, Heung Jae Chun, Young Joo Koh and Moon Suk Kim

      Version of Record online: 12 MAY 2014 | DOI: 10.1002/pola.27230

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      Zwitterionic sulfobetaine end-functionalized poly(ethylene glycol)-b-poly(caprolactone) diblock copolymers were prepared successfully as thermogelling materials. The phase transition and the gelation time of the diblock copolymers were affected by the length of the hydrophobic segments and the zwitterionic end group. Such thermogelling materials can be used as potential injectable drug and cell carriers.

    11. o-nitrobenzyl acrylate is polymerizable by single electron transfer-living radical polymerization (pages 2192–2201)

      Soliman Mehawed Abdellatif Soliman, Cécile Nouvel, Jérôme Babin and Jean-Luc Six

      Version of Record online: 20 MAY 2014 | DOI: 10.1002/pola.27232

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      The living character of o-nitrobenzyl acrylate (NBA) SET–LRP is demonstrated. The effects of CuBr2, and ligand concentrations, as well as Cu(0) wire length on kinetics are shown. First-order kinetics are observed after one induction period. Linear evolution of molecular weight with a narrow distribution is obtained. High initiation efficiency close to 1 and high chain-end functionality are reached. Chain extension of poly(o-nitrobenzyl acrylate) (PNBA) is realized with methyl acrylate. Finally, light-sensitive property of PNBA is checked upon UV irradiation.

    12. Hairy polymeric nanocapsules with ph-responsive shell and thermoresponsive brushes: Tunable permeability for controlled release of water-soluble drugs (pages 2202–2216)

      Lei Chen, Zhiping Peng, Zhipeng Zeng, Yingqi She, Junchao Wei and Yiwang Chen

      Version of Record online: 14 MAY 2014 | DOI: 10.1002/pola.27233

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      A hairy polymeric nanocapsule with pH-responsive P(MAA-co-DVB) inner shell and temperature-responsive PNIPAm brushes were successfully prepared via the combination of the distillation-–precipitation copolymerization and surface thiol-ene click grafting reaction. The permeability and stability of the P(MAA-co-DVB)-g-PNIPAm nanocapsules can be manipulated by tuning the thickness of P(MAA-co-DVB) inner shell, the structural parameters of grafted PNIPAm brushes, the external pH, and temperature. Temperature-dependent and pH-controlled release of encapsulated DOX was investigated in detail.

    13. Synthesis and self-assembly of polyhydroxylated and electropolymerizable block copolymers (pages 2217–2227)

      Satyananda Barik and Suresh Valiyaveettil

      Version of Record online: 14 MAY 2014 | DOI: 10.1002/pola.27234

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      Multihydroxylated methacrylic amphiphilic diblock copolymers are prepared using ATRP polymerization and their structure-property relationship is investigated. The changes in amphiphilicity to the block copolymer resulting in lamella and vesicular morphology are demonstrated.

    14. Insight into the ATRP rate controlling ability of initiator structure: Micromolecular, macromolecular, and immobilized initiators (pages 2228–2238)

      Yin-Ning Zhou and Zheng-Hong Luo

      Version of Record online: 2 JUN 2014 | DOI: 10.1002/pola.27249

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      The effect of initiator type (i.e., micro-molecular, macro-molecular and immobilized initiator) on the ATRP kinetics was studied through a newly developed mathematical model. The results showed that the activities and deactivities of the CuCl/PMDETA heterogeneous catalytic complexes are the highest for Eib-Br, lower for bromopoly(styrene), and the lowest for SiO2-APTS-Br. A homogeneous catalytic system (CuCl/dNbpy) was also investigated to further probe how the model can guide the preparation of fluorinated gradient copolymers.

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