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  • 1
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 45-50 
    ISSN: 0360-6376
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: The principal volatile products observed after γ irradiation of nine different poly(olefin sulfone)s in the solid state were the two comonomers, i.e., the respective olefin and sulfur dioxide. An exponential increase in yield, G(volatile products), with increasing irradiation temperature, Tirr, was observed for each copolymer through the ceiling temperature, Tc, for the corresponding propagation/depropagation equilibrium. Thus the G value increased by ca. 3 orders of magnitude from Tirr = 0.7 Tc to Tirr = 1.3 Tc for all of the poly(olefin sulfone)s. Depropagation sensitivity was considered to be best measured by G(SO2) since radiation induced, cationic homopolymerization of the product olefin occurred to a variable extent. Five of the poly(olefin sulfone)s had similar rates of depropagation at their respective Tc's but the polysulfones of 1-hexene, cyclohexene and 2-butene showed anomalously high depropagation rates. This may be related to greater steric hinderance to segmental chain mobility in the polysulfones of the 1,2 disubstituted olefins. Poly(1-hexene sulfone) appears to be anomalous, as in other respects.
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 19 (1981), S. 1167-1174 
    ISSN: 0360-6376
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Polystyrene of narrow molecular weight distribution, Mw/Mn ≈ 1.03, was subjected to γ irradiation at 100 and 150°C. The yields of scission and crosslinking, G(S) and G(X), where determined from the changes in molecular weight distribution using gel permeation chromatography, (GPC) with supporting evidence from osmometry and viscometry. The ratio G(S)/G(X) increased from 0.02 at 30°C, obtained previously, to 2.8 at 150°C. This was mainly due to a tenfold increase in G(S), whereas G(X) apparently decreased slightly. These results are compatible with increased disproportion of chain scission radicals relative to their combination, analogous to the temperature dependence of mutual termination in the free radical polymerization of styrene. There was no obvious discontinuity through the glass transition temperature, although there may be a change in sign of the temperature coefficient of G(X). This system provides an excellent example of the applicability of measurements of molecular weight distributions and averages to determinations of G(S) and G(X) under conditions when gel measurements are inappropriate, either because of the failure of the system to form gel, or, as in the present case, because of the very large radiation doses required for gel formation.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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