Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 50 Issue 10

15 May 2012

Volume 50, Issue 10

Pages i–iv, 1869–2083

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      Cover Image, Volume 50, Issue 10 (pages i–ii)

      Article first published online: 4 APR 2012 | DOI: 10.1002/pola.26079

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      α-Proparygl amino acid derived polyacetylenes containing unprotected carboxy groups adopt predominantly one-handed helical conformations, as presented by H. Sogawa, M. Shiotsuki, and F. Sanda on page 2008. The helical structures of the polymers are extended upon addition of alkali hydroxides (LiOH, NaOH, KOH) and tetrabutylammonium fluoride, wherein the degree of extension agrees with the order of the cation size. The existence of cations close to the carboxylate moieties results in helix loosening accompanying the extension of conjugation of the polyacetylene backbone. The polymers are expected to function as cation sensors since this ion-responsive conformational transition causes the color change of the polymer solutions that is detectable by the naked eye.

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      Inside Cover, Volume 50, Issue 10 (pages iii–iv)

      Article first published online: 4 APR 2012 | DOI: 10.1002/pola.26080

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      PDMS-b-PEG diblock copolymer brushes are grafted on a silicon substrate via a two-step photo-initiated “thiol-ene” click chemistry, as presented by Muquan Yang, Jun Mao, Wei Nie, Zhixin Dong, Dapeng Wang, Ziliang Zhao, and Xiangling Ji on page 2075. The image shows that the PDMS-b-PEG diblock copolymer brushes exhibit variable responsive behavior to different solvent treatments, i.e., “onion-like” morphologies after water treatment, pinned micelles after toluene treatment, and swollen to a smooth surface after DMF treatment. This is a new example of “thiol-ene” click chemistry used in macromolecular addition.

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      Strategies toward well-defined polymer nanoparticles inspired by nature: Chemistry versus versatility (pages 1869–1880)

      Mahmoud Elsabahy and Karen L. Wooley

      Article first published online: 20 FEB 2012 | DOI: 10.1002/pola.25955

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      Intensive efforts have been directed to biomimicry approaches used for the synthesis, supramolecular assembly, stabilization, and further functionalization of “smart, biomimic” shell-crosslinked knedel-like nanoparticles (SCKs), in which the synthetic SCKs are of similar dimensions (10–100 nm) and can be made to present surface features resembling those of proteins, for example, cationic moieties of the histone core proteins of nucleosomes for packaging of nucleic acids, hydrophilic surfaces and hydrophobic cores like lipoproteins for the function of packaging water-insoluble guests, or internal sites for loading of the nucleic acids in a manner analogous to the behavior of viral capsids.

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    1. Stimuli-responsive self-assembled multilayer azo thin films: Effect of aggregates and salt on significant spectral shifts (pages 1881–1889)

      Nasir M. Ahmad, Syed J. Ali and Mudassara Saqib

      Article first published online: 28 FEB 2012 | DOI: 10.1002/pola.25968

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      Layer-by-layer SAMU thin films of azo dye molecules and PEL exhibited two distinct absorbance maxima in visible and UV regions. This is attributed to the assumption that a fraction of the dye adsorbed as the monomeric form yields a visible peak, while the additional fraction of the oligomeric H-type aggregated form also appeared in the UV region. The UV peak, however, disappeared in films fabricated from salt solution to demonstrate suppression of aggregates and the stimuli-responsive effect.

  4. Articles

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    1. ATNRC and SET-NRC synthesis of PtBA-g-PEO well-defined amphiphilic graft copolymers (pages 1890–1899)

      Yaogong Li, Ming Du, Yaqin Zhang, Yongjun Li, Long Sui, Guolin Lu and Xiaoyu Huang

      Article first published online: 23 FEB 2012 | DOI: 10.1002/pola.25958

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      A series of well-defined amphiphilic graft copolymers consisting of a hydrophilic poly (tert-butyl acrylate) backbone and hydrophilic poly(ethylene oxide) side chains were synthesized by the sequential reversible addition fragmentation chain transfer polymerization and atom transfer nitroxide radical coupling or single electron transfer-nitroxide radical coupling reaction.

    2. Polyfluorene derivatives pending iridium complexes: Improved optoelectronic properties by introducing D-A units and altering pendent mode (pages 1900–1905)

      Hua Tan, Junting Yu, Jianhua Chen, Kaixuan Nie, Qing Chen, Ying Huang, Zhiyong Zhang, Yafei Wang, Yu Liu, Gangtie Lei and Weiguo Zhu

      Article first published online: 20 FEB 2012 | DOI: 10.1002/pola.25959

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      Two D-A-based polyfluorene derivatives (P1 and P2) with pendent red-emitting iridium bi(phenyl-isoquilonato) (picolinato) [Ir(Piq)2(pic)] units and one (P3) with only a pendant Ir(Piq)2(pic) unit are obtained. Their opto-electronic properties are significantly influenced by the D-A units and pendent mode of the Ir(Piq)2(pic) unit. The maximum current efficiency of 0.72 cd/A and the highest luminance of 1398 cd/m2 are obtained in the P1-based device, which are 1.3 and 1.5 times higher than those in the P2-based device, respectively.

    3. Preparation and optical characterization of two photoactive poly(bisphenol a ethoxylate diacrylate) copolymers containing designed amino-nitro-substituted azobenzene units, obtained via classical and frontal polymerization, using novel ionic liquids as initiators (pages 1906–1916)

      Javier Illescas, Jesús Ortíz-Palacios, Jair Esquivel-Guzmán, Yessica S. Ramirez-Fuentes, Ernesto Rivera, Omar G. Morales-Saavedra, Antonio A. Rodríguez-Rosales, Valeria Alzari, Daniele Nuvoli, Sergio Scognamillo and Alberto Mariani

      Article first published online: 23 FEB 2012 | DOI: 10.1002/pola.25962

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      Bisphenol A ethoxylate diacrylate (BPAEDA) was polymerized with two different co-monomers containing azobenzene units by the frontal polymerization (FP) technique. The obtained polymers were characterized by TGA and DSC. The nonlinear optical (NLO) characterizations of the developed BPAEDA/MDR-1 and BPAEDA/4PEGMAN copolymers were performed according to the Z-Scan technique in film samples prepared by classical polymerization. Samples with the highest azo--comonomer contents exhibit outstanding cubic NLO-activity.

    4. Synthesis of tadpole polymers via triple click reactions: Copper-catalyzed azide–alkyne cycloaddition, diels–alder, and nitroxide radical coupling reactions (pages 1917–1925)

      Tuba Dedeoglu, Hakan Durmaz, Gurkan Hizal and Umit Tunca

      Article first published online: 20 FEB 2012 | DOI: 10.1002/pola.25965

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      The copper-catalyzed azide-alkyne cycloaddition click reaction between linear anthracene-, OH-, and azide-terminated PS and α-furan-protected-maleimide-ω-alkyne linkage, afforded l-α-anthracene-OH-ω-maleimide-PS. The cyclization via intramolecular Diels–Alder click reaction of this linear PS and subsequent conversion of the hydroxyl into bromide resulted in the cyclic PS with one bromide located on the ring, (c-PS)-Br. Finally, the c-PS-Br was clicked with either well-defined tetramethylpiperidine-1-oxyl-terminated poly(ethylene glycol) (PEG) or poly(ε-caprolactone) (PCL) yielding the tadpole polymer, (c-PS)-b-PEG or (c-PS)-b-PCL.

    5. Mechanical property tuning of semicrystalline network polymers by controlling rates of crystallization and crosslinking (pages 1926–1932)

      Nobuhiro Oya, Shunsuke Saitoh, Yukiko Furuhashi and Naoko Yoshie

      Article first published online: 20 FEB 2012 | DOI: 10.1002/pola.25966

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      Semicrystalline network polymers were synthesized by the DA reaction of PCLF2 and M3. Controlling the rates of crystallization and crosslinking reaction during the preparation gave materials with various properties from a single prepolymer and a single linker. Especially when crystallization and crosslinking were promoted simultaneously, tough and ductile materials were obtained. Structural analysis showed that this variation was derived from the difference in the crystallinity, crystallite size, and network structure.

    6. Fast copper catalyzed living radical polymerization of acrylonitrile utilizing a high concentration of radical initiator (pages 1933–1940)

      Xiao-hui Liu, Jin Wang, Jian-shi Yang, Shu-lin An, Yuan-lin Ren, Yun-hai Yu and Peng Chen

      Article first published online: 23 FEB 2012 | DOI: 10.1002/pola.25967

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      A fast and controlled LRP of acrylonitrile, evidenced by 81.3% monomer conversion within 40 min and well-defined polymers with polydispersity indices in the range of 1.14−1.38, is reported. This was achieved by utilizing AIBN as radical initiator with a high concentration up to 190 mM and CuBr2 as catalyst with a low concentration down to 50 ppm. The polymerization displayed typical living radical polymerization characteristics, including pseudo first-order polymerization kinetics, linear increase of molecular weight, and low PDI value. 1H NMR and GPC analyses as well as chain extension reaction confirmed high chain-end functionality of polyacrylonitrile.

    7. Synthesis of end-functionalized polyethers by phosphazene base-catalyzed ring-opening polymerization of 1,2-butylene oxide and glycidyl ether (pages 1941–1952)

      Hideki Misaka, Eisuke Tamura, Kosuke Makiguchi, Kensuke Kamoshida, Ryosuke Sakai, Toshifumi Satoh and Toyoji Kakuchi

      Article first published online: 20 FEB 2012 | DOI: 10.1002/pola.25969

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      End-functionalized polyethers, such as poly(1,2-butylene oxide), poly(benzyl glycidyl ether), and poly(t-butyl glycidyl ether), were produced by living ring-opening polymerization (ROP) of corresponding epoxy monomers using t-Bu-P4 as the catalyst and functional alcohol as the initiator. Furthermore, the well-defined cyclic polyethers could be synthesized by the combination of t-Bu-P4-catalyzed ROP and click cyclization.

    8. Effect of molar mass and regioregularity on the photovoltaic properties of a reduced bandgap phenyl-substituted polythiophene (pages 1953–1966)

      Farid Ouhib, Guillaume Dupuis, Rémi de Bettignies, Séverine Bailly, Abdel Khoukh, Hervé Martinez, Jacques Desbrières, Roger C. Hiorns and Christine Dagron-Lartigau

      Article first published online: 23 FEB 2012 | DOI: 10.1002/pola.25970

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      Octyl phenyl substituted polythiophenes of various molar masses and high regioregularities are successfully synthesized via a modified Grignard metathesis polymerization. They exhibit extended absorption spectra towards the infra-red and a bandgap of 1.75 eV. AFM images of poly[3-(4-octylphenyl)thiophene)]POPT and its blends with [6,6]-phenyl C61 butyric acid methyl esterPCBM show the influence of deposition conditions and support discussions on photovoltaic properties.

    9. Systematic study on chemical oxidative and solid-state polymerization of poly(3,4-ethylenedithiathiophene) (pages 1967–1978)

      Shuai Chen, Baoyang Lu, Xuemin Duan and Jingkun Xu

      Article first published online: 23 FEB 2012 | DOI: 10.1002/pola.25971

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      Different types of poly(3,4-ethylenedithiathiophene) (PEDTT) (powders, stable dispersions, and free-standing films) have been achieved via chemical oxidative polymerization of EDTT with FeCl3, (NH4)2S2O8, H2O2/Fe2+, Ce(SO4)2, (NH4)2Ce(NO3)6, (Fe(NO3)3·9H2O, Na2S2O8, or Na2S2O8/Fe3+ in H2O, CH3CN, CH3CN/H2O or aqueous surfactant solutions, and solid-state polymerization of 2,5-dibromo-3,4-ethylenedithiathiophene (DBEDTT) and a novel compound, 2,5-diiodo-3,4-ethylenedithiathiophene (DIEDTT), under solventless and oxidant-free conditions. Systematic discussions of this study will be helpful for the development of analogs of poly(3,4-ethylenedioxythiophene) (PEDOT) and their derivatives.

    10. Synthesis and characterization of two classes of hyperstar polymers bearing hyperbranched cores grafted with linear arms (pages 1979–1990)

      Frank Däbritz, Albena Lederer, Hartmut Komber and Brigitte Voit

      Article first published online: 5 MAR 2012 | DOI: 10.1002/pola.25972

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      New hyperstar polymers (HSP) consisting of two different hyperbranched (hb) cores grafted with linear-polymer arms were successfully synthesized. The hb cores were based on either hb poly(vinylbenzylchloride) (PVBC) synthesized by SCVP-ATRP or hb polyester (PE-OH) from a polycondensation reaction and finally grafted with linear block copolymer arms via controlled radical or cationic polymerization protocols including OH-functionalized monomers.

    11. Preparation of poly(n-butyl acrylate)-b-polystyrene particles by emulsifier-free, organotellurium-mediated living radical emulsion polymerization (emulsion TERP) (pages 1991–1996)

      Yukiya Kitayama, Kazuya Kishida, Hideto Minami and Masayoshi Okubo

      Article first published online: 5 MAR 2012 | DOI: 10.1002/pola.25973

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      The preparation of poly(n-butyl acrylate)-b-polystyrene particles without any coagulation by two-step emulsifier-free, organotellurium-mediated living radical emulsion polymerization (emulsion TERP) using poly(methacrylic acid)–methyltellanyl (TeMe) (PMAA30-TeMe) and 4,4′-azobis(4-cyanovaleric acid) is demonstrated. The final particle size was approximately 30 nm and second particle nucleation was not observed throughout the polymerization. Mn increased linearly in both steps with conversion and blocking efficiency was ∼75%. PDI was improved by increasing radical entry frequency into each polymer particle due to an increase of the polymerization temperature.

    12. Phosphonate-terminated poly(vinyl acetate) synthesized by RAFT/MADIX polymerization (pages 1997–2007)

      P-E. Dufils, G. David, B. Boutevin, G. Woodward, G. Otter, A. Guinaudeau, S. Mazières and M. Destarac

      Article first published online: 23 FEB 2012 | DOI: 10.1002/pola.25974

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      A new series of phosphonate/bisphosphonate-containing xanthates was efficiently synthesized and used as chain transfer agents in the RAFT/MADIX polymerization of VAc. Very good control of the VAc polymerization was obtained for each xanthate, thus leading to PVAc end-capped with either phosphonate or bisphosphonate moieties.

    13. α-Propargyl amino acid-derived optically active novel substituted polyacetylenes: Synthesis, secondary structures, and responsiveness to ions (pages 2008–2018)

      Hiromitsu Sogawa, Masashi Shiotsuki and Fumio Sanda

      Article first published online: 5 MAR 2012 | DOI: 10.1002/pola.25975

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      Novel substituted acetylenes were synthesized from (S)-/(R)-α-propargylglycine and α-propargylalanine, and polymerized with a rhodium catalyst to provide the polymers with moderate molecular weights in good yields. Polarimetric, CD, and UV–vis spectroscopic analyses indicated that the formed polymers took predominantly one-handed helical structures both in polar and nonpolar solvents. Unprotected carboxy group containing polymer changed its conformation upon addition of alkali hydroxides and tetrabutylammonium fluoride, accompanying the red-shift of λmax.

    14. Water-soluble meta-poly(phenylene ethynylene) oligomers with stable helical secondary structure (pages 2019–2028)

      Ha H. Nguyen, James H. McAliley and David A. Bruce

      Article first published online: 28 FEB 2012 | DOI: 10.1002/pola.25976

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      The alternating arrangement of functional groups on the polymer backbone, including ester and ammonium groups, allows the presented meta-poly(phenylene ethynylene) (mPPE) materials to be soluble in water and alcohol solvents, and, more importantly, they enable the polymer to fold into stable helical conformations. These water-soluble mPPE helical structures could find use in a variety of bio-related applications.

    15. Thermodegradable multisegmented polymer synthesized by consecutive radical addition-coupling reaction of α,ω-macrobiradicals and dithioester (pages 2029–2036)

      Qinqin Zhu and Qi Wang

      Article first published online: 20 FEB 2012 | DOI: 10.1002/pola.25977

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      Thermodegradable multisegmented polymers linked by C[BOND]S bonds are synthesized by consecutive radical addition-coupling reaction of α,ω-macrobiradical and ethyl dithiobenzoate. The multisegmented polymer can be thermodegraded in the presence of hydrogen atom donor, and the molecular weight distribution transformed back into shape of its original precursor, since it is conjugated by C[BOND]S bond.

    16. Preparation of main-chain imidazolium-functionalized amphiphilic block copolymers through combination of condensation polymerization and nitroxide-mediated free radical polymerization and their micelle study (pages 2037–2044)

      Xue Li, Xufeng Ni, Zhenhua Liang and Zhiquan Shen

      Article first published online: 23 FEB 2012 | DOI: 10.1002/pola.25978

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      A series of main-chain amphiphilic block copolymers consisting of polyionic liquid and polystyrene blocks were synthesized by an approach of condensation polymerization combined with nitroxide-mediated free-radical polymerization. Spherical micelles could be obtained from the self-assembly of these block copolymers.

    17. Synthesis, characterization, and micellization of PCL-g-PEG copolymers by combination of ROP and “Click” chemistry via “Graft onto” method (pages 2045–2052)

      Kai Zhang, Ying Wang, Weipu Zhu, Xiaodong Li and Zhiquan Shen

      Article first published online: 23 FEB 2012 | DOI: 10.1002/pola.25979

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      Well-defined amphiphilic biodegradable graft copolymers with PEG as hydrophilic side chain and PCL as hydrophobic backbone were synthesized by a combination of ROP and “click” reaction. These amphiphilic graft polymers could undergo self-assembly in aqueous solution to form sphere-like micelles with diverse diameters, depending on the grafting density.

    18. Novel thermo-responsive self-assembly micelles from a double brush-shaped PNIPAM-g-(PA-b-PEG-b-PA)-g-PNIPAM block copolymer with PNIPAM polymers as side chains (pages 2053–2067)

      Yan-Ling Luo, Wei Yu, Feng Xu and Li-Li Zhang

      Article first published online: 23 FEB 2012 | DOI: 10.1002/pola.25980

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      A double brush-shaped polymer with novel architectures is synthesized via combination of free radical chain-transfer, esterification, and an atom transfer radical polymerization (ATRP) routes. The self-assembly micelles from these polymer brushes in aqueous solution and simulated physiological media have good stability, and assume spherical shapes with petaling, double and single cores with temperature and media. The nanoleveled micelles turn out to be low cytotoxicity and safe for intravenous injection and oral drug delivery.

    19. Copolymerization of ethylene with acrylonitrile promoted by novel nonmetallocene catalysts with phenoxy-imine ligands (pages 2068–2074)

      Xinli Zhang, Zhi Liu, Jianjun Yi, Fengjiao Li, Haibing Huang, Wei Liu, Hongpeng Zhen, Qigu Huang, Kejing Gao and Wantai Yang

      Article first published online: 23 FEB 2012 | DOI: 10.1002/pola.25981

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      Novel nonmetallocene catalysts (Cat.1–Cat.9) with phenoxy-imine ligand, MAO using as cocatalyst, were used for producing copolymer of ethylene with acrylonitrile. High-catalytic activity for the copolymerization was exhibited. High-molecular weight and high content of acrylonitrile incorporation of the copolymer were obtained.

    20. Facile synthesis and responsive behavior of PDMS-b-PEG diblock copolymer brushes via photoinitiated “thiol-ene” click reaction (pages 2075–2083)

      Muquan Yang, Jun Mao, Wei Nie, Zhixin Dong, Dapeng Wang, Ziliang Zhao and Xiangling Ji

      Article first published online: 28 FEB 2012 | DOI: 10.1002/pola.25985

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      PDMS-b-PEG diblock copolymer brushes were firstly synthesized by photo-initiated “thiol-ene” click reaction and the thickness of the brushes can be controlled only through the irradiation time. The responsive behaviors of this PDMS-b-PEG diblock copolymer brushes treated with various solvents (both selective and nonselective solvents) are also discussed.

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