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  • 1
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Makroporöse hochvernetzte Copolymere aus Styrol (St) und Divinylbenzol (DVB) wurden durch Lösungs- und Perlpolymerisation hergestellt. Die dargestellten Träger ermöglichten die Pfropfung von Poly(N-vinyl-tert-butylcarbamat) (PVCa) entweder durch Addition von VCa-Makroradikalen an die am unlöslichen Träger anhängenden Doppelbindungen oder durch Termination von VCa-Makroradikalen mit Radikalen, die sich an der Trägeroberfläche befinden. Poly(vinylamin) (PVAm) gepfropft auf St-DVB Träger wurde durch Hydrolyse von gepfropftem PVCa mit HCl und nachfolgende Entfernung von amingebundenem HCl mittels NaOH erhalten. Heterogene bifunktionelle Katalysatoren wurden dargestellt durch Bindung von Kobalt(II) 4,4′,4″,4‴-tetracarboxyphthalocyanin (CoPc(COOH)4) an gepfropftes PVAm. Die hergestellten Katalysatoren wurden zur Oxidation von Thiolen zu Disulfiden, sowohl in vorwiegend apolaren a l s auch in wäßrigen Lösungsmitteln verwendet. Es wurde bewiesen, daß eine große innere Oberfläe, ein hinreichend grolßer mittlerer Porendurchmesser und Zugänglichkeit der anhlngenden Doppelbindungen wichtige Voraussetzungen sind für die Anwendbarkeit vom makroporösen St-DVB Copolymeren als Träger für den PVAm-CoPc(COOH)4 Katalysator.
    Notes: Macroporous highly crosslinked styrene(St)-divinylbenzene(DVB) copolymers were prepared by solution and suspension polymerization techniques. The obtained materials allowed the grafting of poly(N-vinyl-tert-butylcarbamate) (PVCa) either by addition of VCa macroradicals to the solid bound double bonds or by termination involving the reaction of VCa macroradicals with radicals present on the carrier. Poly(vinylamine) (PVAm) grafted on St-DVB carriers was obtained after the hydrolysis of grafted PVCa with HCl and the subsequent removal of the aminebonded HCl by means of NaOH. Heterogeneous bifunctional catalysts were obtained by attachment of cobalt(II) 4,4′,4″,4‴-tetracarboxyphthalocyanine (CoPc(COOH)4) to the grafted PVAm. The prepared catalysts were applied to the autoxidation of thiols to disulfides, both in predominantly apolar media and in aqueous media. It was demonstrated, that important prerequisites for the applicability of macroporous St-DVB copolymers as carriers for the PVAm-CoPc(COOH)4 catalyst include a high surface area, a sufficiently large average pore diameter and accessibility of the pendent double bonds.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 180 (1979), S. 2341-2350 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Complexes of the tetrasodium salt of cobalt(II)-tetrasulfophthalocyanine and poly(vinylamine) were applied as bifunctional catalysts for the autoxidation of thiols to disulfides. Optical and catalytic experiments gave supporting evidence to the hypothesis, that the isolation of cobalt centers and the catalytic activity can be promoted by increasing the relative amount of polymeric base. It appeared that the specific catalytic activity of the polymeric catalysts depends on the number average degree of polymerization (P̄n) of the applied polymer samples. In particular at relatively high cobalt content, samples with comparatively low P̄n give more protection against aggregation of cobalt sites (i.e. inactivation) and, therefore, effect a higher specific catalytic activity. A statistical calculation, suitable to determine the distribution of cobalt sites over the polymeric coils, supports the interpretation of the experimental data.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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