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  • 1
    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 first visual points of turbidity were determined in the ternary system polystyrene/polymethylmethacrylate/benzene. Mathematical equations are given for the dependence of the turbidity points on molecular weight and concentration. It is possible to extrapolate these equations to solid polymers. If the molecular weight of one of the polymers is known, the compatibility in the solid state of the polymers can be calculated. Test measurements on films show, that the method of extrapolation is a valid approximation.
    Notes: Die ersten visuellen Trübungspunkte im ternären System Polystyrol/Polymethyl-methacrylat/Benzol wurden bestimmt. Die Molekulargewichts- und Konzentrationsabhüngigkeiten dieser Trübungspunkte wurden in mathematische Gleichungen gefaßt. Diese lassen Extrapolation auf den Festzustand der Polymeren zu. Gibt man das Molekulargewicht eines der Polymeren vor, so kann man die Verträglichkeitagrenzen der Polymeren im Festzustand berechnen. Testmessungen an Folien bestätigen die näherungsweise Anwendbarkeit der Extrapolationsmethode.
    Additional Material: 3 Ill.
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  • 2
    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: A polystyrene (PS) with M̄w = 9,7 · 104 was investigated by means of light scattering in the isorefractive polymer/solvens-mixture polymethylmethacrylate (PMMA)/benzene. It was found, that the second osmotic virial coefficient A2 of PS was strongly dependent on the average viscosimetric molecular weight M̄v and on the concentration of PMMA, but scarcely on the temperature in the range of 20°C to 60°C. The θ-Point, where A2 is zero, was independent of the temperature within experimental error.By defining the PMMA concentration at the θ-Point as cθ, and by reducing the measured PMMA concentration c to c/cθ, an unequivocal relation was obtained between A2 and c/cθ, which is independent of molecular weight and molecular weight distribution of PMMA.PS shows a high second virial coefficient in dimer and trimer MMA as well as in non-hydrogenated and hydrogenated MMA. The investigated PS constitutes a θ-System in PMMA of a degree of polymerisation of P̄w, ∼ 17without the use of benzene.
    Notes: Ein Polystyrol (PS) mit M̄w = 97000 wurde im isorefraktiven Polymer/Lö-sungsmittelgemisch Polymethylmethacrylat (PMMA)/Benzol mittels Lichtstreuung untersucht. Es zeigte sich, daß der zweite osmotische Virialkoeffizient A2 des PS stark vom mittleren viskosimetrischen Molekulargewicht M̄v und der Konzentration des PMMA abhängt, dagegen zwischen 20°C und 60 °C innerhalb der Meßgenauigkeit kaum von der Temperatur. Der θ-Punkt, bei dem A2 gleich Null ist, erwies sich als praktisch temperaturunabhängig.Bezeichnet man die PMMA-Konzentration am θ-Punkt mit Cθ, und normiert man die vermessene PMMA-Konzentration c auf c/cθ, so erhält man eine eindeutige Beziehung zwischen A2 und c/cθ, die unabhangig vom Molekulargewicht und der Molekulargewichtsverteilung des verwendeten PMMA ist.Im hydrierten und nicht hydrierten MMA sowie im dimeren und trimeren MMA zeigt PS große positive zweite Virialkoeffizienten. Das untersuchte PS bildet in PMMA mit einem Polymerisationsgrad von P̄w ∼ 17 ohne Benzolzusatz ein θ-System.
    Additional Material: 6 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Acta Polymerica 48 (1997), S. 571-578 
    ISSN: 0323-7648
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A number of OH-terminated three-arm star molecules were prepared by anionic polymerization with a specially functionalized initiator. The stars were crosslinked over the OH groups with varying amounts of toluene-2,4-diisocyanate. The samples were fractionated by size exclusion chromatography (SEC) on-line with a low angle laser light scattering (LALLS) and a viscosity (VISC) detector. The Kuhn - Mark - Houwink - Sakurada (KMHS) relationships from the various samples resulted in a common relationship. Shrinking parameters g′j≡[η]j,b/[η]j,lin were determined for each slice and could satisfactorily be interpreted on the basis of the Zimm - Stockmayer theory in connection with a suggestion by Kurata et al. The Kurata suggestion was checked with data from star molecules. The examination revealed that randomly branched and star-branched macromolecules exhibit significantly different hydrodynamic behavior. The ratio of the Fox - Flory coefficients Φb/Φlin in the relationship [η] = Φ(R3g/M) increases in both cases with branching. This is a consequence of the enhanced segment density and the resulting increase in the hydrodynamic interaction.
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  • 4
    ISSN: 0323-7648
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Unter Verwendung kationischer covalent vernetzter hoch gequollener Mikrogele auf Polyallylaminbasis und anionischer Latices aus Methacrylsäure-Epoxypropylmethacrylat-Copolymeren wird die Wechselwirkung dieser Polymerkolloide mit entgegengesetzt geladenen Makroionen mittels Potentiometrie, Konduktometrie und Turbidimetrie untersucht. Die Mikrogele verhalten sich bei der Symplexbildung ähnlich wie gelöste lineare Polyelektrolyte, wenn beide Titrationskomponenten in neutralisierter Form vorliegen, während bei einer Umsetzung zwischen freier Polysäure und freier Polybase primär nur die leicht zugänglichen Ladungszentren der Mikrogele and der Umsetzung mitwirken. Bei den Latices bildet sich bei der Titration eine stabile “Symplex-Dispersion”, während im Falle der Mikrogele Flockung erfolgt. Die Ergebnisse werden hinsichtlich des Einflusses der Zugänglichkeit der Polymerkolloide auf Stöchiometrie und Dispersitätszustand der gebildeten Symplexe diskutiert.
    Notes: Employing cationic, covalently crosslinked polyallylamine-based highly swollen microgels and anionic latices obtained by copolymerization of methacrylic acid and epoxypropyl methacrylate, the interaction of these polymer colloids with oppositely charged linear macroions is investigated by potentiometry, conductometry and turbidimetry. The microgels behave similar to linear macroions in symplex formation, if the components are reacted in the neutralized state, while in a “free acid - free base” titration only the easily accessible sites of the microgels are primarily involved in the interaction. With the more compact polymer latices a stable dispersion is formed, while with the microgels flocculation occurs. The results are discussed with regard to the influence of physical structure of the polymer colloids on stoichiometry and state of dispersion of the symplexes formed.
    Additional Material: 5 Ill.
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  • 5
    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 different behavior of maltotriose and of maltotetra- and maltohexaose as primers in the synthesis of amyloses with phosphorylase from potatoes is studied. In each case multichain mechanism is followed. With maltotetraose and maltohexaose as primers amyloses are synthesized exhibiting POISSON distribution. With maltotriose as primer the synthesized amyloses are composed of a uniform high molecular weight and a broad low molecular weight fraction. The differences show to be due to the fact, that with maltotriose as primer the rate of the starting reaction proves to be 400 times slower as the rate of the growing reaction, whereas with maltotetraose and maltohexaose both are the same.
    Notes: Das unterschiedliche Starterverhalten von Maltotriose einerseits und Maltotetraose und Maltohexaose andererseits bei der Synthese von Amylosen durch Kartoffelphosphorylase wird untersucht. Die Synthese verläuft in jedem Fall nach einem Mehrkettenmechanismus. Mit Maltotetraose und Maltohexaose als Starter werden Amylosen mit einer POISSON-Verteilung synthetisiert. Die mit Maltotriose als Starter synthetisierten Amylosen setzen sich degegen aus einem einheitlichen, hochmolekularen Anteil und einem uneinheitlichen, niedermolekularen Anteil zusammen. Es wird gezeigt, daß die Unterschiede in der Molekulargewichtsverteilung darauf beruhen, daß bei Synthesen mit Maltotriose für die Startreaktion eine 400 mal kleinere Geschwindigkeit gefunden wird als für die Wachstumsreaktion, während bei Synthesen mit Maltotetraose und Maltohexaose Start- und Wachstumsreaktion gleiche Geschwindigkeit besitzen.
    Additional Material: 8 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 80 (1968), S. 407-408 
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Zeitschrift für die chemische Industrie 86 (1974), S. 449-449 
    ISSN: 0044-8249
    Keywords: Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 150 (1971), S. 63-71 
    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 structure of glycogen and of starlike molecules with grafted amylose chains and glycogen as kernel is studied by the uptake of iodine and by light scattering measurements of carbanilate derivatives.The structure of four branching models, partly used by ERLANDER and FRENCH in previous studies was calculated on the basis of the theory of cascade processes developed by GOOD and by GORDON. By comparison of the experimental data with these four models the number of grafted chains, the chain length, and the structure of glycogen could be determined. The results indicate strongly a regular structure for the glycogen kernel.The weight fraction of the grafted chains, determined by light scattering, is for the high molecular weight compounds in good agreement with the ratio of iodine uptake of the branched product to linear amylose. Both values deviate, however, with decreasing molecular weight.
    Notes: Die Struktur von Glykogen und von Sternmolekülen mit aufgepfropften Amyloseketten und Glykogen als Kern wurde durch die Jodaufnahme und durch Lichtstreuungsmessungen an den Tricarbanilaten untersucht.Unter Anwendung der von GOOD und von GORDON entwickelten Theorie der Kaskadenprozesse wurden für vier verschiedene Verzweigungsmodelle, die teilweise auf einer früheren Arbeit von ERLANDER und FRENCH basieren, Strukturberechnungen durchgeführt. Aus einem Vergleich der experimentellen Werte mit diesen vier Modellen konnte die Zahl der aufgepfropften Ketten, ihre Kettenlänge und die Struktur des Glykogenkerns bestimmt werden. Die Ergebnisse lassen auf eine sehr regelmäßige Struktur des Glykogenkerns schließen.Zwischen dem aus der Lichtstreuung bestimmten Gewichtsanteil der aufgepfropften Ketten und dem aus der potentiometrischen Jodtitration ermittelten Wert (Verhältnis der Jodaufnahme der verzweigten Produkte zu Amylose als Bezugssubstanz) besteht bei den hochmolekularen Substanzen eine gute Übereinstimmung; mit abnehmendem Molekulargewicht treten jedoch zunehmend Abweichungen auf.
    Additional Material: 2 Ill.
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  • 9
    ISSN: 0449-2978
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Measurements of flow birefringence of cellulose tricarbanilates were carried out on nine fractions (0.27 × 105 〈 M ≤ 12 × 105) in a temperature range of 55-110°C, with benzophenone as a matching solvent (dn/dc = 0). The ratio of Maxwell constant to intrinsic viscosity, which has been found to be independent of molecular weight for the limiting case of Gaussian molecules, is successfully interpreted as a function of molecular weight in terms of the recent theory of Gotlib and Svetlov (based on the wormlike chain model of Kratky and Porod). From the measurements at 55°C a number of 36.6 monomer units per random link is deduced. This is in accord with results of small-angle x-ray scattering. For the extinction angle curves a clear transition is observed from rodlike to statistical molecules when the molecular weight is increased. At high molecular weights the master curves obtained for anionic polystyrenes and cellulose tricarbanilates coincide. Implications of this observation on the kinetic stiffness of the cellulose tricarbanilate chain are discussed. The intrinsic viscosity-molecular weight relationship is considered. From a comparison with the results of the theory of Eizner and Ptitsyn it is concluded that the cellulose tricarbanilate chain must be highly solvated in benzophenone.
    Additional Material: 10 Ill.
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  • 10
    ISSN: 0006-3525
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The optical activity of the Klebsiella capsular polysaccharides of serotypes K1, K5, K6, K8, K11, K56, and K57 has been studied in aqueous solution. Measurements of ORD in the range 185-450 nm reveal anomalous ORD with Cotton effects near λ0 = 195nm. The results are evaluated quantitatively according to hte Moffitt-Yang and the Drude equations. Straight lines are obtained in the Moffitt-Yang plots, while the corresponding Drude plots yield bent curves. The b0 values, calculated from the slope of the stright lines in the Moffitt-Yang plot, range from 90 to 270 and suggest a helical superstructure for the capsular polysaccyharides. Positive b0 values have been found for K1, K5, and K6 and negative b0 values for K8, k11, K56, ad K57. Circular dichrosim has been mesured, but the CD curves are found to be truncated at the lower-wavelength end due to the 185-nm limit of the spectrometer used. Measurements of the temperature dependence of the specific optical rotation [α] reveal in all cases cooperative order-disorder transitions at temperatures, Tm, fro m298 to 323°K. The van′t Hoff enthalpies derived from the width of the transition curves are found to be similar in value to those of polypeptieds in aqueous solution. The K8 polysaccharide shows a two-step transition. The results are discussed in relation to the known primary structure and x-ray data from oriented and partially crystalline films. A model is suggested for the two-step transition in the K8 polysaccharide.
    Additional Material: 7 Ill.
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