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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 22 (1984), S. 2363-2370 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 13C-NMR spectra of ring carbons and O-acetyl carbonyl carbons of cellulose acetate (CA) in dimethyl sulfoxide-d6 were analyzed. The CA samples with the degree of substitution (DS) ranging from 0.84 and 1.91 were prepared by homogeneous acetylation of cellulose with acetic anhydride in a 10% LiCl/dimethyl acetamide solvent. It was found that the use of these low DS samples permitted easier assignments not only of the ring carbon but also of the O-acetyl carbonyl carbon signals. The assignments were confirmed by comparing with the 1H-NMR spectra of the samples obtained by complete acetylation of the corresponding CA samples with acetyl-d3 chloride. Two methods for determining the distribution of O-acetyl groups of CA, i.e., the relative DS at the three different types of hydroxyl groups, were developed. One is based on the measurements of the relative intensities of the signals for the ring carbons and the other is based on the measurements of the relative intensities of the signals for the O-acetyl carbonyl carbons.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 2
    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: A relationship between apparent specific volume v**1 and molecular weight M1 of polymers in solution has been found by G. V. SCHULZ and M. HOFFMANN, and expressed in the form \documentclass{article}\pagestyle{empty}\begin{document}$ v_1^{**} = A + KM_1^{ - 1} $\end{document} Here A and K are constants which are independent of M1. To explain theoretically this experimental fact a thermodynamical theory for the density of polymer solution on the basis of the McMILLAN-MAYER theory was developed. The physical meaning of density measurement was thus generally discussed. By comparing the theory with the experiment it was theoretically elucidated; 1 that the constant K depends not only upon the thermodynamical properties of the solvent, e.g., the isothermal compressibility, but also upon those of the end-groups attached to a polymer chain, which may be different for different conditions of polymerization, e.g., the kind of catalyst; 2 that the value of A found experimentally corresponds to a monomer unit in the sense of interaction between solute and solvent.
    Notes: Ein Zusammenhang zwischen dem scheinbaren spezifischen Volumen v1** und dem Molekulargewicht M1 der Polymeren in Lösung wurde von G. V. SCHULZ und M. HOFFMANN3 festgestellt und durch \documentclass{article}\pagestyle{empty}\begin{document}$ v_1^{**} = A + KM_1^{ - 1}$\end{document} ausgedrückt. Hierbei sind A und K die von M1 unabhängigen Konstanten. Zur Deutung dieses experimentellen Ergebnisses wurde eine thermodynamische Beziehung für die Dichte von Polymerlösungen auf Grund der McMILLAN-MAYERschen Theorie abgeleitet, und dann wurde die physikalische Bedeutung der Dichtemessung allgemein aufgeklärt. Durch Vergleich der Theorie mit dem Experiment konnte man theoretisch schließen: 1. daß die Konstante K nicht nur von den thermodynamischen Eigenschaften des Lösungsmittels, z. B. der isothermen Kompressibilität, sondern auch von denen der Endgruppe der Polymerkette, die bei wechselnden Polymerisationsbedingungen, z. B. Katalysatoren, verschieden sein darf; 2. daß der experimentell erhaltene Wert von A dem ausgeschlossenen Volumen für ein Grundmolekül der Polymerkette entspricht im Sinne der Wechselwirkung zwischen dem Gelösten und dem Lösungsmittel.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 53 (1962), S. 130-144 
    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: Light scattering measurements were made for solutions of five samples of polyvinyl alcohol prepared under different conditions of polymerization. In this experiment the ability of different methods for the optical cleaning of test solution was especially taken into consideration. ZIMMS plots thus obtained for some of five samples gave usual curves which enables to determine the molecular weight of solute, whereas the other samples showed abnormal forms, suggesting the existence of microgel particles even in dilute solution. Storing the solution at 30°C. a temporal increase in the scattered intensity was observed, which may be caused by formation of new microgel particles. No remarkable changes resulted in by keeping it at 0°C., however. By heating of the solution at 100°C. the microgel particles were only partially dispersed. This suggests that the particle consists of a paracrystalline part and an amorphous region which would be responsible to the disintegration of particle at 100°C. To investigate the relationship between the crystallinity of sample and its solution property, the heat treatment was given to one of the samples in solid state at different temperatures. In plotting the scattered intensity against the temperature, a distinct maximum of the intensity was observed at about 120°C. with a solution cleaned optically by means of ultracentrifugation only. This phenomenon was discussed in terms of the result obtained by the small angle diffraction of X-ray in the solid state.
    Notes: An gelösten, unter verschiedenen Polymerisationsbedingungen hergestellten Proben von Polyvinylalkohol wurden Streulichtmessungen ausgeführt. Es wurde besonders die Wirksamkeit von verschiedenen optischen Reinigungsmethoden berücksichtigt. Die ZIMM-Diagramme für drei von fünf Proben zeigten anormale Kurven, was darauf hinweist, daß noch in verdünnter Lösung Mikrogelteilchen vorhanden sind, während die anderen zwei Proben normale Kurven aufwiesen. Diese ermöglichen, das Molekulargewicht des Gelösten zu bestimmen. Durch Stehenlassen der Lösung bei 30°C trat eine zeitliche Zunahme der Streuintensität auf, die wahrscheinlich durch Bildung weiterer Mikrogelteilchen verursacht wird. Die Aufbewahrung bei 0°C ergab jedoch keine merkliche Veränderung. Durch Erhitzen der Lösung auf 100°C konnten die Mikrogelteilchen nur zum Teil zerlegt werden. Das besagt, daß die Teilchen aus einem parakristallinen und einem amorphen Bereich bestehen und daß nur der letztere Anteil bei 100°C desintegriert wird. Um den Zusammenhang zwischen der Kristallinität einer Probe und deren Lösungsverhalten zu erkennen, wurde ein Präparat im festen Zustand bei verschiedenen Temperaturen vorbehandelt. Der Einfluß dieser Vorbehandlung auf den Lösungszustand wird im Zusammenhang mit der Röntgenkleinwinkelstreuung im festen Zustand diskutiert.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-2: Polymer Physics 7 (1969), S. 609-633 
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molecular weight determinations by light scattering and osmometry and intrinsic viscosity measurements were made in various solvents on fractions of styrene-methyl acrylate copolymers with different compositions and on acrylate homopolymers prepared by free-radical reaction. Relations between intrinsic viscosity [η] and molecular weight M thus established are compared with those reported by other authors. 2-Methylcyclohexanol was found to be a theta solvent for the copolymers and both parent homopolymers, and isoamyl acetate was a theta solvent for poly(methyl acrylate). From theta point viscosity data obtained with these solvents, unperturbed chain dimensions were estimated. The results are compared with the unperturbed dimensions estimated from the [η]-M relations obtained in good solvents. On the basis of the experimental data it was found that the unperturbed dimension depends linearly on the copolymer composition, in contrast to the case of styrene-methyl methacrylate copolymers. Composition dependences of the theta temperature and of the parameter describing the long-range interactions between nonadjacent segments in polymer chains were investigated. The result implies that long-range interactions between monomeric units never disappear even when those between the same monomeric units vanish. The Huggins constant for copolymer is discussed in terms of the excluded volume variable.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 55 (1962), S. 150-166 
    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: The molecular weight determination for some fractionated samples of polyvinyl alcohol (PVA) was made by means of light scattering, under a chosen condition that PVA can be dispersed monomolecularly in water, i.e., at 80°C. The intrinsic viscosity [η] was also measured at 80°C. for the samples. From these experiments it was found: 1) that the relation between [η] and molecular weight M̄w is in a fairly good accordance with that derived by MATSUMOTO and OHYANAGI, with aid of the light scattering measurement in polyvinyl acetate solutions and the polymeranalogous reactions of PVA; 2) that the intrinsic viscosity decreases rapidly with increase in temperature; 3) that the second virial coefficient becomes smaller with elevation of temperature. We discussed furthermore the relation thus obtained on the basis of the recent theory of KURATA, STOCKMAYER, and ROIG for the excluded volume effect in a polymer chain and thus estimated the unperturbed dimension of the chain, which can be measured only at the Θ-temperature.
    Notes: Unter der Annahme, daß sich Polyvinylalkohol (PVA) bei 80°C molekulardispers in wäßrige Lösung bringen läßt, wurde das Molekulargewicht für einige Fraktionen von PVA durch Streulichtmessungen bestimmt. Zugleich wurde der STAUDINGER-Index [η] für dieselben Proben bei 80°C gemessen. Durch beide Versuchsreihen stellte man fest: 1. die Beziehung zwischen [η] und dem Molekulargewicht M̄w stimmt mit derjenigen von MATSUMOTO und OHYANAGI überein, die mit Hilfe von Streulichtmessungen an Polyvinylacetatlösungen und polymeranalogen Umsetzungen zu PVA abgeleitet wurde; 2. der STAUDINGER-Index nimmt mit steigender Temperatur stark ab; 3. der zweite Virialkoeffizient wird mit Erhöhung der Temperatur merklich kleiner. Ferner diskutieren wir die Beziehung zwischen [η] und M̄w auf Basis der neuen Theorie von KURATA, STOCKMAYER und ROIG für den Effekt des ausgeschlossenen Volumens in einer Polymerkette und errechnen den ungestörten Fadenendenabstand der Polymerkette im Wasser, welchen man nur bei der Θ-Temperatur messen kann.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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