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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 181 (1980), S. 1215-1226 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(ethylene oxide) was irradiated with pulses of 16 MeV electrons (pulse length up to 100 ns) in aqueous and acetonitrile solutions in the absence and presence of oxygen. The change of the light scattering intensity (LSI) after the pulse was monitored. In acetonitrile solution, at a concentration of 2,3 · 10-2 base mol/1, main chain rupture occurred both in the presence and in the absence of O2. In aqueous solutions at [PEO] = 2,3 · 10-2 base mol/1 the LSI increased after the pulse in the absence of O2 (crosslinking) and decreased at [O2] = 1,4. 10-3 mol/1 (main chain scission). The rate of LSI decrease was correlated with a diffusion process in the case of O2 free acetonitrile solution and with a chemical reaction in the cases of O2 saturated aqueous and acetonitrile solutions. In the latter two cases it was found that a bimolecular reaction precedes bond scission in the main chain. It is assumed that peroxyl macroradicals (PO2•) react with each other forming oxyl macroradicals (PO•) which decompose relatively rapidly by main chain scission.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 184 (1983), S. 123-134 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: This paper deals with the kinetics of reactions of linear flexible macromolecules in solution possessing initially several reactive sites per macromolecule. It is assumed that the reactive sites interact with each other encounter-controlled and that both intra- and intermolecular reactions are possible. On the basis of the theory of stochastic kinetics in microsystems, equations were derived, describing the kinetics of intramolecular reactions as a function of the molecular weight distribution. An important application of this theoretical treatment pertains to the distribution between inter- and intramolecular reactions. A demonstration for typical reaction conditions reveals the influence of rate parameters and of the average number of reactive sites per macromolecule r̄(0) on the proportionate distribution expressed by fA = f (r̄(0)); (fA = fraction of intramolecular reactions). This function is only weakly influenced by varying the width parameter β in the case of Schulz-Zimm molecular weight distributions from β = 1 to → ∞.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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