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  • 1970-1974  (2)
  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 147 (1971), S. 53-68 
    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: Die Polymerisation von racemischen und optisch-aktiven α-Olefinen mit optischer Reinheit zwischen 10 und 95% wurde mit verschiedenen ZIEGLER-NATTA-Katalysatoren untersucht. Besonders im Fall des 3.7-Dimethyl-1-octens (I) scheint die Polymerisation stereoselektiv zu sein; der überschüssige Antipode wird mit größerer spezifischer Geschwindigkeit polymerisiert. Die Stereoregularität von Polymeren aus I und aus 4-Methyl-1-hexen (II) nimmt mit steigender optischer Reinheit mäßig zu, wie Lösungsmittelextraktion, Drehvermögen und Ultrarotspektrum der Fraktionen zeigen; auch der Katalysator spielt eine wichtige Rolle.Außerdem wurde die Verteilung von R- und S-Einheiten in den verschiedenen stereoregulären Fraktionen durch die Polymerisation eines Gemisches von (R)-II und (S)-II-1-14C untersucht, und die möglichen Beziehungen zwischen Stereospezifität und Stereoselektivität werden diskutiert.Kein besonderer Einfluß der asymmetrischen Struktur des Monomeren auf die Stereochemie der Polymerisation wurde im Falle des 5-Methyl-1-heptens (III) beobachtet.
    Notes: The polymerization of racemic and optically active α-olefins having optical purity from 10 to 95% has been investigated by several ZIEGLER-NATTA catalysts. Especially in the case of 3.7-dimethyl-1-octene (I) the polymerization appears to be stereoselective, the predominant antipode being polymerized with higher specific rate. The stereoregularity of polymers from I and from 4-methyl-1-hexene (II) slightly increases with monomer optical purity as shown by solvents extraction, IR spectra, and optical rotation; however a remarkable role is played by the catalytic system.The distribution of R and S units in polymer fractions having different stereoregularity has been also investigated by polymerizing a mixture of (R)-II and (S)-II-1-14C and possible relationships between stereoregulation and stereoselectivity are discussed.No particular effect of monomer asymmetric structure on polymerization stereochemistry has been observed in the case of 5-methyl-1-heptene (III).
    Additional Material: 8 Tab.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 10 (1972), S. 809-822 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The synthesis of optically active p-sec-butylstyrene (I) has been carried out starting with (S)-2-phenylbutane (II) having optical purity 88-91%. The optical purity of I thus obtained was found to be 73-75%. The polymerization of I with stereospecific coordinated anionic catalysts gave amorphous polymers, as in the case of many other p-substituted styrene derivatives. The fractions obtained from these polymers have very similar rotatory power at 589 nm which is practically equal to that of polymer of I obtained by nonstereospecific radical initiator and of low molecular weight structural models. Accordingly the 1Lb electronic transition of the aromatic chromophore shows a very low rotatory strength in all samples examined. This result is related to the lack in solution of conformations with a predominant single chirality of the main chain of the macromolecules derived from I.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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