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  • 1
    ISSN: 0030-4921
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rates of rotation about the C-9-C-ar bond of 9-(2-isopropylphenyl) fluorene were measured by 1H DNMR, 13C DNMR, double resonance, and a kinetic method. The kinetic data obtained by these methods were critically examined. The DNMR methods afforded satisfactory results if rate data obtained by total line shape analyses of complicated signals with couplings were used, and those derived from simple patterns were abandoned. Agreement among the data yielded by the four different methods was excellent, provided that the data which might contain dubiously large errors were excluded.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 180 (1979), S. 1145-1148 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The ring-opening polymerization of (5S)-1-azabicyclo[3.1.0]hexane (1) derived from L-proline was attempted, by use of a catalytic amount of boron trifluoride etherate as an initiator, in order to obtain optically active polymers. Chiral polymers (2) were indeed easily formed when the above aziridine 1 was polymerized in bulk or in benzene. On the other hand, a stable BF3-adduct was obtained in the form of colorless crystals when the dilute benzene solution (1%) of 1 was allowed to react with an excess of boron trifluoride etherate. The elemental analysis and the NMR (19F, 11B, and 13C) spectra of this adduct showed it to be a (5S)-1-azabicyclo[3.1.0]hexane-boron trifluoride (1:1) complex (3). It was also found that the adduct initiated the polymerization of aziridine 1 more mildly than boron trifluoride etherate.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 176 (1975), S. 3471-3481 
    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: Mit Hilfe der Differentialkalorimetrie (DSC) wurde die Kristallisation von Polyvinyli-denfluorid aus der Schmelze sowohl unter isothermen Bedingungen als auch beim Abkühlen mit verschiedenen Geschwindigkeiten untersucht. Die Auswertung ergab, daß in beiden Fällen homogene Keimbildung mit dreidimensionalem Wachstum der kristallisierenden Einheiten vorlag. Die Schmelzkurven wurden in verschiedenen Stadien der isothermen Kristallisation aufgenommen. Sie lassen erkennen, daß während der Kristallisation ein Dickenwachstum der Kristalle erfolgt, das besser durch die Temperungstheorie als durch eine molekulare Fraktionierung erklärt werden kann.
    Notes: The dynamic cooling and the isothermal crystallizations of poly(vinylidene fluoride) from the melt were investigated using a differential scanning calorimeter. In both the dynamic cooling and isothermal crystallizations, the kinetic treatments indicated that during the crystallization of poly(vinylidene fluoride) the nucleation proceeds homogeneously and the growth occurs three dimensionally. The melting curves were recorded at various stages of the isothermal crystallization, and the thickening of lamellar crystals was observed, which can be explained more reasonably by the annealing theory than by the molecular fractionation theory.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 4
    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: Es wurde ein Übergang 2. Ordnung von Cellulosetriacetat bei ca. 30°C mit Hilfe der Polarisations-Infrarot-Spektroskopie untersucht. Die Temperaturabhängigkeiten des IR Dichroismus der Banden bei 900 cm-1 (C1—H Biegeschwingung) und 600 cm-1 (Acetyl-Gruppenfrequenz) wurden untersucht. Die 900 cm-1 Bande zeigte einen Übergang bei ca. 30°C, während die 600 cm-1 Bande keine bemerkenswerte Änderung zeigte. Diese Ergebnisse legen nahe, daß der hier beobachtete Übergang wahrscheinlich einem Konformationswechsel des Pyranoserings zugeordnet werden kann. Es wird angenommen, daß der Übergangsmechanismus einer Sessel (C 1)-Wannen (B) Konformationsänderung des Pyranoserings bei der Faltung des Cellulosemoleküls zukommt.
    Notes: A second-order transition of cellulose triacetate at approximately 30°C was studied by polarized infrared spectroscopy. The temperature dependences of infrared dichroismus were examined for the 900cm-1 (C1—H bending vibration) and 600 cm -1 (acetyl group frequency) bands. The former changed at about 30°C, whereas the latter did not show any remarkable change. These results suggest that the transition observed here is probably related to the conformational change of the pyranose ring. The transition mechanism is supposed to be associated with the chair (C 1)-boat (B) transformation of the pyranose ring at the folding of the cellulose molecule.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 19 (1975), S. 1013-1015 
    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: Amorphous silk fibroin with random coil conformation shows endothermic and exothermic peaks and endothermic shift on the DSC (differential scanning calorimetry) curve. The endothermic shift observed at 175°C was due to the glass transition. The exothermic peak at 212°C is recognized to be the crystallization, which later was confirmed by x-ray diffraction pattern. The endothermic peak at 280°C is shown to be the degradation.
    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 Applied Polymer Science 20 (1976), S. 2829-2836 
    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: The reaction of cellulose with phosphorous acid in molten urea afforded a white, water-soluble product. The product was a monoester of phosphorous acid, and all the phosphorus residues were in phosphonic form, i.e., cellulose phosphonate. Quantitative addition of acrylonitrile to the P—H bonds in cellulose phosphonate occurred in the presence of sodium ethoxide. By alkali hydrolysis of the adduct, a polyelectrolyte having two different ionization groups, P—OH and COOH, could be prepared. Thermal degradation of three cellulose phosphonates, ammonium cellulose phosphonate (I), ammonium cellulose 2-cyanoethlyphosphonate (II), and ammonium cellulose 2-carboxyethylphosphonate (III), was examined. All three samples decomposed at a temperature around 270°C, but their thermal behaviors were different. Replacement of hydrogen in the phosphonic residue by 2-cyanoethyl and 2-carboxyethyl groups retarded dehydration of cellulose. Sample I had a satisfactory flame retardance; samples II and III were not flame resistant. Reduction of flame retardance may be due to the electron-withdrawing effect of the cyano and carboxyl groups.
    Additional Material: 6 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 21 (1977), S. 585-585 
    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
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 20 (1976), S. 2031-2043 
    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: The viscoelastic properties of aqueous solutions of amylose-iodine at ultrasonic frequencies have been investigated by a torsional method using quartz crystal resonators. The frequency dependences of the storage (G′) and loss (G″) moduli show that the hydrodynamic interaction increases with the addition of iodine. The effects of the intermolecular hydrogen bonds could be observed from the concentration dependence of viscoelastic functions. The concentration dependences of G′ and G″ - ωηs were extremely large, but the concentration dependence decreased with the addition of 2 moles of urea since the effect of hydrogen bonds was minimized. The intramolecular hydrogen bonds seem to affect the hydrogen bonds was minimized. The intermolecular hydrogen bonds seem to affect the tightness of the helical structure of the amylose-iodine complex in water. The frequency dependences of the intrinsic moduli at infinite dilution were compared with the hybrid model theory of Ferry et al. The helical structure of the amylose-iodine complex appears to be more rigid than that of other helical polymers such as poly(γ-benzyl-L-glutamate). However, the flexibility of the helix appears to become more prominent with the addition of urea. When the poor solubility of amylose in water was improved by the addition of ethanol, the conformation of amylose-iodine complex became similar to that in the noncomplex system, where amylose seems to assume a loose and extended helical conformation.
    Additional Material: 14 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 24 (1979), S. 1017-1029 
    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: The fine structure of cotton cellulosic fibers carbamoylethylated and carboxyethylated at 30 and 20°C in the presence of 3% and 20% sodium hydroxide was investigated by measuring moisture regain, water imbibition, x-ray photograph, degree of crystallinity, spacing, and crystallite size under dry and wet conditions. As carbamoylethyl and carboxyethyl substituents are introduced in amorphous regions of the samples reacted with acrylamide in 3% sodium hydroxide, the fine structure of the crystalline regions is not affected by the reaction. On the other hand, in the samples reacted in 20% sodium hydroxide, the substituents are introduced not only in amorphous regions but also in crystalline regions to make them disordered. Although spacing between (101) planes does not change, spacing between (101) planes increases by the reaction in 20% sodium hydroxide. Comparing crystallite sizes normal to (hkl) planes under dry conditions with those under wet conditions, it is supposed that cohesive forces between (101) planes are different from those between (101) planes, and the former is hydrogen bonds and the latter resemble Van Der Waals forces. As a result, carbamoylethyl and carboxyethyl groups are introduced selectively between (101) planes.
    Additional Material: 6 Ill.
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  • 10
    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.
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