Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 50 Issue 14

15 July 2012

Volume 50, Issue 14

Pages i–iv, 2739–2979

  1. Cover Image

    1. Top of page
    2. Cover Image
    3. Highlight
    4. Rapid Communication
    5. Original Articles
    1. You have free access to this content
      Cover Image, Volume 50, Issue 14 (pages i–ii)

      Version of Record online: 3 JUN 2012 | DOI: 10.1002/pola.26197

      Thumbnail image of graphical abstract

      The synthesis of segmented theromotropic copolyesters containing azobenzene through melt polycondensation are depicted, as presented by Chinmay G. Nardele and S. K. Asha on page 2770. The structural design incorporating azobenzene as part of a twin molecule with a central oligooxyethylene spacer facilitates polymerization by meltcondensation by reducing the melting temperature of the twin molecule and also by improving solubility and miscibility in the molten reaction medium. The incompatibility of the polar oligooxyethylene spacer units with the rigid rod-like azobenzene results in segregation leading to mesophase formation. The liquid crystalline (LC) characteristics of the polymer could be tuned depending on the chemical structure of the azo chromophore as well as the length of the central oligooxyethylene segment.

    2. You have free access to this content
      Inside Cover, Volume 50, Issue 14 (pages iii–iv)

      Version of Record online: 3 JUN 2012 | DOI: 10.1002/pola.26198

      Thumbnail image of graphical abstract

      The cover image shows a schematic picture of the intermolecular charge transfer process between the active components of a bulk heterojunction organic solar cell. Photoabsorption promotes electrons in the polymer from the HOMO to the LUMO (computed DFT orbitals represented). An exciton is generated that dissociates at the polymer/fullerene (PCBM) interface through electron transfer to the LUMO of PCBM and subsequently, free charges are produced. In the work by Alessandro Abbotto and colleagues on page 2829, a new heteroarylene-vinylene donor-acceptor polymer, based on the combination of strong donor (benzodithiophene derivative) and acceptor (2,1,3-benzothiadiazole) alternating units together with a vinylene spacer, is experimentally and theoretically investigated. The introduction of the vinylene spacers affords lower bandgaps and improved thermal stability compared to the corresponding species with direct bonding between the heteroaromatic units.

  2. Highlight

    1. Top of page
    2. Cover Image
    3. Highlight
    4. Rapid Communication
    5. Original Articles
    1. You have free access to this content
      A qualitative and quantitative post-mortem analysis: Studying free-radical initiation processes via soft ionization mass spectrometry (pages 2739–2757)

      Dominik Voll, Thomas Junkers and Christopher Barner-Kowollik

      Version of Record online: 25 APR 2012 | DOI: 10.1002/pola.26076

      Thumbnail image of graphical abstract

      The present article highlights the recent progress in qualifying and quantifying the endgroups—via high resolution electrospray ionization mass spectrometry techniques—of thermal-initiated as well as photo-initiated polymers which are generated via free radical polymerizations procedures.

  3. Rapid Communication

    1. Top of page
    2. Cover Image
    3. Highlight
    4. Rapid Communication
    5. Original Articles
    1. You have free access to this content
      Cationic copolymerization of 1,1-diphenylethylene with p-substituted styrenes (pages 2758–2761)

      Kosaku Yasuoka, Shokyoku Kanaoka and Sadahito Aoshima

      Version of Record online: 16 APR 2012 | DOI: 10.1002/pola.26073

      Thumbnail image of graphical abstract

      Controlled cationic copolymerization of nonpolymerizable 1,1-diphenylethylene (DPE) with p-methylstyrene or p-tert-butylstyrene was achieved using an EtAlCl2/SnCl4 initiating system at –78 °C. This is the first example of effective cationic copolymerization of DPE with other vinyl monomers.

  4. Original Articles

    1. Top of page
    2. Cover Image
    3. Highlight
    4. Rapid Communication
    5. Original Articles
    1. End-group composition of poly(3-hexylthiophene)s prepared by in situ quenching of the grignard metathesis polymerization: Influence of additives and reaction conditions (pages 2762–2769)

      W. Michael Kochemba, S. Michael Kilbey II and Deanna L. Pickel

      Version of Record online: 4 APR 2012 | DOI: 10.1002/pola.26057

      Thumbnail image of graphical abstract

      The influence of additives and reaction conditions on the end-group composition of poly(3-hexylthiophene)s (P3HTs) prepared by in situ quenching of the GRIM polymerization with a Grignard reagent is investigated. Additives such as styrene and 1-pentene are shown to alter the end-group composition of tolyl-functionalized P3HTs as determined by matrix assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF MS), and temperature and LiCl also play important roles. Monofunctional P3HT is the major product (72% abundance) when the functionalization is performed in the presence of LiCl and styrene at 0 °C, whereas in the absence of additives the monofunctional product is present only at 11% abundance.

    2. Twin liquid crystals and segmented thermotropic polyesters containing azobenzene—effect of spacer length on LC properties (pages 2770–2785)

      Chinmay G. Nardele and S. K. Asha

      Version of Record online: 5 APR 2012 | DOI: 10.1002/pola.26062

      Thumbnail image of graphical abstract

      Twin azobenzene AA type monomers were used as a design strategy for developing thermotropic main chain segmented polyesters via melt polycondensation route. Although the liquid crystalline (LC) twin molecules preferred to organize in smectic layered phases, incorporation into a nonmesogenic polymer disrupted the layered organization resulting in nematic LC phases. Short non-LC twin P2P at low (5 mol %) incorporation into a crystalline polymer resulted in nematic LC copolymers, whereas at higher (15 mol %) incorporation smectic LC phases were observed.

    3. Manipulation of the bioactivity of glucose oxidase via raft-controlled surface modification (pages 2786–2793)

      Xiong Luo, Jingquan Liu, Guozhen Liu, Rui Wang, Zhen Liu and Aihua Li

      Version of Record online: 5 APR 2012 | DOI: 10.1002/pola.26067

      Thumbnail image of graphical abstract

      The manipulation of the bioactivity of GOx via surface modification using mercaptothiazoline ester functionalized poly[poly(ethyleneglycol) acrylate] which was synthesized by RAFT mechanism is presented. The modified GOx with polymeric chains exhibited reduced enzymatic activity toward the catalytical oxidation of glucose, but with significantly increased thermal stability and elongated lifetime. The more polymer chains or the longer polymer chain attached, the more reduction of the enzymatic activity resulted, however, the longer enzyme lifetime obtained.

    4. Controllable synthesis of novel sandwiched polyaniline/ZnO/polyaniline free-standing nanocomposite films (pages 2794–2801)

      Gui-Wen Huang, Hong-Mei Xiao, Han-Qiao Shi and Shao-Yun Fu

      Version of Record online: 16 APR 2012 | DOI: 10.1002/pola.26068

      Thumbnail image of graphical abstract

      Controllable synthesis of the novel sandwiched PANI/ZnO/PANI free-standing nanocomposite films is reported. It is shown that the coverage of the PANI surface layer on the ZnO interlayer can not only lead to great enhancement in the PL property but also to a maximum PL intensity at a medium PANI surface layer thickness.

    5. Synthesis of single-core and multiple-core core-shell nanoparticles by RAFT emulsion polymerization: Lead sulfide-copolymer nanocomposites (pages 2802–2808)

      Paramita Das and Jerome P. Claverie

      Version of Record online: 17 APR 2012 | DOI: 10.1002/pola.26070

      Thumbnail image of graphical abstract

      A RAFT based simple and direct strategy is proposed to produce core-shell PbS quantum dots/polymer particles. Single-core and multiple-core core-shell particles are respectively formed depending on the concentration of the PbS quantum dots.

    6. High-performance amorphous donor–acceptor conjugated polymers containing x-shaped anthracene-based monomer and 2,5-bis(2-octyldodecyl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione for organic thin-film transistors (pages 2809–2818)

      Joo Bin Lee, Kyung Hwan Kim, Chang Seop Hong and Dong Hoon Choi

      Version of Record online: 25 APR 2012 | DOI: 10.1002/pola.26078

      Thumbnail image of graphical abstract

      New diketopyrrolopyrrole-containing amorphous conjugated polymers such as poly(3-(5-((2,6-bis((4-hexylphenyl)ethynyl)-10-(prop-1-ynyl)anthracen-9-yl)ethynyl)thiophen-2-yl)- 2,5-bis(2-octyldodecyl)-6-(thiophen-2-yl)pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione) were successfully synthesized via Sonogashira coupling reactions under microwave conditions. Copolymer, incorporating a DPP moiety at the 9,10-position of the anthracene ring through a triple bond, showed a low bandgap energy (Eg = 1.81 eV). When the newly synthesized copolymer was used as a semiconductor material in an organic thin film transistor, the best mobility of up to 0.12 cm2 V−1 s−1 (Ion/off = ∼4.4 × 106) was observed.

    7. 2,3-bis(5-Hexylthiophen-2-yl)-6,7-bis(octyloxy)-5,8-di(thiophen-2-yl) quinoxaline: A good construction block with adjustable role in the donor-π-acceptor system for bulk-heterojunction solar cells (pages 2819–2828)

      Shuang Li, Zhicai He, Jian Yu, Su'an Chen, Aoshu Zhong, Hongbin Wu, Cheng Zhong, Jingui Qin and Zhen Li

      Version of Record online: 28 APR 2012 | DOI: 10.1002/pola.26086

      Thumbnail image of graphical abstract

      The preliminary results demonstrated that the three polymers had set a good example of the delicate interplay between the HOMO energy level (affecting Voc) and the band gap (deciding Jsc). The basic construction block BTTQ was not only a good acceptor but also a nice weak donor in composing the D–A copolymers for the application in high performance PSCs.

    8. A vinylene-linked benzo[1,2-b:4,5-b']dithiophene-2,1,3-benzothiadiazole low-bandgap polymer (pages 2829–2840)

      Alessandro Abbotto, Mirko Seri, Milind S. Dangate, Filippo De Angelis, Norberto Manfredi, Edoardo Mosconi, Margherita Bolognesi, Riccardo Ruffo, Matteo M. Salamone and Michele Muccini

      Version of Record online: 30 MAR 2012 | DOI: 10.1002/pola.26046

      Thumbnail image of graphical abstract

      A new heteroarylene-vinylene donor–acceptor polymer P(BDT-V-BTD) with reduced bandgap, comprising an unprecedented combination of a strong donor (4,8-dialkoxy-benzo[1,2-b:4,5-b′]dithiophene, BDT), a strong acceptor (2,1,3-benzothiadiazole, BTD), and a vinylene spacer, is presented. The polymer presented an ambipolar character, with energetic values matching materials-design rules for optimized organic photovoltaic devices. The introduction of the vinylene spacer afforded lower bandgaps compared to the analogous system with no spacer between the aromatic rings. Preliminary photovoltaic investigation afforded power conversion efficiencies of 0.74%, higher than those of previous heteroarylene-vinylene polymers.

    9. Synthesis and self-assembly of amphiphilic brush-dendritic-linear poly[poly(ethylene glycol) methyl ether methacrylate]-b- polyamidoamine-b-poly(ε-caprolactone) copolymers (pages 2841–2853)

      Xiaohua He, Liang Zhong, Xiaomeng Wu, Xin Cai, Meiran Xie, Shaoliang Lin and Deyue Yan

      Version of Record online: 9 APR 2012 | DOI: 10.1002/pola.26060

      Thumbnail image of graphical abstract

      A series of novel amphiphilic brush-dendritic-linear poly[poly(ethylene glycol) methyl ether methacrylate]-b-polyamidoamine-b-poly(ε-caprolactone) copolymers (PPEGMEMA-b-Dm-b-PCL) were synthesized by the combination techniques of click chemistry, ATRP, and ROP. The introduction of PPEGMEMA into PCL can lower the crystallinity of PCL, therefore, adjusting the biodegradation rate and mechanical properties of PCL. The brush-dendritic-linear copolymers can also self-assemble into spherical micellar structures in aqueous solution with average diameters of about 500 nm.

    10. White electroluminescent single-polymer achieved by incorporating three polyfluorene blue arms into a star-shaped orange core (pages 2854–2862)

      Lei Chen, Pengcheng Li, Hui Tong, Zhiyuan Xie, Lixiang Wang, Xiabin Jing and Fosong Wang

      Version of Record online: 5 APR 2012 | DOI: 10.1002/pola.26061

      Thumbnail image of graphical abstract

      White light-emitting diodes based on star-like single-polymer systems have been achieved by incorporating three polyfluorene blue arms to a star-shaped orange core, with a luminous efficiency of 16.62 cd A−1 and CIE coordinates of (0.33, 0.36).

    11. Quadruple click reactions for the synthesis of cysteine-terminated linear multiblock copolymers (pages 2863–2870)

      Ozlem Aldas Candan, Hakan Durmaz, Gurkan Hizal and Umit Tunca

      Version of Record online: 16 APR 2012 | DOI: 10.1002/pola.26063

      Thumbnail image of graphical abstract

      Synthesis of cysteine-terminated linear polystyrene-b-poly(ε-caprolactone)-b-poly(methyl methacrylate)/or poly(tert-butyl acrylate)-b-poly(ethylene glycol) copolymers was carried out by using sequential quadruple click reactions including thiol-ene, copper-catalyzed azide–alkyne cycloaddition, Diels–Alder, and nitroxide radical coupling reactions.

    12. Proton-controlled nitroxide mediated radical polymerization of styrene (pages 2871–2877)

      Yann Le Du, Laurent Binet, Patrick Hémery and Lucien Marx

      Version of Record online: 16 APR 2012 | DOI: 10.1002/pola.26064

      Thumbnail image of graphical abstract

      Simply upon protonation of the pyridyl TIPNO-based nitroxide moiety of the alkoxyamine depicted in the figure, it is possible to decrease the rate of polymerization of styrene and to retain a good control over the number average molecular weight and the molecular weight distribution of PS. The dissociation rate constant kd value of this alkoxyamine is also approximately halved at 100 °C in tert-butyl benzene upon protonation. Finally the protonation decreases the thermal stability of the mediating nitroxide at such extent that the polymerization of n-butyl acrylate cannot be controlled.

    13. Modulating structural stability and acid sensitivity of photosensitive polymer micelles simply via one-batch UV irradiation (pages 2878–2888)

      Yufang Tang, Zhilin Liu, Xuewen Wu, Guhuan Liu, Ke Yang, Yaohua Li, Lican Lu and Yuanli Cai

      Version of Record online: 16 APR 2012 | DOI: 10.1002/pola.26065

      Thumbnail image of graphical abstract

      This article describes the photosensitive polymer micelles whose structural stability and acid sensitivity can be widely tuned simply via one-batch UV irradiation. UV irradiation of the homogeneous solution only induced Z-isomerization, while irradiating these photosensitive polymer chains in nanoscale-confined bulky micellar cores with UV light only induced dimerization. More importantly, the micelles of Z-isomerized copolymer were stabilized effectively without changing their acid sensitivity upon UV irradiation for 3 min, while the acid stability of these micelles was remarkably improved on UV irradiation for 30 min.

    14. Preparation and characterization of monodisperse porous silica microspheres with controllable morphology and structure (pages 2889–2897)

      Jie He, Chengli Yang, Xiaohui Xiong and Biwang Jiang

      Version of Record online: 9 APR 2012 | DOI: 10.1002/pola.26066

      Thumbnail image of graphical abstract

      A novel approach to the preparation of monodisperse silica microspheres with a porous inner structure or a hollow-cage structure is reported. This method offers an easy control of final size, structure, and morphology of silica microspheres.

    15. Highly stereoselective coordination polymerization of β-myrcene from a lanthanide-based catalyst: Access to bio-sourced elastomers (pages 2898–2905)

      Saliha Loughmari, Abderrafia Hafid, Aicha Bouazza, Abdelaziz El Bouadili, Philippe Zinck and Marc Visseaux

      Version of Record online: 16 APR 2012 | DOI: 10.1002/pola.26069

      Thumbnail image of graphical abstract

      Polymerization of β-myrcene with neodymium-based coordination catalysts affords highly stereoregular 100% bio-sourced polydiene.

    16. Nanoprecipitation of poly(methyl methacrylate)-based nanoparticles: Effect of the molar mass and polymer behavior (pages 2906–2913)

      Igor Y. Perevyazko, Antje Vollrath, Christian Pietsch, Stephanie Schubert, Georgy M. Pavlov and Ulrich S. Schubert

      Version of Record online: 28 APR 2012 | DOI: 10.1002/pola.26071

      Thumbnail image of graphical abstract

      In this study, the influence of the polymer characteristics (in particular the molar mass), and polymer behavior in an organic phase, on the formation of nanoparticles by the nanoprecipitation process was studied. A series of poly(methyl methacrylate)s with molar masses ranging from Mw = 7,700 to 274,000 g mol-1 were nanoprecipitated. The nanoparticle formulations were examined in terms of particle size and size-distribution, particle shape as well as zeta-potential.

    17. Bis-hydrophilic and functional triblock terpolymers based on polyethers: Synthesis and self-assembly in solution (pages 2914–2923)

      Markus J. Barthel, Krzysztof Babiuch, Tobias Rudolph, Jürgen Vitz, Stephanie Hoeppener, Michael Gottschaldt, Martin D. Hager, Felix H. Schacher and Ulrich S. Schubert

      Version of Record online: 25 APR 2012 | DOI: 10.1002/pola.26072

      Thumbnail image of graphical abstract

      A triblock terpolymer, poly(ethylene glycol)-block-poly(allyl glycidyl ether)-block-poly (tert-butyl glycidyl ether) (PEG-b-PAGE-b-Pt-BGE), was synthesized by living anionic ring-opening polymerization, and the PAGE block was further modified through the covalent attachment of acetylated thiosugars or cysteine by thiol-ene chemistry. The self-assembly in aqueous solution was investigated by a combination of dynamic light scattering, cryo-transmission electron microscopy, and turbidity measurements.

    18. Mechanistic insight into initiation and chain transfer reaction of CO2/cyclohexene oxide copolymerization catalyzed by zinc[BOND]cobalt double metal cyanide complex catalysts (pages 2924–2934)

      Xue-Ke Sun, Xing-Hong Zhang, Ren-Jian Wei, Bin-Yang Du, Qi Wang, Zhi-Qiang Fan and Guo-Rong Qi

      Version of Record online: 21 APR 2012 | DOI: 10.1002/pola.26074

      Thumbnail image of graphical abstract

      This work presented new evidences that CO2/CHO copolymerization was initiated by Zn–OH bond, yielding poly(cyclohexene carbonate) (PCHC) with “pure” [BOND]OH end groups, and short consecutive ether units were capped in the “head” of PCHC and random CHO insertion during propagation could be minimized.

    19. Benzodifuran-containing well-defined π-conjugated polymers for photovoltaic cells (pages 2935–2943)

      Hui Li, Peng Tang, Yan Zhao, Shi-Xia Liu, Yves Aeschi, Lijun Deng, Jörg Braun, Bin Zhao, Yunqi Liu, Songting Tan, Wolfgang Meier and Silvio Decurtins

      Version of Record online: 16 APR 2012 | DOI: 10.1002/pola.26075

      Thumbnail image of graphical abstract

      Two alternating π-conjugated copolymers containing a soluble electroactive benzodifuran chromophore were synthesized and investigated for photovoltaic application. Their optical, electrochemical, and field-effect charge transport properties were characterized and compared with those of the corresponding homopolymer and random counterparts.

    20. Synthesis of NMP/RAFT inifers and preparation of block copolymers (pages 2944–2956)

      Claude St. Thomas, Hortensia Maldonado-Textle, Antal Rockenbauer, Laszlo Korecz, Nora Nagy and Ramiro Guerrero-Santos

      Version of Record online: 25 APR 2012 | DOI: 10.1002/pola.26081

      Thumbnail image of graphical abstract

      Two different inifers containing an alkoxyamine and a dithiobenzoate were synthesized and used to trigger out a reversible addition-fragmentation chain transfer (RAFT) polymerization or a nitroxyde-mediated polymerization (NMP). In both cases, a α-dithiobenzoate-ω-alkoxyamine-difunctional polymer was produced which was subsequently used as precursor in the formation of block copolymers either by RAFT or NMP. Amphiphilic block copolymers composed of N-isopropylacrylamide or polyethylene oxide methacrylate were prepared starting with a RAFT polymerization to form a α,ω-heterodifunctional homopolymer, which were chain extended with styrene by activating the alkoxyamine moiety. Self-assembled nanostructures of these block copolymers were evidenced by scanning electron microscopy.

    21. Surface promoted redox cationic polymerization of epoxy monomers catalyzed by silver salts (pages 2957–2966)

      David J. Farrell, Ciaran McArdle, Michael Doherty and John M. Kelly

      Version of Record online: 25 APR 2012 | DOI: 10.1002/pola.26082

      Thumbnail image of graphical abstract

      A new approach to the surface promoted redox cationic polymerization of epoxy monomers based on the direct reduction of silver salts of non-nucleophilic anions by metallic substrates was investigated. All surface promoted polymerizations were followed using FTIR-attenuated total reflectance. Ag(I) surface promoted redox cationic polymerization was shown to have the general performance and storage stability of typical redox anaerobic acrylate adhesives, in addition to thermal properties particular to polyethers.

    22. Combination of nitroxide-mediated polymerization and SET-LRP for the synthesis of high molar mass branched and star-branched poly(n-butyl acrylate) characterized by size exclusion chromatography and rheology (pages 2967–2979)

      Sabrina Paillet, Armelle Roncin, Gérald Clisson, Gaëlle Pembouong, Laurent Billon, Christophe Derail and Maud Save

      Version of Record online: 6 MAY 2012 | DOI: 10.1002/pola.26085

      Thumbnail image of graphical abstract

      Monofunctional or trifunctional alkoxyamine were used as initiators for the synthesis of high molar mass branched and star-branched poly(n-butyl) acrylate by nitroxide-mediated copolymerization of nBA and 2-(2-bromoisobutyryloxy) ethyl acrylate. The later incorporated monomer played the role of initiator for subsequent SET-LRP of nBA to create the polymer branches. Kinetics and molar mass evolutions showed the level of the polymerization control. Detailed structural analysis of the resulting linear and branched polymers was performed by size exclusion chromatography and rheology.

SEARCH

SEARCH BY CITATION