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  • 1970-1974  (3)
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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 10 (1972), S. 2237-2244 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of the chemical nature and the concentration of diol cocatalysts in the copolymerization of propylene oxide (PO) and tetrahydrofuran (THF) catalyzed by antimony pentachloride were studied. The least bulky diol, 1,2-ethanediol, was found to be the most active species, judging from the highest rate of copolymerization. The variation of rate was much smaller with the other diols used. Furthermore, the position of the hydroxyl groups did not have much effect on the rate. The concentration of cocatalyst strongly influenced the rate of consumption of both monomers. This is explained by the effect of diol concentration on the equilibrium that exists between the catalyst and the cocatalyst on one side, and the active oxonium complex on the other. The mechanism of cocatalytic effects is discussed in terms of newer concepts of ionic polymerization. Specific solvation of ion-pairs is visualized as partly responsible for the overall effect of the cocatalysts. Water in quantities commeasurable with those of the cocatalyst was found to retard the reaction. It also gave rise to oligomeric products, as evidenced by gel-permeation chromatography.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 10 (1972), S. 1895-1903 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Propylene oxide and tetrahydrofuran were polymerized cationically by an in situ catalytic system composed of antimony pentachloride and 1,2-propanediol. The rates of polymerization were measured by vapor-phase chromatography in the temperature range from -20°C to +20°C. The Arrhenius parameters pertaining to the reaction of each of the comonomers were evaluated and compared with data published earlier for other catalytic systems. The present catalyst system was incapable of initiating a homo-polymerization of tetrahydrofuran in the absence of propylene oxide, while the latter was readily homopolymerized. In a copolymerization system, the rates of consumption of both monomers were first-order in respect to the catalyst, but the reaction ceased when all of the propylene oxide had been consumed. The relative reactivity of the two monomers as characterized by the copolymerization parameters r1 (PO) = 1.15 and r2 (THF) = 0.70 suggests that in the copolymerization system, tetrahydrofuran is capable of a reaction with its own active center. This is discussed in terms of a possible mechanism involving the effects of penultimate units and extensive chain transfer. The latter is well evident from the molecular weights of resulting copolyethers, which do not exceed one thousand.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Publication Date: 1973-01-01
    Print ISSN: 0004-637X
    Electronic ISSN: 1538-4357
    Topics: Physics
    Published by Institute of Physics
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