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  • 1
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molecular weights and structural characteristics of the polymers formed in the system isoprene/oligoisoprenyllithium (OILi)/N,N,N′,N′-tetramethylethylenediamine (TMD)/hexane (mole ratio TMD/OILi-0,01) at various conversions at -30°C were determined. The applied conditions made it possible to judge the relative activity of various types of growing chains. The results obtained suggest an opposite influence of the complex formation with respect to the associated and non-associated organolithium compounds. It was found that the former are activated (in comparison to the non-complexed associates), whereas the latter (in comparison to the non-complexed monomeric forms MnLi) become less active by complex formation. The possible causes of this different behaviour are considered.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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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: N,N,N′,N′-Tetramethylethylenediamine (TMD) causes a significant increase of the polymerization rate and of the content of 3,4-links in the polymers formed in the systems organolithium (RLi)/isoprene already at a mole-ratio [TMD]/[RLi]≈1. In order to clear the nature of these effects fractions of the polymers formed at a ratio [TMD]/[RLi]=0,01 which secured parallel propagation reactions by the RLi-species and their complexes with TMD were investigated. The highest content of 3,4-links was found in the polyisoprene fraction with the lowest molecular weight. A possible mechanism of this phenomenon is discussed.
    Notes: N,N,N′,N′-Tetramethyläthylendiamin (TMD) ruft in den Systemen Organolithium (RLi)/Isopren schon beim Molverhältnis [TMD]/[RLi]≈1 eine beträchtliche Zunahme der Polymerisationsgeschwindigkeit und bevorzugte Bildung von 3,4-Kettengliedern in den Polymeren hervor. Um die Natur dieser Effekte zu klären, wurden Fraktionen der Polymeren untersucht, die sich beim parallelen Verlauf der Wachstumsreaktion an RLi-Agenzien und deren Komplexen mit TMD bilden, was durch die Wahl des Verhältnisses [TMD]/[RLi]=0,01 erreicht wurde. Der höchste Gehalt an 3,4-Gliedern in dem unter dieser Bedingung erhaltenen Polyisopren wurde für die Fraktion mit dem kleinsten Molekulargewicht festgestellt. Es wird ein möglicher Mechanismus für diese Erscheinung vorgeschlagen.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    Library Location Call Number Volume/Issue/Year Availability
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