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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 2591-2600 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of γ-radiation on aqueous polystyrene emulsions were followed by measurements by intrinsic viscosities of soluble polymer in toluene. Estimates of incipient gel dose from intrinsic viscosity data do not coincide closely with those from measurements of gel content. This uncertainty and those in molecular weight averages make it difficult to assign a precise value to G(crosslink), even when the scission crosslinking ratio in the particular system is reliably known. The intrinsic viscosity of sol polymer in the postgel region decreases with increasing dose to an asymptotic value. The decrease is as expected if larger molecules are progressively linked into the gel network and the asymptote may be attributable to cyclization. Present theories of branching do not seem to be applicable for quantitative estimation of scission/crosslinking ratios caused by irradiation of polystyrene. This is probably connected with deficiencies in the theoretical connection between radius of gyration and intrinsic viscosity in good solvents. Diallyl fumarate and diallyl maleate increased crosslinking rates, but only at low doses. Chain scission was enhanced by addition of 1,2-dichloroethylene and 2,5-dimethylhexane-2,5-dihydroperoxide.
    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 Part A-1: Polymer Chemistry 10 (1972), S. 3589-3603 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aqueous polystyrene emulsions were subjected to γ-irradiation at 30°C and 0.6 Mrad/hr dose rate. Analogy with water-soluble systems suggests that such conditions might suppress chain scission and favor crosslinking. The (extrapolated) infinite-dose gel content and gel-permeation analysis of the polymer in the pre-gel region indicate that the extent of chain scission was negligible. The G (crosslink) value obtained from the dose for incipient gelation and molecular weight variations in the pre-gel region is 0.051. Charlesby-Pinner plots were linear, but linearity cannot be construed as indicating that chain scission has produced an effective random molecular weight distribution. Our results are consistent with the conclusions that crosslinking events are random and directly proportional to dose. The probability that a given crosslink is effective in increasing the gel content decreases with dose past the incipient gel point, however, because of cyclization on preformed gel. The crosslink density/dose ratio is a decreasing function of dose in this range. Attempts to predict dose-gel relations with assumptions of various initial molecular weight distributions were unsuccessful, possibly because of the neglected influence of cyclization on the measured gel content.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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