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  • polymerization  (1)
  • radicals  (1)
  • 1
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 2439-2454 
    ISSN: 0887-624X
    Keywords: radiation ; nitrile rubber ; NMR ; ESR ; radicals ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mechanism of radiation-induced structural changes in nitrile rubber with different acrylonitrile contents were investigated by ESR, NMR, and FTIR. To investigate new structures solid-state NMR methods had to be used due to crosslinking of the irradiated rubbers, and higher probe temperatures were used to obtain better resolution. The radicals generated on the acrylonitrile groups were found to abstract hydrogen from the adjacent butadiene units resulting in the formation of allylic radicals. These allylic radicals reacted to form intermolecular crosslinks and cyclisation. Cyclisation of the butadiene units were found to occur in the initial stages of the irradiation. Radiation yields of radicals increased with acrylonitrile content from 1.42, 1.58, to 2.42 for 18, 30, and 45% acrylonitrile rubbers. The radiation yields for intermolecular crosslinking were higher in rubbers with higher acrylonitrile contents, giving G values of 17.8, 21.3, and 24.5 for 18, 30, and 45% acrylonitrile rubbers, respectively. However, the crosslink clustering was found to be less in the rubbers with a higher acrylonitrile content. © 1996 John Wiley & Sons, Inc.
    Additional Material: 15 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 30 (1992), S. 851-863 
    ISSN: 0887-624X
    Keywords: polymerization ; kinetics ; free radical ; transfer ; photolysis ; propagation ; rate coefficients ; termination ; EPR ; copolymerization ; initiation ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The problems of determining reliable, well-characterized values of kinetic parameters in free-radical polymerizations are discussed. The origins of the fact that experimental determinations of rate coefficients of ostensibly identical systems often result in quite different values being reported can be ascribed to subtle mechanistic assumptions made in data interpretation, which are considered in detail. A series of recommendations to assist in overcoming these problems, and to highlight their origins, are presented, with emphasis placed on new techniques including those employing laser photolysis and EPR.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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