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  • Articles  (8)
  • Polymer and Materials Science  (8)
  • 1965-1969  (8)
  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 81 (1965), S. 38-50 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Es wurde der thermische Abbau von Polytetramethylenoxid untersucht. Das Polymere enthielt schwache Bindungen, die beim Erwärmen auf 50 bis 150°C leicht spalteten. In Xylol betrug die Aktivierungsenergie dieses Abbauvorganges 13,3 Kcal/Mol. Wie nachgewiesen wurde, sind die schwachen Bindungen Hydroperoxidgruppen, die sich in Gegenwart der Luft bildeten. Diese Gruppen konnten beim Erhitzen im Vakuum zerstört werden; der sich einstellende Abbaugrad des Polymeren hängt von der Zahl der vorhandenen Hydroperoxidgruppen ab. Messungen der Intrinsic-Viskosität des von schwachen Bindungen befreiten Polytetramethylenoxids zeigten eine regellose Kettenspaltung bei erhöhten Temperaturen, die nach der Gleichung verlief: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log \rm{ }\left[ \eta \right] = - \alpha \cdot \rm{log \ (t } + \rm{ t}_0 )\rm{ } + \rm{ C} $$\end{document} Der Exponent α der KUHN-HOUWINK-Gleichung wurde für das Polymere in benzolischer Lösung und bei 20 °C zu 0,75 bestimmt. Die Analyse der Molekulargewichtsänderungen während des Abbaus bei verschiedenen Temperaturen ergab, daß die Kinetik der Kettenspaltung erster Ordnung war und durch folgende Geschwindigkeitsgleichung erfaßt wurde: \documentclass{article}\pagestyle{empty}\begin{document}$$ \rm{k} = 1,98 \cdot 10^{17} \rm \ { e}^{ - 49700/\rm{RT}} $$\end{document} Dieses Ergebnis wurde mit den Aktivierungsenergien der in Luft und unter Vakuum durchgeführten thermogravimetrischen Analyse verglichen.
    Notes: The thermal degradation of polytetramethylene oxide has been examined in detail. The polymer contained weak links which led to facile chain scission on heating. (50 to 150°C.). The activation energy of this degradation process in xylene solution is 13.3 Kcal/mol. The available evidence indicates that the weak links are hydroperoxide groups formed in the presence of air. These groups could be destroyed by heating in vacuum, the resultant degree of degradation of the polymer depending on the number of hydroperoxide groups present.Measurements of the intrinsic viscosity of polytetramethylene oxide, freed from weak links, showed that the polymer underwent random chain scission at elevated temperatures according to the equation: \documentclass{article}\pagestyle{empty}\begin{document}$ \log \left[ \eta \right] = - \alpha \ {\rm log \ (t} + {\rm t}_0 )\ + {\rm C} $\end{document} The exponent, α, of the KUHN-HOUWINK equation was thus determined to be 0.75 for the polymer in benzene at 20°C. Analysis of the molecular weight changes occurring during degradation at various temperatures showed that the chain scission process obeyed first order kinetics and could be expressed by the rate equation: \documentclass{article}\pagestyle{empty}\begin{document}$ \rm {k} = 1.98 \cdot 10^{17} \rm {e}^{ - 49,700/\rm{RT}} $\end{document} This result is compared with activation energies obtained by thermogravimetry in air and vacuum.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 110 (1967), S. 180-184 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Vernetzung von Poly-[2.2-propan-bis-(4-phenylcarbonat)] durch Erhitzen in einem kontinuierlich evakuierten System wurde bei verschiedenen Temperaturen (295-382°C) untersucht. Der Einfluß von Zeit und Temperatur auf die Viskosität des Polymeren und den Gelgehalt wird diskutiert.
    Notes: The cross-linking of poly [2.2-propane-bis-(4-phenyl carbonate)] by heating in a continuously evacuated system has been examined at various temperatures (295-382°C). The effect of time and temperature on the viscosity of the polymer and the gel content is discussed.
    Additional Material: 3 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 128 (1969), S. 242-251 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Polysulfon, das aus 2.3-Bis-(4-hydroxyphenyl)-propan und 4.4′-Dichlordiphenylsulfon hergestellt wurde, zersetzt sich beim Erhitzen auf 380°C i. Vak. Das Molekulargewicht steigt mit der Erhitzungsdauer an, bis nach etwa 3 Stdn. Gelierung eintritt. Es wird gezeigt, daß neben Vernetzungsreaktionen auch Spaltungsreaktionen auftreten. Der Abbau wird von Gasentwicklung - zumeist SO2 und CH4 — begleitet. Außer Phenol - als nicht gasförmiges Hauptabbauprodukt - werden substituierte Diphenyläther und viele andere Phenole erhalten. Lösungen der abgebauten Polymeren reagieren mit Diphenylpikrylhydrazyl (DPPH) und zeigen an, daß mit zunehmender Erhitzungsdauer die Zahl der Hydroxylgruppen ansteigt. Die Art der Abbauprodukte ergibt, daß die Äther-, Isopropyliden- und Sulfongruppen in die Abbaureaktionen einbezogen werden. Die Reaktionsgeschwindigkeitskonstanten für die Vernetzungsreaktion, die Spaltungsreaktion, die Bildung von Hydroxylgruppen und die Gasentwicklung wurden bestimmt. Es wird diskutiert, welchen möglichen Reaktionen diese Prozesse unterliegen.
    Notes: Polysulphone, prepared from 2.2-bis(4-hydroxyphenyl)propane and 4.4′-dichlorodiphenyl sulphone, degrades when heated at 380°C i. vac. The mol. wt. increases with time of heating until after about 3 hrs gelation occurs. In addition to crosslinking scission processes have been shown to be important. Degradation is also accompanied by the evolution of gas - mainly SO2 and CH4. Other products include a number of substituted diphenyl ethers, phenol, the major non gaseous product, and a variety of other phenols. Solutions of the degraded polymers react with DPPH and suggest the accumulation of hydroxyl groups with time of heating. The range of products indicates that the ether, isopropylidene and sulphone groups linking the phenylene rings are involved in the degradation. The rates of the crosslinking, scission, hydroxyl accumulation and gas evolution processes have been evaluated and the possible reactions underlying these processes discussed.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 4 (1966), S. 1009-1010 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Biopolymers 6 (1968), S. 223-242 
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The optical rotatory dispersion, hypochromism, and proton magnetic resonance were measured for a number of dinucleoside phosphates in both dilute salt solutions and in 25.2% LiCl (which freezes below -70°C.) as a function of temperature. Two models for the “disordering” of dinucleoside phosphates: the two-state model and the oscillating dimer model, are used to analyze the data. Both models fit some of the data, but neither are completely satisfactory. Evidence is given for a dynamic structure of dinucleoside phosphates, in which the bases oscillate with respect to one another, remaining parallel to one another with no solvent in between, even at high temperatures. Implications of this model to the structures of single-strand sections of RNA's are discussed.
    Additional Material: 9 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Biomedical Materials Research 2 (1968), S. 51-79 
    ISSN: 0021-9304
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Medicine , Technology
    Notes: Bioelectric charge transfer at the blood-wall interface may be a crucial factor affecting thrombosis on implant materials. A program of studies was conducted to determine the electrokinetic and other physical properties of a wide spectrum of materials including organic polymers, metals, inorganics, heterogeneous compounds, and animal tissue. From these tests, materials were selected for in-vivo cannulation experiments. In this manner, a search was made to find a correlation between surface charge characteristics and thrombosis on cardiovascular implant materials. It was found that materials exhibiting a substantial positive charge were prone to rapid thrombosis. No clear correlation can be stated, as yet, regarding the thrombogenecity of highly charged negative surfaces or slightly charged surfaces. However, many heterogeneous materials have exhibited prolonged in-vivo patency. It appears necessary to isolate surface effects from volumetric effects to seek the role of bioelectric charge transfer in blood thrombus formation.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 129 (1969), S. 63-72 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Verglichen mit anderen Polymeren, sind Polysulfone gegenüber Bestrahlung mit Elektronen besonders beständig, wie hier gezeigt werden konnte. Das äußert sich in der Erhaltung mechanischer Eigenschaften wie der Biegefestigkeit und des Moduls, selbst nach Dosen von 200 Mrad.Dennoch erzeugt die Bestrahlung mit Elektronen tiefgreifende Änderungen in der chemischen Struktur. Das Molekulargewicht des Polymeren steigt, und es geliert nach 80 Mrad. Dosen größer als 200 Mrad geben einen konstanten Gelgehalt von 70%, woraus folgt, daß sowohl Spaltungs- als auch Vernetzungsvorgänge wichtig sind. G-Werte für Spaltung und Vernetzung wurden mit 0,08 bzw. 0,16 bestimmt.Die Entfärbung von Diphenylpikrylhydrazyl-Lösungen durch Lösungen von bestrahltem Polysulfon zeigten das Anwachsen von Gruppen mit aktivem Wasserstoff. Diese wurden als phenolische Gruppen erkannt.Der medrige G-Wert für das Gesamtgas (0,01) zeigt die Beständigkeit des Polysulfons an, aber die Zusammensetzung des Gases legt nahe, daß die drei Brückenbindungen zwischen den Phenylenringen, nämlich die Sulfon-, Äther- und Isopropylidenbrücke, durch die Bestrahlung angegriffen werden. Mögliche Reaktionen dieser Brückenbindungen und Vorgänge, welche die experimentellen Beobachtungen erklären, werden vorgelegt und erörtert.
    Notes: It has been shown that polysulphone is particularly stable to electron irradiation compared with other polymer systems. This was reflected in the retention of mechanical properties (flexural strength and modulus) even after doses of 200 Mrads.However electron irradiation produces significant changes in the chemical structure. The polymer increased in molecular weight and gelled after 80 Mrads. Doses greater than 200 Mrads gave a constant gel content of about 70 per cent indicating that scission as well as crosslinking processes were important. G values for scission and crosslinking were calculated to be 0.08 and 0.16 respectively.The discolouration of diphenyl picryl hydrazyl solutions by solutions of irradiated polysulphone indicated the accumulation of groups containing an active hydrogen. These groups were deduced to be phenolic.The low G value for total gas (0.01) indicates the stability of polysulphone but the gas composition suggests that the three linkages, sulphone, ether and isopropylidene between the phenylene rings are affected by irradiation. Possible reactions involving these linkages and the processes which may account for the experimental observations are advanced and discussed.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A: General Papers 3 (1965), S. 3753-3762 
    ISSN: 0449-2951
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Tertiary amine-chelated alkyllithium compounds were investigated as catalyst systems for the reactions of olefinic hydrocarbons. Ethylene is polymerized in paraffinic hydrocarbon solution to a high-melting, low molecular weight polyethylene wax having terminal olefinic unsaturation. A chain-transfer reaction is interpreted in terms of an olefin displacement reaction. Other olefins with available allylic hydrogen are metallized in this position. The C4 olefins in conjunction with ethylene were found to undergo a telomerization reaction, involving the olefin as telogen and ethylene as taxogen. The structure and the mechanism of formation of these telomeric olefins are discussed.
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