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  • Polymer and Materials Science  (40)
  • 1980-1984
  • 1955-1959  (40)
  • 1950-1954
  • 1959  (40)
  • 1
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 39 (1959), S. 559-566 
    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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  • 2
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 36 (1959), S. 558-560 
    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
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: High polymers with a regular chain structure have been produced by polymerization of ethylene with complexes containing crystalline organolithium compounds and titanium tetrachloride in organic solvents. For this purpose RLi compounds have been prepared, R being methyl, ethyl, butryl, dodeeyl, tolyl, mesityl, naphthyl, benzyl, and other aliphatic and aromatic groups. The investigation of the polymerization has led to the elucidation of the influence of the nature of the organic radical bound with lithium on the properties of polythene formed. Thermomechanical data, infrared and X-ray spectra, as well as viscometric molecular weight determination, have shown all specimens of polyethylene to be highly crystalline and of a regular chain structure. The polymers obtained have mechanical properties characteristic of polyethylenes of this type but with elongations that strongly differ in polymers produced using organolithium complexes with different radicals at the lithium. With some specimen, elongation has been found to reach extremely high values. Some suggestions have been made as to the causes of influence of different organic radicals in RLi on the properties of polymers.
    Additional Material: 3 Tab.
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  • 4
    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.
    Additional Material: 4 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 32 (1959), S. 37-44 
    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: Sodiumvinylsulphonate (VS-Na) shows a strong tendency for polymerization in concentrated aqueous solutions. The rate of polymerization and the conversion depend on the acidity of the solution. It was found that the molecular weight increases with the time of polymerization and with the conversion. Monomers like styrene, vinylacetate etc., which are insoluble or only partly soluble in water can be copolymerized with VS-Na in homogeneous solution with dimethylsulfoxyd as solvent.
    Notes: Natriumvinylsulfonat (VS-Na) zeigt in konzentrierten wäßrigen Lösungen eine ausgeprägte Polymerisationsneigung. Die Polymerisationsgeschwindigkeit und der erreichte Umsatz hängen stark von der Acidität der Lösungen ab. Es wurde gefunden, daß mit der Polymerisationsdauer und mit wachsendem Umsatz auch die Molekulargewichte der Polymerisate ansteigen. Wasserunlösliche oder nur begrenzt lösliche ungesättigte Verbindungen wie Styrol, Vinylacetat und andere können in Dimethylsulfoxyd in homogener Lösung mit VS-Na copolymerisiert werden.
    Additional Material: 6 Tab.
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  • 6
    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.
    Additional Material: 7 Ill.
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  • 7
    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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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim [u.a.] : Wiley-Blackwell
    Materials and Corrosion/Werkstoffe und Korrosion 10 (1959), S. 377-383 
    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
    Description / Table of Contents: The Reaction Mechanism of the Atmospheric corrosion of Metals in Humid Air Containing sulphur Dioxide ContaminationIn an atmosphere contaminated with sulphur dioxide the course of the reaction is often determined by hydrolytic reactions. This produces solid corrosion products with different physicochemical properties. An explanation is proposed of the effect of sulphur dioxide by means of a reaction mechanism.
    Notes: In einer Atmosphäre, die durch Schwefeldioxyd verunreinigt ist, wird der Reaktionsverlauf häufig durch hydrolytische Reaktionen bestimmt. Dabei entstehen feste Korrosionsprodukte von unterschiedlichen physikalisch-chemischen Eigenschaften. Zur Erklärung der Wirkung des Schwefeldioxydes wird ein Reaktionsmechanismus vorgeschlagen.
    Additional Material: 18 Ill.
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  • 9
    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: A number of fluorinated polyesters have been prepared by condensing hexafluoropentanediol with one or more dibasic acid chlorides, and melting and glass transition temperatures and rates of crystallization have been determined, largely by means of volume dilatometry. The relation between [η] in chloroform at 30° and M̄n for hexafluoropentylene adipate (HFPA) was found to be [η] = 3.20 × 10-5 M̄n. The melting point Tm was found to increase from 34.5° to 104° as the isophthalate content in a series of adipate copolyesters increased from 0 to 100 mole-%. The glass transition Tg increases from -57° to -31° as isophthalate content increases from 0 to 50 mole-%. Tg is raised about 6° by the crosslinking of the polyesters. Rates of crystallization were determined for two HFPA samples with M̄n's of 13,000 and 19,500. Maxima in these rates occurred at about -13° and -15°, respectively. Respective t½ values for (linear) HFPA, vulcanized HFPA, and a copolyester containing 20 mole-% isophthalate are 48, 1140, and 27,200 min., respectively, at -10°. All the crystallization isotherms conform to Avrami's equation, (Vt - V∞)/(Vt - V∞) = exp {-αt″} for n = 6 over the initial stages of the process. At 1° both HFPA isotherms agree with the above equation over a large part of the process; however, as the isotherm temperature decreases, the equilibrium degree of crystallinity, as judged by the overall specific volume change, decreases and the isotherms diverge from Avrami's equation over progressively larger portions of the process. The product of the maximum rate of crystallization for each isotherm with either t½ or τi, the “induction time,” decreases with decreasing temperature, as would be expected in view of Avrami's equation. The value of 6 observed for n, a constant determined by the nucleation and growth mechanisms, is anomalous since only values of 1 to 4 are theoretically predictable. Values over the range of 1 to 4 have been observed experimentally by other workers for a variety of polymers.
    Additional Material: 7 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 1 (1959), S. 43-49 
    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: Common secondary aromatic amine and alkylated phenolic antioxidants lose much of their activity in polyethylene containing carbon black. In contrast their thioether derivatives provide more protection against oxidation than the sum of the separate contributions of carbon black and the sulfur compounds. Organic disulfides and some thio-ethers without amino or phenolic hydrogen also safeguard polyethylene from oxidation but only in the presence of carbon black. Likewise thiols are excellent protectants in combination with carbon black but not in clear polymer. Aliphatic thiols, disulfides, and their polymeric derivatives and related selenium compounds exhibit similar activity.
    Additional Material: 8 Ill.
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