Journal of Polymer Science Part A: Polymer Chemistry

Cover image for Journal of Polymer Science Part A: Polymer Chemistry

1 June 2003

Volume 41, Issue 11

Pages 1553–1743

  1. Articles

    1. Top of page
    2. Articles
    3. Rapid Communication
    4. Articles
    1. Modeling the reversible addition–fragmentation transfer polymerization process (pages 1553–1566)

      Aileen R. Wang and Shiping Zhu

      Version of Record online: 2 APR 2003 | DOI: 10.1002/pola.10701

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      A model has been developed for reversible addition–fragmentation transfer polymerization. The model predicts the monomer conversion, number-average molecular weight, and polydispersity for four types of chain species: propagating radical, adduct radical, dormant, and dead. The effects of various reactant concentrations and rate constants on the kinetics and polymer chain properties are thoroughly investigated. The figure shows the development of the molecular weight and the addition–fragmentation equilibrium constant.

    2. Synthesis and radical polymerization of hydrophilic methacrylates with oxyethylene units in the pendant chain (pages 1567–1579)

      F. García, J. M. García, F. Rubio, J. L. de la Peña, J. Guzmán and E. Riande

      Version of Record online: 2 APR 2003 | DOI: 10.1002/pola.10703

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      Different synthetic procedures were used to obtain high-purity methacrylic monomers containing three, four, five, or six oxyethylene units in the ester residue. The kinetics of polymerization of these monomers were studied with NMR spectroscopy and electron paramagnetic resonance spectroscopy techniques to determine the values of the propagation and termination rate coefficients.

    3. Bioengineering functional copolymers. III. Synthesis of biocompatible poly[(N-isopropylacrylamide-co-maleic anhydride)-g-poly(ethylene oxide)]/poly(ethylene imine) macrocomplexes and their thermostabilization effect on the activity of the enzyme penicillin G acylase (pages 1580–1593)

      Volkan Köseli, Zakir M. O. Rzaev and Erhan Pişkin

      Version of Record online: 16 APR 2003 | DOI: 10.1002/pola.10702

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      Stimuli-responsive poly[(N-isopropylacrylamide-co-maleic anhydride)-g-poly(ethylene oxide)]/poly(ethylene imine) macrobranched macrocomplexes and their conjugates with the enzyme penicillin G acylase were synthesized and characterized. The thermostabilization effect of the prepared systems on the enzyme activity was evaluated. A significant increase in the thermal stability of the enzyme (three times at 45 °C and two times at 65 °C) was observed.

    4. Synthesis of transition-metal-ion-selective poly(N-isopropylacrylamide) hydrogels by the incorporation of an Aza crown ether (pages 1594–1602)

      Dirk Kuckling and Pradeep Pareek

      Version of Record online: 7 APR 2003 | DOI: 10.1002/pola.10708

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      Transition-metal-ion-sensitive hydrogels were obtained by the polymerization of a functionalized cyclam with N-isopropylacrylamide and N,N′-methylene bisacrylamide. The phase-transition temperature of the pure poly(N-isopropylacrylamide) (PNIPAAm) gel was weakly influenced by the presence of any transition-metal ions, such as Cu2+, Ni2+, Zn2+, and Mn2+. The addition of Cu2+ or Ni2+ to the PNIPAAm/cyclam gel reduced the phase-transition temperature of the polymer gel by approximately 12 °C.

    5. Thermal characterization of polyester–melamine coating matrices prepared under nonisothermal conditions (pages 1603–1621)

      N. J. W. Gamage, D. J. T. Hill, C. A. Lukey and P. J. Pomery

      Version of Record online: 8 APR 2003 | DOI: 10.1002/pola.10698

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      Thermal analysis methods [differential scanning calorimetry (DSC), thermogravimetric analysis, and dynamic mechanical thermal analysis (DMTA)] were used to characterize the crosslinking behavior of polyester–melamine surface coatings prepared under nonisothermal (rapid-cure) conditions. Although DSC showed a single glass transition, DMTA tan δ curves clearly showed two transitions, which were attributed to the formation of two networks (a cocondensed polyester–melamine network and a self-condensed melamine–melamine network), the relative concentrations of which varied with the melamine concentration and the cure conditions. The described approach can be used to monitor the mechanical attributes (flexibility, hardness, durability, etc.) of finished coatings and, therefore, their suitability for projected end uses.

    6. Structure–property transition-state model for the copolymerization of ethene and 1-hexene with experimental and theoretical applications to novel disilylene-bridged zirconocenes (pages 1622–1631)

      Hanne Wigum, Kjell-Arne Solli, Jon Andreas Støvneng and Erling Rytter

      Version of Record online: 8 APR 2003 | DOI: 10.1002/pola.10709

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      During the copolymerization of ethene and 1-hexene with tetramethyldisilylene-bridged L2ZrCl2/methylaluminoxane catalytic solutions (where L represents Me4Cp, 2-Ind, or 2-H4Ind ligands), the incorporation of 1-hexene was much lower with Me4Cp ligands than with 2-Ind or 2-H4Ind ligands. The comonomer response was correlated with the structural properties of the catalyst, as derived from density functional calculations.

    7. Photocurable and thermally stable polymers based on 1,4-pentadien-3-one-1-p-hydroxyphenyl-5-p-phenyl methacrylate: Copolymerization with ethyl acrylate (pages 1632–1640)

      A. Arun and B. S. R. Reddy

      Version of Record online: 8 APR 2003 | DOI: 10.1002/pola.10705

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      A new monomer, 1,4-pentadien-3-one-1-p-hydroxyphenyl-5-p-phenyl methacrylate (PHPPMA), was synthesized. Thermally stable and photocrosslinkable copolymers of PHPPMA with ethyl acrylate were prepared. The photocrosslinking behavior of the polymers was examined with a UV spectrophotometer. Reactivity ratios were estimated with Kelen–Tudos and extended Kelen–Tudos methods. The photocrosslinking properties of the polymers were analyzed by UV absorption spectroscopy.

    8. Novel acrylic macromonomer with amphiphilic character derived from Triton X-100: Radical copolymerization with methyl methacrylate and thermal properties (pages 1641–1649)

      Elena Larraz, Carlos Elvira and Julio San Román

      Version of Record online: 8 APR 2003 | DOI: 10.1002/pola.10710

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      The synthesis and characterization of a new acrylic macromonomer (MT) with amphiphilic character derived from poly(ethylene glycol) tert-octylphenyl ether (Triton X-100) are described. Identically, a parallel study of a lower-molecular-weight monomer (MTm), which reproduces the reactive structure of the macromonomer, was carried out to compare its reactivity toward methyl methacrylate (MMA) in radical polymerization reactions. The compositional diagrams revealed a clear correlation between the experimental points of the model monomer MTm and the macromonomer MT. The reactivity ratios of the copolymers were rMTm = 0.97 and rMMA = 0.95, suggesting a tendency for the formation of random copolymers. The glass-transition temperatures (Tg's) of the prepared copolymers were deviated from the Fox equation and are discussed on the basis of treatments that consider the influence of the monomeric units along the copolymer chains, determining the Tg of the corresponding alternating dyads.

    9. Novel route to synthesis of allyl starch and biodegradable hydrogel by copolymerizing allyl-modified starch with methacrylic acid and acrylamide (pages 1650–1658)

      Sankar Prasad Bhuniya, Safikur Rahman, Anshul J. Satyanand, Mahendrasinh M. Gharia and Ashok M. Dave

      Version of Record online: 15 APR 2003 | DOI: 10.1002/pola.10711

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      Maize starch under partially soluble state was reacted with allyl chloride interfacially in the presence of cetyltrimethyl ammonium bromide as a phase-transfer catalyst and pyridine as an acid acceptor. Consequently allyl starch was formed after 24h reaction under room temperature. Then allyl starch was polymerized with methacrylic acid and optionally acrylamide at 50 °C for 10h and 70 °C for 6h in an aqueous medium using the 0.1% potassium persulfate as an initiator. The developed starch-based crosslinked polymer was neutralized by sodium carbonate under wet conditions and finally a granular shaped neutral hydrogel was obtained after drying.

    10. Nanodroplets of polyisoprene fluid contained within poly(acrylic acid-co-acrylamide) shells (pages 1659–1668)

      Haiyong Huang, Tomasz Kowalewski and Karen L. Wooley

      Version of Record online: 10 APR 2003 | DOI: 10.1002/pola.10712

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      The shell crosslinking of amphiphilic block copolymer micelles allowed for the entrapment of fluid hydrophobic polymer chain segments within a nanoscopic domain while attached to the inner surface of the crosslinked shell. The entire nanoscale object then exhibited interesting shape-adaptable behavior upon adsorption onto substrates.

    11. Polymerization of ethylene oxide with a calixarene-based precursor: Synthesis of eight-arm poly(ethylene oxide) stars by the core-first methodology (pages 1669–1676)

      Daniel Taton, Myriam Saule, Jennifer Logan, Randolph Duran, Sijian Hou, Elliot L. Chaikof and Yves Gnanou

      Version of Record online: 11 APR 2003 | DOI: 10.1002/pola.10673

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      Well-defined eight-arm poly(ethylene oxide) stars consisting of a calixarene core were derived by the core-first approach. This was achieved by anionic polymerization of ethylene oxide in tetrahydrofuran as a solvent with a novel octahydroxylated precursor on the basis of tert-butylcalix[8]arene and diphenylmethyl potassium as the deprotonating agent of the hydroxyls.

  2. Rapid Communication

    1. Top of page
    2. Articles
    3. Rapid Communication
    4. Articles
    1. Synthesis of hexylated triethylenetetramine: New ligand for homogeneous atom transfer radical polymerization (pages 1677–1680)

      Metin H. Acar and Niyazi Bicak

      Version of Record online: 15 APR 2003 | DOI: 10.1002/pola.10716

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      A new linear amine ligand with long alkyl chains was synthesized and then used as a ligand in atom transfer radical polymerization of styrene and methyl methacrylate. Homogeneous conditions were observed during polymerizations. Controlled molecular weight and low polydispersities were obtained with reaction rate comparable to literature values.

  3. Articles

    1. Top of page
    2. Articles
    3. Rapid Communication
    4. Articles
    1. Preparation and characterization of crosslinked poly(N,N-diethylacrylamide-co-2-hydroxyethyl methacrylate) resins and their application as support in solid-phase peptide synthesis (pages 1681–1690)

      Zheng Wang, Zhengji Song and X. X. Zhu

      Version of Record online: 17 APR 2003 | DOI: 10.1002/pola.10706

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      Crosslinked poly(N,N-diethylacrylamide-co-2-hydroxyethyl methacrylate) resins were prepared by inverse suspension polymerization. High loading and good thermosensitivity were obtained by adjusting the molar ratio of the monomers in the feed before polymerization. The resins were macroporous with good swelling properties and thermosensitivity in a variety of solvents and can be used in solid-phase peptide synthesis.

    2. Identification of free radicals trapped in solid methacrylated resins (pages 1691–1699)

      Delphine Truffier-Boutry, Xavier A. Gallez, Sophie Demoustier-Champagne, Jacques Devaux, Michèle Mestdagh, Benoît Champagne and Gaëtane Leloup

      Version of Record online: 11 APR 2003 | DOI: 10.1002/pola.10692

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      The polymerization of methacrylated resins is a free-radical process. By studying the reactional mechanism, observing the electron paramagnetic resonance spectra, and simulating them, two free radicals were identified. The propagator radical that gives a nine-line spectrum is superimposed to an allylic radical that gives a five-line spectrum.

    3. Copolymerization of α-terpineol with styrene: Synthesis and characterization (pages 1700–1707)

      Sarika Yadav and A. K. Srivastava

      Version of Record online: 15 APR 2003 | DOI: 10.1002/pola.10704

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      Radical copolymerization of α-terpineol with styrene (Sty) initiated by azobisisobutyronitrile in xylene at 80 ± 0.1 °C for 2 h followed ideal kinetics and resulted in the formation of a functional and alternating copolymer as evidenced by spectral analysis. The activation energy was 28 kJ/mol. α-Terpineol underwent copolymerization as well as a chain-transfer reaction. The values of the monomer reactivity ratios calculated by the Kelen–Tüdos method were r1 (Sty) = 0.033 and r2 (α-terpineol) = 0.004. The Alfrey–Price Q-e parameters for α-terpineol were calculated as 0.104 and 3.052, respectively. The mechanism of copolymerization is elucidated, and it is concluded that the double bond present in the monocyclic ring of α-terpineol is an activesite for copolymerization.

    4. Roles of rhenium diimine complexes as metal-ion probes and photosensitizers in functional polyurethanes (pages 1708–1715)

      Ching Sum Hui, Lillian Sze Man Lam, Chun Yin, Wai Kin Chan and Aleksandra B. Djurišić

      Version of Record online: 15 APR 2003 | DOI: 10.1002/pola.10715

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      A series of polyurethanes containing rhenium diimine complexes were synthesized. The electronic absorption properties of the polymers in solution were modulated by the addition of metal ions. The complexes also acted as photosensitizers, and the photoconducting properties of the polymers were studied in detail.

    5. Homopolymerization of methyl methacrylate by novel salicylaldiminate-nickel/methylaluminoxane catalysts obtained by oxidative addition of the chelate ligand to a nickel(0) precursor (pages 1716–1724)

      Carlo Carlini, Marco Martinelli, Anna Maria Raspolli Galletti and Glauco Sbrana

      Version of Record online: 17 APR 2003 | DOI: 10.1002/pola.10707

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      Novel nickel complexes obtained by oxidative addition of nitro-substituted salicylaldimine ligands to bis(1,5-cyclooctadiene)nickel(0) [Ni(cod)2] were prepared and used in combination with methylaluminoxane (MAO) in the homopolymerization of methyl methacrylate (MMA). The influence of reaction parameters as well as the ligand structure on polymer characteristics and catalysts activity were examined. The activation of the catalytic systems by ethylene atmosphere during their preparation was also investigated.

    6. Conformational analysis of dipeptide-derived polyisocyanides (pages 1725–1736)

      Jeroen J. L. M. Cornelissen, W. Sander Graswinckel, Alan E. Rowan, Nico A. J. M. Sommerdijk and Roeland J. M. Nolte

      Version of Record online: 17 APR 2003 | DOI: 10.1002/pola.10713

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      The conformational properties of polymers derived from isocyanodipeptides have been investigated with a combination of model calculations, X-ray diffraction, and circular dichroism spectroscopy. Depending on the configuration of the side chains, defined arrays of hydrogen bonds along the polymeric backbone are formed. This leads to a well-defined conformation as, for example, expressed in the formation of lyotropic liquid-crystalline phases and increased helical stability. Upon the disruption of the hydrogen bonds by a strong acid, a less well-defined macromolecular conformation is observed.

    7. Synthesis and self-assembly of a chiral alternating sexithiophene–undeca(ethyleneoxy) block copolymer (pages 1737–1743)

      Oliver Henze, Michel Fransen, Pascal Jonkheijm, E. W. Meijer, W. James Feast and Albertus P. H. J. Schenning

      Version of Record online: 17 APR 2003 | DOI: 10.1002/pola.10720

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      An oligothiophene/chiral oligo(ethyleneoxy) block copolymer (PolyT6) has been synthesized in which a sexithiophene block alternates with a well-defined chiral undeca(ethyleneoxy) block. The aggregation of PolyT6 occurs in dioxane; however, no helicity is present in this aggregate. This behavior illustrates that although the processability and mechanical robustness of block copolymers may be superior to those of analogous oligomers, the degree of self-assembled order found in oligomer-based systems may be lost in the polymers.

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