Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 52 Issue 16

15 August 2014

Volume 52, Issue 16

Pages i–iv, 2239–2393

  1. Cover Image

    1. Top of page
    2. Cover Image
    3. Articles
    1. You have free access to this content
      Cover Image, Volume 52, Issue 16 (pages i–ii)

      Article first published online: 4 JUL 2014 | DOI: 10.1002/pola.27293

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      On page 2279 (DOI: 10.1002/pola.27246), Ruairí P. Brannigan, Anthony Walder, and Andrew P. Dove report that the organocatalytic ring-opening polymerization of 9-phenyl-2,4,8,10-tetraoxaspiro[5,5]undecanone from an α,ω-dihydroxy poly(caprolactone) (PCL) macroinitiator yields a thermoplastic material with superior tensile and altered crystallization properties compared to that of the PCL homopolymer.

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      Cover Image, Volume 52, Issue 16 (pages iii–iv)

      Article first published online: 4 JUL 2014 | DOI: 10.1002/pola.27294

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      The ligands of nickel catalysts are optimized to establish a living system of “Negishi-type catalyst-transfer polycondensation” (NCTP). Eisuke Goto, Saki Nakamura, Susumu Kawauchi, Hideharu Mori, Mitsuru Ueda, and Tomoya Higashihara report on page 2287 (DOI: 10.1002/pola.27243) on the use of a zincate complex as a synthetic method for well-defined poly(3-hexylthiophene) (P3HT) with predictable molecular weight and low dispersity (Đ). The ligand of 1,2-bis(dicyclohexylphosphino)ethane produce P3HTs with highly controlled number average molecular weights (1650–32,800) and very low -D values (1.03–1.17). The synthesis of P3HT-b-poly(3-octadecylthiophene) is the first demonstration of block copolymerization by NCTP using zincate complexes.

  2. Articles

    1. Top of page
    2. Cover Image
    3. Articles
    1. Synthesis and characterization of crystalline graft polymer poly(ethylene oxide)-g-poly(ɛ-caprolactone)2 with modulated grafting sites (pages 2239–2247)

      Yingying Ma, Jian Huang, Kunyan Sui and Guowei Wang

      Article first published online: 23 MAY 2014 | DOI: 10.1002/pola.27239

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      The graft polymer poly(ethylene oxide)-g-poly(ɛ-caprolactone)2 (PEO-g-PCL2) with modulated grafting sites was synthesized by the combination of ring-opening polymerization, an efficient Williamson reaction, and a thiol–ene addition. By changing the main chain and functional group, various graft polymers with spaced segments can be prepared by this versatile synthetic route.

    2. Synthesis and selective recognition toward zinc ion of chiral poly(imine-triazole) (pages 2248–2257)

      Jinting Zhou, Wei Lu, Fangyu Hu, Mengyu Zhang, Liming Jiang and Zhiquan Shen

      Article first published online: 10 MAY 2014 | DOI: 10.1002/pola.27223

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      A clickable monomer (S)-2-[(2-azido-1-phenylethylimino)methyl]-5-propargyloxyphenol was created and used to synthesize the corresponding polytriazoles by the thermally induced polyaddition. These chiral polymers not only exhibited highly selective “turn-on” fluorescence response toward Zn2+ over other cations, but also produced distinctive changes in the CD spectra on complexation with Zn2+. This allowed for the discrimination of this ion in the presence of other species tested, including those interfering ions observed in the fluorescent detection.

    3. Crosslinkable citronellol containing polyphosphazenes and their biomedical potential (pages 2258–2265)

      Jessica L. Nichol, Nicole L. Morozowich, Thomas E. Decker and Harry R. Allcock

      Article first published online: 14 MAY 2014 | DOI: 10.1002/pola.27236

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      The high injury rate associated with torn ligaments and tendons has stimulated research into their repair using tissue engineering. Polyphosphazenes with anti-inflammatory and antimicrobial citronellol side groups have been synthesized for possible use as tissue engineering matrices for ligament and tendon regeneration.

    4. Doubly thermoresponsive brush-linear-linear ABC triblock copolymer nanoparticles prepared through dispersion RAFT polymerization (pages 2266–2278)

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

      Article first published online: 13 MAY 2014 | DOI: 10.1002/pola.27235

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      Doubly thermoresponsive brush-linear-linear triblock copolymer nanoparticles are prepared by dispersion RAFT polymerization. The nanoparticles exhibited two-step phase-transition with a temperature increase.

    5. Spotlight Article

      Block copolymer materials from the organocatalytic ring-opening polymerization of a pentaerythritol-derived cyclic carbonate (pages 2279–2286)

      Ruairí P. Brannigan, Anthony Walder and Andrew P. Dove

      Article first published online: 9 JUN 2014 | DOI: 10.1002/pola.27246

      Thumbnail image of graphical abstract

      The organocatalytic ring-opening polymerization of 9-phenyl-2,4,8,10-tetraoxaspiro[5,5]undecanone from an α,ω-dihydroxy poly(caprolactone) (PCL) macroinitiator yielded a thermoplastic material with superior tensile and altered crystallization properties compared to that of the PCL homopolymer.

    6. Precision synthesis of regioregular poly(3-hexylthiophene) with low dispersity using a zincate complex catalyzed by nickel with the ligand of 1,2-bis(dicyclohexylphosphino)ethane (pages 2287–2296)

      Eisuke Goto, Saki Nakamura, Susumu Kawauchi, Hideharu Mori, Mitsuru Ueda and Tomoya Higashihara

      Article first published online: 30 MAY 2014 | DOI: 10.1002/pola.27243

      Thumbnail image of graphical abstract

      The ligands of Ni catalyst were optimized to establish a living system of “Negishi-type catalyst-transfer polycondensation” (NCTP). The zincate complex was used in this synthetic method to prepare well-defined poly(3-hexylthiophene) (P3HT) with a predictable molecular weight (MW) and low dispersity (Đ). The ligand of 1,2-bis(dicyclohexylphosphino) ethane produced P3HTs with highly controlled number average MWs (1650–32,800) and very low -D values (1.03–1.17). The synthesis of P3HT-b-Poly(3-octadecylthiophene) is the first demonstration of block copolymerization by NCTP using a zincate complex.

    7. Prodendronic polyamines from stable or labile methacrylates obtained by selective Michael addition onto asymmetric diacrylic compounds (pages 2297–2305)

      Juan Alfonso Redondo, Rodrigo Navarro, Enrique Martínez-Campos, Mónica Pérez-Perrino, Rodrigo París, José Luis López-Lacomba, Carlos Elvira, Helmut Reinecke and Alberto Gallardo

      Article first published online: 20 MAY 2014 | DOI: 10.1002/pola.27240

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      A new synthetic strategy for the preparation of special methacrylic monomers and polymers carrying stable or labile β-amino acyl groups is presented. The approach is based on the selective Michael addition of amines, such as the dendronic N,N,N′,N′-tetraethyldiethylenetriamine used in this work, to the acrylic moiety of asymmetric acrylic–methacrylic crosslinkers. The new dendronic aminopolymers, which are sensitive to pH and to temperature, exhibited similar properties to standard polyethylenimine in in vitro DNA transfection studies.

    8. Spotlight Article

      N-heterocyclic carbenes as organocatalysts in controlled/living ring-opening polymerization of O-carboxyanhydrides derived from l-lactic acid and l-mandelic acid (pages 2306–2315)

      Haidong Xia, Suli Kan, Zhenjiang Li, Jia Chen, Saide Cui, Wenzhuo Wu, Pingkai Ouyang and Kai Guo

      Article first published online: 26 MAY 2014 | DOI: 10.1002/pola.27241

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      N-heterocyclic carbenes (NHCs) have been first evaluated as nucleophilic catalysts for the controlled/living ring-opening polymerizations of O-carboxyanhydrides (OCAs). Polylol initiators were used to produce α,ω-dihydroxy telechelic, 3-, and 4-armed star-shaped polymers. Moreover, star-shaped diblock copolymers bearing methyl and phenyl side chains, have been successfully synthesized with the OCAs/NHCs system.

    9. Synthesis and characterization of fully aliphatic polyimides from an aliphatic dianhydride with piperazine spacer for enhanced solubility, transparency, and low dielectric constant (pages 2316–2328)

      Pradip Kumar Tapaswi, Myeon-Cheon Choi, Young Sik Jung, Hun Jeong Cho, Deok Jin Seo and Chang-Sik Ha

      Article first published online: 20 MAY 2014 | DOI: 10.1002/pola.27242

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      Fully aliphatic polyimides based on a novel aliphatic dianhydride monomer 2,2′-(1,4-piperazinediyl)-disuccinic anhydride, having a heterocyclic piperazine spacer, were synthesized. The presence of the aminomethylene (−NCH2) moiety in fully aliphatic polyimides has interesting effects on their optical, mechanical, and electric properties. Most of the polyimide films can be procesed in solution, are light-coloured, and are freestanding with good thermal-mechanical stabilities. The dielectric constant of one of the synthesized aliphatic polyimide was as low as 2.14.

    10. Synthesis and in situ doping of highly conductive polypyrrole nanocomplexes with binary acids (pages 2329–2336)

      Seung Hwan Lee, Sunjong Lee, Hyun Woog Ryu, Hongkwan Park, Yong Seok Kim and Jung Hyun Kim

      Article first published online: 2 JUN 2014 | DOI: 10.1002/pola.27244

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      Highly conductive polypyrrole nanocomplexes are synthesized through a simple Fe3+-catalyzed oxidative polymerization and in situ doping with a binary acid mixture. Different counter-ions in the binary acids play the role of “size controller” in polypyrrole. As a result, the electrical conductivity of the doped polypyrrole nanocomplexes is enhanced from 0.88 to 4.5 S/cm, and the average particle size is controlled from 280 to 30 nm.

    11. Synthesis, characterization, and ion-complexing properties of polymers displaying densely packed arrays of crown-ethers as lateral substituents (pages 2337–2345)

      Ming Liu, Sandrine Peyrat, Nicolas Illy, Véronique Wintgens, Blandine Brissault, Jacques Penelle and Valessa Barbier

      Article first published online: 28 MAY 2014 | DOI: 10.1002/pola.27245

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      Novel poly(crown-ethers) can be obtained via the anionic ring-opening polymerization of cyclopropane-1,1-dicarboxylates bearing 15-crown-5 or 18-crown-6. They exhibit excellent initial alkali ion binding and display high selectivity for K+. Sandwich complexes formed by a cooperative action of two neighboring crown-ethers units in the polymer chain are observed for systems involving 15-crown-5 and K+.

    12. Bifunctional aluminum porphyrin complex: Soil tolerant catalyst for copolymerization of 2 and propylene oxide (pages 2346–2355)

      Wei Wu, Xingfeng Sheng, Yusheng Qin, Lijun Qiao, Yuyang Miao, Xianhong Wang and Fosong Wang

      Article first published online: 12 JUN 2014 | DOI: 10.1002/pola.27247

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      By incorporating the environmentally friendly metal aluminum, soil tolerant catalysts for the copolymerization of CO2/polypropylene oxide were prepared. These complexes exhibited the highest known TOF values among catalysts incorporating the nontoxic metal center for the copolymerization of CO2/polypropylene oxide.

    13. Diketopyrrolopyrrole-based acceptor–acceptor conjugated polymers: The importance of comonomer on their charge transportation nature (pages 2356–2366)

      Cong-Wu Ge, Chong-Yu Mei, Jun Ling, Fu-Gang Zhao, Hong-Jiao Li, Long Liang, Jin-Tu Wang, Jin-Cheng Yu, Wei Shao, Yong-Shu Xie and Wei-Shi Li

      Article first published online: 2 JUN 2014 | DOI: 10.1002/pola.27248

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      Two kinds of acceptor–acceptor (A–A) conjugated copolymers were designed and synthesized based on diketopyrrolopyrrole in combination with the second electron-deficient unit, perylenediimide and thienopyrroledione. Their organic field-effect transistor devices showed a different charge transportation nature; n-channel for the former and p-channel for the latter.

    14. Synthesis of poly(5,6-difluoro-2,1,3-benzothiadiazole-alt-9,9-dioctyl-fluorene) via direct arylation polycondensation (pages 2367–2374)

      Xiaojie Zhang, Yao Gao, Sida Li, Xincui Shi, Yanhou Geng and Fosong Wang

      Article first published online: 2 JUN 2014 | DOI: 10.1002/pola.27251

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      Optimizations of direct arylation polycondensation of 5,6-difluoro-2,1,3-benzothiadiazole with 2,7-dibromo-9,9-dioctylfluorene were conducted by varying the Pd catalysts, ligand, carboxylic acid additive, base, and solvent. Under the optimized conditions, the combination of Pd(OAc)2/PtBu2Me-HBF4/PivOH/K2CO3/toluene gave the corresponding polymer with Mn up to 41,000, which provided an economically and ecologically benign alternative to the traditional crosscoupling method.

    15. Spotlight Article

      NMR investigation of effect of dissolved salts on the thermoresponsive behavior of oligo(ethylene glycol)-methacrylate-based polymers (pages 2375–2385)

      Cheng Zhang, Hui Peng and Andrew K. Whittaker

      Article first published online: 28 MAY 2014 | DOI: 10.1002/pola.27252

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      Thermo- and ionic-responsive poly(OEGMA-co-TFEA)s with different lengths of OEGMA side chain were synthesized via RAFT polymerization. The solution behavior of the polymers in the presence of dissolved salts was found to depend on the length of the OEGMA side chains, the copolymer composition, and the type of salt. NMR measurements show that motion of the segments in or near the main chain is more sensitive to the temperature in salt solution than the segments in the OEGMA side chain.

    16. Cationic polymerization of isobutylene by complexes of alkylaluminum dichlorides with diisopropyl ether: An activating effect of water (pages 2386–2393)

      Dmitriy I. Shiman, Irina V. Vasilenko and Sergei V. Kostjuk

      Article first published online: 29 MAY 2014 | DOI: 10.1002/pola.27253

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      The simple and industrially relevant initiating system consists of externally added H2O as initiator and RAlCl2 × 0.8OiPr2 (R = iBu or Et) as co-initiator is proposed to synthesize HR PIB (exo-olefin content is 83–89%) with desired low molecular weight (Mn = 1000–2000 g mol-1) in a high yield (70–90% in 20 min) at 10 °C and high monomer concentration ([IB] = 5.8 M).

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