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  • Chemistry  (6)
  • Biochemistry and Biotechnology
  • 1980-1984  (4)
  • 1970-1974  (2)
  • 1820-1829
  • 1
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: A Novel Example of Reversible Ring Opening: The Epimerization at C(3) of Sugar 3-Hydroxy-Δ1-pyrazolinesReaction of 1 (either geometrical isomer) with hydrazine followed by in situ Ag2O oxidation led to two pairs of interconverting isomers 4 ⇄ 5 and 6 ⇄ 7. By the same treatment, (Z)-10 and (or) (E)-10 gave the pair 11 ⇄ 12. Acetylation of 4 ⇄ 5 led to a non interconverting mixture of 8 and 9. This fact, and the lack of incorporation of 18O when the epimerization took place in the presence of H218O indicated that the most probable mechanism consisted in a reversible ring opening (D ⇄ E ⇄ F). The kinetic parameters of these reactions are given and structural assignments proposed for the new compounds.
    Zusätzliches Material: 1 Tab.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    ISSN: 0025-116X
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Beschreibung / Inhaltsverzeichnis: The radiation induced solid-state polymerization of tetroxane and trioxane was investigated. The influence of radiation-dose, reaction-time and temperature on yield and molecular weight was studied. Post-polymerization of both monomers shows a limiting conversion which increases with increasing reaction temperature. The activation energy of the post-polymerization was determined to 24 ± 2 (kcal/mole) in the case of tetroxane and was 36-38 (kcal/mole) in the case of trioxane. Time(t)-conversions(x)-curves for tetroxane could be described by the empirical equation: \documentclass{article}\pagestyle{empty}\begin{document}$$x = k_1 t/(1 + k_2 t)$$\end{document} whereby k1 and k2 are constants which could be evaluated by an appropriate plotting of the experimentally obtained data. Contrary to the post-polymerization of trioxane a pro-portionality between molecular weight, conversion and polymerization temperature was found in the case of tetroxane such that with increasing conversion higher molecular weights were obtained and an increase of reaction-temperature gave rise to higher molecular weights at constant conversion. The highest molecular weight obtained by post-polymerization of tetroxane was of the order of 8·105 and ca. 4·105 in the case of trioxane. The probability of chain-transfer is considerably higher with the polymerization of trioxane as compared with tetroxane.The morphology and texture of the originating polymers can be connected - at least qualitatively - with the reaction kinetics. It is highly probable that the kinetics of the polymerization of tetroxane are governed to some extent by relaxation processes of the growing polymer chains.
    Notizen: Die strahlungsinduzierte Polymerisation von kristallinem Tetroxan und Trioxan wurde untersucht und der Einfluß von Strahlendosis, Reaktionszeit und -temperatur auf den Umsatz und das Molekulargewicht der entstehenden POM, insbesondere bei der Nachpolymerisation, studiert. Die Zeit-Umsatz-Kurven für die Nachpolymerisation laufen bei beiden Monomeren asymptotisch gegen einem Grenzwert des Umsatzes, der mit steigender Reaktionstemperatur ansteigt. Die Aktivierungsenergie der Nachpolymerisation wurde zu 24 ± 2 kcal/Mol für Tetroxan und zu 36-38 kcal/Mol für Trioxan bestimmt. Die Zeit(t)-Umsatz(x)-Kurven für Tetroxan lassen sich durch die empirische Gleichung: \documentclass{article}\pagestyle{empty}\begin{document}$$x = k_1 \cdot t/(1 + k_2 t)$$\end{document} beschreiben, wobei k1 und k2 Konstanten sind, die durch geeignete Auftragung der Meßwerte ermittelt werden können. Im Gegensatz zu Trioxan findet man bei Tetroxan eine Proportionalität zwischen Molekulargewicht, Umsatz und Polymerisationstemperatur in der Weise, daß mit steigendem Umsatz höhere Molekulargewichte beobachtet werden und bei konstantem Umsatz mit steigender Temperatur auch höhere Molekulargewichte auftreten. Bei der Nachpolymerisation von Tetroxan lagen die höchsten erreichbaren Molekulargewichte bei 8·105, während bei Trioxan nur Werte von 4·105 erreicht wurden. Die Wahrscheinlichkeit für übertragungsschritte ist bei der Polymerisation von Trioxan wesentlich höher als bei Tetroxan.Zwischen der morphologischen Beschaffenheit und Textur der entstehenden Polymeren und den kinetischen Befunden lassen sich qualitative Beziehungen herstellen. Danach wird die Reaktionskinetik im Fall der Polymerisation von Tetroxan wesentlich durch Relaxationsvorgänge an den sich bildenden Polymerketten beeinflußt.
    Zusätzliches Material: 13 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 27 (1982), S. 2151-2165 
    ISSN: 0021-8995
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Physik
    Notizen: An investigation has been carried out for determining the effect of coupling agents on the mechanical properties of polymer-impregnated mortars. Mortar specimens were impregnated with methyl methacrylate (MMA) monomer and α, α-azobis-isobutyronitrile initiator, and polymerized thermally in water. Three titanate coupling agents, KR-33CS, KR-55, and KR-138s, and one silane coupling agent, the A-174, were used for the investigation. Varying amounts of coupling agent were used in impregnating the mortars in situ or in pretreating the mortars with a solvent system. Bulk polymerization of MMA shows no appreciable influence of the coupling agents in the reaction kinetics; however, with the exception of KR-138S, all polymers obtained in the presence of coupling agents came out as insolble. Similar results were obtained for polymers extracted with acetone from mortars. The mechanical property results show an improvement of properties in mortars containing 5.0 vol% of KR-33CS and A-174 after impregnation in situ. A slightly better improvements of mechanical properties were obtained by pretreating the mortar specimens with acetone or toluene/xylene containing coupling agents. Microscopic observation of the fracture surface showed no noticeable difference in the surfaces prepared with and without coupling agents.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 4
    Digitale Medien
    Digitale Medien
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 29 (1984), S. 1187-1202 
    ISSN: 0021-8995
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Physik
    Notizen: The morphologies of the as-produced polyethylenes obtained by slurry polymerization process of ethylene in n-heptane, using heterogeneous conventional and supported Ziegler-Natta catalysts, were investigated. The ability of four different catalytic systems in controlling the size and shape of the nascent polymer particles were tested. The catalytic systems employed were: the original Ziegler type catalyst produced by reduction of TiCl4 with Et2AlCl, the Natta type catalyst TiCl3-AA, the reduced TiCl4 with the metal carbonyls [Mo(CO)6 and Mn2(CO)10], and the supported TiCl4 on three commercial silicas having different surface areas: Davison 951, 952, and also the Dart 1000. It was found that the carriers affect the catalytic activity of the final catalyst and also its kinetic behavior. The supported Ziegler-Natta catalysts control more easily the nascent polymer particles (size, shape, and porosity) than the conventional ones. In addition the morphology of the catalysts and the subsequent polymer particles are closely related to the parent morphology of the silicas used as carriers. Furthermore, the nascent morphology of the polyethylenes obtained with the conventional TiCl4-Et2AlCl catalytic system can be modified by using different |Al|/|Ti| ratios, resulting in more dense, spherical, and bigger polymer particles by increasing this ratio. On the other hand, detailed studies on the texture or arrangement of the polymer particles reveal the existence of mainly two fine morphologies (globular and wormlike), which are the result of the order of the primary or elementary catalyst particles (microspheres and platelets), the force linking them together, and the activity of the polymerization centers placed on their surface.
    Zusätzliches Material: 10 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 5
    Digitale Medien
    Digitale Medien
    Hoboken, NJ : Wiley-Blackwell
    Journal of Biomedical Materials Research 18 (1984), S. 643-654 
    ISSN: 0021-9304
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Medizin , Technik allgemein
    Notizen: On clot-promoting surfaces, intact normal blood or plasma deposits fibrinogen and then supplants it with high molecular weight kininogen (HMWK). On glass, plasma layers of less than about 25 μm thick, while still containing enough fibrinogen to coat the surrounding surfaces, lack sufficient HMWK per surface area to remove this fibrinogen deposit. Thus normal intact citrated plasma allowed to enter the space between a glass slide and a convex lens resting belly-down on the slide will leave a disc of fibrinogen where the thickness of plasma layer was below this “critical height” H. The discs of fibrinogen left by plasma that lacks HMWK pathologically or by activation or dilution, are larger - the required H being greater. The present study shows that plasma dilution (final volume divided by original plasma volume) plotted against H yields a straight line. In preliminary series, the slope of this line increases with the atomic weight of five metals whose oxidized surfaces were used as substrates. In whole blood collected in either heparin or ACD, a circle of platelets adheres to oxidized silicon, anodized tantalum, or glass; this circle is similar in size to the one of fibrinogen left by plasma.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 6
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 148 (1971), S. 331-334 
    ISSN: 0025-116X
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Zusätzliches Material: 2 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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