Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 49 Issue 3

1 February 2011

Volume 49, Issue 3

Pages 551–819

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      Building nanostructures using RAFT polymerization (pages 551–595)

      Cyrille Boyer, Martina H. Stenzel and Thomas P. Davis

      Version of Record online: 8 DEC 2010 | DOI: 10.1002/pola.24482

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      This highlight, with more 650 references, present a general update of the Reversible Addition Fragmentation Chain Transfer (RAFT) to build complex architectures, such as micelles, nanoparticles, star polymers. Nanostructured surfaces have been also described using the self-organization of polymer films or by the utilization of polymer brushes.

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    1. Synthesis of amphiphilic polyacetal by polycondensation of aldehyde and polyethylene glycol as an acid-labile polymer for controlled release of aldehyde (pages 596–602)

      Yanmei Wang, Hisatoyo Morinaga, Atsushi Sudo and Takeshi Endo

      Version of Record online: 16 DEC 2010 | DOI: 10.1002/pola.24425

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      A new linear acid-labile polyacetal synthesized by polycondensation of hydrophilic poly(ethylene glycol) (PEG) and hydrophobic aldehyde exhibited amphiphilicity. The acetal linkages in the main chain were hydrolyzed under mild acid conditions to release hydrophobic aldehyde. The release rate of aldehyde can be controlled by the chain length of PEG.

    2. New carbazole-based conjugated polymers containing pyridylvinyl thiophene units for polymer solar cell applications: Morphological stabilization through hydrogen bonding (pages 603–611)

      So-Lin Hsu, Chia-Min Chen, Yu-Hsin Cheng and Kung-Hwa Wei

      Version of Record online: 2 DEC 2010 | DOI: 10.1002/pola.24465

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      We have synthesized two conjugated polymers (P1, P2) containing alternating electron-donating (N-alkyl-2,7-carbazole) and -accepting [4,7-di(thiophen-5-yl)-2,1,3-benzothiadiazole] units and featuring various amounts of 3-[2-(4-pyridyl)vinyl]thiophene units. The presence of hydrogen bonds between the pyridyl groups and added [6,6]-phenyl-C61-butyric acid provided bulk heterojunction of thin films with a more stable morphology and photovoltaic properties after annealing for 5 h relative to those of the analogous system lacking such hydrogen bonding.

    3. Degradable multisegmented polymers synthesized by consecutive radical addition-coupling reaction of α,ω-macrobiradicals and nitroso compound (pages 612–618)

      Chengyu Zhang and Qi Wang

      Version of Record online: 2 DEC 2010 | DOI: 10.1002/pola.24469

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      Different multisegmented polymers have been prepared from α,ω-dibromo-polystyrene, poly(t-butyl acrylate), and poly(t-butyl acrylate-b-styrene-b-t-butyl acrylate). The multisegmented polymer can be degraded in the presence of hydrogen atom donor or air, and the molecular weight distribution transformed back into shape of its original precursor as it is conjugated by alkoxyamine moieties.

    4. Anionic alternating copolymerization of epoxide and six-membered lactone bearing naphthyl moiety (pages 619–624)

      Atsushi Sudo, Yuan Zhang and Takeshi Endo

      Version of Record online: 7 DEC 2010 | DOI: 10.1002/pola.24470

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      A six-membered aromatic lactone, which was derived from 2-naphthol, was exploited as a comonomer for its anionic alternating copolymerization with epoxide. The copolymerization allowed successful introduction of the lactone-derived naphthalene moieties into the main chain to afford the corresponding copolymer with a higher glass transition temperature than that of the copolymer obtained by using an analogous monomer, 3,4-dihydrocoumarin.

    5. Crown-ether and azobenzene-containing liquid crystalline polymers: An influence of macromolecular architecture on optical properties and photo-orientation processes (pages 625–633)

      Alexander Ryabchun, Alexey Bobrovsky, Alexey Medvedev and Valery Shibaev

      Version of Record online: 8 DEC 2010 | DOI: 10.1002/pola.24472

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      A series of novel crown ether-containing photochromic comb-shaped liquid crystalline polyacrylates with different macromolecular structure of side groups was synthesized and investigated. Phase behavior, optical and photo-optical properties of thin spin-coated films of these polymers were studied. A special attention was paid to a comparative study of the photo-orientation phenomena occurring in the polymer films under polarized light action. It was shown that complex formation with potassium ions results in the decrease in the degree of the photoinduced order that can be used for the creation of new materials for sensor devices.

    6. Waterborne polyurethane nanocomposites having shape memory effects (pages 634–641)

      Soo Kyung Lee, Sung Ho Yoon, Ildoo Chung, Andreas Hartwig and Byung Kyu Kim

      Version of Record online: 2 DEC 2010 | DOI: 10.1002/pola.24473

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      The incorporation of functionalized silica particles into the polymer chains by covalent bonding as multifunctional cross-links provided the waterborne polyurethane with over 99% shape fixity and shape recovery for the repeated cycles along with excellent mechanical properties. The maximum reinforcement and shape memory performance were obtained with 1% silica.

    7. Pd(0)-catalyzed polycondensation of aryl-substituted propargylic carbonates with bifunctional nucleophiles promoted by aryl group on the acetylenic terminal carbon (pages 642–649)

      Noriyuki Nishioka and Toshio Koizumi

      Version of Record online: 7 DEC 2010 | DOI: 10.1002/pola.24475

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      A Pd(0)-catalyzed polycondensation of bifunctional nucleophiles and propargylic carbonates having an aryl group was investigated. The aryl group on the acetylenic terminal carbon remarkably promoted the formation of high molecular weight polymers.

    8. Vinylcarbonates and vinylcarbamates: Biocompatible monomers for radical photopolymerization (pages 650–661)

      Christian Heller, Martin Schwentenwein, Günter Russmüller, Thomas Koch, Doris Moser, Christian Schopper, Franz Varga, Jürgen Stampfl and Robert Liska

      Version of Record online: 2 DEC 2010 | DOI: 10.1002/pola.24476

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      The fabrication of 3D scaffolds by lithography-based additive manufacturing technology (AMT) represents an appealing approach for tissue engineering. As meth)acrylates have some serious limitations for biomedical applications we have developed new photopolymers based on vinyl carbonates and –carbamates. The new generation of biocompatible monomers show low cytotoxicity, are sufficiently photoreactive and rates of degradation of the polymers can be easily tuned. Beside non-acidic and non-toxic degradation products of low molecular weight, initial in vivo experiments were carried out successfully.

    9. New conjugated copolymers based on benzo[1,2-b; 3,4-b′]dithiophene and derivatives of benzo[g]quinoxaline for bulk heterojunction solar cells (pages 662–670)

      Po-I Lee, Steve Lien-Chung Hsu, Jung Feng Lee, Hung-Yi Chuang and Piyun Lin

      Version of Record online: 2 DEC 2010 | DOI: 10.1002/pola.24477

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      A series of new low-band gap copolymers based on dioctyloxybenzo[1,2-b;3,4-b′′] dithiophene and bis(2-thienyl)-2,3-bis-(4-phenyl)benzo[g]quinoxaline monomers have been synthesized via a Stille reaction. The best performance of the photovoltaic device was obtained by using PbttpmobQ as the active layer with power conversion efficiency (PCE) of 1.42%.

    10. Kinetic analyses of disulfide formation between thiol groups attached to linear poly(acrylamide) (pages 671–679)

      Nobuharu Hisano, Hiroo Iwata, Yuji Teramura, Hao Chen and Yoshito Ikada

      Version of Record online: 2 DEC 2010 | DOI: 10.1002/pola.24478

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      Hydrogels have been used for biomedical devices and scaffolds in tissue engineering. However, chemical reactions, however, employused to prepare hydrogels have destructive effects on living cells. In this study, kinetic analyses were carried out for formation of disulfide cross-linkages by auto-oxidation or through the thiol-disulfide exchange reaction induced by addition of gluthathione. We found that the thiol-disulfide exchange reaction is suitable for the cell encapsulation than the thiol auto-oxidation.

    11. Synthesis and chiroptical properties of chiral binaphthyl-containing polyfluorene derivatives (pages 680–689)

      Zi-Tong Liu, Yi-Yong Huang, Yong Li, Yan-Mei He and Qing-Hua Fan

      Version of Record online: 7 DEC 2010 | DOI: 10.1002/pola.24479

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      New kind of chiral polyfluorene derivatives bearing different binaphthyl units in the polymer backbone were synthesized through Suzuki polycondensation in hope of combining the desirable chiral and physical properties of binaphthyl unit into polyfluorene. All the copolymers exhibit good photophysical performances and obvious the linearly polarized photoluminescent properties, especially, for the phosphine oxide-containing copolymers, which exhibited high-quantum yields both in solutions and films, stable polarized photoluminescent properties, and excellent thermal stability.

    12. Thermo- and pH-responsive gradient and block copolymers based on 2-(2-methoxyethoxy)ethyl methacrylate synthesized via atom transfer radical polymerization and the formation of thermoresponsive surfaces (pages 690–700)

      Sandra Medel, José Manuel García, Leoncio Garrido, Isabel Quijada-Garrido and Rodrigo París

      Version of Record online: 8 DEC 2010 | DOI: 10.1002/pola.24480

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      Several thermoresponsive polymers based on 2-(2-methoxyethoxy)ethyl methacrylate and decorated with ionizable carboxylic acid groups (gradient and block copolymers) have been synthesized via atom transfer radical polymerization in a controlled way. Their thermal properties in aqueous solution have been studied, observing that they showed lower critical solution temperature values dependent on pH, monomeric distribution, and composition. Moreover and due to their carboxylic acid functionalization, they were successfully bound to biocompatible and biodegradable films of poly(3-hydroxybutyrate-co-3-hydroxyhexanoate), obtaining thermosensitive surfaces in which the hydrophilicity is function of the temperature.

    13. Benzo[2,1-b;3,4-b′]dithiophene-based low-bandgap polymers for photovoltaic applications (pages 701–711)

      Mingjian Yuan, Andrew H. Rice and Christine K. Luscombe

      Version of Record online: 3 DEC 2010 | DOI: 10.1002/pola.24481

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      The synthesis of four alternating copolymers using benzo[2,1-b;3,4-b′]dithiophene (BDP) as the common donor unit is presented. Before the synthesis, theoretical calculations predicted that the incorporation of BDP, which consists of fused dithiophene units with a benzene ring, into these polymers would produce a low-lying highest occupied molecular orbital (HOMO) energy level. Low-lying HOMO levels are desirable to produce high open circuit voltages in organic bulk heterojunction (BHJ) photovoltaic devices. As a result, high open circuit voltage values of 0.81 and 0.82 V were obtained from two polymers: PBDPBT and PBDPDPP. In initial investigations, the highest power conversion efficiency achieved was 1.11% for PBDPBT because of low short-circuit current densities.

    14. Incorporation of titanium dioxide particles into polymer matrix using block copolymer micelles for fabrication of high refractive and transparent organic–inorganic hybrid materials (pages 712–718)

      Shuhei Yamada, Emiko Mouri and Kohji Yoshinaga

      Version of Record online: 3 DEC 2010 | DOI: 10.1002/pola.24483

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      We have developed synthesis of TiO2 particles within hydrophilic core, formed from poly(methyl methacrylate-block-acrylic acid) (PMMA-b-PAA) in toluene, via sol–gel process using titanium isopropoxide and then incorporation of TiO2 particles into PMMA matrix. Figures represent photographs of polymer micelles loaded with TiO2 precursors (a), and plots of TiO2 content versus refractive index and transmittance of TiO2/PMMA hybrid films at 500 nm (b).

    15. Adjusting conformational switching behavior of helical polycarbodiimides through substituent induced polarity effects (pages 719–728)

      Justin G. Kennemur, Chris A. Kilgore and Bruce M. Novak

      Version of Record online: 3 DEC 2010 | DOI: 10.1002/pola.24484

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      The ability for a select series of helical polycarbodiimides to undergo dramatic changes in chiro-optical activity is shown to be highly dependant upon the electronic nature of the polyarene pendant groups which span outward from the helical backbone scaffolding and create a secondary layer of constricted conformational chirality. Through substituent effects on these pendant groups, it is shown that the energy associated with these conformational changes highly deviate with respect to solvent and the chosen substituent. These low energy changes occur reversibly without the use of external chiral stimulant and without helical inversions or aggregation of polymer chains.

    16. Benzotriazole derivatives as long wavelength photosensitizers for diaryliodonium salt initiators (pages 729–733)

      Umut Bulut, Abidin Balan and Cagin Caliskan

      Version of Record online: 3 DEC 2010 | DOI: 10.1002/pola.24485

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      BEBT and HTBT are efficient electron transfer photosensitizers for diaryliodonium salt photoinitiators. Since they possess strong absorption bands between 340 and 460 nm, it was possible to carry out the photoinitiated cationic polymerization of epoxides and vinyl ethers using long wavelength UV and visible light as well as solar irradiation. Furthermore, alkyl substituents impart higher solubility in a variety of cationically polymerizable monomers.

    17. Copoly(arylene ether nitrile) and copoly(arylene ether sulfone) ionomers with pendant sulfobenzoyl groups for proton conducting fuel cell membranes (pages 734–745)

      Elin Persson Jutemar and Patric Jannasch

      Version of Record online: 3 DEC 2010 | DOI: 10.1002/pola.24486

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      Fully aromatic ionomers with naphthalene moieties and pendant sulfobenzoyl side chains were prepared via polycondensations involving 2,6-difluoro-2′-sulfobenzophenone and various comonomers. Mechanically strong proton-exchange membranes based on the copolymers showed high degradation temperatures and high glass transition temperatures. The membranes also reached high proton conductivities, above 0.3 S cm−1, under fully humidified conditions. At ion-exchange capacities above ∼1.6 meq g−1, the copolymer membranes reached higher proton conductivities than Nafion® in the range between −20 and 120 °C.

    18. Syntheses of 3-arm and 4-arm star-branched polystyrene Ru(II) complexes by the click-to-chelate approach (pages 746–753)

      Chunhong Zhang, Xiande Shen, Ryosuke Sakai, Michael Gottschaldt, Ulrich S. Schubert, Shiho Hirohara, Masao Tanihara, Shigenobu Yano, Makoto Obata, Nao Xiao, Toshifumi Satoh and Toyoji Kakuchi

      Version of Record online: 3 DEC 2010 | DOI: 10.1002/pola.24487

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      3-Arm and 4-arm star branched polystyrene Ru(II) complexes were successfully prepared by means of ATRP technique followed by azide substitution and click-to-chelate approach. The resulting polymer architectures were established by analytical techniques of polymer chemistry and coordination chemistry as well.

    19. Poly(ε-caprolactone)-based shape memory polymers with variable polydimethylsiloxane soft segment lengths (pages 754–761)

      Dawei Zhang, Melissa L. Giese, Stacy L. Prukop and Melissa A. Grunlan

      Version of Record online: 16 DEC 2010 | DOI: 10.1002/pola.24488

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      Inorganic-organic hybrid shape memory polymers (SMPs) comprised of polydimethylsiloxane (PDMS) soft segments and poly(ε-caprolactone) (PCL) switching segments were prepared by photochemical cure of diacrylated AcO-PCL40-block-PDMSm-block-PCL40-OAc (m = 20, 37, 66, and 130). By altering the PDMS segment length, SMPs with excellent shape memory properties and tunable mechanical properties were produced.

    20. Highly fluorinated low-molecular-weight photoresists for optical waveguides (pages 762–769)

      Ying Wan, Xu Fei, Zuosen Shi, Juan Hu, Xiaolong Zhang, Lisha Zhao, Changming Chen, Zhanchen Cui and Daming Zhang

      Version of Record online: 7 DEC 2010 | DOI: 10.1002/pola.24489

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      The highly fluorinated low-molecular-weight polymers displayed excellent thermal stability, good film-forming properties and tunable refractive indicates. The film which was made by spinning coated the highly fluorinated photoresist had good UV lithography sensitivity. Obtained low-loss optical waveguides with very smooth surface exhibited low propagation loss at 1550 nm (0.25 dB/cm).

    21. Optical properties of chiral nematic side-chain copolymers bearing cholesteryl and azobenzene building blocks (pages 770–780)

      Jui-Hsiang Liu, Yen-Ling Chou, Rathinam Balamurugan, Kai-Hsin Tien, Wen-Tung Chuang and Ming-Zu Wu

      Version of Record online: 7 DEC 2010 | DOI: 10.1002/pola.24490

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      Thermotropic chiral nematic (N*) copolymers were synthesized using nematic, chiral, and photochromic units as building blocks to investigate their structure–property relationships. The thermal and optical properties of the copolymers were studied with respect to type and content (feed ratio) of the functional monomers. On cooling from an isotropic melt, the N* copolymers exhibited a selective reflection of visible light that changed from short to long wavelengths.

    22. Grafting of functional nitroxyl free radicals to polyolefins as a tool to postreactor modification of polyethylene-based materials with control of macromolecular architecture (pages 781–795)

      Francesca Cicogna, Serena Coiai, Elisa Passaglia, Irene Tucci, Lucia Ricci, Francesco Ciardelli and Antonio Batistini

      Version of Record online: 8 DEC 2010 | DOI: 10.1002/pola.24493

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      The stoichiometric functionalization post reactor modification of a polyethylene based polymer with TEMPO derivatives was achieved under free radical conditions in the melt at 190 or 170 °C. Varying the reaction conditions, the functionalization was carried out with a very good control of the macromolecular architecture with minor modification of both Mn and Mw. The maximum conversion of the nitroxides was reached during the first minutes of reaction before the increase of melt viscosity thus suggesting that the macroradical cross-coupling can be avoided.

    23. Synthesis and characterization of new copolyacrylates containing porphyrin units as pendant groups and their use as sensors (pages 796–802)

      S. Dattilo, P. Mineo, E. Scamporrino, E. Spina and D. Vitalini

      Version of Record online: 8 DEC 2010 | DOI: 10.1002/pola.24494

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      Some copolyacrylates, containing porphyrin units as pendant groups, are able to detect the presence of traces of acid vapors or NO2 (a gas which may be associated with certain kind of explosives) by changing immediately their UV–vis spectra in a reproducible and reversible way.

    24. Block copolymers via macromercaptan initiated ring opening polymerization (pages 803–813)

      Catherine Lefay, David Glé, Marion Rollet, Jérôme Mazzolini, Denis Bertin, Stéphane Viel, Christina Schmid, Christophe Boisson, Franck D'Agosto, Didier Gigmes and Christopher Barner-Kowollik

      Version of Record online: 8 DEC 2010 | DOI: 10.1002/pola.24496

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      Macromercaptanes derived from thiocarbonyl thio capped precursor polymers prepared via the RAFT process can be employed in ring opening polymerizations to allow for a switch of the polymerization mechanism forming polymers with degradable and non-degradable strands.

    25. Rapid synthesis of block and cyclic copolymers via click chemistry in the presence of copper nanoparticles (pages 814–819)

      Eric D. Pressly, Roey J. Amir and Craig J. Hawker

      Version of Record online: 8 DEC 2010 | DOI: 10.1002/pola.24504

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      A new method for the rapid and efficient coupling of polymers to yield block and cyclic copolymers using the 3 + 2 π Huisgen copper catalyzed cyclo-addition reaction has been developed using commercially available Cu nanoparticles that are tolerant to O2, easily removable and recyclable.