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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
    Notes: The hydroperoxides formed on thermal oxidation of polyethylene have been used to examine their photolysis. The kinetics and mechanisms of the photolytically induced decomposition of these hydroperoxides are considered. The difficulties encountered with the mechanism based on homolysis of the hydroperoxy bond are discussed. New mechanisms of hydroperoxide photolysis based on bimolecular reactions are proposed. They are in agreement with the products found experimentally - mainly ketones and trans-vinylene groups - and with the kinetics of the product formation. The mechanisms envisaged are easily adapted to polyolefins other than polyethylene and polymers in general.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 182 (1990), S. 85-109 
    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: Der Einfluß der Foliendicke auf die Photooxidation von PE-LD-Folien hängt stark von dem für die künstliche Bewitterung verwendeten Gerät ab. Mit künstlichen Bewitterungsgeräten, die eine große UV-Intensität aufweisen, ist die Carbonylbildung der Foliendicke praktisch proportional. Mit Geräten, die weniger beschleunigend wirken, und in der Freibewitterung nimmt die Carbonylbildung deutlich weniger mit der Foliendicke zu; dann bleibt ein wesentlicher Teil der Gesamtoxidation auf die Oberflächenschichten der Folien begrenzt. Die mit Polyethylen-Folien beobachteten Unterschiede zwischen Geräten werden auf die Abwesenheit von Kettenreaktionen bei den mit hoher UV-Intensität arbeitenden Belichtungsgeräten zurückgeführt. Mit weniger beschleunigenden Geräten und in der Freibewitterung laufen oxidative Kettenreaktionen hauptsächlich in den äußersten Schichten der Folien ab, wobei in wesentlichen Oxidationsprodukte daran beteiligt sind.
    Notes: The variation of the photooxidation of PE-LD films as a function of film thickness depends heavily on the exposure device used for artificial weathering. Carbonyl development is practically proportional to film thickness if high UV intensity artificial exposure devices are used. With less accelerating devices and on outdoor exposure, only limited increase with film thickness is observed. Then, an appreciable part of total oxidation is restricted to the surface layers. The differences between exposure devices are attributed to the absence of chain reactions in polyethylene with high UV intensity devices. With other accelerating devices and on outdoor exposure, chain reactions occur especially in the surface layers of the films where they involve usually oxidation products.
    Additional Material: 26 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 190 (1991), S. 111-136 
    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: Relative Wirksamkeit und Stabilisierungsmechanismen sekundärer und tertiärer HALS sind immer noch umstritten. In dieser Arbeit wird die Wirksamkeit von sekundären HALS mit der von entsprechenden Verbindungen mit unterschiedlicher Substitution am Stickstoff verglichen. Die Mehrzahl der Ergebnisse bezieht sich auf unpigmentiertes PP und auf den Vergleich der NH- mit den N-Methyl-Verbindungen. Es wird gefunden, daß in PP-Folien, PP-Multifilamenten, PP-Bändern und spritzgegossenen PP-Platten die sekundären HALS und die entsprechenden N-Methyl-Verbindungen innerhalb der Fehlergrenze die gleiche Wirkung aufweisen. Die zur Zeit verfügbaren Ergebnisse mit PE-HD-Folien, PE-HD-Bändern und PE-LD-Folien führen zum gleichen Schluß. Andere gesättigte Alkylgruppen, größer als die Methylgruppe, weisen ebenfalls vergleichbare Wirkung auf. Der Einfluß ungesättigter Gruppen, wie z. B. Allyl- oder Benzylgruppen sowie von Sauerstoffatomen (Nitroxyl-Radikale) ist unterschiedlich. Es wird eine deutliche Abhängigkeit von der Polymerlieferung festgestellt, so daß deren Wirkung gleich, besser oder schlechter sein kann als die der entsprechenden NH/N-Methyl-Verbindungen.
    Notes: There is still controversy over the relative efficiency and stabilization mechanisms of secondary and tertiary HALS. In this study the performance of secondary HALS is compared with that of corresponding hindered amines bearing various substitutents at the sterically hindered nitrogen atom. The bulk of the stabilization data concerns unpigmented polypropylene and the comparison of N-H and N-methyl derivatives. It is found that in PP films, PP multifilaments, PP tapes and injection molded PP plates the secondary HALS and the corresponding N-methyl derivatives give the same performance within experimental error. The results available, so far, with PE-HD films, PE-HD tapes and PE-LD films lead to the same conclusion. Saturated alkyl groups other than methyl show also comparable performance. The effect of unsaturated groups such as allyl and benzyl and of oxygen atoms (nitroxyl radicals) varies. Depending on the particular polypropylene batch used, the performance can be comparable, superior or inferior to that of the corresponding NH/N-methyl compounds.
    Additional Material: 2 Ill.
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  • 4
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The mechanisms of photooxidation usually envisaged, are perfected by taking into account photoreactions of peroxy radicals. They involve interaction of a peroxy radical with the polymer to yield a hydroperoxy radical and a pair of macroradicals. After peroxidation, this pair will usually undergo bimolecular termination. The influence of such a reaction on photooxidation kinetics is particularly important for polyethylene. Then, chain termination occurs mainly by interaction of two hydroperoxy radicals or of a hydroperoxy radical with a macroperoxy radical. The reaction does not only affect kinetics of photooxidation but also the nature of the photooxidation products. The latter is more important for polypropylene than for polyethylene.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The HALS stabilization mechanisms usually envisaged do not explain the experimental facts. New mechanisms are proposed instead. They include quenching of excited charge-transfer complexes (CTC) polymer-oxygen by CTC HALS-oxygen. In addition, the formation of CTC between peroxy radicals and NH-HALS is of prime importance. These CTC HALS-peroxy radicals can either react photolytically after absorption of UV radiation or with a second peroxy radical, thus promoting termination between two peroxy radicals.Initiation of photooxidation in HALS stabilized polyethylene involves usually CTC HALS-oxygen throughout the useful lifetime of the polymer. In contrast to that, initiation of photooxidation in HALS stabilized polypropylene is classical and due to photolysis of tertiary hydroperoxides.The formal kinetics based on the mechanisms envisaged explain the experimental results observed with HALS stabilized polyethylene and polypropylene. On the one hand, they concern, the performance of HALS: in polyethylene it is a linear function of the square root of HALS concentration whereas in polypropylene it increases linearly with HALS concentration as long as the last does not become too high. On the other hand, the experimental facts explained, concern the decrease of the HALS concentration during W exposure of HALS-stabilized polyethylene and polypropylene. The decrease is first order in both polymers but is independent of the initial HALS concentration in polyethylene, whereas it decreases with increasing initial HALS concentration in polypropylene. This is in agreement with the corresponding initiation mechanisms envisaged for polyethylene and polypropylene.
    Additional Material: 22 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 182 (1990), S. 111-134 
    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: Verschiedene Mechanismen für die Bildung von Oxidationsprodukten (Ketone, Carbonsäuren, Vinylgruppen) bei der Photooxidation von PE-LD werden vorgeschlagen. Die Kinetik der Produktbildung wird eingehend diskutiert. Die experimentellen Ergebnisse können erklärt werden, wenn man annimmt, daß die Geschwindigkeit der Ketonbildung mit der Belichtungsdauer linear ansteigt. Mögliche Gründe hierfür werden erörtert.
    Notes: Various mechanisms are proposed to explain the formation of the photooxidation products of the PE-LD films (ketones, carboxylic acids, vinyl groups). The kinetics of product formation are discussed in detail. The experimental results can be explained on the assumption that the rate of ketone formation increases linearly with exposure time. Possible explanations are proposed.
    Type of Medium: Electronic Resource
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