Journal of Polymer Science Part A: Polymer Chemistry

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

1 September 2002

Volume 40, Issue 17

Pages 2895–3092

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      Ruthenium-based metathesis initiators: Development and use in ring-opening metathesis polymerization (pages 2895–2916)

      Ulrich Frenzel and Oskar Nuyken

      Version of Record online: 10 JUL 2002 | DOI: 10.1002/pola.10324

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      For many years now, olefin metathesis has been a central topic of research because of its great synthetic utility. Suitable initiators cover a wide range of compounds, from simple transition-metal salts to highly sophisticated and well-defined alkylidene complexes. This article focuses on recent developments in the field of ruthenium-based catalysts for olefin metathesis. Initiators and their applications for the synthesis of advanced polymeric materials are briefly reviewed.

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    1. Characterization of the surface content, hydrolysis ratio, and condensation degree of polyalkoxysiloxane segregated to the surface of a polyurethane crosslinked film by X-ray photoelectron spectroscopy (pages 2917–2926)

      R. Tomita, S. Urano and S. Kohiki

      Version of Record online: 11 JUL 2002 | DOI: 10.1002/pola.10331

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      Unmonochromatized Mg Kα X-ray irradiation of the surface of a film extremely accelerated the decomposition of alkoxy groups of polyalkoxysiloxane. The surface content and hydrolysis ratio of polyalkoxysiloxane were determined from C 1s, Si 2p, and N 1s spectral intensities measured with monochromatized Al Kα X rays after decomposition by unmonochromatized Mg Kα X-ray irradiation. The condensation degree was determined by the kinetic energy of the silicon KLL Auger electron after decomposition. A method for characterizing the practical properties of coating film surfaces (i.e., the water contact angle and crack density) was established.

    2. Synthesis and characterization of luminescent polyethers with 2,5-distyrylthiophene and aromatic oxadiazole chromophores (pages 2927–2936)

      Yun Chen, Yu-Yi Huang and Tzi-Yi Wu

      Version of Record online: 12 JUL 2002 | DOI: 10.1002/pola.10383

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      Two luminescent copolyethers (P1 and P2) with isolated 2,5-distyrylthiophene-emitting segments and electron-transporting 2,5-diphenyl-1,3,4-oxadiazole chromophores were synthesized by the Horner–Wadworth–Emmons reaction. Their solubility, optical, and electrochemical properties were investigated and correlated with nonlinear thiophene and 1,3,4-oxadiazole groups. P2 was soluble in common organic solvents such as chloroform, tetrahydrofuran, and C2H2Cl4. The copolyethers were thermally stable below 345 °C, with glass-transition temperatures higher than 110 °C. They were yellow-greenish emitting materials with band gaps around 2.57–2.58 eV. Incorporating the thiophene moiety narrowed the band gaps of the copolyethers. The photophysical and electronic properties of the polymer and the preliminary electroluminescent device made from the polymer demonstrate that the polymer may be a potential candidate material for the fabrication of polymeric light-emitting devices.

    3. Synthesis of thioether derivatives of brominated poly(isobutylene-co-isoprene): Direct coupling chemistry for silica reinforcement (pages 2937–2944)

      J. Scott Parent, Greg D. F. White and Ralph A. Whitney

      Version of Record online: 11 JUL 2002 | DOI: 10.1002/pola.10381

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      Base-mediated nucleophilic substitutions of the allylic halide within halogenated poly(isobutylene-co-isoprene) with thiols were demonstrated. The resulting thioether products were characterized with spectroscopic analysis of the polymer and NMR and mass spectrometry analysis of an appropriate model compound. The desired substitution products were produced in high yields under conditions that limited the extent of base-catalyzed air oxidation of the thiol to disulfide.

    4. Radical polymerization behavior of ethyl ortho-(4-phenyl-1,3-dioxolan-2-yl)phenyl fumarate (pages 2945–2955)

      Makiko Seno, Seigo Sunagawa and Tsuneyuki Sato

      Version of Record online: 12 JUL 2002 | DOI: 10.1002/pola.10374

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      Radical polymerization of ortho-(4-phenyl-1,3-dioxolan-2-yl)phenyl fumarate (EPDPF) proceeds in a complicated manner involving vinyl addition, intramolecular hydrogen abstraction, and ring opening of the cyclic acetal. The homogeneous polymerization system involves ESR-observable polymer radicals under the actual polymerization conditions. The apparent rate constants of propagation and termination were determined by electron spin resonance.

    5. Facile synthesis of comb, star, and graft polymers via reversible addition–fragmentation chain transfer (RAFT) polymerization (pages 2956–2966)

      John F. Quinn, Rodney P. Chaplin and Thomas P. Davis

      Version of Record online: 15 JUL 2002 | DOI: 10.1002/pola.10369

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      Reversible addition–fragmentation chain transfer (RAFT) polymerization has been shown to be a facile means of synthesizing comb, star, and graft polymers of styrene. The precursors required for these reactions were synthesized readily from RAFT-prepared poly(vinylbenzyl chloride) and poly(styrene-co-vinylbenzyl chloride), which gave intrinsically well-defined star and comb precursors.

    6. Synthesis and functionalization of poly(ether sulfone)s based on 1,1,1-tris(4-hydroxyphenyl)ethane (pages 2967–2978)

      Hans R. Kricheldorf, Lali Vakhtangishvili and Detlev Fritsch

      Version of Record online: 11 JUL 2002 | DOI: 10.1002/pola.10372

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      The polycondensation of silylated tris(4-hydroxyphenyl)ethane with 4,4′-difluorodiphenyl sulfone yielded cyclic and branched poly(ether sulfone)s. The pendant hydroxy groups were functionalized by various alkylation and acylation reactions.

    7. Supported stereospecific metallocene binary catalyst for propylene polymerization (pages 2979–2986)

      Maria de Fátima Vieira Marques, Carla Camargo Pombo, Rodrigo Azevedo Silva and Anunciata Conte

      Version of Record online: 17 JUL 2002 | DOI: 10.1002/pola.10380

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      In this work, propylene was polymerized with isospecific and syndiospecific catalysts in homogeneous and heterogeneous systems. The binary metallocene system of both isospecific and syndiospecific catalysts in the heterogeneous system was also used. Besides the type of catalyst, parameters such as polymerization temperature and pressure were varied to achieve the better conditions for the polymerization. The objective of this work is to investigate the influence of these parameters on the characteristics of the produced polymer.

    8. Poly(4-vinylpyridine) as the host ligand of metal-containing chromophores for second-order nonlinear optical active materials (pages 2987–2993)

      Ugo Caruso, Antonella De Maria, Barbara Panunzi and Antonio Roviello

      Version of Record online: 18 JUL 2002 | DOI: 10.1002/pola.10386

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      The synthesis and characterization of a new class of metallated polymers obtained by the grafting of organometallic fragments to poly(4-vinylpyridine) is reported. The facile synthetic route for the polymers and the nonlinear optics (NLO) properties of organometallic chromophores make these materials promising for second-order NLO applications.

    9. Reactive surfactants in heterophase polymerization: Colloidal properties, film-water absorption, and surfactant exudation (pages 2994–3000)

      Javier I. Amalvy, Maria J. Unzué, Harold A. S. Schoonbrood and José M. Asua

      Version of Record online: 18 JUL 2002 | DOI: 10.1002/pola.10385

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      The performances of latexes prepared with a maleate ionic polymerizable surfactant (surfmer) and a conventional ionic surfactant were compared. The latex prepared with the surfmer had better mechanical stability. In addition, water adsorption is less and exudation of surfactant to the film surface can be prevented with the surfmer.

    10. Polymerizable benzophenone derivatives for labeling vinyl acetate-butylacrylate latex particles (pages 3001–3011)

      Jung Kwon Oh, Jun Wu, Mitchell A. Winnik, Gary P. Craun, Jude Rademacher and Rajeev Farwaha

      Version of Record online: 18 JUL 2002 | DOI: 10.1002/pola.10384

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      Three new polymerizable benzophenone derivatives [2-acryloxy-5-methyl benzophenone (8), 4′dimethylamino-2-acryloxy-5-methyl benzophenone (9), and 4′dimethylamino-2-(β-acryloxyethyl)oxy-5-methyl benzophenone (10)] were synthesized. These monomers can be successfully incorporated into vinyl acetate (VA) copolymer latex aprticles. These particles were prepared by semicontinuous emulsion polymerization and mini-emulsion polymerization of VAc with butylacrylate (BA) for Vac/BA = 4/1 by weight. The two monomers 9 and 10 bearing the 4′-dimethylamino group satisfy the important spectroscopic criteria required of a dye to serve as an acceptor chromophore for nonradiative energy transfer from phenanthrene (Phe) as the donor. Their UV absorption spectra show significant overlap with the emission spectrum of Phe, which can be incorporated into P(VAc-BA) latex through copolymerization with 9-acryloxymethyl Phe (2). In addition, these chromophores provide a window in their absorption spectra for excitation of the Phe chromophore at 300 nm.

    11. Photoimageable polyimides derived from α,α-(4-amino-3,5-dimethylphenyl)phenylmethane and aromatic dianhydride (pages 3012–3020)

      Z. G. Qian, Z. Z. Pang, Z. X. Li, M. H. He, J. G. Liu, L. Fan and S. Y. Yang

      Version of Record online: 19 JUL 2002 | DOI: 10.1002/pola.10390

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      Inherent photoimageable polyimides were prepared from α,α-(4-amino-3,5-dimethylphenyl)phenylmethane (BADP) and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA). The polyimides possessed good combined chemical and physical properties. The solubility of the polyimides was improved by the combined effects of the pendant phenyl groups and the methyl groups in the polymer backbone. Homogeneous polyimide solutions in common organic solvents with solid contents as high as 20 wt % were prepared. Fine patterns were processed by direct exposure of the polyimide coatings to UV i-line, followed by development with an organic developer.

    12. Peroxide-mediated crosslinking of poly(ethylene oxide) (pages 3021–3026)

      Shahriar H. Emami, Ronald Salovey and Thieo E. Hogen-Esch

      Version of Record online: 19 JUL 2002 | DOI: 10.1002/pola.10367

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      The chemistry of the crosslinking of poly(ethylene oxide) (PEO) in the presence of bisperoxides is likely to lead to acetals and/or orthoesters or similar species that are predicted to undergo PEO cleavage upon the swelling of gels in dilute acids. This idea is supported by the decrease in the elastic modulus loss with time in the presence of 0.02 M sulfuric acid. Unmodified PEO does not undergo similar chain cleavage, as demonstrated by viscosity measurements.

    13. Synthesis and characterization of a fluorinated polyanhydride (pages 3027–3036)

      Sarjit Kaur, Allison Doerr, Adrienne Thompson and Charlie Dalby

      Version of Record online: 19 JUL 2002 | DOI: 10.1002/pola.10388

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      The synthesis of a fluorinated aromatic polyanhydride (B) from mixed anhydrides of an aromatic diacid (A) is reported. Polymer B was soluble in tetrahydrofuran and chloroform, was amorphous with a glass-transition temperature of 176 °C, and showed an enhanced rate of degradation in an aqueous phosphate buffer of pH 7.4 at 37 °C.

    14. Synthesis and properties of waterborne self-crosslinkable sulfo-urethane silanol dispersions (pages 3037–3045)

      Kevin Lewandowski, Larry R. Krepski, Daniel E. Mickus, Ralph R. Roberts, Steven M. Heilmann, Wayne K. Larson, Mark D. Purgett, Steven D. Koecher, Stephen A. Johnson, Daniel J. McGurran, Chris J. Rueb, Sadanand V. Pathre and Khalid A. M. Thakur

      Version of Record online: 22 JUL 2002 | DOI: 10.1002/pola.10389

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      A novel type of crosslinkable waterborne polyurethane ionomer was prepared by the acetone process. Two new types of sulfonated diols compatible with this process were synthesized. Isocyanate-terminated polyurethane oligomers were prepared from the sulfonated diols with various combinations of diols and diisocyanates and subsequently reacted with amino silane derivatives. Stable, low-volatile organic chemical, waterborne dispersions of the sulfo-urethane silanol polymers spontaneously crosslink upon drying without extra additives or processing steps. Tensile strengths up to 6000 psi with elongations between 300 and 600% were obtained for the crosslinked films.

    15. Phthalide as an activating group for the synthesis of poly(aryl ether phthalide)s by nucleophilic aromatic substitution (pages 3046–3054)

      Daniel M. Knauss and Jack T. Bender

      Version of Record online: 22 JUL 2002 | DOI: 10.1002/pola.10387

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      The phthalide ring of 3,3-bis(4-fluorophenyl)phthalide was examined as an activating group for nucleophilic aromatic substitution both experimentally and by theoretical calculations. Polymers were produced from bisphenol A, hydroquinone, and phenolphthalein and were characterized by gel permeation chromatography, matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, NMR spectroscopy, and differential scanning calorimetry.

    16. Photocrosslinking system based on a poly(vinyl phenol)/thermally degradable diepoxy crosslinker blend (pages 3055–3062)

      Haruyuki Okamura, Shogo Toda, Masahiro Tsunooka and Masamitsu Shirai

      Version of Record online: 22 JUL 2002 | DOI: 10.1002/pola.10394

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      Photocrosslinkable systems with thermally cleavable properties based on blends of poly(vinyl phenol) (PVP) and diepoxides were investigated. Thermally cleavable diepoxides as crosslinkers were prepared and characterized. PVP/crosslinker blended films containing photoacid generators (PAGs) became insoluble in solvents after UV irradiation and subsequent post-exposure-bake (PEB) treatment. With a rise in the PEB temperature, the insoluble fraction of the irradiated films increased, passed through a maximum value, decreased, and increased again at elevated baking temperatures. The insolubilization profiles of the irradiated films were complicated and strongly dependent on the type of PAG used, the structure of the crosslinkers, and the PVP/crosslinker ratio.

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      Micelle formation of poly(vinyl phenol)-block-polystyrene by α,ω-diamines (pages 3063–3067)

      Eri Yoshida and Shigeru Kunugi

      Version of Record online: 23 JUL 2002 | DOI: 10.1002/pola.10399

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      A well-defined poly(4-vinyl phenol)-block-polystyrene (PVPh-b-PSt) diblock copolymer was prepared by 2,2,6,6-tetramethylpiperidinyl-1-oxy-mediated living radical polymerization. The block copolymer dissolved only in good solvents for both poly(4-vinyl phenol) and polystyrene blocks. This nonamphiphilic PVPh-b-PSt copolymer showed micellization in the solvents in the presence of α,ω-diamines. Dynamic light scattering demonstrated that PVPh-b-PSt with 9610-b-68,800 as the molecular weight formed micelles with 25–30-nm hydrodynamic radii in the presence of ethylenediamine, 1,4-butanediamine, or hexamethylenediamine. Steric hindrance in diamines and excessively long chains between amino groups prevented micellization of the copolymer.

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    1. Poly(acrylamide) grafts on spherical bead polymers for extremely selective removal of mercuric ions from aqueous solutions (pages 3068–3078)

      H. Bulbul Sonmez, B. F. Senkal and N. Bicak

      Version of Record online: 23 JUL 2002 | DOI: 10.1002/pola.10392

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      Poly(acrylamide) grafted from solid polymer particles provides a simple solution for extremely selective removal of mercuric ions from aqueous solutions. The grafting of polyacrylamide has been performed, in high yields (166%), by redox initiation from iminoacetic acid groups created on crosslinked spherical beads (210–420 μm) of glycidyl methacrylate/methyl methacrylate/ethylene glycol dimethacrylate terpolymer.

    2. Influence of diluent composition on the porous structure of methacrylate copolymers (pages 3079–3085)

      Barbara Gawdzik and Małgorzata Maciejewska

      Version of Record online: 23 JUL 2002 | DOI: 10.1002/pola.10397

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      Three different copolymers were synthesized—styrene-divinylbenzene, ethylene glycol dimethacrylate-divinylbenzene, and 1,4-phenylene dimethacrylate-divinylbenzene. All the copolymers were porous. As a pore-forming diluent, the mixture of toluene (good solvent) and n-dodecane (nonsolvent) was used. The influence of the composition of two-component diluent on the porous structure of the copolymers (surface areas, pore volumes, pore size distributions, skeletal and apparent densities, and swellability coefficients) was determined.

    3. Copolymerization of 1,3-butadiene and isoprene with cobalt dichloride/methylaluminoxane in the presence of triphenylphosphine (pages 3086–3092)

      Dilip C. D. Nath, Takeshi Shiono and Tomiki Ikeda

      Version of Record online: 23 JUL 2002 | DOI: 10.1002/pola.10395

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      The copolymerization of 1,3-butadiene and isoprene was achieved at 0 °C with cobalt dichloride in combination with methylaluminoxane and triphenylphosphine (Ph3P). The copolymerization proceeded only in the presence of Ph3P. Both the yield and molecular weight of the copolymer decreased with an increasing amount of isoprene in the feed, and this was followed by an increase in the isoprene content in the copolymer. The monomer reactivity ratios, r1 (1,3-butadiene) and r2 (isoprene), were estimated to be 2.8 and 0.15, respectively. Although the 1,3-butadiene content in the copolymer was strongly dependent on the comonomer composition in the feed, the ratio of 1,2-inserted units to 1,4-inserted units of 1,3-butadiene was constant.

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