Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 49 Issue 7

1 April 2011

Volume 49, Issue 7

Pages 1517–1734

  1. Articles

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Notes
    5. Erratum
    1. Conversion of poly(ethylene-alt-tetrafluoroethylene) copolymers into polytetrafluoroethylene by direct fluorination: A convenient approach to access new properties at the ETFE surface (pages 1517–1527)

      Gérard Calleja, Axel Houdayer, Sylvie Etienne-calas, David Bourgogne, Valérie Flaud, Gilles Silly, Sota Shibahara, Atsushi Takahara, Alex Jourdan, André Hamwi and Bruno Ameduri

      Article first published online: 24 FEB 2011 | DOI: 10.1002/pola.24588

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      The surface of a poly(ethylene-alt-tetrafluoroethylene) copolymer sheet was converted to PTFE by direct exposure to pure fluorine gas as confirmed by different analytical tools such as Confocal Micro Raman spectroscopy. Fluorination penetrated the processed polymer within tens of microns from the surface without altering its bulk properties, providing a layered material with surface properties related to its new perfluorinated nature.

    2. Synthesis, characterization, and property of amphiphilic fluorinated abc-type triblock copolymers (pages 1528–1534)

      Wenjuan Guo, XinDe Tang, Jing Xu, Xin Wang, Ye Chen, Faqi Yu and MeiShan Pei

      Article first published online: 3 FEB 2011 | DOI: 10.1002/pola.24573

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      Novel amphiphilic fluorinated ABC-type triblock copolymers poly(ethylene oxide)-block-polystyrene-block-poly(perfluorohexylethyl acrylate) (MeOPEO-b-PSt-b-PFHEA) were synthesized by atom transfer radical polymerization. Water contact angle measurements revealed that the triblock copolymer exhibits more hydrophobic than the corresponding diblock copolymer (MeOPEO-b-PSt). Bovine serum albumin (BSA) adsorption experiments indicated its excellent protein-resistant character prior to MeOPEO-b-PSt and polydimethylsiloxane (PDMS). These amphiphilic fluoropolymers can expect to have potential applications for antifouling coatings and antifouling membranes

    3. Synthesis and characterization of materials prepared via the copolymerization of ethylene with 1-octadecene and norbornene using a [(π-cyano-nacnac)Cp] zirconium complex (pages 1535–1542)

      Alan R. Cabrera, Yanika Schneider, Mauricio Valderrama, Griselda B. Galland and Rene S. Rojas

      Article first published online: 8 FEB 2011 | DOI: 10.1002/pola.24574

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      [(B(C6F5)3-NC-nacnac)CpZrCl2] precatalyst (2) can be treated with low concentrations of methylaluminoxane to generate active sites capable of copolymerizing ethylene with 1-octadecene or norbornene under mild conditions. This is due to the coordination of the Lewis acid to the exocyclic nitrogen site on the propagating cationic species, which gives rise to a highly active polymerization site. This system produced copolymers with a branching content of about 8 mol %. And in the case ethylene–norbornene a quasi-alternating structure with isolated norbornene units and norbornene blocks separated by ethylene units.

    4. Copolymerization of 2-hydroxyethyl methacrylate with a comonomer with spiroacetal moiety (pages 1543–1551)

      Aurica P. Chiriac, Loredana E. Nita and Manuela T. Nistor

      Article first published online: 3 FEB 2011 | DOI: 10.1002/pola.24575

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      The copolymerization process between a hydrophilic and a hydrophobic monomer, respectively, 2-hydroxyethyl methacrylate and 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane, determined the formation of a network polymeric structure with special characteristics, for example, biodegradability and biocompatibility, gel formation capacity, binding properties, amphilicity, good oxidative and thermal stability, good films formers, and acid pH sensitivity.

    5. Preparation of pH-sensitive star-shaped aliphatic polyesters as precursors of polymersomes (pages 1552–1563)

      Raphaël Riva, Wenda Lazzari, Leen Billiet, Filip Du Prez, Christine Jérôme and Philippe Lecomte

      Article first published online: 3 FEB 2011 | DOI: 10.1002/pola.24576

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      The synthesis of a new pH-sensitive amphiphilic A2B mikto-arm star-shaped aliphatic copolyester (with A = PCL and B = tertiary amine-bearing PCL) with two hydrophobic arms and one hydrophilic arm when protonated at pH = 5.5. The copper mediated azide-alkyne cycloaddition was used for the synthesis of the star copolyester and to impart the pH sensitivity to the hydrophilic arm by grafting of tertiary amine groups onto azide bearing PCL chain. The formation of polymersomes in water at pH 5 was assessed by DLS and TEM analyses.

    6. Synthesis of poly(2-ethylhexyl acrylate)/clay nanocomposite by in situ living radical polymerization (pages 1564–1571)

      Dhruba J. Haloi and Nikhil K. Singha

      Article first published online: 8 FEB 2011 | DOI: 10.1002/pola.24577

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      Living radical polymerization of 2-ethylhexyl acrylate (EHA) was successfully carried out in bulk at 90 °C using acetone and nanoclay as additive. There was appreciable increase in the rate of polymerization while maintaining a very good control over molecular weight and PDI of the polymer. The resultant polymer composite had predominantly intercalated morphology as evidenced by WAXD and TEM analyses.

    7. Design and synthesis of a fluorescently end-labeled poly(β-amino ester): Application to the characterization of degradable polyelectrolyte multilayers (pages 1572–1581)

      Shane L. Bechler and David M. Lynn

      Article first published online: 8 FEB 2011 | DOI: 10.1002/pola.24578

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      We report the synthesis of a fluorescently end-labeled poly(β-amino ester) (PBAE) and demonstrate its use as a tool for characterization of polyelectrolyte-based thin films. The approach is based on the synthesis of an acrylate end-functionalized PBAE and introduction of end-labels by treatment with amine-functionalized fluorophores. Layer-by-layer fabrication of degradable polyelectrolyte multilayers (PEMs) using end-labeled polyamine permitted characterization of film erosion and release of polyamine by using fluorescence-based methods. Our results shed new light on the behaviors of the cationic components of these PEMs and provide tools that could be used to characterize PBAEs in a range of other contexts.

    8. An efficient way to functionalize graphene sheets with presynthesized polymer via ATNRC chemistry (pages 1582–1590)

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

      Article first published online: 3 FEB 2011 | DOI: 10.1002/pola.24579

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      Well-defined PNIPAM prepared by SET-LRP was grafted onto graphene sheets via ATNRC reaction combining with the grafting-onto strategy under mild conditions to afford PNIPAM/graphene sheets nanocomposites with excellent dispersibility and thermoresponsibility.

    9. Visible light induced free radical promoted cationic polymerization using thioxanthone derivatives (pages 1591–1596)

      Gorkem Yilmaz, Selim Beyazit and Yusuf Yagci

      Article first published online: 8 FEB 2011 | DOI: 10.1002/pola.24582

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      Two thioxanthone photoinitiators acting in the visible light, namely thioxanthone-fluorene carboxylic acid and thioxanthone-carbazole are synthesized and characterized. Their ability to initiate cationic polymerization in conjunction with proper oxidants is tested. The presence of radical and proton scavengers in the reaction media totally inhibits the polymerization, which proves that the mechanism involves oxidation of photochemically generated radicals and the initiating species are Bronsted acids.

    10. Combining cationic ring-opening polymerization and click chemistry for the design of functionalized polyurethanes (pages 1597–1604)

      Malgorzata Basko, Melania Bednarek, Leen Billiet, Przemyslaw Kubisa, Eric Goethals and Filip Du Prez

      Article first published online: 8 FEB 2011 | DOI: 10.1002/pola.24583

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      Alkyne-functionalized polytetrahydrofuran (PTHF) diols were obtained by the cationic ring-opening copolymerization of tetrahydrofuranTHF and glycidyl propargyl ether (GPE). These PTHF prepolymers were used for the preparation of linear polyurethanes with latent functionalization sites. The polyether segments of the polyurethanes have then been coupled with several types of functionalized azides by the azide-alkyne “click” chemistry.

    11. Novel electroactive poly(arylene ether sulfone) copolymers containing pendant oligoaniline groups: Synthesis and properties (pages 1605–1614)

      Danming Chao, Xiaoteng Jia, Hongtao Liu, Libing He, Lili Cui, Ce Wang and Erik B. Berda

      Article first published online: 24 FEB 2011 | DOI: 10.1002/pola.24584

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      A series of novel copolymers of poly(arylene ether sulfone) with oligoaniline groups as pendants were synthesized by nucleophilic polymercondensation. The structures of the copolymers were confirmed by FTIR, 1H NMR, and GPC. The obtained PES-S-AT copolymers exhibit a broad and strong absorption in visible region, good solubility in the organic solvents, and excellent thermal stability. Furthermore, the electroactivity, electrochromic performance, electrical and dielectric properties of the PES-S-AT copolymers were investigated in detail.

    12. Borohydrido rare earth based coordinative chain transfer copolymerization: A convenient tool for tuning the microstructure of isoprene/styrene copolymers (pages 1615–1620)

      Andreia Valente, Philippe Zinck, André Mortreux and Marc Visseaux

      Article first published online: 8 FEB 2011 | DOI: 10.1002/pola.24585

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      Borohydrido rare earths mediated coordinative chain transfer copolymerization of isoprene and styrene: a convenient tool for the control over both the regioselectivity of the reaction and the composition of the copolymer.

    13. Synthesis and characterization of polystyrene-graphite nanocomposites via surface RAFT-mediated miniemulsion polymerization (pages 1621–1632)

      Hussein M. Etmimi, Matthew P. Tonge and Ronald D. Sanderson

      Article first published online: 24 FEB 2011 | DOI: 10.1002/pola.24586

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      Polystyrene-graphite oxide (PS-GO) nanocomposites were synthesized by surface reversible addition-fragmentation chain transfer (RAFT)-mediated polymerization. GO was prepared and immobilized with dodecyl isobutyric acid trithiocarbonate RAFT agent. The resultant modified GO was used to prepare PS nanocomposites in miniemulsion polymerization. The molar mass and polydispersity index of PS in the nanocomposites depended on the amount of RAFT-grafted GO in the system, in accordance with the features of the RAFT process. The PS-GO nanocomposites were of exfoliated morphology, as confirmed by X-ray diffraction and transmission electron microscopy measurements. The thermal stability of the synthesized nanocomposites was better than that of the neat PS. Furthermore, the mechanical properties (i.e., storage and loss modulus) of the obtained nanocomposites improved significantly as the amount of modified GO increased and were dependent on the modified graphite loading.

    14. Dispersion polymerization using hydroxy-functional macroazoinitiators as an inistab (pages 1633–1643)

      Syuji Fujii, Motomichi Suzaki, Yuichi Kakigi, Kodai Aono, Shin-Ichi Yusa and Yoshinobu Nakamura

      Article first published online: 24 FEB 2011 | DOI: 10.1002/pola.24587

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      Hydroxy-functional macroazoinitiators with central azo unit have been synthesized by atom transfer radical polymerization of 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate in methanol. Dispersion polymerizations of styrene using the hydroxy-functional macroazoinitiators as an inistab (initiator + colloidal stabilizer) in 2-propanol or 2-propanol/water media resulted in submicrometer-sized polystyrene latex particles with hydroxy-functional polymer hair. The synthesized particles behaved as an effective particulate emulsifier for the stabilization of oil-in-water emulsions.

    15. Ethylene polymerization with FI complexes having novel phenoxy-imine ligands: Effect of metal type and complex immobilization (pages 1644–1654)

      Agata Krasuska, Marzena Białek and Krystyna Czaja

      Article first published online: 24 FEB 2011 | DOI: 10.1002/pola.24589

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      A series of vanadium and zirconium complexes with novel phenoxy-imine ligands having naphthyl and anthryl group at nitrogen atom was synthesized and investigated in ethylene polymerization and ethylene/1-octene copolymerization. Moreover, some complexes with different types of metallic centers, that is, M = V, Zr, or Ti were immobilized on magnesium carrier MgCl2(THF)2/Et2AlCl, and the effect of immobilization and the effect of the type of metallic center in the supported catalysts on their catalytic behavior were verified.

    16. Synthesis of poly(p-phenylene)-poly(4-diphenylaminostyrene) bipolar block copolymers with a well-controlled and defined polymer chain structure (pages 1655–1663)

      Itaru Natori, Shizue Natori, Hiroyuki Sekikawa, Kosuke Tsuchiya and Kenji Ogino

      Article first published online: 24 FEB 2011 | DOI: 10.1002/pola.24590

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      A poly(p-phenylene) (PPP)-poly(4-diphenylaminostyrene) (PDAS) bipolar block copolymer was synthesized for the first time. A prerequisite prepolymer, poly(1,3-cyclohexadiene) (PCHD)-PDAS binary block copolymer, in which the PCHD block consisted solely of 1,4-cyclohexadiene (1,4-CHD) units, was synthesized by living anionic block copolymerization of 1,3-cyclohexadiene and 4-diphenylaminostyrene. To obtain the PPP-PDAS bipolar block copolymer, the dehydrogenation of this prepolymer with quinones was examined, and tetrachloro-1,2-(o)-benzoquinone was found to be an appropriate dehydrogenation reagent. This dehydrogenation reaction was remarkably accelerated by ultrasonic irradiation, effectively yielding the target PPP-PDAS bipolar block copolymer. The hole and electron drift mobilities for PPP-PDAS bipolar block copolymer were both on the order of 10−3 to 10−4 cm2/V·s, with a negative slope when plotted against the square root of the applied field. Therefore, this bipolar block copolymer was found to act as a bipolar semi-conducting copolymer.

    17. Easily available niobium(V) mixed chloro-alkoxide complexes as catalytic precursors for ethylene polymerization (pages 1664–1670)

      Fabio Marchetti, Guido Pampaloni, Yogesh Patil, Anna Maria Raspolli Galletti and Stefano Zacchini

      Article first published online: 8 FEB 2011 | DOI: 10.1002/pola.24591

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      Mixed chloro-alkoxide complexes of niobium(V), in combination with aluminium co-catalysts, promote ethylene polymerization. In general, the catalytic activity does not dipend on the relative chlorine content within the niobium precursor, and is decreased by hindered alkoxy-substituents. The structurally characterized mononuclear NbCl42-OCH2CH2OMe] has shown the highest activity reported to date for a niobium-based catalyst in olefin polymerization reactions.

    18. Concerted reactions of aldehyde groups during polymerization of an aldehyde-functional benzoxazine (pages 1671–1677)

      Qi-Chao Ran and Yi Gu

      Article first published online: 8 FEB 2011 | DOI: 10.1002/pola.24593

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      As the polymerization reactions of aldehyde-functional benzoxazine (4HBA-a) proceed, some aldehyde groups has not involved in the polymerization reaction and retained in the polymer structure (crosslinkd structure a), and the reactive aldehyde groups contain two parts. A part of aldehyde groups are oxidized and turn to CO2 (crosslinkd structure b), and the other part of aldehyde groups occur crosslink reactions with the ortho position of phenol (crosslinkd structure c). The new crosslinked structures appear in the ortho and para position of phenol via these pathways, which leads to the increase of the crosslink destinies.

    19. Correlation of architecture with excimer emission in 100% pyrene-labeled self-assembled polymers (pages 1678–1690)

      K. Kaushlendra, V. D. Deepak and S. K. Asha

      Article first published online: 24 FEB 2011 | DOI: 10.1002/pola.24596

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      Fluorescence lifetime decay and variable temperature steady-state emission studies highlighting the differences in the nature of origin of the emitting species in side chain urethane methacrylate polymers of different architecture having pyrene as the fluorescent pendant unit.

    20. Induction and inversion of chirality in poly-L-lysine and methyl orange complex (pages 1691–1698)

      Daisuke Takahashi, Ryoichi Tanabe and Tsuyoshi Izumi

      Article first published online: 24 FEB 2011 | DOI: 10.1002/pola.24599

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      A dependence of the inversion of the ICD on the methyl orange concentration was observed in the poly-L-lysine (PLL) - methyl orange complexes at constant PLL concentration, which has not been reported for a constant dye concentration system. The ICD values at peak top wavelength shown in CD spectra depended on the length of alkyl groups (methyl and ethyl) as well as the formation of stoichiometric complexes with uniform size. Therefore, the alkyl group substituent in the dye, dye concentration, and temperature play important roles in the formation of PLL-azo dye complex and ICD appearance.

    21. Solid-state NMR as a tool to describe and quantify the morphology of photoactive layers used in plastic solar cells (pages 1699–1707)

      Raoul Mens, Sabine Bertho, Sylvain Chambon, Jan D'Haen, Laurence Lutsen, Jean Manca, Jan Gelan, Dirk Vanderzande and Peter Adriaensens

      Article first published online: 24 FEB 2011 | DOI: 10.1002/pola.24600

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      The nanostructure of the morphology of thin poly(2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylene-vinylene)/[6,6]-phenyl-C61butyric acid methyl ester (MDMO-PPV/PCBM) films is studied quantitatively by solid-state NMR relaxation experiments. Whereas film casting from toluene results in the development of well-defined PCBM crystallites, casting from chlorobenzene leads to the formation of PCBM-rich domains containing substructures of weakly organized PCBM.

    22. Poly(siloxane-urethane) crosslinked structures obtained by sol-gel technique (pages 1708–1718)

      Mihaela Alexandru, Maria Cazacu, Mariana Cristea, Alexandra Nistor, Cristian Grigoras and Bogdan C. Simionescu

      Article first published online: 24 FEB 2011 | DOI: 10.1002/pola.24602

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      Three new crosslinked siloxane-urethane structures have been prepared starting from isophorone and α,ω-bi(hydroxybutyl)-oligo-dimethylsiloxane using in different proportion a siloxane diol containing additional hydrolysable groups. The increase of crosslinking degree takes to an improving of the mechanical properties and the water vapor sorption capacity. Based on the transitions in 20–80°C temperature range detected by DMA at various frequencies, the shape memory capability of two of the prepared structures was revealed.

  2. Rapid Communications

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Notes
    5. Erratum
    1. Nitroxide-mediated stabilizer-free inverse suspension polymerization of N-isopropylacrylamide in supercritical carbon dioxide (pages 1719–1723)

      Padraig O'connor, Per B. Zetterlund and Fawaz Aldabbagh

      Article first published online: 8 FEB 2011 | DOI: 10.1002/pola.24580

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      The first inverse dispersed phase controlled/living polymerization in supercritical carbon dioxide (scCO2) is described. The nitroxide-mediated radical polymerization of N-isopropylacrylamide proceeded in the absence of stabilizer to high conversion giving a dry powder. The polymerization and purification does not require the use of environmentally damaging volatile organic compound.

    2. Functional benzoxazines containing ammonium salt of carboxylic acid: Synthesis and highly activated thermally induced ring-opening polymerization (pages 1724–1729)

      Atsushi Sudo, Ryoichi Kudoh and Takeshi Endo

      Article first published online: 8 FEB 2011 | DOI: 10.1002/pola.24594

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      Highly reactive 1,3-benzoxazine monomers having carboxylate moieties were synthesized from the corresponding tetrabutylammonium salts of achiral amino acids, glycine, and β-alanine.

  3. Notes

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Notes
    5. Erratum
    1. You have free access to this content
      Synthesis and anti-HIV activity of β-cyclodextrin-C6-sulfate/3-azido-3′-deoxythymidine inclusion complex (pages 1730–1733)

      Mihaela Silion, Andrei Dascalu, Bogdan C. Simionescu, Mariana Pinteala and Cezar Ungurenasu

      Article first published online: 8 FEB 2011 | DOI: 10.1002/pola.24581

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      The regioselective synthesis of β-CD-6-Sulfate and its β-CD-6-Sulfate/3-Azido-3′-deoxythymidine (AZT) inclusion complex followed three steps. In the first step, β-Cyclodextrin 1 was treated with a sulfur trioxide/pyridine complex using different SO3/CD ratios to produce β-CD-6-Sulfates 2. In the second step, the β-CD-6-(OH)3(SO3Na)4 was reacted with AZT to yield β-CD-6-(OH)3(SO3Na)4/AZT inclusion complex 3. The anti-HIV activity of sulfated β-CD-AZT inclusion complex 3 is of the same order of magnitude (0.02 μM for complex vs. 0.01 μM for AZT molecule) and in terms of cytotoxicity it is 7.5 times (97.000:13.000) more potent than AZT molecule.

  4. Erratum

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Notes
    5. Erratum
    1. You have free access to this content
      Erratum: Facile, one-pot synthesis of aromatic diamine-based phosphinated benzoxazines and their flame-retardant thermosets (page 1734)

      Ching Hsuan Lin, Hung Tse Lin, Jhao Wei Sie, Kuen Yuan Hwang and An Pang Tu

      Article first published online: 24 FEB 2011 | DOI: 10.1002/pola.24620

      This article corrects: