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  • Polymer and Materials Science  (9)
  • 1945-1949  (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: The course of the reactions of benzoyl peroxide with cyclohexane and cyclohexene may be accounted for by a mechanism involving free radicals and radical chain reactions. With cyclohexane, the average length of the chain hardly exceeds one step and one mole of hydrocarbon reacts with one mole of peroxide. With cyclohexene, chains of two and three steps also occur and about two and one-half moles of hydrocarbon per mole of peroxide take part in the reaction. It is shown that this is due to the one-sided addition of the primary radicals (originating from the peroxide) to the double bond, yielding a new radical without a double bond which can in turn react in the same way with another unsaturated molecule, thus giving rise to polycyclic compounds (chain formation). This polymerization reaction is, however, soon halted by a competitive side reaction involving substitution of the α- (or β)-methylene group, which leaves the double bond intact. In polymerizable vinyl derivatives in which no reactive α-methylene group is present, the competitive reaction cannot occur and the radical chain reaction continues to form a growing chain of interlinked monomeric molecules with annihilation of the double bonds. The two terminal groups of the macromolecules of the final polymerizate are radicals originating from the peroxide used as a catalyst. If a solvent is used, radicals of the latter may also appear occasionally as terminal groups of the polymer. The mechanism of the catalytic action of diacyl peroxides in the polymerization of vinyl derivatives is thus clarified. The molecule linking reaction induced by free radicals in unsaturated compounds also provides an explanation of the action of benzoyl peroxide as a rubber vulcanizer; the peroxide radicals are found as substituents in the rubber molecule.
    Additional Material: 5 Tab.
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  • 2
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The swelling of vulcanized natural rubber, Buna S, neoprene, Perbunan, and Perbunan Extra was measured in various organic liquids. The essential influence of polarizability and polarity on the swelling equilibrium is illustrated by comparing series of solvents and polymers with gradually changing geometrical and chemical structure. Experiments on the influence of temperature and of strain on the swelling equilibrium are reported. The swelling properties of ebonites and similar derivatives allow some conclusions on the amount of cross linking in these polymers.
    Additional Material: 13 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 381-386 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The permeability of vulcanized gutta-percha membranes to gases was determined in relation to the rate of diffusion and solubility. The measurements, as functions of temperature, with four gases were taken below and above the melting point of gutta-percha. The evidence is that the rates of permeation and diffusion increase sharply at approximately 45°C., due to melting of the gutta-percha. In the same way, although to a lesser degree, the solubility of the gas likewise increases at the melting point. The activation energies of permeation and diffusion with the heat of solution were computed from the temperature function of those quantities. It follows from the results that crystallization of the elastomer reduces the gas-solubility, the diffusivity, and the permeability - and increases the activation energy of diffusion. The interpretation of this high activation energy of diffusion is that, because of the crystallization, the macromolecules of the membrane adhere so firmly that greater energy is required to admit the gas molecules.
    Additional Material: 2 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 2 (1947), S. 583-592 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Various problems related to the determination with x-rays of the atomic configuration of organic fibers are discussed. Because of the approximate nature of the underlying theory, too far-reaching conclusions should be avoided, especially since, in the case of organic fibers, the situation is much less simple than in the case of sodium chloride powder or metallic wires, for example. Because of these facts, and because of the relative poorness of fiber patterns, the atomic coordinates as well as the space group of the structure can be found only within certain limits. Though the use of macroscopic models is very helpful in visualizing the spatial arrangement, no conclusions of a quantitative nature can be reached with their aid because the assumptions embodied in these models are too numerous and too inexact to justify speculations on details of the structure. In the case of cellulose fibers, it is shown that the problem cannot yet be solved completely; the outlook for a really unique solution is not hopeful. The structure proposed by Meyer and Misch is still the best approximation available. More recent propositions are shown to be less well founded; the atomic configuration introduced by Peirce, being at variance with chemical, crystallographic and x-ray evidence, is to be discarded.
    Additional Material: 5 Ill.
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  • 5
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Methods for the preparation of fiber-forming polymeric amides from ω-amino acids and The variation in melting points of the polymeric their amide-forming derivatives are described. The variation in melting points of the polymeric amides with increasing chain length of the recurring unit is discussed.
    Additional Material: 1 Ill.
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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 inhibitor and initiator action of 33 compounds on the bulk polymerization of pure isoprene has been studied. Picric acid was found to be the most powerful inhibitor at 100°C. The conclusion reached in Part I, that the initiator activity of diazoaminobenzene is superior to all other compounds has been found to be valid also between 100-150°C. The heat polymerization of isoprene between 100-150°C. in the presence of picric acid leads only to the formation of dimers. Three of the four possible isomers have been separated. The solid complex compound of diprene (I) with silver nitrate has been used to separate it from dipentene (II) and the hydrocarbon of Lebedew (III, IV) has been identified as a monochloride. The relative yields (I): (II): (III+IV) = 16:1:2 are in agreement with the relative availability and localization of π-electrons in isoprene. Observations on the properties of polyisoprene are in agreement with the more extensive work by d'Ianni. Some remarks on polymers from bulk polymerization are added. Isoprene acts as a powerful inhibitor on the polymerization of vinylidene chloride. This effect is independent of the method of polymerization.
    Additional Material: 4 Ill.
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  • 7
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Previous observations make it probable that one or both ends of a longchain molecule produced by catalyzed vinyl polymerization contain fragments of the initiator. If one uses acid peroxides as initiators, these fragments can contain a carbonyl group. It is the purpose of this paper to investigate whether these carbonyl groups which are present only in a very small amount can be detected by infrared absorption. It seems that in the case of polystyrene initiated with benzoyl peroxide, infrared absorption spectra reveal the presence of a small amount of some carbonyl groups in the polymer. Their amount appears to be in agreement with chemical measurements and with the molecular weight of the material.
    Additional Material: 3 Tab.
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  • 8
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 1 (1946), S. 49-57 
    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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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 4 (1949), S. 105-112 
    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 discussion is given of the formulae obtained by Münster and Schulz for the entropy of dilution of dilute macromolecular solutions. For large spherical solute molecules both authors find results slightly different from that, which can be predicted from the classical theory of gases. According to Schulz, and contrary to the results of other authors, molecular flexibility should have a considerable influence on the entropy of dilution of chain molecules. This discrepancy originates from a slip in his calculations, correction of which leads to an entropy of dilution equal to that found for rigid chain molecules.
    Notes: Die Ergebnisse der Münsterschen und Schulzschen Berechnungen der Verdünnungsentropie verdünnter makromolekularer Lösungen werden diskutiert. Es zeigt sich, daß beide Autoren für kugelförmige Makromoleküle ein etwas anderes Ergebnis erhalten, als nach der klassischen Gastheorie zu erwarten ist. Für fadenförmige Makromoleküle schließt Schulz, im Gegensatz zu den Aussagen anderer Autoren, auf einen großen Einfluß der inneren Beweglichkeit. Es wird gezeigt, daß dies auf einem Versehen beruht.
    Type of Medium: Electronic Resource
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