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  • Chemistry  (3)
  • 1990-1994  (3)
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  • 1
    ISSN: 0018-019X
    Schlagwort(e): Chemistry ; Organic Chemistry
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Constitutional Isomerism in Polycondensates. Synthesis and Properties of Perfectly Regular and Random Bipolyamides from cis-2,6-Dimethylpiperazine and 1,2,5-Thiadiazole-3,4-dicarbonyl DichlorideThe synthesis of constitutionally perfectly regular and random alternating copolyamides from the ‘symmetric’ monomer 1,2,5-thiadiazol-3,4-dicarbonyl dichloride (4) and the ‘non-symmetric’ monomer cis-2,6-dimethylpiper-azine (7) by solution and interfacial polycondensation methods is described. Their constitutional regularities (s values) were determined by high-resolution 13C-NMR spectroscopy in CDCl3 solutions. Ordered and random copolyamides were amorphous with Tg values of ca. 200°. However, the regular head/tail and the random copolyamides with low molecular weights could be partially crystallized by annealing and showed large differences in their melting points (54°). Beside other physical properties, the membrane properties of the copolyamides were carefully investigated. In H2O desalination by reverse osmosis, no differences in salt rejections and permeabilities between constitutionally regular and random copolyamides were found (within experimental errors). In contrast, the regular head/head/tail/tail- and head/tail-type copolyamides showed considerably larger separation factors in the gas separation (methane/hydrogen) than the random ones.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 2
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 191 (1990), S. 1677-1688 
    ISSN: 0025-116X
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The enantioselective protio(deuterio)oligomerization of propene, 1-pentene and 4-methyl-1-pentene was carried out with the diastereomerically pure catalyst precursor (-)-(R)-ethylenebis [1-3a,7a-η-(4,5,6,7-tetrahydro-1-indenyl)]zirconium (S)-1,1′-bis-2-naphtholate (3) and/or with (-)-(R)-ethylene [1-3a,7a-η-bis(4,5,6,7-tetrahydro-1-indenyl]dimethylzirconium (1) in the presence of methylalumoxanes. The enantioselectivity of both reactions which take place (deuteration and oligomerization) is from fair to high and essentially independent of the catalyst precursor. In the hydrooligomerization the enantioface of the olefinic monomer which prevailingly reacts is from a geometric point of view the same for all three substrates. In the case of 1-pentene and 4-methyl-1-pentene the enantioface prevailing embedded in the oligomers is opposite to that prevailingly deuterated. The significance of the growing chain for enantioface selection during stereospecific polymerization is thus emphasized.
    Zusätzliches Material: 5 Tab.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 3
    Digitale Medien
    Digitale Medien
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 194 (1993), S. 223-232 
    ISSN: 0025-116X
    Schlagwort(e): Chemistry ; Polymer and Materials Science
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie , Physik
    Notizen: The stability of the helical conformation in optically active poly(triphenylmethyl methacrylate) (PTrMA) was investigated by heating the polymer solutions at 100°C. The optical rotation slowly disappeared with time, and some preliminary experiments showed that this phenomenon is not due to a typical racemization process, as it is accompanied by a loss of triphenylmethyl (Tr) groups due to secondary reaction. Experimental results in the presence of methanol indicated that the decrease of optical activity occurs according to first-order kinetics and qualitatively methyl triphenylmethyl ether was isolated from the final solution. In order to explain the above results, full characterization of copolymers obtained by interrupting the methanolysis at different conversions was performed. As a working hypothesis, it was assumed that the reaction starts at the end of the helices with a Tr-oxygen bond fission and the reaction proceeds along the chain mainly with formation of block copolymers consisting of one block of PTrMA and one block of a probably random methacrylic acid anhydride/methacrylic acid copolymer.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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