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  • 1975-1979  (8)
  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Analytical chemistry 48 (1976), S. 89-95 
    ISSN: 1520-6882
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Journal of thermal analysis and calorimetry 11 (1977), S. 423-430 
    ISSN: 1572-8943
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Description / Table of Contents: Résumé Application de la nouvelle technique d'analyse des particules organiques à l'étude des réactions de décomposition thermique de divers types de composés organiques (par ex. les acétylacétonates métalliques, les isocyanates bloqués, les alkyldithiocarbamates métalliques, les acides arénosulfoniques et leurs sels aminés). A quelques exceptions près, la plupart des composés de ces différentes classes montrent de fortes caractéristiques d'organoparticulation aux températures inférieures à 200°, qui se manifestent par leur influence sur le courant de sortie d'un détecteur à chambre d'ions. Il n'a pas été possible, en général, de mettre en évidence une corrélation directe entre les températures de fusion et de décomposition et les intervalles des températures de l'organoparticulation des composés. Dans plusieurs cas, les valeurs de l'intervalle des températures d'organoparticulation étaient nettement supérieures ou nettement inférieures au point de fusion connu et aux températures de décomposition des composés. Afin d'expliquer les propriétés d'organoparticulation de ces composés, l'association en phase vapeur de molécules polaires (par ex. les phénols, les amines, les acides carboxyliques, etc.) semble être nécessaire pour donner des organoparticules de grandeur décelable par les instruments actuels. Une autre possibilité serait la formation d'une suspension “aérosol” de molécules organiques dans des gaz comme SO2, CS2, CO2, qui pourrait se produire avec quelques-uns de ces composés.
    Abstract: Zusammenfassung Die neue Technik der organischen Partikelanalyse wurde zur Untersuchung der thermischen Zersetzungsreaktionen verschiedener Typen organischer Verbindungen (z. B. Metall-Acetylacetonate, blockierte Isocyanate, Metall-Alkyldithiocarbamate, Arensulfonsäuren und ihre Aminsalze) eingesetzt. Mit einigen Ausnahmen weist der Grossteil dieser Verbindungsklassen starke, bei Temperaturen unter 200ℴ organische Partikelcharakteristika auf, wie an Hand ihrer Wirkung auf den austretenden Strom eines Ionenkammerdetektors nachgewiesen werden kann. Im Allgemeinen konnte kein direkter Zusammenhang zwischen den Schmelz- und Zersetzungstemperaturen und den Temperaturbereichen der Organopartikulierung der Verbindungen festgestellt werden. In mehreren Fällen lagen die Temperaturbereiche der Organopartikulierung deutlich oberhalb oder unterhalb des bekannten Schmelzpunktes und der Zersetzungstemperaturen der Verbindungen. Um die organopartikulierenden Eigenschaften dieser Verbindungen zu erklären, scheint eine Dampfphasenassoziierung polarer Moleküle (wie z. B. Phenole, Amine, Carbonsäuren, usw.) nötig um mit der derzeitigen Instrumentierung nachweisbare Partikelgrössen zu ergeben. Als andere Möglichkeit könnte die Bildung einer “Aerosol”-Suspension organischer Moleküle in Gasen (wie z. B. SO2, CS2, CO2) bei einigen dieser Verbindungen gesehen werden.
    Notes: Abstract The new technique of organoparticulate analysis has been used to investigate the thermal decomposition reactions of various types of organic compounds (i.e., metal acetylacetonates, blocked isocyanates, metal alkyldithiocarbamates, arenesulfonic acids and their amine salts). With a few exceptions, most of the compounds in these classes exhibit strong organoparticulation characteristics at temperatures below 200° as indicated by their influence on the output current of an ion chamber detector. In general, no direct correlation between the melting and decomposition temperatures and their organoparticulation temperature ranges was evident. In several instances, the organoparticulation temperature range values lay well above or well beneath the known melting point and decomposition temperatures of the compounds. To explain the organoparticulating properties of these compounds, vapor phase association of polar molecules (such as phenols, amines, carboxylic acids, etc.) would appear to be necessary to give organoparticulate sizes detectable with the present instrumentation. Alternatively, the formation of an “aerosol” suspension of organic molecules in gases, such as SO2, CS2, CO2, might be occurring with some of these compounds.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 23 (1979), S. 1385-1396 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Quaternary phosphonium compounds have been found to be extremely effective latent accelerators for anhydride-cured bisphenol A epoxy resins; at concentrations from 0.01% to 0.25%, fast gel times are found in the temperature range of 135°-200°C combined with very good storage properties at ambient temperatures. Using these materials as accelerators, it is possible to formulate long-life, one-component epoxy resins. From gel time data, Arrhenius plots were made for some of these phosphonium compounds, and results indicate low activation energy values of the order of 16.1 kcal/mole. Reaction mechanisms are proposed to explain the effectiveness of these phosphonium compounds as latent accelerators. The initiation mechanism probably involves the formation of hydrogen-bonded phosphonium-epoxy or phosphonium-anhydride complexes which rearrange on the application of heat to form activated species resulting in polymerization of the epoxy-anhydride components. The transfer of a proton from the phosphonium complex(es) to other epoxy or anhydride molecules would appear to be the rate-determining step in this initiation mechanism. Comparison of other well-known accelerators used for the anhydride cure of bisphenol A epoxy resins shows quaternary phosphonium compounds to be among the most effective accelerators disclosed to date.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1411-1418 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electroinitiated polymerizations of styrene, 2-vinylnaphthalene, and 9-vinylanthracene were compared in sulfolane and acetone solvents in the presence of ZnCl2. The relative orders of polymerization rates and polymerization efficiencies, in both solvents, were 9-vinylanthracene 〉 2-vinylnaphthalene 〉 styrene, with faster rates and higher efficiencies occurring in sulfolane. Data obtained from viscosity and gel permeation chromatography (GPC) studies indicate that the molecular weights of the polymers produced in these systems are extremely low, 〈5000. Chemical composition and infrared (IR) spectral data suggest that abnormal transfer reactions (possibly from solvent) may be occurring in the electroinitiated 9-vinylanthracene polymerizations. The polymerization mechanism appears to be cationic in these monomer-solvent systems with ZnCl2.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2673-2684 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The zinc chloride-catalyzed polymerization of 2-vinylnaphthalene (VN) with both photoinitiation and electronitiation methods was examined. Good yields were obtained with both methods, the electroinitiated process being somewhat faster. The mechanism for polymerization initiation was investigated through a detailed comparison of the kinetics. Both initiation methods show a similar response to increasing input energy and to change in salt to monomer mole ratio. Both methods indicate formation of a ZnCl2-(2-VN)2 complex as intermediate with the formation of the species being rate-determining. These results, together with other similar investigations, are then used to deduce a mechanism that involves the formation of an electronically excited donor-acceptor complex. It is argued that in certain salt-stabilized, electron-delocalized, aromatic systems, such excitation is possible in electroinitiation.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1563-1571 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: As part of a program to extend the range of donor-acceptor-initiated polymerization processes, the electroinitiation of 2-vinylnaphthalene in a zinc chloride-sulfolane solution has been studied. Good conversion yields of well-characterized (NMR, IR, GPC, elemental analysis) poly(vinylnaphthalene) were obtained with the process showing several mechanistic similarities to other donor-acceptor salt electropolymerization systems.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 1555-1562 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electrochemically initiated polymerization of styrene in methylene chloride solvent with the use of platinum electrodes and tetraalkyl and -aryl group VA halides (i.e., quaternary ammonium, phosphonium, and arsonium compounds) as electrolyte has been investigated. The order of reactivity of the electrolytes with respect to polymerization rate and initiation efficiency was found to be: arsonium 〉 phosphonium 〉 ammonium. Mechanisms involving the electroreduction of the group VA quaternary halides to species capable of electroinitiating polymerization are postulated. The observed losses in solution conductivities during polymerization with the quaternary phosphonium and arsonium electrolytes indicate possible interaction between the initiating radical-ionic species and the supporting electrolyte. In an attempt to further elucidate the mechanism of initiation in these systems, a separate series of experiments, employing the nonpolymerizing monomer, 1,1-diphenylethylene, has been carried out.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1153-1161 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: To elucidate mechanisms in electroinitiated polymerization reactions a comparison was conducted between ultraviolet (UV) photoinitiation and electroinitiation of N-vinyl phthalimide with zinc chloride as a catalyst. Both methods give low yields of a complex polymer product. A detailed analysis, infrared (IR), gel permeation chromatography (GPC), elemental, and molecular weight, conducted on the polymeric products, indicated that phthalimide ring opening was occurring and that complex mixtures of poly(N-vinyl phthalimide) derivatives were formed. Both initiation methods gave comparable results, which further indicated mechanistic similarity between photo-and electroinitiation in these donor-acceptor charge transfer polymerizations.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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