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  • Wiley-Blackwell  (8)
  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 109 (1967), S. 120-131 
    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 Wirkung des Druckes im Bereich von 1 bis 5000 atm auf die durch Strahlen verursachte Polymerisation des β-Propiolactons in Substanz bei Teraperaturen zwischen -196 and -78°C untersucht. Die Polymerisationsgeschwindigkeiten, die Viskositäten, die Schmelzpunkte and die Infrarotspektren der entstandenen Produkte werden bestimmt.Die Polymerisationsgeschwindigkeit wird durch Druck bei Temperaturen unter -98°C erhöht. Die Aktivierungsenergien für 1 and 5000 atm zeigen Unterschiede: 0,01 kcal/Mol bei Normaldruck, 0,18 kcal/Mol bei 5000 atm.Die Wirkung des Druckes wird ausgehend von der Initiierung über die Wachstums- und Abbruchsreaktion erörtert und dabei der Einfluß von Zusätzen auf die Polymerisation berücksichtigt.Aus den vorliegenden Untersuchungen kann geschlossen werden, daß der Einfluß des Druckes/ auf die Wachstumsreaktion am wirksamsten ist und daß dieser Effekt nicht nur auf einer änderung der Aktivierungsenthalpie, sondern auch auf einer äuderung der Aktivierungsenthalpie beruht.
    Notes: The effect of pressure on the radiation-induced solid state polymerization of β-propiolactone has been investigated in the range of 1 to 5000 atm over a temperature region of -196 to -78°C. Rates of polymerization, viscosities, melting points and infrared spectra have been measured.It was found that the rate of polymerization is accelerated by pressure at temperatures below -98°C, and that the activation energies change for polymerizations at 1 and 5000 atm from 0.01 kcal/mole to 0.18 kcal/mole.The pressure effect was discussed from the point of initiation, propagation and termination reactions, taking the effect of additives on the polymerization into consideration.It may be concluded from the study that the effect of pressure on the propagation reaction is most important and the pressure effect is not only due to the change of the activation enthalpy but also the change of the activation entropy.
    Additional Material: 17 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 85 (1965), S. 91-101 
    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: Tetrafluoräthylen und Isobuten copolymerisieren in einem weiten Bereich von Konzentrationsverhältnissen zu alternierend aufgebauten kristallinen Copolymeren.Die Copolymerisation wurde bei -45 und -78°C durch 60Co-γ-Strahlung ausgelöst. Für -45°C wurden die Copolymerisationsparameter r1(C4H8) und r2(C2F4) aus der Zusammensetzung der Polymeren zu 0,2 bzw. 0 gefunden; für -78°C war eine exakte Bestimmung nicht möglich, eine grobe Abschätzung ergab r1(C4H8)≅r2(C2F4)≅0.Die Tendenz zur alternierenden Copolymerisation mag auf die gegenteilige Polarisierung der beiden Monomeren zurückzuführen sein, nämlich die Elektronenacceptorwirkung der Fluoratome im Tetrafluoräthylen und die Elektronendonatorwirkung der Methylgruppen im Isobuten.Aus der Abhängigkeit der Copolymerisationsgeschwindigkeit vom Konzentrationsverhältnis der Monomeren läßt sich ableiten, daß bei hoher Isobutenkonzentration als Abbruchsreaktion wahrscheinlich die degenerative Kettenübertragung auf das Isobuten angenommen werden muß.
    Notes: It was found that tetrafluoroethylene copolymerizes with isobutene and a crystalline, alternating copolymer could be obtained over a wide range of the monomer composition in the copolymerization.The copolymerizations were carried out by 60Co-γ-ray irradiation at -45 and -78°C. The monomer reactivity ratios, r1(C4H8) and r2 (C2F4), were determined from an elementary analysis of the copolymers to be 0.2 and 0 at -45°C., respectively; while the reactivity ratios at -78°C. could not be determined exactly, but were roughly estimated to be r1(C4H8)≅r2(C2F4)≅0.The alternating tendency of this copolymer may be due to the opposite polarities of the monomers, that is, the electron with-drawing property of the fluorine atoms of tetrafluoroethylene and the electron-donating property of methyl groups of isobutene.It may suggested from the monomer composition dependence of the copolymerization rate that the termination reaction takes place mainly via a degradative chain transfer of the growing radical to isobutene at a high isobutene concentration in the monomer mixture.
    Additional Material: 5 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 10 (1972), S. 2941-2949 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radiation-induced copolymerization of tetrafluoroethylene with various vinyl ethers has been studied. It was found that tetrafluoroethylene can be copolymerized with vinyl ethers to give alternating copolymers over a wide range of the initial monomer concentration in the monomer mixture. The monomer reactivity ratios were determined for the copolymerization of tetrafluoroethylene with n-butyl vinyl ether as 0.005 (rTFE) and 0.0015 (rNBVE). The rate of copolymerization is extremely high and has a maximum at an equimolar concentration of two monomers. The alternating structure of the copolymers was confirmed by the analysis of NMR spectra. Some thermal properties of the copolymers were measured by DSC and DTA.
    Additional Material: 7 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A: General Papers 2 (1964), S. 2445-2453 
    ISSN: 0449-2951
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Radiation-induced copolymerization of tetrafluoroethylene with isobutene was carried out in the liquid state of the monomers at low temperature. The composition curve of the tetrafluoroethylene-isobutene copolymer was obtained. Infrared spectra, x-ray diffraction, and melling points of the copolymers obtained were also measured. It was concluded from these experimental results that an alternating crystalline isobutene tetrafluoroethylene copolymer can be obtained by a radical process induced by ionizing radiation. This seems to be the first case in which an alternating crystalline copolymer was obtained by a radical mechanism over an extremely wide range of molar concentration of the components in the monomer mixture.
    Additional Material: 6 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Letters 6 (1968), S. 715-720 
    ISSN: 0449-2986
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Letters 7 (1969), S. 375-378 
    ISSN: 0449-2986
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Letters 10 (1972), S. 295-299 
    ISSN: 0449-2986
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Letters 4 (1966), S. 669-672 
    ISSN: 0449-2986
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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