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  • 1
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Improvements in physical properties of polyvinyl alcohol fibers were attempted by means of both crosslinking and graft copolymerization. By using the ceric iron redox system on synthetic fibers spun from polymer blends containing polyvinyl alcohol (PVA) and its partially (about 15 mole-%) N-methylolcarbamoylethylated products (PVM) in which the blend ratios were 0/100, 10/90, 15/85, and 20/80 by weight, methyl methacrylate (MMA) was grafted at 30°C. in the aldehyde-free acetone-water system after crosslinking by heat treatment or successive acid treatment. Grafting increases with increasing PVM component. This may be ascribed to the coarsening of the fiber texture caused by polymer blending and the increasing of methylol groups as a reducing agent. Moisture regains decrease with increasing graft fraction, but these appear to be greater than the additive values of backbone and graft polymer. Less shrinkage in boiling water is obtained with the increase of PVM component and grafting; the decreased shrinkage is significant in the acid-treated PVM-PVA fibers, and it reaches a nearly sufficient value at about 50% graft-on. The PVA fibers do not give sufficient shrink-proofing. The inherent tenacity and elongation of the grafted fibers increase slightly with increasing graft-on or denier except at the high grafting above about 100, 150, and 300 in the PVA, acid-treated, and acid-untreated PVM/PVA fibers, respectively; whereas the tensile strength in grams/denier decreases with grafting. Although at high grafting, a destruction in the fiber texture will perhaps occur, the coarser the texture of backbone fiber, the harder the change by grafting. The knot/normal ratios in tensile strength or elongation of the grafted fibers have been retained at above 90%. The elastic recovery of the grafted fibers is considerably improved as compared to the conventional Vinylon fibers. The improvements in the acid-treated and grafted PVM/PVA (20/80) fibers are significantly greater above and below 50% graft-on, especially in the range of lower extension. As expected, the thermosetting property is also appreciably imparted with grafting. In the conventional Vinylon fibers, the formalization for shrink-proofing is usually at a sacrifice of elastic recovery. But MMA grafting in the PVM/PVA fibers gives a fairly good elastic recovery and less shrinkage in addition to thermosetting property, making the most of the characteristics in the longer intermolecular crosslinkages formed between methylol groups or PVA-OH groups and methylol groups.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of polymer dilution on the acid-catalyzed gelation of partially N-methylolcarbamoylethylated polyvinyl alcohol has been studied viscometrically and chemically. The result that the higher the degree of dilution the greater the extent of reaction at gelation, especially in the polymer concentration below 15% by weight, indicates that a certain increase of intramolecular crosslinking with dilution occurs. However, sufficient agreement with Kilb's theory could not be found. Also, even when the extent of reaction at gelation was extrapolated to infinite concentration of polymer, it was far greater than that obtained from Flory's theory. The discrepancy may presumably be attributed to the fact that in addition to the intramolecular crosslinking, all the methylol groups on the polymer chains which are coiled, entangled, and strongly solvated prior to crosslinking are not equally reactive sterically.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 68 (1963), S. 31-47 
    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: Dimethylketen kann mit metallorganischen Katalysatoren zu Produkten verschiedener Struktur polymerisiert werden. Der Einfluß des Lösungsmittels und des Kations des Initiators auf die Zusammensetzung des Polymeren wurde mit Hilfe der IR-Spektren untersucht. Die Änderung dieser Zusammensetzung kann durch die Zwitterstruktur des Polydimethylketenanions erklärt werden.Die durch C-Acetylierung des Enolatanions gebildete Polyketonstruktur wird vor allem in nichtpolaren Lösungsmitteln mit Lithium- oder Magnesiumkatalysatoren erhalten. Das Wachstum geht wahrscheinlich über ein chelatiniertes Ionenpaar.Lithium- oder Magnesiumkatalysatoren, die aus raumerfüllenden Alkylhalogeniden herrestellt wurden, erhöhen den Polyketongehalt. Dies zeigt eindeutig, daß assoziierte Gegenionen vorhanden sind. Die durch alternierende O- und C-Acetylierung gebildete Polyesterstruktur ist in nichtpolaren Lösungsmitteln Hauptprodukt. Es wird ein weiterer Chelatkomplex vorgeschlagen.
    Notes: By means of organometallic compounds, dimethylketene can be polymerized to products with varying structure. The influence of solvent and the cation of the initiator on the composition of the polymer were investigated by means of IR spectra. The variation of composition can be explained by the ambident nature of the polydimethylketene anion. Polyacetal structure formed by O-acylation of the enolate anion is preferred in dipolar aprotic solvents especially in dilute solutions and propagation through the free ion mechanism was assumed. Polyketone structure formed by C-acylation of the enolate anion is preferred in non-polar solvents with lithium or magnesium type catalysts and propagation through chelated ion pair intermediate was assumed. Lithium or magnesium catalysts prepared from bulkier alkyl halide increase polyketone content, which shows clearly the existence of the associated counter ions. Polyester structure formed by alternative O- and C-acylation is the major product in non-polar solvents and another chelated complex was suggested.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gelation velocity and reaction rate for the acid-catalyzed condensation reaction in the aqueous solution (10-22%) of partially N-methylolcarbamoylethylated polyvinyl alcohol (about 20 mole-% degree of methylolcarbamoylethylation) have been investigated by the falling ball viscosity method and the chemical analysis of methylol groups including the effects of kinds of acid, concentrations of acid and polymer, and temperatures of reaction. For the reciprocal gel point, 1/tg, and the hydrogen ion concentration, [H+], the following equation holds: \documentclass{article}\pagestyle{empty}\begin{document}$ 1/t_g = c[{\rm H}^ +]^\alpha $\end{document} where α and c are constants independent of the kind of acid; also α is independent of temperature and polymer concentration, while c increases with increasing temperature or polymer concentration. The 1/tg is approximately proportional to the concentration of polymer in the range of a concentrated polymer solution above about 15% by weight. From this fact, it is suggested that, in a concentrated polymer solution, the intermolecular crosslinking proceeds predominantly as a bimolecular reaction with respect to methylol groups. Assuming that the increase of the apparent viscosity of the reacting system is mainly due to that of the structural viscosity which should be increased by a bimolecular crosslinking reaction, the following expression was derived for the gelation velocity: \documentclass{article}\pagestyle{empty}\begin{document}$ \eta _0 /(\eta _t - \eta _0) = A(1/i - 1/t_g) $\end{document} in which, \documentclass{article}\pagestyle{empty}\begin{document}$ \begin{array}{*{20}c} {A/t_g = 1 - x_g /a} & {{\rm and}} & {k = x_g /(a^2 A)} \\ \end{array} $\end{document} where η0 and ηt are the apparent viscosities at time 0 and t, respectively, A is a measure of gelation velocity, a is the initial number of methylol groups, xg is the number of crosslinked methylol groups at the gel point, and k is the bimolecular rate constant. The experimental results of viscosity changes have shown a fairly good agreement with the above expression except in the early stage of condensation. The extent of reaction at the gel point (xg) has been estimated to be about 0.03-0.05 regardless of concentration of polymer and acid, kinds of acid, and temperature. Also, it has been observed that the rate constant of reaction is independent of the concentration of polymer and is proportional to the concentration of hydrogen ions. The above expression and estimation have been verified by the chemical analysis of methylol groups in the condensation processes. However, the extent of reaction at the gel point is about ten times that predicted by Flory's theory. This discrepancy may presumably be attributed to the fact that all of the methylol groups on the polymer chains which are coiled, entangled, and strongly solvated prior to the crosslinking are not equally reactive sterically and a certain extent of intramolecular crosslinking occurs. The activation energy of reaction has been estimated to be about 21 kcal./mole.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Letters 2 (1964), S. 851-854 
    ISSN: 0449-2986
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Biochemical and Microbiological Technology and Engineering 3 (1961), S. 395-403 
    ISSN: 0368-1467
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: To collect microbes from suspensions by a process other than centrifugation, it has been found effective to add inorganic and organic electrolytes in the colloidal state. The addition of electrolytes causes a neutralization of charges on the particles in suspension resulting in their coagulation and precipitation. High-molecular-weight compounds which form micelles also promote coagulation and precipitation. It is believed that chemical collection is an extremely efficient method of treatment for the mass production of microbial suspensions.
    Type of Medium: Electronic Resource
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