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  • 1
    Digitale Medien
    Digitale Medien
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 58 (1962), S. 1243-1252 
    ISSN: 0022-3832
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The following possibilities of introducing hydroxyl endgroups in polymers have been experimentally realized: (1) redox initiation by ferrous sulfate + H2O2 (Fenton's reagent), N2H4, H2O + H2O2, FeCl3 + H2O2; photoinitiation by Fe(OH)++ + light, H2O2 + ultraviolet light or sunlight, and initiation by unstable Ag+++ complex in dark; (2) copolymerization with a trace of allyl alcohol or with traces of vinyl acetate and allyl acetate and subsequent hydrolysis; (3) chain transfer with butyl alcohols. The method of detection consists in first converting hydroxyl endgroups to carboxyl endgroups by refluxing with phthalic anhydride or 3-nitrophthalic anhydride in benzene and pyridine medium or with maleic anhydride in benzene medium and testing the resulting polymer for carboxyl endgroup by the dye-interaction test with rhodamine 6GX dye extract. The hydroxyl endgroup was also quickly converted to a strong acid endgroup like OSO3H by reacting the polymer with chlorosulfonic acid in chloroform medium under controlled conditions and tested by the dye-interaction test or a dye-partition test with methylene blue. This test is not entirely satisfactory, as the reagent attacks the thermal polymers slightly.
    Zusätzliches Material: 7 Tab.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A: General Papers 2 (1964), S. 4433-4440 
    ISSN: 0449-2951
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: Quantitative determination of endgroups of poly(methyl methacrylate), polystyrene and poly(vinyl acetate) obtained by aqueous initiation with K2S2O8 under varied conditions have been made by the application of two sensitive dye techniques, called the dye partition technique and the dye interaction technique. The description of the dye techniques are given in detail. Sulfate (OSO3-) and hydroxyl (OH) endgroups are generally found to be incorporated in the polymers to an average total of 1.5 to 2.5 endgroups per polymer chain. Hydroxyl endgroups are always present to a fairly large extent. The proportion of sulfate endgroups in polymers is highly dependent on the pH of the polymerizing medium; it increases with the alkalinity of the medium and sharply decreases under acid conditions.
    Zusätzliches Material: 3 Tab.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 5 (1967), S. 135-149 
    ISSN: 0449-296X
    Schlagwort(e): Physics ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A few redox systems containing thiourea as reductant have been found to be quite effective in initiating vinyl polymerization in aqueous media and polymers obtained in the process have all been found to contain amino endgroups to various extents by the application of dye techniques. Quite a few oxidants have so far been utilized for this purpose; among them are ferric chloride (Fe3+), ethylene dibiguanide complex salts of tripositive silver (Ag3+), hydrogen peroxide (H2O2), persulfate (S2O82-), bromate (BrO3-) + hydrochloric acid (HCl). In case of oxidants Fe3+ and Ag3+, amino endgroups are mainly incorporated in polymers; but in case of oxidants H2O2 and S2O82-, fragments of oxidants are also incorporated as hydroxyl and sulfate endgroups. BrO3-, however, forms a very efficient redox-initiating system with thiourea, as is evidenced by its capability of polymerizing even hydroquinone-stabilized water-soluble vinyl monomers at very low temperature (∼0°C.) and at a quite rapid rate. Besides amino endgroups, sulfonate endgroups have also been detected in polymers in this case, and the relative extents of these two types of endgroups depend generally on the acid concentration of the system. Evidences so far collected indicate the generation of S—C(=NH)NH2 radicals in the system by oxidation of isothiourea, HS—C(=NH)NH2, and these are incorporated in polymers as endgroups. Sulfonate endgroups may be generated by oxidation of these amino-bearing endgroups. Suitable initiation mechanisms have been suggested in each case.
    Zusätzliches Material: 5 Tab.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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