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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 80 (1964), S. 208-219 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Polymerisation einiger Vinylmonomerer wie z. B. Methylmethacrylat, Äthylmethacrylat, Methacrylsäure und Styrol wird in wäßriger Phase durch Bisulfit ausgelöst. Bei anderen Vinylverbindungen, wie. z. B. Acrylnitril, Vinylacetat, Methylacrylat und Acrylsäure tritt unter den gleichen Bedingungen Jedoch Keine Polymerisation ein.Der Mechanismus der Startreaktion wird diskutiert.In bezug auf die Bisulfit-Konzentration verläuft die Polymerisation des Methylmethacrylats nahezu nach der 0,5 ten Ordnung.Die quantitative Endgruppenbestimmung mittels einer kolorimetrischen Technik ergab einen Gehalt von etwa 2 Sulfonat-Endgruppen (-SO3H) pro Makromolekül. Sulfat-Endgruppen (-OSO3H) wurden nicht gefunden. Bei sehr geringen Initiatorkonzentrationen ( 〈 0,005 mol/l) wurden einige Hydroxylgruppen gefunden; jedoch ergab sich auch in diesen Fällen die Summe von Sulfonat- und Hydroxylendgruppen zu 2 pro Makromolekül.
    Notes: Bisulfite initiates aqueous polymerization of certain vinyl monomers such as methyl methacrylate, ethyl methacrylate, methacrylic acid and styrene but it fails in case of acrylonitrile, vinyl acetate, methylacrylate, and acrylic acid under identical conditions.The mechanism of initiation has been discussed.Catalyst exponent of this initiator with respect to methyl methacrylate is near about 0.5. Quantitative determination of endgroup by dye techniques of the polymers obtained show that about 2 sulfonate (-SO3H) endgroups are present per chain in almost all cases. No sulphate endgroup (-OSO3H) is ever found. In case of very low initiator concentration ( 〈 0.005 mole/1.), some hydroxyl endgroups are also found in general but the total (sulfonate and hydroxyl combined) amounts to about 2 per polymer chain.
    Additional Material: 3 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: General Papers 2 (1964), S. 4441-4451 
    ISSN: 0449-2951
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(methyl methacrylate) samples obtained by aqueous redox initiation with persulfate in conjuction with reducing sulfoxy compounds such as HSO3-, SO3-, S2O3-S2O4-, and S2O5- are found by dye techniques to contain both hydrolyzable sulfate endgroups (derived from persulfate) and nonhydrolyzable sulfonate endgroups or the like (derived from the activator) to an average total of about 2 endgroups per polymer molecule. Sulfide (S-) is unique as an activator, as only sulfate endgroups ( no sulfonate or hydroxyl) have been found in the polymers. Persulfate used in conjunction with other activators (such as Ag+, Fe++ hydrazine and hydroxylamine, aliphatic amines, alcohols, reducing acids and their salts, etc.) produce polymers with both sulfate and hydroxyl endgroups. Incorporation of sulfate endgroups is favored under basic conditions and tends to be suppressed under acid conditions.
    Additional Material: 2 Tab.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 901-906 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Polymerization of methyl methacrylate was carried out in aqueous and nonaqueous media in the presence of some sulfonated and carboxylic organic compounds, hydroxyl radicals generated from hydrogen peroxide being used as initiators of polymerization. The occurrence of radical transfer reactions by way of hydrogen atom abstraction from the organic substrates by the ȮH radicals was demonstrated by the detection of sulfonate and carboxyl endgroups in the respective polymers. It was found that the radical transfer reactions were more favored in aqueous media than in nonaqueous systems.
    Additional Material: 2 Tab.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A: General Papers 2 (1964), S. 4433-4440 
    ISSN: 0449-2951
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: 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.
    Additional Material: 3 Tab.
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