Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 52 Issue 10

15 May 2014

Volume 52, Issue 10

Pages i–iv, 1369–1507

  1. Cover Image

    1. Top of page
    2. Cover Image
    3. Rapid Communications
    4. Articles
    1. You have free access to this content
      Cover Image, Volume 52, Issue 10 (pages i–ii)

      Article first published online: 3 APR 2014 | DOI: 10.1002/pola.27178

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      The Friedel–Crafts sulfonylation reaction was the inspiration for the strategy of sulfonating polyarylenes for future proton exchange membranes (PEM) for fuel cells, as presented by Stephen M. Budy and Douglas A. Loy on page 1381 (DOI: 10.1002/pola.27139). This approach involves treating dilute solutions of polyarylenes with 1,3,5-benzenetrisulfonyl chloride and Lewis acids to attach pendant aryl groups with multiple sulfonic acid groups. Since the relative positions of the sulfonic acid groups are already established in the benzene ring in the reagent, attention can be directed to the regiochemistry of the sulfonations along the polymeric chain and their contributions, if any, from cross-linking. Near quantitative addition is demonstrated for one and two equivalents of sulfonated polyarylenes, affording high proton conductivity, chemical and thermal stability, and robust films.

    2. You have free access to this content
      Cover Image, Volume 52, Issue 10 (pages iii–iv)

      Article first published online: 3 APR 2014 | DOI: 10.1002/pola.27179

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      Hydrocarbon polymeric materials are important as engineering plastics because of characteristic properties such as high transparency, thermostability, chemical resistance, and low moisture absorbency. On page 1392 (DOI: 10.1002/pola.27133), Masashi Shiotsuki and Takeshi Endo report a novel hydrocarbon polymer, its hydrogenation, and optical properties including stimuli responsible fluorescence. An eight-membered cyclic monomer bearing a dibenzobicyclic moiety is polymerized via Ru-catalyzed ring-opening metathesis to afford high polymers. Hydrogenation quantitatively proceeds with a homogeneous transition metal catalyst under a H2 atmosphere. Mechanical grinding of the polymers induces the formation of anthracene in a solid state, transforming the polymers into blue-luminescent materials under UV irradiation.

  2. Rapid Communications

    1. Top of page
    2. Cover Image
    3. Rapid Communications
    4. Articles
    1. A convenient approach to amphiphilic hyperbranched polymers with thioether shell for the preparation and stabilization of coinage metal (Cu, Ag, Au) nanoparticles (pages 1369–1375)

      Sunny Skaria, Ralf Thomann, Carlos J. Gómez-Garcia, Luc Vanmaele, Johan Loccufier, Holger Frey and Salah-Eddine Stiriba

      Article first published online: 5 MAR 2014 | DOI: 10.1002/pola.27134

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      Partially functionalized hyperbranched polyglycerols with thioether units have been straight forwardly prepared, leading to globular polymers with core-shell structure. They are been used as an excellent platform for the preparation and stabilization of long-term stable coinage metal nanoparticles such as copper (less than 4 nm) and silver (1 to 2 nm) nanoclusters, as well as aggregated gold nanoparticles (12 nm).

    2. Preparation of self-doped conducting polycyclopentadithiophene and its incorporation into silica (pages 1376–1380)

      Nobuaki Kumazawa, Makoto Towartari, Takahiro Uno, Takahito Itoh and Masataka Kubo

      Article first published online: 3 MAR 2014 | DOI: 10.1002/pola.27137

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      A novel water-soluble intrinsically conducting polymer was prepared. Sol-gel-reaction of tetraethoxysilane was carried out in the presence of the self-doped polymer to obtain organic/inorganic hybrid conducting material. Incorporation of electrically conducting polymer into silica is considered to be an effective methodology to improve environmental and mechanical stability. Such hybrid-conducting materials should be interesting candidates for touch panel screens, sensors, antistatic coatings, and transparent conductive films.

    3. Spotlight Article

      Highly sulfonated polyelectrolytes through friedel–crafts sulfonylation of polyarylenes (pages 1381–1384)

      Stephen M. Budy and Douglas A. Loy

      Article first published online: 6 MAR 2014 | DOI: 10.1002/pola.27139

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      Friedel–Craft sulfonylation of polyarylenes with 1,3,5-benzenetrisulfonylchloride has been demonstrated to yield soluble and processable, highly sulfonated polyarylenes (IEC 1.9-2.9 milliequivalents/gram) that do not swell in water and are stable to 280 °C. The new method provides an alternative, more efficient approach to sulfonating aromatic polymers.

  3. Articles

    1. Top of page
    2. Cover Image
    3. Rapid Communications
    4. Articles
    1. Optimization of an α-(Amino acid)-N-carboxyanhydride polymerization using the high vacuum technique: Examining the effects of monomer concentration, polymerization kinetics, polymer molecular weight, and monomer purity (pages 1385–1391)

      Robert A. Kowtoniuk, Tao Pei, Caitlin M. DeAngelo, Jacob H. Waldman, Erin N. Guidry, J. Michael Williams, Robert M. Garbaccio and Stephanie E. Barrett

      Article first published online: 5 MAR 2014 | DOI: 10.1002/pola.27132

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      The use of poly(peptides) containing l-ornithine in drug delivery is known, however, few studies have been conducted looking at the details of polymerization. The effects of monomer concentration, polymerization kinetics, polymer molecular weight, and monomer purity are investigated using l-carboxybenzyl-ornithine as a model monomer. l-ornithine is chosen due to its ability to be further functionalized which makes it an ideal monomer for drug delivery applications where post-polymerization chemistry is desired.

    2. Synthesis of hydrocarbon polymers containing bulky dibenzobicyclic moiety by ROMP and their characteristic optical properties (pages 1392–1400)

      Masashi Shiotsuki and Takeshi Endo

      Article first published online: 8 MAR 2014 | DOI: 10.1002/pola.27133

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      The eight-membered cyclic monomer bearing a dibenzobicyclic moiety was polymerized via Ru-catalyzed ring-opening metathesis (ROMP) to afford high polymers. Hydrogenation of the obtained polymer quantitatively proceeded with a homogeneous transition metal catalyst under H2 atmosphere. Self-standing membranes of the nonhydrogenated and hydrogenated polymers showed high transparency in the region greater than 300 nm. Mechanical grinding of the polymers induced the formation of anthracene in the solid state, transforming the polymers into blue-luminescent materials under UV irradiation.

    3. Two-Step direct arylation for synthesis of naphthalenediimide-based conjugated polymer (pages 1401–1407)

      Yuta Nohara, Junpei Kuwabara, Takeshi Yasuda, Liyuan Han and Takaki Kanbara

      Article first published online: 5 MAR 2014 | DOI: 10.1002/pola.27140

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      A two-step direct arylation reaction of ethylenedioxythiophene gives a naphthlaenediimide-based conjugated polymer, which is ordinarily difficult to synthesize by direct arylation. The physical properties of the obtained polymer are characterized and the polymer shows an ambipolar property in OFET.

    4. Synthesis, characterization, and properties of hydroxyl-terminated copolysiloxanes containing γ-cyanopropyl groups (pages 1408–1421)

      Tao Hu, Lina Dai, Xiyin Gao, Jiang Xie, Wenchun Xie, Zemin Xie and Zhijie Zhang

      Article first published online: 19 FEB 2014 | DOI: 10.1002/pola.27126

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      Copolysiloxanes containing both cyanopropyl-methylsiloxane and dimethylsiloxane units were synthesized via ring-opening polymerization. Structures and properties were investigated and correlations between them were discussed. With the random incorporation of cyanopropyl group, crystallization of the polymer was inhibited and high temperature stability was increased. Meanwhile, the damping properties as well as the fuel resistant properties were greatly improved. All these properties changed continuously with the gradual increase of cyanopropyl group content.

    5. Synthesis and characterization of iPP-sPP stereoblock produced by a binary metallocene system (pages 1422–1434)

      Camille Descour, Tibor Macko, Dario Cavallo, Matthew Parkinson, Gerhard Hubner, Anne Spoelstra, Maurizio Villani and Robbert Duchateau

      Article first published online: 13 MAR 2014 | DOI: 10.1002/pola.27127

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      Two metallocene catalysts of different symmetry, producing either isotactic or syndiotactic polypropylene chains, are mixed in the presence of aluminum and zinc alkyls. A careful microstructure elucidation is carried out to prove the formation of stereoblocks, comprising of both isotactic polypropylene (iPP) and syndiotactic polypropylene (sPP) moieties on the same polymer chains.

    6. Nanocomposites based on crosslinked polyacrylic latex/silver nanoparticles for waterborne high-performance antibacterial coatings (pages 1435–1447)

      Onur Yilmaz, Mikko Karesoja, A. Candas Adiguzel, Gokhan Zengin and Heikki Tenhu

      Article first published online: 26 FEB 2014 | DOI: 10.1002/pola.27130

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      A novel way to prepare ductile functional coating materials has been developed. Silver nanoparticles covalently attached to a low molecular weight PAAm via thiol groups have been synthesized. They are used to crosslink a pre-synthesized P(BA-co-MMA)-core / PGMA-shell acrylic copolymer latex to produce functional nanocomposite coatings. The nanocomposite films show good antibacterial properties with a retarded release of silver as well as significantly increased mechanical strength.

    7. Thiol-functionalized 1,3-benzoxazine: Preparation and its use as a precursor for highly polymerizable benzoxazine monomers bearing sulfide moiety (pages 1448–1457)

      Asei W. Kawaguchi, Atsushi Sudo and Takeshi Endo

      Article first published online: 27 FEB 2014 | DOI: 10.1002/pola.27131

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      A thiol-functionalized benzoxazine has been prepared from a bi-functional benzoxazine bearing disulfide linkage through reductive scission and used as a precursor for novel functional benzoxazines that exhibited much higher polymerizability than conventional benzoxazines.

    8. Spotlight Article

      Synthesis of poly(4-hydroxystyrene)-based block copolymers containing acid-sensitive blocks by living anionic polymerization (pages 1458–1468)

      Daniel P. Sweat, Xiang Yu, Myungwoong Kim and Padma Gopalan

      Article first published online: 5 MAR 2014 | DOI: 10.1002/pola.27138

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      Anionic polymerization of an acetal protected 4-hydroxystyrene monomer, 4-(2-tetrahydropyranyloxy)styrene, along with the synthesis of block copolymers is demonstrated. The monomer is synthesized in a high yield and with a high degree of purity to allow well-controlled anionic polymerization. Mild deprotection using a catalytic amount of acid allows the incorporation of PDMS and P(MAPOSS) blocks to yield PHS based block copolymers. Thus, P(HS-b-DMS) and P(HS-b-MAPOSS) are successfully synthesized for the first time by sequential living anionic polymerization.

    9. Functional aramids: Aromatic polyamides with reactive azido and amino groups in the pendant structure (pages 1469–1477)

      Miriam Trigo-López, Jesús Luis Pablos, Félix Clemente García, Felipe Serna and José Miguel García

      Article first published online: 5 MAR 2014 | DOI: 10.1002/pola.27141

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      Functional aromatic copolyamides with pendant azide and primary amine groups are presented as easily derivatizable parent copolymers, producing high-performance materials with a number of functional groups with a la carte properties.

    10. Construction of PIB-b-PDEAEMA well-defined amphiphilic diblock copolymers via sequential living carbocationic and RAFT polymerization (pages 1478–1486)

      Chunhong Ren, Xue Jiang, Guolin Lu, Xiuyu Jiang and Xiaoyu Huang

      Article first published online: 9 MAR 2014 | DOI: 10.1002/pola.27142

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      The synthesis of polyisobutylene-b-poly(2-(diethylamino)ethyl methacrylate) well-defined amphiphilic pH-responsive diblock copolymers via the combination of living carbocationic polymerization and RAFT polymerization is reported.

    11. Spotlight Article

      Conjugated polymers for the fluorescent detection of nitroaromatics: Influence of side-chain sterics and π-system electronics (pages 1487–1492)

      Tyler L. Duniho, Brynna J. Laughlin, Ashley A. Buelt, William F. Baker, Catherine A. Conrad and Rhett C. Smith

      Article first published online: 6 MAR 2014 | DOI: 10.1002/pola.27143

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      The current study was undertaken with the aim of determining the relationship between a luminescent polymer structure and its ability to detect nitroaromatic explosives such as TNT. Eight new polymers were studied and compared with data from prior studies.

    12. Effect of tetra-n-butylammonium bromide salt on the cationic polymerization of dimethylketene and on the thermal properties of the obtained polyketones (pages 1493–1499)

      Hanbin Wang, Nicolas Desilles and Fabrice Burel

      Article first published online: 17 MAR 2014 | DOI: 10.1002/pola.27144

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      Aliphatic polyketones are a family of specialty polymers that exhibit a unique combination of mechanical, high temperature, chemical resistance, and barrier properties. An original way to synthesize these polymers lies in the cationic polymerization of ketenes, such as dimethylketene. Since several properties of the obtained polyketones depends on the chain length, herein the effect of a salt, n-tetrabutylammonium bromide, on the control of the cationic polymerization of dimethylketene is presented.

    13. Semiconductor nanoparticles for photoinitiation of free radical polymerization in aqueous and organic media (pages 1500–1507)

      Sajjad Dadashi-Silab, Abdullah Mohamed Asiri, Sher Bahadar Khan, Khalid A. Alamry and Yusuf Yagci

      Article first published online: 21 MAR 2014 | DOI: 10.1002/pola.27145

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      Semiconductor nanoparticles are reported to initiate free radical polymerization of vinyl monomers under UV light irradiation. Zinc oxide and iron-doped zinc oxide nanoparticles are shown to successfully initiate the free radical polymerization of acrylamide and methyl methacrylate in aqueous and organic media, respectively. The process is achieved by combination of different coinitiators. After the polymerization, the nanoparticles can be easily separated from the polymer mixture and reused for further polymerizations with no decreasing in the photocatalytic activity.

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