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  • 1
    ISSN: 0003-3146
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: The heterogeneous polymerization of acrylonitrile in aliphatic hydrocarbons is in its kinetic behaviour similar to the bulk polymerization. This is particularly the case at low conversions (〈50%). The results obtained in single-stage continuous polymerizations with short residence times are discussed in this context.The redox initiator system employed, consisting of tert.-butylhydroperoxide, sulphur dioxide and trichloroacetic acid, leads to special characteristics in the chemical structure of the acrylonitrile polymers. Parallel with the polymerization, the redox components react with acrylonitrile to form N-tert.-butylacrylamide, which can be incorporated into the growing polymer chain. A further effect of the initiator system is that the polymers formed contain a comparatively high proportion of sulphur fixed in the polymer, mainly in form of sulphonate groups. This is due to specific initiating and terminating reactions. As a result of hydrolysis the polymers also have relatively high concentrations of carboxyl groups.
    Notes: Die Fällungspolymerisation von Acrylnitril in aliphatischen Kohlenwasserstoffen steht in inherm kinetischen Erscheinungsbild der Acrylnitril-Massepolymerisation nahe. Dies gilt insbesondere für den Bereich niedriger Umsätze (〈50%). In diesem Zusammenhang werden Ergebnisse diskutiert, die bei der einstufigen kontinuierlichen Polymerisation unter Einstellung kurzer Verweilzeiten erhalten wurden.Das eingesetzte Redoxstartersystem, bestehend aus tert.-Butylhydroperoxid/Schwefeldioxid/Trichloressigsäure, führt zu charakteristischen Besonderheiten im chemischen Aufbau der Acrylnitril-Polymeren. In einer parallel zur Polymerisation ablaufenden Umsetzung der Redoxkomponenten mit Acrylnitril entsteht N-tert.-Butylacrylamid, das als Struktureelement in die wachsende Polymerkette eingebaut werden kann. Das Initiatorsystem bewirkt weiterhin, daß die anfallenden Polymeren durch spezifische Start- und Abbruchreaktionen einen vergleichsweise hohen Gehalt and polymerfixiertem Schwefel, vorwiegend in Form von Sulfonatgruppen, aufweisen und durch Hydrolyse eine relative hohe Konzentration an Carboxylgruppen besitzen.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 2
    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: Comparative calculations are conducted for triad models of polyacrylonitrile (PAN) and poly(vinyl chloride) (PVC) using the semiempirical MNDO method. By comparing the so obtained geometrical, thermodynamical, and electronic values it is possible to obtain information concerning the variation in the properties of PAN with stereochemically different structures. Consequently, the glass transition temperature of syndiotactic PAN is predicted to be higher than that of the isotactic form. As in case of PVC, it is expected that decreasing the polymerization temperature would lead to the preferred formation of syndiotactic segments in PAN. The necessary temperature is, however, in the latter case much lower. The calculated acidities indicate that a higher tendency toward racemization is to be expected for syndiotactic PAN as compared with isotactic PAN.
    Notes: Zusammenfassend läßt sich sagen, daß sich die Modelle für die Diastereomere des PAN in ihren Stabilitäten und Reaktivitäten noch weniger unterscheiden als die entsprechenden PVC-Modelle. Daraus läßt sich der Schluß ziehen, daß eine Beeinflussung der Stereoregularität des PAN allein durch Erniedrigung der Polymerisationstemperatur nicht zu erreichen ist.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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