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  • 1
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 92 (1980), S. 121-132 
    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: Die Reaktion von Carbonsäurechloriden mit Polyvinylalkohol wurde untersucht. Die Struktur der modifizierten Polymeren wurde durch IR-, UV-, NMR-Spektroskopie und chemische Analysen bestimmt. Durch die Reaktion des Polyvinylalkohols mit n-Buttersäurechloride entstehen Vinylalkohol-Vinylbutyrat-Copolymere. Wenn der Umsatz dieser Reaktion kleiner als 50% ist, findet man eine Kinetik zweiter Ordnung mit einer Aktivierungsenergie von 9.9 kcal/mol. Wenn Pyridin als Katalysator verwendet wird, nimmt die Reaktionsgeschwindigkeit bemerkenswert zu, unabhängig von dem verwendeten Säurechlorid. Wenn man Triäthylamin als Katalysator verwendet, dann erscheinen aufgepfropfte β-Ketoester-Gruppen in den Polymerketten. Wegen der sterischen Hinderung dieser Nebengruppen wird der Umsatz nicht höher als 30%. Je größber der Gehalt an Estergruppen ist, um so weniger hydrophil ist das Polymere, wie durch Quellungsmessungen der Vinylalkohol-Vinylbutyrat-Copolymeren in Wasser festgestellt wurde.
    Notes: This work deals with some features of the reaction of organic acid chlorides with poly(vinyl alcohol). The structure of the modified polymers was determined by means of IR, UV and NMR spectroscopy as well as by chemical analysis. Vinyl alcohol-vinyl butyrate copolymers were obtained by reaction of poly(vinyl alcohol) with n-butyryl chloride without any catalyst. The reaction appeared to satisfy a second order kinetics for conversions no higher than 50%. The activation energy found was of 9.9 kcal/mol. The use of pyridine as a catalyst involved a noticeable increase of the reaction rate, but this effect was found to be independent of the acid chloride used. When triethylamine was used as a catalyst, β-keto ester groups were found to be grafted onto the polymer chain. The steric hindrance of these groups were thought to be sufficiently important for the conversion to reach a limit of about 30%. The observed swelling in water of vinyl alcohol-vinyl butyrate copolymers made it reasonable to conclude that the hydrophilic character of the copolymers decreased progressively when the ester group content increased.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Angewandte Makromolekulare Chemie 126 (1984), S. 115-124 
    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: Es wurde die Kinetik der Verseifung von Vinylalkohol-Vinyl-n-alkylcarbonat Copolymeren in Abhängigkeit von der Säure- und Basen-Konzentration, der Temperatur und der Art der Carbonatgruppen untersucht. Die homogene basenkatalysierte Verseifung verläuft nach einer Reaktion erster Ordnung in bezug auf die Hydroxyl-und Carbonatgruppen-Konzentration, während die säurekatalysierte Verseifung in Bezug auf die Säure-Konzentration eine Reaktion erster Ordnung ist. Die heterogene basenkatalysierte Verseifung hängt von der Konzentration und der Art der Carbonatgruppen ab. Für die saure und basische homogene_Verseifung wurden Aktivierungsenergien von 13.8 und 10.0 kcal/mol erhalten. Für die heterogene basenkatalysierte Verseifung ist eine Aktivierungsenergie von 10.3 kcal/mol erhalten worden. α-Chymotrypsin zeigte sich als unwirksam bei den hier durchgeführten Verseifungsreaktionen.
    Notes: A kinetic study of the hydrolysis of vinyl alcohol-vinyl n-alkyl carbonate copolymers has been made as a function of the base or acid concentration, the temperature, and the structure of the carbonate units. The homogeneous hydrolysis in alkaline medium was found to be first order with respect to both the hydroxyl ion and the carbonate; the acid hydrolysis was of first order with respect to the acid concentration. The heterogeneous hydrolysis in alkaline medium followed a pseudo-first-order kinetics with respect to the base concentration; the hydrolysis rate was affected by the carbonate content and the structure of the carbonate units. The activation energies obtained for the acid and base catalyzed homogeneous hydrolysis and the base catalyzed heterogeneous hydrolysis were 13.8, 10.0, and 10.3 kcal/mol, respectively. α-Chymotrypsin was inactive in the hydrolysis experiments carried out with these copolymers.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Poly(N-aryl maleimide)s of characteristic structures have been synthesized and some of their physical properties studied. These include N-(2-fluoro phenyl), N-(3-fluoro phenyl), N-(4-fluoro phenyl), N-(2,4-difluoro phenyl), N-(2,5-difluoro phenyl), N-(2,3,5,6-tetrafluoro phenyl), and N-(pentafluoro phenyl). The polymerization of N-(fluoro phenyl) maleimides by free-radical initiation in bulk or in solution and by anionic catalyst have been studied to compare the characteristics of polymerization by γ-ray irradiation with that by free-radical initiation. The polymers were characterized by elemental analysis, intrinsic viscosity, spectroscopy (IR and NMR), programmed thermogravimetric analysis, and x-ray diffraction. Spectra of polymers prepared by radiation and anionic polymerization were nearly identical with those of polymers prepared by free-radical polymerization initiated by AIBN in bulk or in solution and by the self-initiated thermal polymerization. A variety of reaction conditions were tried, but all attempts to change the molecular structure of the polymers were unsuccessful. Rates of thermal degradation for poly[N-(fluoro phenyl) maleimide]s have been analyzed by using a multiple-heating-rate procedure. Overall activation energy, order of reaction, and frequency factor have been evaluated. On the basis of the comparison between the overall activation energy of the thermal degradation of poly[N-(fluoro phenyl) maleimide]s and NMR spectra of their corresponding monomers, it can be concluded that the 1H shifts due to ethylenic protons are so characteristic in sign and magnitude as to be useful in thermal stability elucidation. Some qualitative explanations were given on the stability of these polymers as affected by the type and size of the substituent. The x-ray diffractograms of all samples show two rather broad peaks indicative of noncrystalline structures. The location of the peaks does not depend upon preparation conditions and temperature. Poly(N-maleimide)s of fluoroanilines have not been hitherto described.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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