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  • nuclear magnetic resonance (NMR) of polyethylene melts with persistent ordered regions  (1)
  • radiation  (1)
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  • 1
    Electronic Resource
    Electronic Resource
    Mechanism of radiation degradation of polyisobutylene (1996)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 971-984 
    Details
    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.
    Type of Medium: Electronic Resource
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    Paper (German National Licenses)
  • 2
    Electronic Resource
    Electronic Resource
    Persistence of regions with high segment density in polyethylene melts (1992)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 30 (1992), S. 1247-1260 
    Details
    ISSN: 0887-6266
    Keywords: polyethylene melts, persistence of high segmental density regions in ; nuclear magnetic resonance (NMR) of polyethylene melts with persistent ordered regions ; relaxations in polyethylene melts, NMR study of ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Proton nuclear magnetic resonance (NMR) spin-spin relaxation measurements were made on three commercial-grade polyethylenes in the melt state, free of solvent. All samples exhibit a three-component relaxation behavior, with components being assigned to amorphous low-molecular weight material (non-network fraction), amorphous entangled network fraction, and an ordered or high-segmental-density fraction, in order of decreasing relaxation times. Sample thermal history is shown to have a considerable effect on the overall relaxation behavior, and therefore on the relative amounts of each of the three components in the melt. An adequate thermal treatment of samples produces an equilibrium melt with invariant composition of the three fractions. The effects of thermal history on the relative amount of high-segment-density regions in the melt parallels its effect on the fraction of crystalline material in the solid polymer. These results are evidence for the persistence of ordered regions in polyethylene at temperatures well above the crystalline melting point of the polymer. We further comment on the nature of the two slower relaxing components and present examples of how the components manifest themselves in other polymer characterization techniques. © 1992 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/polb.1992.090301110
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