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  • 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 34 (1996), S. 971-984 
    ISSN: 0887-624X
    Keywords: radiation ; polyisobutylene ; NMR ; GC/MS ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: GC, GC/MS, GPC, and Solution NMR spectra were used to study the γ radiolysis of polyisobutylene (PIB) in vacuum to different total doses (0-900 kGy) and at different temperatures (77-423 K). NMR spectra show a large number of new resonances with relatively narrow line widths, and a variety of NMR techniques have been employed to determine and quantify the structures associated with these new resonances. Chemical shift assignments were made by comparison with those for small molecule model compounds and predictions based upon calculations according to several different schemes. Chain-end structures have been proposed that account well for the majority of the new resonances, all being the result of an initial chain scission reaction initiated by the radiation. These assignments support some previous proposals for the mechanism of radiation degradation of polyisobutylene and exclude others. For example, NMR provides no evidence for the formation of ethyl chain ends and some of the main chain unsaturated structures previously proposed. NMR also indicate that at higher doses the chain end products formed during initial stages undergo secondary reactions. GC/MS data show the formation of oligomers during irradiation, which may be due to a backbitting mechanism. © 1996 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Applied Organometallic Chemistry 5 (1991), S. 159-165 
    ISSN: 0268-2605
    Keywords: Organotin ; thermal ; analysis ; decomposition ; Mössbauer ; NMR ; Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Simultaneous thermogravimetry and differential thermal analysis studies on a variety of mono- and di-organotin oxides and carboxylates were performed; for the carboxylates, these studies followed 119Sn NMR spectroscopic investigation. All the organotin compounds thermally degrade to tin (;IV) oxide (;SnO2) in either air or oxygen, as was confirmed by Mössbauer spectroscopy in the cases of RSn(;O)OH (;R=butyl, octyl) and Bu2SnO.The organotins are less stable than previously believed since evidence for degradation was obtained in many cases at approximately 160-170 °C.In addition it was found that oxygen influences the thermal stability of the organotins, since Bu2SnO did not degrade when heated for 1 h at 280 °C under nitrogen, yet readily broke down at 170 °C in air. Furthermore, pure oxygen had the effect of lowering reaction temperatures by approximately 10-12°C compared with those in air.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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