Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 49 Issue 22

15 November 2011

Volume 49, Issue 22

Pages i–iv, 4721–4925

  1. Cover Image

    1. Top of page
    2. Cover Image
    3. Rapid Communications
    4. Articles
    5. Notes
    1. You have free access to this content
      Cover Image, Volume 49, Issue 22 (pages i–ii)

      Version of Record online: 12 OCT 2011 | DOI: 10.1002/pola.25028

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      The article on page 4735 by Anika Schrade, Viktoria Mikhalevich, Katharina Landfester, and Ulrich Ziener gives insight into the synthesis and characterization of positively charged, silica-armored polymer particles prepared by using styrene and different hydrophilic monomers in miniemulsion copolymerization. By changing the reaction parameters, the influence on the colloidal characteristics is analyzed via various methods providing insight into the interactions between the silica particles and the polymer surface. Those surfactant-free cationic hybrid particles are highly intriguing for cellular uptake experiments. The illustration combines the schematic synthesis, structural investigation, as well as preliminary cell experiments, visualizing the cationic silica-armored hybrid nanoparticles internalized in vital HeLa cells.

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      Inside Cover, Volume 49, Issue 22 (pages iii–iv)

      Version of Record online: 12 OCT 2011 | DOI: 10.1002/pola.25029

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      Symmetrical ABA-type block copolymers are prepared by tandem enhanced spin capturing polymerization (ESCP) and nitroxide mediated polymerization (NMP), as presented by Thomas Junkers, Lin Zang, Edgar H.H. Wong, Nico Dingenouts, and Christopher Barner-Kowollik on page 4841. Activity of the ESCP-derived midchain-functionalized polymers, made by simple addition of a nitrone to a conventional radical polymerization mixture, towards NMP chain extension is tested systematically with respect to chain length of the precursors. Polystyrene-block-tert-butyl acrylate-block-polystyrene polymers of various block length were synthesized and kinetic studies as well as MALLS and SAXS measurements of the molecular weight confirm the success of this simple and versatile synthesis approach.

  2. Rapid Communications

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    2. Cover Image
    3. Rapid Communications
    4. Articles
    5. Notes
    1. Continuous SET-LRP of acrylonitrile in iron tube without any ligand (pages 4721–4724)

      Hou Chen, Min Zhang, Mengmeng Yu and Hongyan Jiang

      Version of Record online: 17 AUG 2011 | DOI: 10.1002/pola.24920

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      Iron tube was applied as catalyst source in the design of continuous SET-LRP of AN without any ligand using BPN as initiator in NMP and DMF, respectively. First-order kinetics of polymerization with respect to the monomer concentration, linear increase of the molecular weight, and narrow polydispersity with monomer conversion showed the controlled radical polymerization characters. An increase in polymerization rate in NMP was observed compared with in DMF. The living feature of PAN was verified by chain extensions of PAN with MMA.

    2. Synthesis of poly(m-phenyleneisophthalamide) by solid-state polycondensation of isophthalic acid with m-phenylenediamine (pages 4725–4728)

      Cenyao Zhang, Yu Shoji, Tomoya Higashihara, Akimitsu Tsukuda, Takashi Ochi and Mitsuru Ueda

      Version of Record online: 27 AUG 2011 | DOI: 10.1002/pola.24934

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      The synthesis of poly(m-phenyleneisophthalamide) was performed by thermal solid-phase polymerization from isophthalic acid and m-phenylenediamine without using any solvents or condensation agents. The two-stage heating process was conducted. The oligo(m-phenyleneisophthalamide) was first synthesized at a relatively low temperature (260 °C for 1 h), followed by the polycondensation at 400 °C for 1 min under reduced pressure to produce the aramid with an inherent viscosity of 0.55 dL/g.

    3. Poly(N-vinylimidazole)-l-poly(tetrahydrofuran) amphiphilic conetworks and gels. II. Unexpected dependence of the reactivity of poly(tetrahydrofuran) macromonomer cross-linker on molecular weight in copolymerization with N-vinylimidazole (pages 4729–4734)

      Csaba Fodor and Béla Iván

      Version of Record online: 14 SEP 2011 | DOI: 10.1002/pola.24972

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      In the course of the synthesis of poly(N-vinylimidazole)-l-poly(tetrahydrofuran) (PVIm-l-PTHF; “-l- “stands for “linked by”) amphiphilic conetworks, it was surprisingly found that higher molecular weight methacrylate-telechelic PTHF (PTHFDMA) bismacromonomers were incorporated into the conetworks with higher extent than that of shorter chains. This striking observation of the enhanced apparent reactivity of PTHFDMA with its increasing molecular weight is explained by uneven partitioning of VIm between the solution and the volume occupied by the hydrophobic PTHF attached with the growing chain.

  3. Articles

    1. Top of page
    2. Cover Image
    3. Rapid Communications
    4. Articles
    5. Notes
    1. Synthesis and characterization of positively charged, alumina-coated silica/polystyrene hybrid nanoparticles via pickering miniemulsion polymerization (pages 4735–4746)

      Anika Schrade, Viktoria Mikhalevich, Katharina Landfester and Ulrich Ziener

      Version of Record online: 14 SEP 2011 | DOI: 10.1002/pola.24932

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      Positively charged, silica-armored polymer nanoparticles were prepared by miniemulsion copolymerization of styrene and hydrophilic comonomers. Investigations of the reaction parameters on the colloidal characteristics give insight into the interactions between the silica particles and the polymer surface. Those positively charged hybrid particles are highly intriguing for cellular uptake experiments.

    2. Functionalization of graphene oxide towards thermo-sensitive nanocomposites via moderate in situ SET-LRP (pages 4747–4755)

      Yan Deng, Yongjun Li, Jing Dai, Meidong Lang and Xiaoyu Huang

      Version of Record online: 17 AUG 2011 | DOI: 10.1002/pola.24919

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      PPEGEEMA polymer chains were in situ grown from the surface of “TRIS” modified graphene oxide sheets via SET-LRP under mild conditions to afford polymer/graphene oxide hybrid material with excellent dispersibility and thermo-responsibility.

    3. SET-LRP of methyl acrylate catalyzed with activated Cu(0) wire in methanol in the presence of air (pages 4756–4765)

      Nga H. Nguyen and Virgil Percec

      Version of Record online: 17 AUG 2011 | DOI: 10.1002/pola.24922

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      SET-LRP of MA in methanol, catalyzed with nonactivated and activated Cu(0) wires, performed in the presence of nondeoxygenated reagents under a simple blanket of nitrogen was investigated. The addition of a small amount of hydrazine hydrate mediates the deoxygenation of the reaction mixture through its use in the oxidation of Cu(0) to Cu2O, followed by the reduction of Cu2O with hydrazine back to the active Cu(0).

    4. Preparation of amphiphilic poly(ethylene oxide)-block-polystyrene macrocycles via glaser coupling reaction under CuBr/pyridine system (pages 4766–4770)

      Yannan Zhang, Guowei Wang and Junlian Huang

      Version of Record online: 23 AUG 2011 | DOI: 10.1002/pola.24923

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      Cyclic poly(ethylene oxide)-block-polystyrene [c-(PEO-b-PS)] was synthesized by cyclization of propargyl-telechelic poly(ethylene oxide)-block-polystyrene-block-poly(ethylene oxide) ([TRIPLE BOND][BOND]PEO-b-PS-b-PEO[BOND][TRIPLE BOND]) via Glaser coupling. The linear precursors and final product were characterized by GPC, 1H NMR, and FTIR in detail.

    5. A kinetic investigation of surfactant-free emulsion polymerization of styrene using laponite clay platelets as stabilizers (pages 4771–4784)

      Nida Sheibat-Othman, Ana-Maria Cenacchi-Pereira, Amilton Martins Dos Santos and Elodie Bourgeat-Lami

      Version of Record online: 31 AUG 2011 | DOI: 10.1002/pola.24924

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      Synthesis of Laponite-armored latex particles by soap-free emulsion polymerization in the presence of poly(ethylene glycol) monomethyl ether methacrylate (PEGMA). The clay platelets together with PEGMA promote radical entry and increase the polymerization rate.

    6. Well-defined polyoxazoline-based alkoxyamines as efficient macroinitiators in nitroxide-mediated radical polymerization of styrene (pages 4785–4793)

      Lucien Marx, Gisele Volet and Catherine Amiel

      Version of Record online: 9 SEP 2011 | DOI: 10.1002/pola.24925

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      The synthesis of two well-defined TIPNO-terminated poly(2-methyl-2-oxazoline) with narrow dispersity (Mw/Mn = 1.1) has been achieved, for the first time, using a method based on the “terminating reagent method”. These macroinitiators have been used successfully for nitroxide mediated radical polymerization (NMP) of styrene. The well control of NMP has been proved by a good agreement between theoretical and experimental molecular weights and by narrow dispersity (Mw/Mn < 1.2). Different types of well-defined multiblock copolymers have been prepared.

    7. A novel use of Ti-POSS as initiator of L-lactide ring-opening polymerization (pages 4794–4799)

      Orietta Monticelli, Dario Cavallo, Sergio Bocchini, Alberto Frache, Fabio Carniato and Alessandro Tonelotto

      Version of Record online: 23 AUG 2011 | DOI: 10.1002/pola.24926

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      A novel initiator of L-lactide ring-opening polymerization, based on a metal-polyhedral oligomeric silsesquioxanes, has been assessed. The presence of silsesquioxane molecules, attached to one end of the polymer chains, appreciably affect the crystal nucleation density.

    8. Thermoresponsive oligo(ethylene glycol) methacrylate colloids with antifouling surface properties (pages 4800–4808)

      Mustafa Selman Yavuz, Fatih Buyukserin, Zuleyha Zengin and Sevket Tolga Camli

      Version of Record online: 23 AUG 2011 | DOI: 10.1002/pola.24927

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      Here, we introduce the preparation of cross-linked PEGEEM colloids that display a reversible volume phase transition as well as very low non-specific protein adsorption and no apparent cytotoxicity. A simple precipitation polymerization was used to prepare these cross-linked particles which were characterized by dynamic light scattering and transmission electron microscopy.

    9. Synthesis and characterization of photosensitive liquid crystalline poly(benzylidene-ether)s with alkanones and methylene spacers in the main chain (pages 4809–4819)

      K. Balaji and S. C. Murugavel

      Version of Record online: 27 AUG 2011 | DOI: 10.1002/pola.24928

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      Main chain liquid crystalline poly(benzylidene-ether)s were synthesized by polycondensation fo 4,4′-Diformyl-α,ω-diphenoxyalkanes with acetone, cyclopentanone and cyclohexanone. Length of methylene spacer on phase transition was investigated with DSC and proved that Ti decreases as the spacer length increases. Polarized optical microscopic study showed that polymers exhibit nematic texture, birefrigent and stirred opalescence property. Photosensitivity study revealed the EZ photoisomerization proceeds in the moderate molecular weight poly(benzylidene-ether)s system.

    10. Magnetic poly(N-propargylacrylamide) microspheres: Preparation by precipitation polymerization and use in model click reactions (pages 4820–4829)

      Hana Macková, Vladimír Proks, Daniel Horák, Jan Kučka and Miroslava Trchová

      Version of Record online: 9 SEP 2011 | DOI: 10.1002/pola.24930

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      Magnetic poly(N-propargylacrylamide) microspheres were prepared by the precipitation polymerization in the presence of magnetite nanoparticles. Morphology, size, polydispersity and iron content of the magnetic microspheres were influenced by the concentration of monomer, the amount of magnetite, the polarity of the medium and polymerization temperature. Alkyne groups of the microspheres enabled a click reaction with 4-azidophenylalanine and azido-end functionalized model peptide (radiolabeled azidopentanoyl-GGGRGDSGGGY(I25I)-NH2).

    11. Soluble, redox-active, and blue-emitting poly(amide-hydrazide)s and poly(amide-1,3,4-oxadiazole)s containing pyrenylamine units (pages 4830–4840)

      Yi-Chun Kung and Sheng-Huei Hsiao

      Version of Record online: 31 AUG 2011 | DOI: 10.1002/pola.24931

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      New pyrenylamine-containing poly(amide-hydrazide)s (PAHs) and poly(amide-1,3,4-oxadiazole)s (PAOXs) have been successfully prepared from N,N-di(4-carboxyphenyl)-1-aminopyrene with p-aminobenzoyl hydrazide and m-aminobenzoyl hydrazide, respectively. The PAOXs exhibited good solubility, thin film-forming ability, and high thermal stability. All the polymers showed strong blue photoluminescence in both solution and thin film states. In addition, these polymers displayed ambipolar electrochemical and electrochromic properties.

    12. Formation of triblock copolymers via a tandem enhanced spin capturing—nitroxide-mediated polymerization reaction sequence (pages 4841–4850)

      Thomas Junkers, Lin Zang, Edgar H.H. Wong, Nico Dingenouts and Christopher Barner-Kowollik

      Version of Record online: 9 SEP 2011 | DOI: 10.1002/pola.24970

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      A tandem ESCP-NMP reaction sequence is used as a facile avenue for the generation of ABA-type block copolymers.

    13. Preparation of phosphinated bisphenol from acid-fragmentation of 1,1,1-tris(4-hydroxyphenyl)ethane and its application in high-performance cyanate esters (pages 4851–4860)

      Ching Hsuan Lin, Hung Tse Lin, Yu Wei Tian, Shenghong A. Dai and Wen Chiung Su

      Version of Record online: 7 SEP 2011 | DOI: 10.1002/pola.24936

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      SdocA phosphinated bisphenol (2) was first prepared by acid-fragmentation of 1,1,1-tris(4-hydroxyphenyl)ethane, followed by nucleophilic addition of 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide. A dicyanate ester derivative (3) was prepared from (2) to enhance the flame retardancy and reduce dielectric properties of dicyanate ester of bisphenol A without sacrificing the thermal properties.

    14. Pi-conjugated chain extenders for the synthesis of optoelectronic segmented polyurethanes (pages 4861–4874)

      Christopher P. Harvey and John D. Tovar

      Version of Record online: 7 SEP 2011 | DOI: 10.1002/pola.24937

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      A series of oligothiophene diols or diamines and a naphthalene diimide diol have been synthesized for incorporation into pi-conjugated hard domains of segmented polyurethanes and polyureas featuring polytetramethylene oxide chains as soft segments. Mechanical alteration of electronic coupling within hard domain aggregates may result in a mechanochromic response.

    15. Thiazolothiazole-containing polythiophenes with low HOMO level and high hole mobility for polymer solar cells (pages 4875–4885)

      Qinqin Shi, Haijun Fan, Yao Liu, Jianming Chen, Zhigang Shuai, Wenping Hu, Yongfang Li and Xiaowei Zhan

      Version of Record online: 12 SEP 2011 | DOI: 10.1002/pola.24938

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      Two regiochemically defined polythiophenes containing thiazolothiazole acceptor unit were synthesized. Compared to P1 with head-to-head coupling of two middle thiophenes, P2 with head-to-tail coupling of two middle thiophenes exhibits 40 nm red shift of absorption spectrum in film and 0.3 eV higher HOMO level. Both polymers exhibit field-effect hole mobility as high as 0.02 cm2 V−1 s−1. The PSC based on P1:PC71BM (1:2, w/w) exhibits a power conversion efficiency of 2.7% under AM 1.5, 100 mW cm−2, two times of that based on P2:PC71BM. The higher efficiency is attributed to lower HOMO (−5.6 eV) and smaller phase separation scale in P1:PC71BM blend.

    16. Amphiphilic PEG-grafted poly(ester-carbonate)s: Synthesis and diverse nanostructures in water (pages 4886–4893)

      Weipu Zhu, Ying Wang, Qiujin Zhang and Zhiquan Shen

      Version of Record online: 9 SEP 2011 | DOI: 10.1002/pola.24944

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      Well-defined amphiphilic biodegradable graft copolymers with poly(ethylene glycol) as hydrophilic side chain and poly(DTC-co-CL) as hydrophobic backbone were synthesized by a combination of ring-opening polymerization and “click” reaction. These amphiphilic graft polymers could undergo self-assembly in aqueous solution to form micelles with diverse nanostructures, which could be controlled by both grafting density and PEG side chain length.

    17. Stereoregular polycarbonate synthesis: Alternating copolymerization of CO2 with aliphatic terminal epoxides catalyzed by multichiral cobalt(III) complexes (pages 4894–4901)

      Wei-Min Ren, Ye Liu, Guang-Peng Wu, Jie Liu and Xiao-Bing Lu

      Version of Record online: 9 SEP 2011 | DOI: 10.1002/pola.24945

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      Completely stereoregular polycarbonate synthesis was first achieved with the use of dissymmetric multi-chiral cobalt-based complexes bearing a derived chiral -BINOL and an appended 1,5,7-triabicyclo[4.4.0] dec-5-eneTBD as catalyst for the copolymerization of CO2 and aliphatic terminal epoxides at mild conditions. Completely alternating copolymers are obtained with more than 99% head-to-tail linkages.

    18. Electrospun poly(aniline-co-ethyl 3-aminobenzoate)/poly(lactic acid) nanofibers and their potential in biomedical applications (pages 4902–4910)

      Marija Gizdavic-Nikolaidis, Sudip Ray, Jared Bennett, Simon Swift, Graham Bowmaker and Allan Easteal

      Version of Record online: 9 SEP 2011 | DOI: 10.1002/pola.24946

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      Nanofibrous blends of poly(aniline-co-ethyl 3-aminobenzoate) with poly(lactic acid), 3EABPANI-PLA were easily fabricated by electrospinning and have a continuous three-dimensional network which shows enhanced mammalian cell growth, antioxidant and antimicrobial capabilities, and electrical conductivity. These results suggest that 3EABPANI-PLA nanofibrous blends might provide a novel bioactive conductive material for biomedical applications.

    19. Light-driven and aggregation-induced emission from side-chain azoindazole polymers (pages 4911–4920)

      Ying Li, Nianchen Zhou, Wei Zhang, Feng Zhang, Jian Zhu, Zhengbiao Zhang, Zhenping Cheng, Yingfeng Tu and Xiulin Zhu

      Version of Record online: 9 SEP 2011 | DOI: 10.1002/pola.24947

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      The well-defined azoindazole-containing homopolymer poly(6-{6-[(4-dimethylamino) phenylazo]-indazole}-hexyl methacrylate) and amphiphilic diblock copolymer, poly({6-[6-(4-dimethylamino)phenylazo]-indazole}-hexyl methacrylate)-b-poly(2-(dimethylamino)ethylmethacrylate) were successfully prepared via reversible addition-fragmentation chain transfer polymerization technique. The homopolymer and amphiphilic diblock copolymer in CH2Cl2 exhibited intense fluorescence emission accompanied by trans-cis photoisomerization of azoindazole group under UV irradiation. On the other hand, the intense fluorescence emission of amphiphilic diblock copolymers in water/tetrahydrofuran mixture was observed, which increased with the volume ratio of water in the mixed solvent.

  4. Notes

    1. Top of page
    2. Cover Image
    3. Rapid Communications
    4. Articles
    5. Notes
    1. You have free access to this content
      Molecular weight dependence of helical conformation of amino acid-based polyphenylacetylenes (pages 4921–4925)

      Masashi Shiotsuki, Shohei Kumazawa, Naoya Onishi and Fumio Sanda

      Version of Record online: 9 SEP 2011 | DOI: 10.1002/pola.24941

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      A well-defined living polymerization catalyst, [(nbd)Rh{C(Ph)=CPh2}(PPh3)]/PPh3, produced a series of amino acid based polyphenylacetylene derivatives having a wide range of molecular weights (Mn: 1500–128,800) with relatively narrow polydispersity. On the basis of the CD and UV–vis spectra of the obtained polymers measured in DMF, plotting the [θ] and Kuhn dissymmetry factor, g, against the molecular weight revealed that their predominantly one-handed helical conformation strongly depended on their molecular weights.

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