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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 250 (1972), S. 9-19 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Summary TheF/A isotherms of a series ofα,ω-dimethylsiloxane diols of various chain lengths and of two hydroxyalkyl-and two cyclohexylaminomethyl-substituted siloxanes, all of roughly comparable chain lengths, were recorded and discussed. All the preparations show the typical behaviour of hydrophilic substituted siloxanes and belong to the earlier defined Group II. Characteristic features are the formation of twodimensional “hydrate phases” of high water content at pointA 1, that is to say where a relatively large area is offered, and the strong attachment to the subphase, which, on the one hand, makes it impossible for the spreading chain to be transformed into the helix, and, on the other hand, causes the film pressures to rise to an unusually large extent during compression. With regard to the hydration at pointA 1, values were obtained which, though they cannot be highly accurate, indicate that OH groups situated at the chain ends in the form of silanol, methylol or propylol substituents have a similar capacity to bind water. Cyclohexylaminomethyl groups, also situated at the chain ends, are somewhat more strongly hydrated. The largest hydration is shown by films consisting of siloxanes with lateral silanol and cyclohexylaminomethyl groups. Silanol-containing intermediate stages are determinable in the hydrolysis of Si-H-siloxanes in the film on water. The measurements also suggest that silanol groups are formed during the oxidation of a permethylated siloxane by air.
    Notes: Zusammenfassung Es wurden die F/A-Isothermen einer Reihe vonα,ω-Dimethylsiloxandiolen unterschiedlicher Kettenlänge, von zwei hydroxyalkyl- und zwei cyclohexylaminomethyl-substituierten Siloxanen, alle von etwa vergleichbarer Kettenlänge, aufgenommen und diskutiert. Alle Präparate zeigen das typische Verhalten hydrophil substituierter Siloxane und gehören der früher definierten Gruppe II an. Kennzeichnend sind die Ausbildung wasserreicher zweidimensionaler „Hydratphasen“ im PunkteA 1, d. h. bei relativ großem Flächenangebot, sowie die starke Verhaftung zur Subphase, die einerseits die Transformation der Spreitungskette in die Helix unmöglich macht, andererseits die Filmdrucke bei Kompression ungewöhnlich stark ansteigen läßt. Für die Hydratation im PunkteA 1 wurden Maßzahlen ermittelt, die, wenn auch ihre Genauigkeit nicht groß sein kann, erkennen lassen, daß kettenendständige OH-Gruppen in Form von Silanolen, von Hydroxymethyl- und Hydroxypropyl-Substituenten ähnliches Wasserbindungsvermögen haben. Ebenfalls kettenendständige Cyclohexylaminomethyl-Gruppen sind etwas stärker hydratisiert. Den höchsten Gehalt an „Schwarmwasser“ zeigen Filme von Siloxanen mit seitenständigen Silanol- und Cyclohexylaminomethyl-Gruppen. Bei der Hydrolyse von Si-H-Siloxanen im Film auf Wasser sind Silanol-haltige Zwischenstufen faßbar. Ebenso sprechen die Messungen dafür, daß bei Luftoxydation eines permethylierten Siloxanes Silanolgruppen gebildet werden.
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Naturwissenschaften 71 (1984), S. 192-198 
    ISSN: 1432-1904
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology , Natural Sciences in General
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Colloid & polymer science 250 (1972), S. 836-847 
    ISSN: 1435-1536
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Description / Table of Contents: Summary Perfluoralkylcarbonamide-(FCA-)substituted siloxanes spread on water at a speed similar to that of permethylated siloxanes to give monomolecular films whose F/A isotherms should be placed within the range between the types I and II of the system suggested by us previously. In spite of the complicated build-up of the molecules, quantitative evaluation of the film structures in the transformation pointB is possible with convincing precision. It is based on a comparison of the experimental data for the area requirement of the molecules with values resulting from model discussions using the increments of the participating siloxane units. In accordance therewith there is inB a closely packed monomolecular film in which the molecules have the conformation of the αs spreading chain and the FCA substituents are steeply pressed upwards, the hydrophilic carbonamide bridge also being lifted off from the water. The film pressure inB is relatively high because of the force required. For the transformations A2 and A1, an αs conformation must also be assumed, in which, however, the hydrophilic carbonamide bridge has contact with the water surface and additionally more or less binds “swarm water”. The smooth run of the curve within the range of A2 indicates the poor definition of these “hydrate” states, it being necessary for the hydrophobic perfluoralkyl radical to be angled off from the water surface. In the antagonistic interplay of forces between the hydrophilic and the hydrophobic partner of the substituents, the former therefore proves to be the stronger one as long as the molecule is offered the possibility of developing itself freely on the water surface, which means if it is offered sufficient area.
    Notes: Zusammenfassung Perfluoralkyloarbonamid-(FCA)-substituierte Siloxane spreiten auf Wasser ähnlich schnell wie permethylierte Siloxane und geben monomolekulare Filme, deren F/A-Isothermen in dem Bereich zwischen den Typen I und II des früher von uns aufgestellten Systems anzusiedeln sind. Trotz des komplizierten Baues der Moleküle ist eine quantitative Auswertung der Filmstrukturen im TransformationspunktB mit überzeugender Genauigkeit möglich. Sie basiert auf einem Vergleich der experimentellen Daten für den Flächenbedarf der Moleküle mit Werten, die sich aus Modelldiskussionen unter Zuhilfenahme der Inkremente der beteiligten Siloxaneinheiten ergeben. Danach liegt inB ein dichtgepackter monomolekularer Film vor, in dem die Moleküle die Konformation der αs-Spreitungskette besitzen und die FCA-Substituenten steil nach oben gedrückt sind. Hierbei wird auch die hydrophile Carbonamidbrücke vom Wasser abgehoben. Infolge des erforderlichen Kraftaufwandes ist der Filmdruck inB relativ hoch. Für die Transformationen A2 und A1 muß ebenfalls eine αs-Konformation angenommen werden, bei der nunmehr aber die hydrophile Carbonamidbrücke Kontakt mit der Wasseroberfläche hat und zudem in mehr oder weniger starkem Maße „Schwarmwasser“ bindet. Der weiche Kurvenverlauf im Bereich von A2 deutet auf die schlechte Definiertheit dieser „Hydrat” zustände. Der hydrophobe Perfluoralkylrest muß dabei von der Wasseroberfläche abgewinkelt sein. In dem antagonistischen Kräftespiel zwischen dem hydrophilen und dem hydrophoben Partner der Substituenten erweist sich also der erstere als stärker, solange dem Molekül freie Entfaltungsmöglichkeit auf der Wasseroberfläche, d. h. genügend Fläche angeboten wird.
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  • 4
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 73 (1961), S. 807-807 
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 5
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 71 (1959), S. 701-701 
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 78 (1966), S. 596-596 
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction between molten potassium and carbon monoxide (without solvent) has been studied. The reaction products obtained have been shown to be a mixture of potassium acetylenediolate, an organometallic compound, and the potassium salt of hexahydroxybenzene, the relative amounts of which vary with temperature. At reaction temperatures near the melting point of potassium (62,3°), potassium acetylenediolate and the organometallic compound are the major products, whereas at temperatures higher than 180° the potassium salt of hexahydroxybenzene predominates.
    Additional Material: 6 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 46 (1963), S. 2111-2120 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrophoric products obtained from the alkalimetals lithium, sodium, potassium, rubidium, and cesium with carbon monoxide in liquid ammonia are shown to be mixtures of the metal acetylene diolates, MOC ≡ COM, with an organometallic compounds, the possible structures of which are discussed.
    Additional Material: 4 Tab.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Helvetica Chimica Acta 49 (1966), S. 1145-1150 
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Isocyanides RNC and the isomeric nitriles, RCN, reacting with alkali or alkaline earth metals in liquid ammonia undergo reductive fission to metal cyanides and carbanions R-. The latter are ammonolized to the corresponding hydrocarbons.
    Additional Material: 3 Tab.
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  • 10
    ISSN: 0018-019X
    Keywords: Chemistry ; Organic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The solid compounds resulting from the reaction between carbon monoxide and potassium, either molten or dissolved in liquid ammonia, have been shown by EPR. spectroscopy to contain low concentrations of free radicals. These solids dissolve in water to give deeply coloured solutions which also display EPR. spectra. It has been shown that the radical in the product formed from molten potassium at 250°C is mainly the potassium salt of tetrahydroxybenzosemiquinone, while the product from either molten potassium at 70°C or potassium dissolved in liquid ammonia contains at least two radicals. From the measurements made on the aqueous solutions, one of these has been shown to be the potassium salt of 2,5-dihydroxy-1,4-benzosemiquinone. The other radical is thermally instable and is probably a non-linear open-chain radical. Dihydroxybenzoquinone seems to be formed during the removal of the ammonia.
    Additional Material: 11 Ill.
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