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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 3043-3056 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: γ-Radiolysis of model ketones of the general structure R(C=O)R, neat and in hydrocarbon solution, show that the radio-chemical degradation of these aliphatic ketones can be explained by mechanisms analogous to those generally accepted for the photochemical decompositions of the same compounds. The G (type I) and G (type II) yields are found to decrease with increasing total chain length of the ketone as monitored by the products (R—H) and (CH3CO—R), respectively. Differences in the relative yields of type I and II products are attributed to the higher incident energies involved in γ-radiolysis as compared to ultraviolet photolysis. Evidence is presented for energy transfer from paraffinic solvents to aliphatic ketonic solutes. Solid- and condensed-phase studies show the importance of rotational and diffusional mobility to the yields of the type II and I processes, respectively.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 1469-1491 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The γ-radiolysis of copolymers of ethylene and carbon monoxide (CO-PE) containing 0-9 wt-% of CO has been studied in the solid phase under vacuum with respect to hydrogen production, scission, and crosslinking. In this regard, the introduction of carbonyl groups into polyethylene increased both the scission and crosslinking efficiency. However, a theoretical statistical treatment for random scission and crosslinking, which was used to calculate G(s) and G(x) yields, predicted gelation with irradiation dose; this was confirmed experimentally. The increased G(x) values are attributed to the localization of absorbed energy in the carbonyl group arising from preferential trapping of thermalized secondary electrons. A stoichiometric balance is shown to be consistent with the reduction of one carbonyl group to a secondary alcohol per excess crosslink observed. The G(H2) yield is reduced by the presence of ketone groups to a level which is in close agreement with the yield obtained for the model ketone 12-tricosanone. This quenching of H2 production is explained by intramolecular electronic energy transfer along the chain to the carbonyl group with concomitant intermolecular charge transfer between neighboring molecules.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 3057-3070 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: γ-Radiolysis of copolymers of styrene and methyl vinyl ketone shows that the introduction of pendant carbonyl groups markedly increases the G(s) value as compared to the homopolymer of styrene. The G(x) value is only slightly affected. These efficiencies are determined by employing an established statistical theory for random crosslinking and scission coupled with gel-permeation chromatography as the analytical tool required to follow the changes in the MWD of polymers. Also the G(H2) values are unaltered by the introduction of carbonyl groups in polystyrene. These results are in marked contrast to the effects of carbonyl groups in polyethylene when subjected to γ-radiolysis and can be attributed to the protective role played by the aromatic phenyl groups in polystyrene.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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