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  • Polymer and Materials Science  (9)
  • Analytical Chemistry and Spectroscopy
  • Lunar and Planetary Science and Exploration
  • 1955-1959  (9)
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Year
  • 1
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Radiotagged acrylamide was polymerized in a solution containing untagged polyacrylamide in order to study branch formation. Polymerizations were carried out at 50°C. and at 78°C. with a persulfate-bisulfite catalyst. At 78°C., polymer with from one to seven branches was formed, while at 50°C. even with larger amounts of catalyst, the polymer was almost exclusively linear. The intrinsic viscosity of branched polyacrylamide, in water at 30°C., was compared with the predictions of the Zimm and Stockmayer equation for the intrinsic viscosity of trifunctionally branched molecules. This equation gave values which agreed well with measured values of the number of branches.
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  • 2
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 38 (1959), S. 63-72 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Crystalline poly(tert-butyl acrylate) was prepared with lithium dispersions, n-butyllithium, and lithium plus n-butyllithium as catalysts. Methyl acrylate, n-, see-, and iso-butyl acrylate gave only amorphous polymer under the conditions that produced crystalline poly(iert-butyl acrylate). Very pure monomer was necessary for the preparation of crystalline poly(tert-butyl acrylate) with lithium dispersions. That the poly(tert-butyl acrylate) was crystalline was shown by x-ray diffraction, observation with the polarizing microscope (preparation of birefringent spherulites) and the electron microscope, study of infrared absorption, softening point, and density, and finally by preparation of crystalline polymethyl acrylate from crystalline poly(tert-butyl acrylate) by ester interchange. The nuclear magnetic resonance spectrum of the crystalline poly(tert-butyl acrylate) showed no evidence of band splitting and the viscosity-slope constant, k′, was the same for crystallizable and noncrystallizable polymer.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 2 (1959), S. 302-307 
    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: Cinnamic acid esters of poly(vinyl alcohol) and of cellulose are insolubilized by ultraviolet radiation. This response may be increased by the inclusion of simple organic compounds such as Crystal Violet carbinol and Michler's ketone. A method of measuring this response (in terms of a sensitivity value, S) based upon photographic sensitometry has been devised. Preliminary study indicates that an increase in S is accompanied by an increase in response to the longer wavelengths of light.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 2 (1959), S. 308-311 
    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: It was reported in Part I of this series that coatings of various polymers containing cinnamic ester groups are rendered insoluble by exposure to ultraviolet radiation, and that the rate of insolubilization may be increased by the inclusion of certain organic compounds. A continued systematic examination of the behavior of several hundred organic compounds has revealed that the ability to sensitize to some degree is quite general, provided that no complicating factors are present. The sensitivity of poly(vinyl cinnamate) is decreased by the presence of reducing groups in the addend, and sensitizing activity is lowered by interaction between adjacent groups. It is enhanced by the introduction of increasing conjugation and of ketone, nitro, or amino groups. Spectrograms of polymer-sensitizer combinations indicate that, with increasing sensitivity value, the sensitivity shifts towards, and, in some cases, into, the visible portion of the spectrum.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 32 (1959), S. 112-123 
    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: Bei der mit Natriumhydroxyd katalysierten Phenol-Formaldehyd-Reaktion war es möglich, die ersten zwei Parallelreaktionen, die zur Bildung von o- und p-Methylolphenol führen, zu isolieren und mittels quantitativer aufsteigender Papierchromatographie ihre Kinetik und Energetik zu untersuchen. Die Reaktionen sind kinetisch von 2. Ordnung, abhängig von der Phenolat-Ionen- und der Formaldehyd-Konzentration. Bei überschüssigem Phenol und bei gegebener Katalysator-Konzentration sind die Reaktionen nur von der Formaldehyd-Konzentration abhängig. Die Reaktionsgeschwindigkeitskonstanten 1. Ordnung für die Bildung von o- und p-Methyllphenol bei 80°C betragen 2,69 bzw. 2,84·10-5 sec-1 und haben ungefähr die gleiche Aktivierungsenergie von 19,77 kcal/Mol.Innerhalb des untersuchten Bereichs von pH 7-9 ist die Reaktionsgeschwindigkeit der Alkali-Konzentration proportional, so daß die Geschwindigkeitskonstanten l. Ordnung mit Hilfe der Beziehung k2 = k1/Katal.konz. in die wahren Konstanten 2. Ordnung überführt werden können. Die Resultate zeigen, daß bezüglich der Anlagerung von Formaldehyd die para-Stellung des Phenols doppelt so reaktionsfähig ist wie die ortho-Stellung.Es wird ein Reaktionsmechanismus vorgeschlagen, der den gefundenen Ergebnissen und dem allmählichen Anstieg der Geschwindigkeitskonstanten mit dem entsprechenden Phenolüberschuß gerecht wird.
    Notes: In the sodium hydroxide-catalyzed phenol-formaldehyde reaction, it has now been possible to isolate the first two parallel reactions leading to the formation of o- and p-methylol phenols and to study, by means of quantitative ascending paper chromatography, their kinetics and energetics. The reactions are kinetically of second order, one with respect to phenate ion and one in formaldehyde, but at excess phenol concentration and a given catalyst concentration, they depend only on formaldehyde (concentration). The first order rate constants for production of o- and p-methylol phenols, at 80°C., are 2.68 and 2.84·10-5 sec-1 respectively, with about the same energy of activation of 19.77 kcal/mole. Within the pH range of 7-9 studied, the reaction rate is proportional to the alkali concentration, so that the first order rate constants can readily be converted into the true second order constants by means of the relationship, k2 = k1/cat. conc. The results indicate that the para position in phenol is twice as reactive in regard to the addition of formaldehyde as the ortho position. A reaction mechanism is suggested to account for the observed results and for the gradual increase of the rate constants with the relative excess concentration of phenol.
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  • 6
    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.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 32 (1959), S. 130-138 
    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: Im fall der von Natriumhydroxyd katalysierten equimolaren (0.2 M) Phenol-Formaldehyd-Reaktion treten selbst am Anfang der Reaktion Di- und Trimethylophenole auf. Es wird versucht, die Änderung der Mono, Di- und Trimethylophenole mit der Zeit mit Hilfe der in Teil I und II angegebenen Geschwindigkeitskonstanten und Aktivierungsenergien zu erklären, ebenso auch die sich widersprechenden kinetischen Beobachtungen frühere Untersuchungen, die hauptsächlich auf der Geschwindigkeit des Verbrauchs an Formaldehyd basierten.
    Notes: In the case of equimolar (0.2 M) phenol-formaldehyde reaction catalyzed by sodium hydroxide, even in the early stages of the reaction the di- and tri-methylol phenols make their appearance. Attempt is made to account for the variation of mono-, di- and trimethylol phenols with time in terms of the rate constants and activation energies reported in Parts I and II, and also for the conflicting observations in regard to kinetic order made in earlier investigations which were based essentially on the rate of disappearance of formaldehyde.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 32 (1959), S. 124-129 
    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 die Bildung von Dimethylolphenolen bei der Einwirkung von Formaldehyd auf o- und p-Methylophenole in Gegenwart von Natriumhydroxyd als katalysator kinetisch untersucht. In Gegenwart von 0,006 M NaOh und bei weniger als 10%iger Reaktion zeigt sich das Verhalten einer Reaktion 1. Ordnung. Für die Bildung von 2,4-Dimethylolphenol aus p-Methylolphenol und Formaldehyd bei 80°C beträgt die Geschwindigkeitskonstante 1.17·10-5 sec-1, die Aktivierungsenergie 23,92 kcal/Mol., für die Bildung der 2,6- und 2,4-Dimethylolphenole aus o-Methylolphenol dagegen sind die Geschwindingkeitskonstanten 0,55 bzw. 1,11·10-5 sec-1 und die Aktivierungsenergien 25,10 und 23,37 kcal/Mol. Aus diesen Daten und denen von Teil I werden die relativen Reaktivitäten der freien ortho- und para-Stellungen bei Phenol und bei substituierten Phenolen bestimmt, die, ungleich denen von FREEMAN und Mitarbeitern5, sowohl unter sich als auch mit den theoretischen Erfordernissen übereinstimmen.
    Notes: The kinetic study has been made of the sodium hydroxide-catalyzed interaction of o- and p-methylol phenols with formaldehyde to give dimethylol phenols. At 0.006 M NaOH and within less than 10% of the reaction, first order kinetic behaviour was obtained. The rate constant, at 80°C., for the formation of 2,4-dimethylol phenol from p-methylol phenol and formaldehyde, was found to be 1.17·10-5 sec-1 and the activation energy, 23.92 kcal/mole, whereas for formation of 2,6- and 2,4-dimethylol phenols from o-methylol phenol, the rate constants were respectively 0.55 and 1.11·10-5 sec -1, the corresponding activation energies being, 25.10 and 23.37 kcal/mole. In terms of these data and those present in Part I, the relative reactivites of the free ortho and para positions in phenol and substituted phenols are evaluated and shown to be, unlike those reported by FREEMAN et al.5, consistent among themselves and with theoretical requirements.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 24 (1957), S. 25-49 
    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: Using an improved process, polyacrylamidoxime is obtained by reacting hydroxylamine on polyacrylonitrile in dimethylformamide medium. The improvement consists in replacing hydroxylamine hydrochloride by a hydroxylamine solution in DMF. As could be expected, the polymers are polyampholytes belonging to a new class with well defined structure, characterized by the fact that each substituent bears acidic and basic groups.It is found that the reaction is of first order with respect to NH2OH and polyacrylonitrile separately; the overall rate being of the second order. The k-value amounts to nearly 1,5 · 10-4 (mol/lit)-1 sec-1.From a careful examination of the reaction it appears that no NH3 is split off, neither during the reaction, nor during the subsequent washing and drying. This leads to the conclusion that, contrary to the results reported in a previous paper, the adjacent amidoxime groups do not mutually react giving rise to the formation of glutaroimidedioxime rings, but the amidoxime groups remain free.This structure is further demonstrated by acid hydrolysis of the polymer itself as well as of products which previously were subjected to alkaline hydrolysis or to heating. In all the cases examined, the quantities of NH3 and of NH2OH liberated are practically the same.The reaction products are also examined by poteritiometric - respectively conductometric methods, and by IR-spectrography and the results are compared to those of glutarodiamidoxime.
    Notes: Nach einem verbesserten Verfahren wird Polyacrylamidoxim durch Reaktion von Hydroxylamin auf Polyacrylnitril in Anwesenheit von Dimethylformamid erhalten. Der Fortschritt wird dadurch erreicht, daß statt Hydroxylaminchlorhydrat eine Lösung von Hydroxylamin in DMF verwendet wird. Wie vorauszusehen war, sind die Polymere Polyampholyte, welche einer neuen Klasse mit wohlbestimmter Struktur angehören, und die dadurch gekennzeichnet sind, daß jeder Substituent saure oder basische Gruppen trägt.Es wurde gefunden, daß in bezug auf NH2OH und Polyacrylnitril je für sich die Reaktion erster Ordnung ist, während die Totalgeschwindigkeit zweiter Ordnung ist. Der k-Wert beträgt zirka 1,5 · 10-4 (mol/l.)-1 sek-1.Aus einer eingehenden Prüfung der Reaktion ergibti sich, daß weder während der Reaktion, noch beim weiteren Waschen und Trocknen NH3 abgespalten wird. Hieraus wird gefolgert, daß, im Widerspruch zu den in einer vorigen Veröffentlichung bekanntgegebenen Ergebnissen, die benachbarten Amidoximgruppen nicht miteinander unter Bildung von Glutarimiddioximringen reagieren, sondern daß die Amidoximgruppen völlig frei bleiben.Eine weitere Bestätigung dieser Struktur erfolgt aus der Säurehydrolyse des Polymeren selbst sowie der Produkte, welche zuvor der Alkalihydrolyse oder dem Erwärmen unter worfen wurden. In sämtlichen Fällen sind die freigegebenen NH3 und/oder NH2OH-Quanten praktisch gleich.Die Reaktionsprodukte werden auch nach potentiometrischen bzw. konduktometrischen Methoden und auf IR-spektrographischem Wege geprüft und die Ergebnisse mit diesen des Glutardiamidoxims verglichen.
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