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  • Articles: DFG German National Licenses  (3)
  • Electronic Resource  (3)
  • 1970-1974  (3)
  • Polymer and Materials Science  (3)
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  • Articles: DFG German National Licenses  (3)
Material
  • Electronic Resource  (3)
Years
Year
  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 2209-2223 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The influence of the reactivity of the starting compounds and reaction conditions on the formation of the macromolecules of copolymers has been investigated for a nonequilibrium copolycondensation in solution by acceptor-catalytic polyesterification. In the nonequilibrium copolycondensation in solution, copolymers with different distributions of units may be formed, depending on various factors. Introduction of all amounts of acid chloride (intermonomer) in the beginning of the nonequilibrium copolycondensation leads to the formation of copolymers with statistical distribution of the units independent of the difference in reactivity of the comonomers used. For synthesis of copolymers with a block structure by one-stage nonequilibrium polycondensation in solution the initial comonomers must have different reactivities (r ≠ 1) and the rate of intermonomer introduction must be lower than that of its reaction with the more reactive comonomer. On varying the above factors, block copolymers with different lengths of block segments may be obtained.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The propagation rate constant Kp was used as a measure of reactivity of propagation centers in ethylene polymerization with oxide catalysts. This constant was determined by a radiotracer quenching technique for oxide catalysts of different compositions and activation conditions. For catalysts based on various transition metal oxides, an increase of Kp was observed in the series W 〈 Mo 〈 Cr and V 〈 Cr. In the case of chromium oxide catalyst it was shown that Kp value does not depend on the content of the transition metal in a catalyst. A change of propagation center reactivity was found when oxides of different composition (SiO2, Al2O3, ZrO2, TiO2) were used as supports. An increase of the vacuum activation temperature of a catalyst results in increasing Kp. Pretreatment of catalyst with different reducing agents (SO2, CO2, NH3, HCN) results in the change of Kp value in comparison in comparison with the catalyst activated by the vacuum treatment only. The data obtained on the variation of the reactivity of the propagation centers permit one to draw a conclusion about the composition of surface compounds as acitve centers of the oxide polymerization catalysts.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 9 (1971), S. 3129-3146 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The quenching of polymerization with a chromium oxide catalyst by radioactive methanol 14CH3OH enables one to determine the concentration of propagation centers and then to calculate the rate constant of the propagation. The dependence of the concentration of propagation centers and the polymerization rate on reaction time, ethylene concentration, and temperature was investigated. The change of the concentration of propagation centers with the duration of polymerization was found to be responsible for the time dependence of the overall polymerization rate. The propagation reaction is of first order on ethylene concentration in the pressure range 2-25 kg/cm2. For catalysts of different composition, the temperature dependence of the overall polymerization rate and the propagation rate constant were determined, and the overall activation energy Eov and activation energy of the propagation state Ep were calculated. The difference between Eov and Ep is due to the change of the number of propagation centers with temperature. The variation of catalyst composition and preliminary reduction of the catalyst influence the shape of the temperature dependence of the propagation center concentration and change Eov.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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