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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. 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.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 57 (1995), S. 271-286 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A commercial linear low density polyethylene (1-hexene comonomer) was reacted with dicumyl peroxide at appropriate levels to initiate chain extension without crosslinking. The peroxide modification was carried out both in the presence and absence of a common hindered phenolic antioxidant. Thermal treatment of the resin was also completed with and without antioxidant present to evaluate the contribution of classical thermooxidative degradation to the peroxide modification process. In terms of pure thermal degradation, the phenolic antioxidant was found to be effective in prevention of reduction of molecular weights at the high end of the molecular weight distribution, as reflected in changes in Mz. At the low end of the distribution, the opposite effect is seen, where the removal of the antioxidant actually allows an increase in the value of Mn, through chain coupling reactions. Processing of the resin with addition of the organic peroxide significantly increases the molecular weights of both antioxidant containing and antioxidant free resins. Increasing the reaction temperature increases the rate of degradative chain scission and nonenlarging disproportionation reactions. At low temperatures, the presence of the antioxidant acts negatively with respect to chain enlargement reactions, and an overall reduction is seen in the efficiency of the peroxide in its role of increasing molecular weights. As the reaction temperature is increased, chain scission reactions become more predominant, and the antioxidant free resin shows very substantial decreases in molecular weight. Retention of the antioxidant at higher reaction temperatures is beneficial to maintaining high molecular weights, both with and without peroxide present. As in the peroxide free case, branching is essentially unchanged by the absence of antioxidant in peroxide modification. © 1995 John Wiley & Sons, Inc.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 49 (1993), S. 785-798 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: A commercial-grade LLDPE resin was cross-linked using three different dialkyl peroxides, at three different concentrations. The peroxides were ranked in order of their Cross-linking efficiency and their effectiveness at increasing the storage modulus of the virgin resin at the cure temperature. The chemical mechanism by which the cross-linking occurs is shown to be closely related to the changes in concentrations of reactive vinyl species on the polyethylene molecules, which follows well with proposed mechanisms of previous publications. Finally, a direct relationship is shown to exist between the rate of peroxide decomposition and the rate of increase in storage modulus of the rubbery modified resin during the curing reaction. © 1993 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 34 (1996), S. 1893-1902 
    ISSN: 0887-6266
    Keywords: Proton NMR ; T2 relaxation ; polyethylene ; polymer melts ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Three commercially produced polymer samples (polyethylene, polypropylene, and polystyrene) have been analyzed in the melt state using proton nuclear magnetic resonance (NMR) T2 relaxation methods using the Carr-Purcell-Meiboom-Gill (CPMG) spin-echo pulse sequence. Samples were run with exposure to air and again after extensive degassing at a vacuum of 10-4 mmHg for periods of not less than 96 h. The comparison is made by initially considering the presence of microscopic voids in the samples as a source of local field inhomogeneity and how they affect the T2 relaxation behavior. For PP and PS samples, degassing caused a decrease in all T2 time constants associated with the multicomponent decays. The component intensities each of the time constants was also significantly altered. For the PE sample, degassing caused a decrease in the time constants associated with the amorphous material in the molten polymer. Examination of the fastest relaxing component of the three component decay showed approximate invariance in the T2 decay constant. This result supports our previously reported model in which that fast relaxing component is attributable to regions of local order or high segmental density within the molten polyethylene, a remnant of the crystalline material which exists in the premelting bulk polymer. The results of this research are of particular significance to those who wish to use this NMR technique as a quantitative method of determination of NMR distinct morphological regions within heterogeneous polymers. © 1996 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 30 (1992), S. 1247-1260 
    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.
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  • 6
    Publication Date: 1997-05-01
    Print ISSN: 0014-3057
    Electronic ISSN: 1873-1945
    Topics: Chemistry and Pharmacology , Physics
    Published by Elsevier
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  • 7
  • 8
    Publication Date: 2003-09-16
    Print ISSN: 0888-5885
    Electronic ISSN: 1520-5045
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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