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  • Polymer and Materials Science  (11)
  • 1980-1984
  • 1955-1959  (11)
  • 1950-1954
  • 1956  (11)
Collection
Publisher
Years
  • 1980-1984
  • 1955-1959  (11)
  • 1950-1954
Year
  • 1
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A light scattering photoelectric photometer was built and calibrated by a narrow fraction of polystyrene for which the molecular weight was assigned by the viscosity method. The instrument was used to determine the molecular weights of polyvinyl acetate fractions. The light scattering molecular weights of the polyvinyl acetates, up to a value of 477,000, agreed with those obtained from viscosity data employing the Nakajima equation: [η] = 8.91 × 10-3 × P0.62, where [η] is the intrinsic viscosity in benzene and P is the degree of polymerization. k′ and μ values lie in the expected ranges. The rootmean-square end-to-end distances of the polyvinyl acetate molecules determined by the dissymmetry method are found to be much smaller than those calculated by Fox-Flory relation from viscosity data.
    Additional Material: 4 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 19 (1956), S. 379-380 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 1 Tab.
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  • 3
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 7 (1956), S. 204-204 
    ISSN: 0947-5117
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
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  • 4
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 22 (1956), S. 408-408 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 18 (1956), S. 437-454 
    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: During the inhibition period an exactly alternative copolymerisation of methacrylate and molecular oxygen occurs. The alternation is caused by the high rate constant of the reaction of oxygen with a growing chain compared with the addition of a monomer. The chain length of this copolymerisation is about 1/65 of that of normal polymerisation. The termination of those chains involves two radicals carrying oxygen at the growing ends.The rate equations for this mechanism are developed and proved by measuring the length of the inhibition period (τ) as a function of the initiator, monomer and oxygen concentrations. The rate constant for the addition of oxygen to the growing end is at least 5 orders of magnitude higher than that for the addition of a monomer.
    Notes: Während der Inhibierungsperiode findet eine streng alternierende Copolymerisation zwischen molekularem Sauerstoff und dem monomeren Methacrylat statt. Die Alternierung kommt dadurch zustande, daß die Anlagerung von O2 an ein radikalisches Kettenende mit einer um mindestens 5 Größenordnungen höheren Geschwindigkeitskonstante erfolgt als die Anlagerung des Monomeren. Die Reaktionsfähigkeit des Sauerstoffs bei dieser Reaktion entspricht somit der eines freien Radikals. Die Länge der hierbei auftretenden Reaktionsketten liegt in der Größenordnung 102, das ist 2 Größenordnungen kleiner als die Ketten bei der normalen Polymerisation. Der Abbruch der Copolymerisationsketten erfolgt zwischen zwei Radikalen, die an ihren Enden Sauerstoff tragen (RO2·). Die Länge der Induktionsperiode in Abhängigkeit von den Konzentrationen des Initiators, des Monomeren und des Sauerstoffs wird auf Grund des Reaktionsmechanismus berechnet und experimentell bestätigt. Das entstehende Copolymerisat ist instabil, so daß es bei 50°C schon während der Inhibitionsperiode teilweise zerfällt.
    Additional Material: 3 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 20 (1956), S. 46-56 
    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 Änderungen in der UR-Absorption von Kautschuk nach Cyklisierung werden beschrieben. Die Spektren von cyklisiertem Kautschuk, der bei Einwirkung von Schwefelsäure auf stabilisierten Hevea Milchsaft dargestellt wurde, zeigen, daß Cyklisierung auch bei Zimmertemperatur stattfindet. Die Spektraländerungen werden noch deutlicher wenn die Reaktion bei 80°C durchgeführt wird. Ein Vergleich der Spektren von cyklisiertem Kautschuk und 1,2-Dimethyl-Cyclohexen-1 deutet an, daß der cyklisierte Kautschuk substituierte Cyclohexen-Ring-Systeme enthält. Eine Absorption bei 13,17 μ war charakteristisch für cyclisierten Kautschuk.Die Änderungen in den UR-Absorption-Spektren von cyklisiertem Kautschuk nach Chloraddition werden ebenfalls diskutiert. Cyklisierter Kautschuk zeigt nach Chlorierung charakteristische Absorption von beiden, chloriertem und cyklisiertem Kautschuk.
    Notes: The changes in the infra-red absorption spectra of rubber following cyclization are reported. The spectra of cyclized rubber prepared by the action of sulphuric acid on stabilized Hevea latex have shown that cyclization starts even at room temperature. The spectral changes were more pronounced when the reaction was carried out at 80°C. From a comparison of the spectra of cyclized rubber with that of 1,2-dimethyl-cyclohex-1-ene, it is inferred that cyclized rubber contain substituted cyclohexene type rings. Absorption at 13.17 μ appeared to be characteristic of cyclized rubber.The changes in the infra-red absorption spectra of cyclized rubber, following additive chlorination are also discussed. Chlorinated cyclized rubber showed absorptions, characteristic of cyclized rubber and chlorinated rubber.
    Additional Material: 4 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 21 (1956), S. 131-168 
    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: After a short survey of the literature with regard to the question of structural differences in polystyrenes which have been prepared under various conditions, an investigation on thermally polymerized polystyrene is communicated. Carefully purified styrene was polymerized at temperatures ranging from 0°C to 132°C with conversions of from 1% to 65%. The fractionated products followed the well-known relationship [η] = K.Ma in the molecular weight range from 50 000 up to a million. K and a were independent of the polymerization temperature; their values were practically the same as those for polystyrenes obtained from either radically or ironically initiated polymerizations which had been carried out under usual conditions. The above relationship also applied to the products obtained by partially degrading the thermal polymers with S2Cl2 in the presence of UV-light. The osmotic molecular weights agreed well with the viscosimetric molecular weights which resulted from viscosity measurements in cyclohexane at the Flory-point. The degradation of polystyrene by S2Cl2 was investigated and a radical-mechanism for this process is discussed.
    Notes: Nach einem Überblick über die frühere Literatur in Hinsicht auf die Frage, ob verschieden hergestellte Polystyrole strukturelle Unterschiede aufweisen, wird über Untersuchungen an rein thermisch hergestellten Polystyrolen berichtet. Die Polymerisationstemperaturen wurden zwischen 0 und 132°C, die Umsätze zwischen 1 und 65% variiert. Die erhaltenen fraktionierten Polystyrole folgen im Molekulargewichtsbereich von 50 000 bis ca. einer Million unabhängig von der Polymerisationstemperatur einheitlich der bekannten Beziehung [η] = K · Ma, wobei K und a praktisch dieselben Werte haben wie bei radikalisch oder ionisch initiierten Produkten übelicher Herstellung. Polystyrole, die durch Abbau von thermischen Polymerisaten mit S2Cl2 im UV-Licht gewonnen wurden, folgen ebenfalls der obigen Glecichung. Die osmotischen Molekulargewichte von Fraktionen verschieden hergestellter Polystyrole stimmen gut überein mit den viskosimetrischen Molekulargewichten, die sich in Cyclohexan bei der Flory-Temperatur ergeben. Der Abbau von Polystyrol mit S2Cl2 wird verfolgt und ein radikalischer Mechanismus hierfür diskutiert.
    Additional Material: 19 Ill.
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  • 8
    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: An experimental method is worked out, to dissolve natural Rubber excluding the action of oxygen and to purify the solution for optical measurements using an ultracentrifuge. Light scattering is measured as a function of concentration, angle, wave length and temperature. By determining molecular weight, diameter of the coiled molecule and thermodynamic quantities (Δμ1, Δh1, Δs1) in this way it is possible to get information on branching of the rubber molecules.The method is used for cyclohexene solutions of a carefully tapped crěpe-rubber. The molecular weight is 1,3.106, the end to end distance of the coil 1750 Å, the heat of dilution is positive (endothermic), the B-value nearly as high as found in benzene solution by osmotic measurements. Comparing these results with measurements on unbranched polymethacrylate and polyisobutylene one can conclude, that these rubber molecules are not or only slightly branched.
    Notes: Es wird eine Versuchsmethode ausgearbeitet, um natürlichen Kautschuk unter Vermeidung der Einwirkung von Luftsauerstoff zu lösen, die Lösungen durch Ultrazentrifugierung zu reinigen und dann deren Lichtstreuung in Abhängigkeit von der Konzentration, dem Beobachtungswinkel, der Wellenlänge und der Temperatur zu messen. Indem man hierbei das Molekulargewicht, den Durchmesser des Molekülknäuels und weiterhin die thermodynamischen Größen (osmotischer Druck bzw. chemisches Potential des Lösungsmittels, Verdünnungswärme und -entropie) bestimmt, kann man durch Vergleich mit den an synthetischen Hochpolymeren gewonnenen Erfahrungen auch Aufschluß über eventuell vorhandene Molekülverzweigungen erhalten.Die Methode wird zunächst an einem unter schonenden Bedingungen gewonnenen Crěpekautschuk ausprobiert, wobei als Lösungsmittel Cyclohexen verwendet wird. Das Molekulargewicht ergibt sich zu 1,3.106; der statistische Fadenendenabstand ist 1750 Å. Die Verdünnungswärme ist positiv (endotherm), der B-Wert annähernd so hoch wie osmotisch an Benzol gefunden wurde. Ein Vergleich mit analogen Messungen an unverzweigtem Polymethylmethacrylat und Polyisobutylen ergibt, daß die untersuchten Kautschukmoleküle nicht oder nur schwach verzweigt sind.
    Additional Material: 10 Ill.
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  • 9
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The dilute solution viscosity properties of fractions of two linear and one branched sample of polyvinyl acetate in benzene and of two linear and one branched fraction in several solvents were measured at 35°C. Values of total slope, b (from plots of ηsp/c vs. c), and intrinsic viscosities were obtained under the requirement that k′ + β = 0.500 ± 0.002. Empirical plots of log b vs. log [η] gave lines which were straight within the limits of accuracy of the data. For the linear fractions in benzene, Huggins' k′ was constant and the slope of the log b vs. log [η] line was 2; for the branched fractions in benzene, k′ increased with [η] and the slope of the log b vs. log [η] line was greater than 2. The log b vs. log [η] plots form the basis for a “one-point” method for determining [η]. Consideration of these data along with results reported in the literature indicates that k′ is measurably sensitive to branching only for fractions possessing a certain minimum combination of size and complexity. However, in some cases where the variations of k′ are inconclusive, use of the slope of the log b vs. log [η] line may provide a reliable indication of branching. It was found that a comparison between the branched and linear series could also be made at constant values of [η] or b. Two linear fractions in different solvents obeyed a type of Huggins relationship in which k′ did not vary with solvent and the slope of the log b vs. log [η] line was 2. For a higher molecular weight branched fraction, however, k′ varied from solvent to solvent and the slope of the log-log plot was about 1.7. These data do not support a reference point concept of “true” intrinsic viscosity based on a simple linear relationship between b and [η]. Preliminary results dealing with the effects of the shear rate indicated that the measured viscosity properties of branched fractions may be more seriously affected by changes in shear rate than those of linear fractions.
    Additional Material: 5 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 19 (1956), S. 111-121 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Additional Material: 3 Ill.
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