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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2033-2043 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The action of hydrazine on desulfurized tetrasulfide polymer obtained from bis-2-chloroethyl formal leads to S—S bond splitting and depolymerization. Our studies show that successful depolymerization can be initiated only in a strong alkali medium at 95-98°C. During this process cleavage of the disulfide bonds and the formation of polymers of lower molecular weight with —SH end groups takes place. From the results of the experiments performed it can be seen that the degree of depolymerization increases with an increase in the amount of hydrazine, in the mole ratio of sodium hydroxide, and in the time of reaction. When 0.7-1.0 mole of hydrazine per segment of polymer and 4 mole of sodium hydroxide per mole of hydrazine are used, a polymer of low average molecular weight in the form of water-soluble sodium salt (fraction I) and a polymer in dispersion form (fraction II) are obtained. Similar results could be attained if the amount ot hydrazine were decreased and the mole ratio of sodium hydroxide were simultaneously increased to more than 4 mole per segment of hydrazine used. In a constant amount of sodium hydroxide with a smaller quantity of hydrazine or a shorter reaction time the amount of water-soluble polymer (as a sodium salt) decreases and the amount of polymer in dispersion form increases. If a portion of the polymer in dispersion is coagulated with a portion of the polymer in the mother liquid, the yield of the depolymerized product is higher, but the average molecular weight is also higher than those of fraction I. The influence of the average contents of sulfur on the efficiency of the depolymerization is tested in polymers that contain 2.5 (i.e., 3) atoms of sulfur per segment of polymer. The result is that the depolymerization of the polysulfide polymer could be carried out without previous desulfurization, but the molecular weights of the products obtained with an equivalent quantity of hydrazine are much higher than those obtained by depolymerization of the disulfide polymer.
    Additional Material: 6 Tab.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Berichte der deutschen chemischen Gesellschaft 92 (1959), S. 855-857 
    ISSN: 0009-2940
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch Umsetzung von SCl2 bzw. S2Cl2 mit S7NH konnten die Schwefelnitride S15N2 und S16N2 als kristallisierte Substanzen gewonnen werden. Von diesen ist besonders S15N2 resonanzstabilisiert.
    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 8 (1970), S. 3259-3264 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The action of sodium dithionite, Na2S2O4 on desulfurized tetrasulfide polymers leads to their depolymerization. Our studies showed that successful depolymerization can be initiated only in an alkali medium when 1.9-3.2 mole of sodium hydroxide per mole of dithionite is used, and that this leads to the cleavage of disulfide bonds and the formation of polymers of lower molecular weight with —SH end groups. Liquid polymers of 1000-5000 molecular weight are obtained when 0.388-0.155 mole sodium dithionite per segment of polymer is used for depolymerization in the presence of the above-mentioned quantity of sodium hydroxide per mole of dithionite. The depolymerization of poly-sulfide polymers with sodium dithionite in the presence of sodium hydroxide was followed by determination of the molecular weight and sulfur content of the polymer and analysis of the mother liquid.
    Additional Material: 4 Tab.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 10 (1972), S. 2573-2582 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The results of our studies show that it is possible to depolymerize polysulfide polymers with a nominal sulfur content in excess of 2 per segment of polymer, without previous desulfurization, in order to obtain disulfide polymers. For this purpose it is necessary to take larger amounts of sodium dithionite per segment of polymer, than with a disulfide polymer, to obtain approximately the same of the average molecular weight of the depolymerized product. It is also possible to complete depolymerization with an amount below 2 moles of sodium hydroxide per mole of sodium dithionite, though the upper limit of the ratio of Na2S2O4 to NaOH, at which depolymerization occurs, remains unchanged, i.e., 1:4. During the depolymerization reaction the occurrence of larger or smaller amounts of hydrosulfide, depending on the labile sulfur content, as well as the change of the color of the reaction dispersion, first white, then bright yellow or gray, thereafter white again and, finally, dingy pink, was observed. The reaction, representing in the best way the optimum conditions of depolymerization and the actual relations in the reaction system, is proposed.
    Additional Material: 6 Tab.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 10 (1972), S. 2583-2589 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: By double or triple depolymerization with sodium hydrogen sulfide in the presence of sodium sulfite, polysulfide polymers of a very low molecular weight can be obtained from disulfide polymers prepared from bis-2-chloroethyl formal. The products are mixtures consisting chiefly of dimers and trimers with monomers. The effect of depolymerization will be greater when three depolymerization processes, instead of two, are completed with the same total amount of NaHS and Na2SO3. When depolymerization is repeated, the degree of depolymerization will be higher with polymers of a higher molecular weight. If depolymerization is made with sodium dithionite, the same effect will be achieved by either single or double depolymerization, provided that the same total amount of dithionite has been used.
    Additional Material: 4 Tab.
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