Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Vol. 48 Issue 14

15 July 2010

Volume 48, Issue 14

Pages 2961–3215

  1. Articles

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Erratum
    1. Synthesis and self-assembly of well-defined cyclodextrin-centered amphiphilic A14B7 multimiktoarm star copolymers based on poly(ε-caprolactone) and poly(acrylic acid) (pages 2961–2974)

      Peng-Fei Gou, Wei-Pu Zhu, Ning Xu and Zhi-Quan Shen

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24066

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      Well-defined cyclodextrin-centered amphiphilic A14B7 multimiktoarm star copolymers [CDS(PCL-PAA)] were successfully synthesized via the combination of CROP, ATRP, and selective hydrolysis. 1H NMR and SEC analyses confirmed the designed structure. These copolymers could self-assemble into various morphologies in aqueous solution, which were characterized by DLS, TEM, and AFM.

    2. Polymerization and characterization of self-assembled β-cyclodextrin-threaded chiral monomers (pages 2975–2981)

      Yi-Hong Chiu and Jui-Hsiang Liu

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24070

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      In this investigation, the existence of β-CD threaded on the monomer is considered to induce helical structure. This construction is supported by the molecular interaction between the inclusion complexes of β-cyclodextrin threaded monomer. After polymerization, due to the decrease of molecular distance, both the diameter and the pitch of the fibrous structure decreased, leading to the formation of rod-like (an almost solid-helix with a smaller pitch) construction. In addition, the helical structure was fixed through the entanglement of polymers. Accordingly, after the removal of β-CD from polymer side chain, the helical structure was maintained.

    3. pH responsive surfaces with nanoscale topography (pages 2982–2990)

      Antoine Bousquet, Emmanuel Ibarboure, Francisco J. Teran, Leire Ruiz, María Teresa Garay, José Manuel Laza, José Luis Vilas, Eric Papon and Juan Rodríguez-Hernández

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24076

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      We prepared nanostructured adaptive polymer surfaces by diffusion of an amphihilic block copolymer towards the interface. The surface segregation of a diblock copolymer, polystyrene-block-poly(acrylic acid) (PS-b-PAA), occurred when blended with polystyrene employed as a matrix. Surface enrichment on diblock copolymer by water vapor annealing led to self-assembly occurring at the interface. Moreover, the PAA segments placed at the interface respond to pH and can switch from an extended hydrophilic state at basic pH values to a collapsed hydrophobic state in acidic media. Accordingly, the surface morphology changed from swelled micelles to nanometer size holes.

    4. Investigation of nitroxide radical coupling reaction in wide temperature range and different catalyst system (pages 2991–2999)

      Wencheng Lin, Bing Huang, Qiang Fu, Guowei Wang and Junlian Huang

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24077

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      The effect of temperature, catalyst system, and the structure of bromine connected groups on the nitroxide radical coupling (NRC) reaction is investigated. It was found that the catalyst system of CuBr/Cu0/PMDETA is the best one for NRC reaction, in which the NRC reaction could be conducted in high efficiency in the wide temperature range from room temperature to high temperature.

    5. Synthesis and characterization of a hyperbranched hydrogen bond acidic carbosilane sorbent polymer (pages 3000–3009)

      Bernadette A. Higgins, Duane L. Simonson, Eric J. Houser, James G. Kohl and R. Andrew Mcgill

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24078

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      A sorbent hydrogen bond acidic carbosilane polymer (HCSFA2) was prepared via a Grignard reaction followed by functionalization with hexafluoroacetone. Utilizing inverse gas chromatography the resulting HCSFA2 polymer showed a significant improvement in sorption of hydrogen bond basic analytes compared with other previously developed hydrogen bond acidic sorbent polymers.

    6. Synthesis and characterization of sulfonated copolyethersulfones (pages 3010–3023)

      Filippo Samperi, Salvatore Battiato, Concetto Puglisi, Vincenzo Asarisi, Antonino Recca, Gianluca Cicala and Raniero Mendichi

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24079

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      Sulfonated copolyether sulfones (S-PES)s with controlled degree of sulfonation and having unsulfonated PES blocks were synthesized through nucleophilic aromatic substitution polycondensation reaction of controlled amount of sodium salt of sulfonated dichloro difenilsulfone (S-DCDPS) with hydroxyl-ended PES polymers with an Mn of 4000 or 7000 g/mol, at 180 °C for 12 h. MALDI-TOF MS and 1H NMR spectra show the presence either of chloro-disulfonated and hydroxyl-difenilsulfone units as end chains; then some S-PES copolymers were postpolymerizate at 180 °C for another 24 h and 48 h, to increase their molar masses (Mw and Mn). All samples were studied also by DMA and SEC-viscosimetry tools.

    7. One-step synthesis of hyperbranched polyethylene macroinitiator and its block copolymers with methyl methacrylate or styrene via ATRP (pages 3024–3032)

      Wen-Jun Wang, Pingwei Liu, Bo-Geng Li and Shiping Zhu

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24080

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      Block copolymers of hyperbranched polyethylene (PE) and linear polystyrene (PS) or poly(methyl methacrylate) (PMMA) were synthesized via ATRP with hyperbranched PE macroinitiators. The PE macroinitiators were synthesized through a “living” polymerization of ethylene catalyzed with Pd-diimine and end-capped with 4-chloromethyl styrene as a chain quenching agent in one step. The hyperbranched PE chains had narrow molecular weight distribution and contained a single terminal benzyl chloride per chain. Both hyperbranched PE and linear PS or PMMA blocks had well-controlled molecular weights.

    8. Preparation of α,ω-telechelic hexyl acrylate polymers with [BOND]OH, [BOND]COOH, and [BOND]NH2 functional groups by RAFT (pages 3033–3051)

      Norma A. Cortez-Lemus, Rodolfo Salgado-Rodríguez and Angel Licea-Claveríe

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24082

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      Two new chain transfer agents (CTA's) based on dithiobenzoate bearing OH and protected-NH2 groups were synthesized: 2-hydroxyethoxy-carbonylphenylmethyl dithiobenzoate and 2-(2-(tert-butoxycarbonyl)ethylamino)-2-oxo-1-phenylethyl benzodithioate. The CTA's were successfully used for RAFT polymerizations of hexyl acrylate (HA), and were compared to other dithiobenzoates bearing COOH and OH groups in terms of kinetics and molecular weight distribution control. The new CTA's have a long shelf lifetime (over a year). α,ω-Telechelic polymers, with [BOND]OH, [BOND]COOH, and [BOND]NH2 functional groups were prepared by using a postpolymerization reaction with functionalized azo-compounds in a 5 to 1 ratio. The OH-telechelic polymer was converted to a methacrylate-telechelic polymer easily.

    9. Bioconjugation of D-glucuronic acid sodium salt to well-defined primary amine-containing homopolymers and block copolymers (pages 3052–3061)

      Alp H. Alidedeoglu, Adam W. York, Dale A. Rosado, Charles L. McCormick and Sarah E. Morgan

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24083

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      Well-defined carboxylic acid-functionalized glycopolymers were prepared via one-step postpolymerization modification of poly(N-[3-aminopropyl] methacrylamide) (PAPMA) with D-glucuronic acid sodium salt through reductive amination in alkaline medium. The conjugation resulted in near complete conversion. A similar bioconjugation reaction was conducted with poly(2-aminoethyl methacrylate) (PAEMA) and (poly(2-aminoethyl methacrylate-b-poly(N-[2-hydroxypropyl]methacrylamide)) (PAEMA-b-PHPMA).

    10. Bis(β-enaminoketonato) vanadium (III or IV) complexes as catalysts for olefin polymerization (pages 3062–3072)

      Ji-Qian Wu, Bai-Xiang Li, Sen-Wang Zhang and Yue-Sheng Li

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24084

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      A series of novel vanadium complexes bearing β-enaminoketonato ligands have been synthesized, characterized, and investigated as the catalyst precursors for olefin polymerization.

    11. Synthesis and properties of cationic polyelectrolyte with regioregular polyalkylthiophene backbone and ionic-liquid like side groups (pages 3073–3081)

      Dmitrij Bondarev, Jiří Zedník, Ivana Šloufová, Ahmed Sharf, Marek Procházka, Jiří Pfleger and Jiří Vohlídal

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24085

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      High-regioregular poly{3-[6-(1-methylimidazolium-3-yl)hexyl]thiophene-2,5-diylbromide}, PMHT-Br, has been prepared that is soluble in water, methanol and DMSO and shows solvatochromism; λmax (nm): 423 (H2O); 435 (MeOH); 452 (DMSO). Broadening of absorption band of PMHT-Br in aqueous solution together with NMR spectra in D2O suggests a micelle-like structure of PMHT-Br molecules: poly(3-hexylthiophene) core and 1-methylimidazolium bromide shell. Plot of electrical conductivity of PMHT-Br vs 1/T shows a break at ca 70 °C same as the temperature dependence of λmax of PMHT-Br film. These breaks indicate an increase in the mobility of polymer segments and ions above this temperature.

    12. Influence of compatibilizing agent molecular structure on the mechanical properties of phosphate glass fiber-reinforced PLA composites (pages 3082–3094)

      Papia Haque, Ian A. Barker, Andrew Parsons, Kristofer J. Thurecht, Ifty Ahmed, Gavin S. Walker, Christopher D. Rudd and Derek J. Irvine

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24086

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      Interfacial shear strengths (IFSS) of phosphate glass fibers treated with different compatibilizing agents was studied. Of these agents, glycerol-2-phosphate disodium pentahydrate (GP) and low molecular weight PLA with a sodium salt terminal group (PLA-Na) showed the highest IFSS values. The SEM images of those hydrolyzed fiber samples revealed clearly that GP and PLA-Na agents had been removed from the surface of the fiber leaving behind a surface containing fewer defects compared to the control. The micrograph of PLA-Na sized fiber showed the attachment of oligomeric PLA-Na on the fiber surface after hydrolytic degradation of the fibers for 7 days.

    13. Multiple micellar morphologies from tri- and tetrablock copoly(2-oxazoline)s in binary water–ethanol mixtures (pages 3095–3102)

      Charles-André Fustin, Hanneke M. L. Thijs-Lambermont, Stephanie Hoeppener, Richard Hoogenboom, Ulrich S. Schubert and Jean-François Gohy

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24089

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      The micellization behavior of tri- and tetrablock copoly(2-oxazoline)s in water-ethanol mixtures is studied. The copolymers are based on different combinations of 2-methyl-, 2-ethyl-, 2-phenyl-, and 2-nonyl-2-oxazoline. Their solvophilic/solvophobic balance can be tuned thanks to the solubility dependence of the poly(2-phenyl-2-oxazoline) on the solvent composition. The size and morphology of the obtained micelles depend on the solvophobic content of the copolymers and on the block order. Spherical micelles are always obtained when poly(2-nonyl-2-oxazoline) is the only solvophobic block. When both the poly(2-phenyl-2-oxazoline) and poly(2-nonyl-2-oxazoline) are the solvophobic blocks, spherical and cylindrical micelles as well as vesicles are observed.

    14. Grafting of polyaniline onto the surface of 4-aminobenzoyl-functionalized multiwalled carbon nanotube and its electrochemical properties (pages 3103–3112)

      In-Yup Jeon, Sang-Wook Kang, Loon-Seng Tan and Jong-Beom Baek

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24091

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      Polyaniline was grafted on the surface of 4-aminobenzoyl-functionalized multiwalled carbon nanotube. The resultant polyaniline-grafted multiwalled carbon nanotube composite displayed improved thermooxidative stability and electrical conductivity compared to those of polyaniline. Specifically, the electrical conductivity was improved 10–900 times depending upon the level of doping. The capacitance of the composite is also greatly enhanced.

    15. Synthesis of networked polymers with lithium counter cations from a difunctional epoxide containing poly(ethylene glycol) and an epoxide monomer carrying a lithium sulfonate salt moiety (pages 3113–3118)

      Kozo Matsumoto and Takeshi Endo

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24092

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      Poly(ethylene glycol)-based networked polymers that had lithium sulfonate salt structures were prepared by heating a mixture of poly(ethylene glycol) diglycidyl ether (PEGGE), poly(ethylene glycol) bis(3-aminopropyl) terminated, and an ionic epoxy monomer, lithium 3-glycidyloxypropylsulfonate. The obtained polymers showed low ionic conductivity at room temperature under a dry condition, whereas the samples swollen in lithium-salt propylene solution showed much higher ionic conductivity.

    16. Synthesis and morphology of model PS-b-PDMS copolymers (pages 3119–3127)

      Mario D. Ninago, Angel J. Satti, Andrés E. Ciolino, Enrique M. Vallés, Marcelo A. Villar, Daniel A. Vega, Alejandro Sanz, Aurora Nogales and Daniel R. Rueda

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24093

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      Model linear poly(styrene-b-dimethylsiloxane) PS-b-PDMS copolymers were synthesized by using sequential addition of monomers and anionic polymerization (high-vacuum techniques). The microphase separation during thermal treatment in synthesized model diblock copolymers has been followed by synchrotron X-ray scattering. The samples with higher content of PDMS develop well-defined lamellar and hexagonally packed cylinders morphologies, whereas those samples with low-PDMS content (<8 wt %) either remained disordered after thermal treatment or are phase separated with an imperfect lattice structure.

    17. Preparation and characterization of polymer/silica nanocomposites via double in situ miniemulsion polymerization (pages 3128–3134)

      Jianan Zhang, Nannan Liu, Mozhen Wang, Xuewu Ge, Mingyuan Wu, Jianjun Yang, Qingyun Wu and Zhilai Jin

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24094

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      Polymer/SiO2 nanocomposite microspheres were fabricated via the in situ miniemulsion polymerization of monomers and the in situ hydrolysis-condensation of TEOS under basic conditions using γ-methacryloxy(propyl)trimethoxysilane (MPS) as functional monomer. By taking full advantage of phase separation between the growing polymer particles and TEOS, TEOS phase was compressed and pushed out of the initially formed P(MMA-b-BA) particles as nodules because of the naturally different miscibility of TEOS and the growing polymer. The film-forming nanocomposite microspheres were obtained in a one-step process after the formation of SiO2 particles and the completion of the polymerization of organic monomers via the double in situ polymerization method.

    18. Superparamagnetic pH-sensitive multilayer hybrid hollow microspheres for targeted controlled release (pages 3135–3144)

      Bin Mu, Peng Liu, Yun Dong, Chunyin Lu and Xueli Wu

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24095

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      Novel superparamagnetic pH-sensitive multilayer hybrid hollow microspheres have been fabricated using the layer-by-layer assembly technique for the targeted controlled release with citrate-modified ferroferric oxide nanoparticles (Fe3O4-CA) as hybrid anion and chitosan (CS) as polyelectrolyte cation.

    19. Injectable supramolecular hybrid hydrogels formed by MWNT-grafted-poly(ethylene glycol) and α-cyclodextrin (pages 3145–3151)

      Kunyan Sui, Song Gao, Wenwen Wu and Yanzhi Xia

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24097

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      The complexation of α-CDs with PEG segments grafted on MWNTs and the hydrophobic interaction between the MWNTs resulted in the formation of a strong network of supramolecular hybrid hydrogels. Thermal analysis showed that the hybrid hydrogel thermal stability was substantially improved by up to 110 °C higher than that of the native hydrogels. The resultant hybrid hydrogels were found to be thixotropic and reversible. The mechanical strength of the hybrid hydrogels was greatly improved in comparison with that of the corresponding native hydrogels.

    20. On the evolution of the rate of polymerization, number and size distribution of particles in styrene emulsion polymerization above CMC (pages 3152–3160)

      Shirley Carro, Jorge Herrera-Ordonez and Jorge Castillo-Tejas

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24098

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      Bimodal particle size distributions for the emulsion polymerization of styrene above CMC were detected by means of asymmetrical field-flow fractionation. This evidence reveals that primary particles are colloidally stable, in contrast to coagulative theory states. Nevertheless, the evolution of particle number and polymerization rate shows minimums that indicate their coagulation. These results suggest that primary particles stability is between the predicted by the coagulative theory and that which considers them completely stable.

    21. Multiwalled carbon nanotubes covalently functionalized with poly(N-vinylcarbazole) via RAFT polymerization: Synthesis and nonliner optical properties (pages 3161–3168)

      Bin Zhang, Jun Wang, Yu Chen, Daniel Früchtl, Bo Yu, Xiaodong Zhuang, Nan He and Werner J. Blau

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24099

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      New MWNTs covalently functionalized with poly(N-vinylcarbazole) [MWNT-PVK] are prepared by using RAFT polymerization method. The significant nonlinear optical responses manifest this material a suitable candidate for viable optical limiting devices.

    22. Synthesis and characterization of indenofluorene-based copolymers containing 2,5-bis(2-thienyl)-N-arylpyrrole for bulk heterojunction solar cells and polymer light-emitting diodes (pages 3169–3177)

      Vellaiappillai Tamilavan, Pachagounder Sakthivel, Yinan Li, Myungkwan Song, Chul-Hyun Kim, Sung-Ho Jin and Myung Ho Hyun

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24101

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      Two novel indenofluorene-based copolymers containing 2,5-bis(2-thienyl)-N-(4-octylphenyl)pyrrole or 2,5-bis(2-thienyl)-N-(2,6-diisopropylphenyl)pyrrole were prepared for bulk hetrojunction solar cells and polymer light-emitting diodes.

    23. Synthesis, characterization, and molecular recognition of sugar-functionalized nanoparticles prepared by a combination of ROP, ATRP, and click chemistry (pages 3178–3187)

      Emile Jubeli, Laurence Moine and Gillian Barratt

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24105

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      We report the preparation of amphiphilic copolymer bearing sugar residues by a combination of click chemistry, ring-opening polymerization, and atom transfer radical polymerization. Nanoparticles prepared from this copolymer show molecular recognition with concanavalin A and are not cytotoxic toward human umbilical vein endothelial cells. Such systems have great potential as an intravenous drug delivery system based on sugar–protein recognition.

    24. On the origin of ionic liquid-induced variations in hydroxypropyl methacrylate propagation rate coefficients (pages 3188–3199)

      Aleksandra Jeličić, Franziska Köhler, Alette Winter and Sabine Beuermann

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24107

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      The propagation kinetics of hydroxypropyl methacrylate (HPMA) in ionic liquids and common organic solvents were investigated by pulsed laser-initiated polymerizations to study the complex interplay of competing interactions between HPMA molecules and between HPMA and solvent molecules. The results suggest that interactions between the hydroxyl groups of the monomer and the anions are dominant compared with classical hydrogen bonding between carbonyl and hydroxyl groups of the monomer units. The solvent influence is strongly determined by dipolarity and polarizability of the solvent as well as by its hydrogen bond–donating ability.

    25. Direct synthesis of terminally “clickable” linear and hyperbranched polyesters (pages 3200–3208)

      S. G. Ramkumar, K. A. Amala Rose and S. Ramakrishnan

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24108

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      A straightforward approach for the preparation of propargyl-terminated linear and hyperbranched polyesters has been developed. Quantitative functionalization of the terminal propargyl groups with a variety of organic azides, such as water-solublizing PEG units or anthracene chromophores, etc., using the click reaction demonstrated the potential to utilize these polymers as scaffolds that could pave way for some interesting applications.

  2. Rapid Communications

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Erratum
    1. You have free access to this content
      Effect of catalyst composition on chain-end-group of polyethylene produced by salen-type complexes of titanium, zirconium, and vanadium (pages 3209–3214)

      Marzena Białek

      Article first published online: 14 JUN 2010 | DOI: 10.1002/pola.24096

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      The chain end structures of polyethylenes produced by salen complexes of titanium, zirconium, and vanadium, activated by MAO or common alkylaluminium compounds were investigated by 1H NMR and FTIR spectroscopy. The polymerization process with the use of vanadium complexes was found to produce polymers with only vinyl end groups in practice. In the processes catalyzed by titanium and zirconium complexes activated by MAO or Et2AlCl, not only β-hydrogen elimination and/or chain transfer to the monomer occurs but also the chain termination reaction takes place in which an organoaluminium cocatalyst is involved. That reaction proceed particularly easily in the systems: titanium complex/Et2AlCl.

  3. Erratum

    1. Top of page
    2. Articles
    3. Rapid Communications
    4. Erratum
    1. You have free access to this content

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