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  • 1
    ISSN: 0935-9648
    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
    Additional Material: 5 Ill.
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  • 2
    ISSN: 0935-9648
    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
    Additional Material: 3 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 11 (1967), S. 1431-1438 
    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: Several phosphorus derivatives of methyl 2-(chloromethyl)acrylate, including three phosphonium salts and one phosphonate ester have been prepared. A brief study was made of their polymerization characteristics under free-radical conditions. Several factors were noted which prevented the synthesis of methyl 2-[(diethoxyphosphinyl)-methyl]acrylate in high yields in initial experiments. Homopolymerization of these phosphorus derivatives does not take place readily in the presence of free-radical initiators.
    Additional Material: 2 Tab.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 7 (1963), S. 383-391 
    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: A homologous series of polyoxymethylene di-isopropyl ethers [R—O(CH2O)n—R] from n = 1 through n = 6 has been prepared and characterized by gas/liquid partition chromatography, infrared spectroscopy, and other techniques. The acid hydrolyses of the series indicated no rate dependence on chain length between the endgroups, which suggests that the rate of hydrolysis is not dependent on the remaining intermediate group. The rate constants and activation energy are reported, as well as those from the literature. The conclusion is reached that hydrolytic degradation studies of formaldehyde-crosslinked cellulose cannot yield information on the chain lengths of the crosslinks.
    Additional Material: 5 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 9 (1965), S. 933-940 
    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: A study of the copolymerization of 3-methyl-1-pentene (3-MP) and 4-methyl-1-pentene (4-MP) showed that the poly-4-MP crystal lattice is capable of incorporating large quantities of 3-MP without a sharp lowering of melting point or adverse effect on physical and mechanical properties. The reactivity ratio of the two monomers in copolymerization are r(4-MP) = 6.2 ± 0.2 and r(3-MP) = 0.1 ± 0.1. As a result, mixed feeds containing up to 80% 3-MP produce copolymers composed primarily of repeating 4-MP units, with a random insertion of 3-MP monomer units. Calculations indicate that in a copolymer containing 37% 3-MP, the probability of finding a sequence of 2 units of 3-MP is only a little better than 5%. This copolymer shows a somewhat increased resistance to deformation under load than homopoly 4-MP. Its crystalline melting point is 248°C.
    Additional Material: 4 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 10 (1970), S. 21-48 
    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: The phase separation behavior of dilute polydisperse polymer solutions primarily depends on the partial concentration of each polymer component. So the equilibrium data obtained by turbidimetric titration with “calibration” fractions and their mixtures can be used for the construction of a solubility diagram (Claesson-diagram) which generally allows to describe fractionation processes.It can be shown that the characteristic features of precipitation fractionations can well be derived from the solubility diagram. This diagram then offers the possibility for a complete discussion of parameter variation (concentration, step of γ-variation, process-scheme, temperature, solvent/nonsolvent-system) on the efficiency of a fractionation step.On one hand these results correspond - as for the concentration variation - to well known experimentell experiences. On the other hand it is possible for the first time to give definite predictions for the influence of temperature and the solvent/nonsolvent system. The temperature selection can be shown to be inconsiderable for the separation effect. The usual characterization of solvents and nonsolvents as “good” or “poor” is absolutely insufficient, if not misleading, for there is no connection between these properties and the shape of the solubility diagram.Based on the analysis of the single parameters the optimum conditions for the preparation of narrow preparation of narrow precipitation fractions can be derived.
    Notes: Da das Entmischungsverhalten verdünnter polydisperser Lösungen im wesentlichen durch die Partialkonzentrationen der einzelnen Polymerkomponenten bestimmt wird, kann die Polymerfraktionierung auf der Basis des Fällungsverhaltens von Eichfraktionen und ihrer Mischungen mit Hilfe eines Löslichkeitsdiagramms (CLAESSON-Diagramm) beschrieben werden.Es kann zunächst gezeigt werden, daß die charakteristischen Merkmale der Fällfraktunmerung durch das Löslichkeitsdiagramm richtig wiedergegeben werden. Das Diagramm erlaubt dann in einfacher Weise, den Einfluß der Variation der einzelnen Verfahrensparameter (Konzentration, Schrittbreite δγ, Verfahrensschema, Temperatur und Lösungsmittel/Fällungsmittel-(L/F-)System) auf die Einheitlichkeit einer Fraktion wiederzugeben. Diese Ergebnisse entsprechen zum einen-wie z. B. bezüglich der Konzentrationsabhängigkeit-den bekannten experimentellen Erfahrungen. Zum anderen können darüber hinaus erstmals definierte Aussagen zum Einfluß der Temperatur und der Auswahl des L/F-Systems gemacht werden. Danach ist die Wahl der Temperatur für den Trenneffekt unerheblich. Die übliche qualitative Charakterisierung von Lösungsmittel und Fällungsmittel durch „gut“ und „schlecht“ ist als Auswahlkriterium unzureichend, teilweise sogar irreführend, da kein Zusammenhang zwischen diesen Angaben und der Form des Löslichkeits-diagramms besteht.Auf der Grundlage der Analyse der Einzelparameter können die optimalen Arbeitsbedingungen zur Gewinnung einer möglichst einheitlichen Fällfraktion angegeben werden.
    Additional Material: 15 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 10 (1970), S. 49-67 
    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: With the aid of polystyrenes with different polydispersity (M̄w/M̄n = 2,6 to 1,01) the effect of the charge, the γ-gradient, the interval Δgamma; between two fractions and the contact time on the discontinuous and continuous solution fractionation was tested. For the discontinuous fractionation of samples with broad distributions no effect was found on the integral distribution curve by the variation of these experimental conditions. For narrower distributions (M̄w/M̄n ≤ 1,5) however it is necessary to pay attention to following points: 1st the charge must be below 2mg/g sand, 2nd the γ-gradient must be specially accommodated to the conditions of solubility, 3rd the interval Δγ should be smaller than 0,002 and 4th the contact time should be at least two hours. With growing uniformity the charge has to be reduced further and the contact time has to be increased.Compared to the discontinuous solution fractionation the continuous fractionation produces insufficient results under equal experimental conditions. Even for broad distributions the charge and the y-gradient must be reduced for approaching the results of the discontinuous fractionation. Furthermore the elution chromatography shows no improvement compared to the simple continuous fractionation. All column methods  -  including the BAKER WILLIAMS fractionation  -  can be shown to be single stage processes.
    Notes: An Hand von Polystyrolen verschiedener Einheitlichkeit (M̄w/M̄n = 2,6 bis 1,01) wurde der Einfluß von Beladung, γ-Gradient, Schrittbreite Δγ und Kontaktzeit auf die diskontinuierliche und kontinuierliche Lösefraktionierung geprüft. Während sich bei der diskontinuierlichen Fraktionierung von Proben mit breiten Verteilungen bei der Variation dieser Versuchsparameter kein Einfluß auf die intergrale Verteilungskurve zeigt, stellt sich bei engeren Verteilungen ab etwa M̄w/M̄n = 1,5 heraus, daß die Beladung unter 2 mg/g Sand bleiben soll, der γ-Gradient den Löslichkeitsbedingungen genau angepaßt werden muß, die Schrittbreite ≤ 0.002 sein und die Kontaktzeit nicht unter 2 Stunden liegen soll. Mit zunehmender Einheitlichkeit ist die Beladung weiter zu verkleinern und die Kontaktzeit zu vergtern.Die kontinuierliche Lösefraktionierung erzielt bei gleichen Arbeitsbedingungen schlechtere Ergebnisse als die diskontinuierliche. Auch bei breiten Verteilungen müssen Beladung und γ-Gradient verkleinert werden, um die Ergebnisse denen der diskontinuierlichen Fraktionierung anzunähern. Weiterhin bringt die Elutions-chromatographie keine Verbesserung gegenüber der einfachen kontinuierlichen Lösefraktionierung. Sie ist ebenso wie die Lösungs-Fällungs-Chromatographie mit Temperaturgradient ein einstufiges Trennverfahren.
    Additional Material: 15 Ill.
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  • 8
    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 retention data, as e.g. the retention index, can be determined much easier and more accurately than absolute retention values. For polystyrene, poly(vinyl acetate) and poly(ethy1ene oxide) as stationary phases the retention indices have been measured for benzene, ethanol, methylethylketone, nitromethane and pyridine as polar test molecules. Based on these data the significance of the index in the framework of “Inverse gas-chroma-tography” is discussed. The mobile/stationary-phase interaction-and therefore the reten-tion-is usually the result of a superposition of different sorption mechanisms, where adsorption at different interfaces (gas-support, gas-polymer, polymer-support, polymer-polymer) and absorption into the polymer-bulk phase have to be considered. It is shown, that the different sorption behavior of polar and nonpolar (n-alkanes) test molecules at the polymer surface must lead to systematic index-variations with different amounts of polymer coating. For polymers however, investigated at temperatures Sufficiently above the glass transition and melting point and at high liquid loadings on inert support materials, mainly the bulk phase solution of the test molecule will be relevant for the index value.Under these conditions it seems to be possible to characterize the “polarity” of a polymer by application of test molecules whose functional groups reflect characteristic interaction forces. The method proposed by Rohrschneider is discussed with respect to this problem.
    Notes: Die Bestimmung von Retentionsindices ist im Vergleich zu absoluten gaschromatographischen Retentionsdaten bei geringerem apparativen aufwand einfacher und genauer durchzuführen. Am Beispiel von Polystyrol, Polyvinylacetat und Polyäthylenoxid als stationärer Phase werden Die Retentionsindices von Benzol, Äthanol, Methyläthylketon, Nitromethan und Pyridin bestimmt und Die Aussagekraft der Indices im Rahmen der “Inversen Gaschromatographie” diskutiert. Das Wechselwirkungsverhalten zwischen mobiler und stationärer Phase und damit Die Retention ist in der Regel durch eine Überlagerung verschiedener Sorptionsmechanismen bestimmt. Zu berücksichtigen sind dabei Die Adsorptionen an den Gas/Träger-, Gas/Polymer-, Polymer/Träger-und Polymer/Polymer-Grenzflächen sowie Die Absorption im Polymeren (Lösung). Es wird gezeigt, daß durch ein unterschiedliches Sorptionsverhalten der polaren Testsubstanzen und der n-Alkane an der Polymeroberfläche beispielsweise systematische Abhängigkeiten der Indices von der Belegungsmenge auftreten müssen.Wird das Polymere bei Temperaturen oberhalb des Schmelzpunktes bzw. der Glastemperatur vermessen und werden hohe Beladungsmengen und möglichst inerte Trägermaterialien verwendet, so ist der Index vorwiegend durch Die Wechselwirkung der gelösten Substanz mit der flüssigen Polymerphase bestimmt. Eine Charakterisierung der Polymeren ist dann z. B. unter Verwendung von Testsubstanzen möglich, Die entsprechend ihrer funktionellen Gruppe für bestimmte Weschselwirkungskräfte typisch sind. Die von Rohrschneider vorgeschlagene Methode zur Charakterisierung stationärer Phasen wird in diesem Zusammenhang untersucht.
    Additional Material: 8 Ill.
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  • 9
    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: Blends and copolymers in the poly(butadien/styrene) system have been investigated by inverse gaschromatography. Using probe molecules of polar (benzene, nitromethane, methyl-ethylketone) and non polar (n-alkanes) character absolute as well as relative retention data as function of temperature can be reported.At temperatures T 〉 140°C retention behaviour is, independent of the polymer type, only a function of the average chemical composition. Due to the glass transition behaviour of the styrene component additional information about the morphology of the stationary polymer phase can be obtained by measurements at T 〈 140°C.
    Notes: Mischungen und Copolymere im System Poly-(butadien/Styrol) wurden mit Hilfe der inversen Gaschromatographie analysiert. Durch Verwendung von polaren (Benzol, Nitromethan, Methyläthylketon) als auch unpolaren (n-Alkane) Testsubstanzen können neben absoluten Retentionsdaten vor allem auch retentionsindices als Funktion der temperatur angegeben werden.Bei temperaturen T 〉 140°C wird das Retentionsverhalten, unabhängig vom Typ des Polymeren, allein durch die chemische Bruttozusammensetzung bestimmt. Bedingt durch das Glasübergangsvehalten der Styrolphase können durch Messungen im Bereich T 〈 140°C zusätzliche Informationen über die Morphologie der Polymerphase gewonnen werden.
    Additional Material: 9 Ill.
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  • 10
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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