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  • Wiley-Blackwell  (2)
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  • 1
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: When heated in a vaccum at 325° to 375°C., polystyrene yields mainly the monomer and some dimer, trimer, tetramer, etc., indicating that the breaks in the molecular chains occur largely at the ends. Polyethylene, under similar conditions, but at a some-what higher temperature, yields fragments of an average molecular weight of about 700, indicating that the molecular chains break, mostly at random positions. A study was made of rates of thermal degradation of these two polymers by measuring rates of loss of weight of samples by means of a very sensitive tungsten spring balance enclosed in a vaccum. The samples were limited to 5-6 mg. in order to avoid spattering during degradation. Rate curves plotted against per cent loss of weight by volatilization indicate that in the case of polystyrene the process is intermediate between a zero and first order reaction, while in the case of polyethylene, the process approximates a first order reaction. Activation energies were calculated on the basis of rates of degradation at various temperatures. The values thus obtained for polystyrene and polyethylene are 58 and 68 kilocalories, respectively.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 4 (1949), S. 639-664 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Samples of polyisobutene, polyisoprene, polybutadiene, GR-S, and polyethylene, weighing about 25 to 50 mg., were pyrolyzed in a vacuum of about 10-6mm. of mercury in a specially designed apparatus at temperatures ranging between 300 to 475°C. The volatile products of pyrolysis were separated into four fractions: (IV) gaseous, volatile at -196°; (IIIA) liquid, at -75°, (IIIB) liquid, at 25°; and (II) waxlike fraction, volatile at the temperature of pyrolysis. The gaseous fraction was analyzed in the mass spectrometer and was found to consist in all cases of CH4. The liquid fraction, IIIA, was analyzed similarly and was found to give a mass spectrum characteristic for any given polymer. A molecular weight determination of the waxlike fraction by the micro freezing point-lowering method, showed it to vary from 543 to 739, depending on the polymer from which the fraction was obtained. It is shown that the method of pyrolytic fractionation of high molecular weight polymers, in conjunction with mass spectrometer analysis of the more volatile fractions, can serve as a means of identifying the polymers.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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