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  • 1
    Electronic Resource
    Electronic Resource
    D2-m-carborane-siloxanes. III. Preparation and properties of trifluoropropyl-modified polymers (1977)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 973-981 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Linear D2-m-carborane-siloxanes with one, two, and three trifluoropropyl moieties per repeat unit were prepared by the condensation reaction between bisureidosilanes and carborane disilanol. Molecular weights between 100,000 and 220,000 were obtained. Compared to fluorosilicones, the trifluoropropyl-modified carborane-siloxanes exhibited greater thermal and oxidative stability and in certain cases comparable solvent resistance. The swelling index for carborane-siloxane elastomers decreased with increasing trifluoropropyl content, although this fluorocarbon moiety did compromise the thermal stability of the carborane system.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1977.170150418
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  • 2
    Electronic Resource
    Electronic Resource
    The photo- and electroinitiated polymerization of N-vinyl phthalimide (1979)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1153-1161 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To elucidate mechanisms in electroinitiated polymerization reactions a comparison was conducted between ultraviolet (UV) photoinitiation and electroinitiation of N-vinyl phthalimide with zinc chloride as a catalyst. Both methods give low yields of a complex polymer product. A detailed analysis, infrared (IR), gel permeation chromatography (GPC), elemental, and molecular weight, conducted on the polymeric products, indicated that phthalimide ring opening was occurring and that complex mixtures of poly(N-vinyl phthalimide) derivatives were formed. Both initiation methods gave comparable results, which further indicated mechanistic similarity between photo-and electroinitiation in these donor-acceptor charge transfer polymerizations.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1979.170170419
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  • 3
    Electronic Resource
    Electronic Resource
    Electroinitiated polymerization of 2-vinylnaphthalene (1977)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1563-1571 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: As part of a program to extend the range of donor-acceptor-initiated polymerization processes, the electroinitiation of 2-vinylnaphthalene in a zinc chloride-sulfolane solution has been studied. Good conversion yields of well-characterized (NMR, IR, GPC, elemental analysis) poly(vinylnaphthalene) were obtained with the process showing several mechanistic similarities to other donor-acceptor salt electropolymerization systems.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1977.170150704
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  • 4
    Electronic Resource
    Electronic Resource
    Electrochemically initiated polymerization of styrene with tetraalkyl and -aryl group VA halide support electrolytes (1977)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1555-1562 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electrochemically initiated polymerization of styrene in methylene chloride solvent with the use of platinum electrodes and tetraalkyl and -aryl group VA halides (i.e., quaternary ammonium, phosphonium, and arsonium compounds) as electrolyte has been investigated. The order of reactivity of the electrolytes with respect to polymerization rate and initiation efficiency was found to be: arsonium 〉 phosphonium 〉 ammonium. Mechanisms involving the electroreduction of the group VA quaternary halides to species capable of electroinitiating polymerization are postulated. The observed losses in solution conductivities during polymerization with the quaternary phosphonium and arsonium electrolytes indicate possible interaction between the initiating radical-ionic species and the supporting electrolyte. In an attempt to further elucidate the mechanism of initiation in these systems, a separate series of experiments, employing the nonpolymerizing monomer, 1,1-diphenylethylene, has been carried out.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1977.170150703
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  • 5
    Electronic Resource
    Electronic Resource
    Photoinitiation and electroinitiation in the polymerization of 2-vinylnaphthalene (1977)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2673-2684 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The zinc chloride-catalyzed polymerization of 2-vinylnaphthalene (VN) with both photoinitiation and electronitiation methods was examined. Good yields were obtained with both methods, the electroinitiated process being somewhat faster. The mechanism for polymerization initiation was investigated through a detailed comparison of the kinetics. Both initiation methods show a similar response to increasing input energy and to change in salt to monomer mole ratio. Both methods indicate formation of a ZnCl2-(2-VN)2 complex as intermediate with the formation of the species being rate-determining. These results, together with other similar investigations, are then used to deduce a mechanism that involves the formation of an electronically excited donor-acceptor complex. It is argued that in certain salt-stabilized, electron-delocalized, aromatic systems, such excitation is possible in electroinitiation.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1977.170151112
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  • 6
    Electronic Resource
    Electronic Resource
    Electroinitiated polymerization of arylvinyl monomers (1979)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1411-1418 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electroinitiated polymerizations of styrene, 2-vinylnaphthalene, and 9-vinylanthracene were compared in sulfolane and acetone solvents in the presence of ZnCl2. The relative orders of polymerization rates and polymerization efficiencies, in both solvents, were 9-vinylanthracene 〉 2-vinylnaphthalene 〉 styrene, with faster rates and higher efficiencies occurring in sulfolane. Data obtained from viscosity and gel permeation chromatography (GPC) studies indicate that the molecular weights of the polymers produced in these systems are extremely low, 〈5000. Chemical composition and infrared (IR) spectral data suggest that abnormal transfer reactions (possibly from solvent) may be occurring in the electroinitiated 9-vinylanthracene polymerizations. The polymerization mechanism appears to be cationic in these monomer-solvent systems with ZnCl2.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1979.170170515
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  • 7
    Electronic Resource
    Electronic Resource
    Cyclopolymerization of diallylsilanes (1977)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 675-681 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A survey has been made of the polymerizability of diallysilanes, including a number of new compounds. Rates of polymerization are generally low with radical or Ziegler-Natta techniques, but excellent yields are often obtained when the initiator is aluminum bromide.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1977.170150314
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  • 8
    Electronic Resource
    Electronic Resource
    Photodegradation of aramids. I. Irradiation in the absence of oxygenIssued as NRCC No. 16 878. (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 2353-2363 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis reactions of a series of isomeric fully aromatic polyamides (aramids) have been investigated in the absence of oxygen by ultraviolet and luminescence spectroscopy. Several of the aramids were found to undergo photo-Fries rearrangements to give 2-aminobenzophenone backbone units when irradiated either as films, fibers, or dissolved in liquids. Quantum yields for this rearrangement were low, 〈 1 × 10-6 mole/einstein, and increased with decreasing aramid glass transition temperature and increasing backbone mobility. The formation of gel, carbon monoxide, and a strong ESR signal were consistent with a free-radical mechanism for the rearrangement.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1978.170160922
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  • 9
    Electronic Resource
    Electronic Resource
    Photodegradation of aramids. II. Irradiation in airIssued as NRCC No. 16 875 (1978)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 16 (1978), S. 2365-2376 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of isomeric fully aromatic polyamides (aramids) were photodegraded in the presence of oxygen. Films and fibers of these aramids gave carboxylic acids as the major products when measured by infrared spectroscopy and potentiometric titration. These acids probably resulted from the oxygen interception of the radicals generated by photocleavage of the amide bonds. In contrast to results found upon irradiation in the absence of oxygen, carboxylic acid formation was accompanied by a rapid loss in molecular weight, and a decrease in useful mechanical properties. Quantum yields for carboxylic acid formation were ≤5.5 × 10-5 mole/einstein and decreased along the aramid series roughly in agreement with increases in Tg. The photo-Fries rearrangement product was observed in aramid fibers irradiated in air, whereas no rearrangement product was seen in films irradiated in air.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1978.170160923
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  • 10
    Electronic Resource
    Electronic Resource
    ESCA applied to polymers. XXII. An investigation of sample charging phenomena for polymeric films on gold (1979)
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 627-638 
    Details
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Sample charging phenomena arising in the ESCA experiment have been investigated for gold and polymer films of known thickness ranging from 5 Å to 20 μ deposited on gold either insulated from or in electrical contact with the spectrometer. Charging induced by a monochromatic x-ray source is typically an order of magnitude greater than that induced by a nonmonochromatized source and exhibits a marked time dependence. A novel source of secondary electrons which employs a low-power, low-pressure mercury lamp external to the spectrometer source chamber as an alternative to an electron flood gun is described, and the charging and biasing characteristics of polymer films as a function of film thickness are discussed and demonstrated to provide an extra informational dimension for the study of polymeric materials.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/pol.1979.170170302
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