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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 7 (1969), S. 1379-1384 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The grafting of acrylic acid in aqueous solution to nylon 6 film has been studied in the presence of ferrous, ferric, and cupric salts. The mutual irradiation technique was adopted using a 60Co source. The anions were found to have no effect on the grafting or homopolymerization, but both of these processes were suppressed by the cations in the following order of effectiveness: Cu2+ 〉 Fe2+ 〉 Fe3+. The rate constant for the capture of hydroxyl radicals by acrylic acid has been determined as 6 × 109 1. mole-1 sec-1 by pulse radiolysis using the CNS- competition method. By invoking this result, mechanisms have been suggested for the process of chain termination by metal cations.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 7 (1969), S. 2983-2994 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bond structure of the complex in the alkaline ferric-tartrate system (FeTNa) was examined and related to the cellulose-dissolving ability of the system. The subject of bonding was approached by magnetic susceptibility and absorption spectrophotometric techniques. The magnetic moment of the Fe(III) in the iron-tartrate system was found to depend on the pH of the system. With an iron molarity of 0.1 an iron/tartrate mole ratio of 1 : 3, and 2 moles of NaOH/mole of tartaric acid, a minimum magnetic moment of 3.9 BM was observed. In alkaline media the magnetic moment depended on the Fe(III) concentration and the iron/tartrate ratio. The Fe(III) in the cellulose-solvent FeTNa was found to be in a high-spin state (5.9 BM). With a large excess of tartrate, the absorption spectrum of the alkaline FeTNa was recorded and analyzed in terms of the Tanabe-Sugano determinants. Values of 13200 cm-1 and 0.66 were obtained for the parameters Δ and β, respectively. In addition, it was shown that the Fe(III) in the cellulosesolvent FeTNa is coordinated with less than the maximum possible amount of tartrate. This tartrate deficiency is apparently responsible for the solvent properties of the system. From the use of glycerol as a model for cellulose, it appears that cellulose coordinates with the iron in the solvent FeTNa in much the same manner as does additional tartrate.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 5 (1967), S. 987-991 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of polyisobutene and polystyrene fractions was subjected to gel-permeation chromatography at 150°C. The two types resulted in distinctly different calibration curves in a plot of projected, extended chain length versus elution volume. The average end-to-end distances of the samples were determined by intrinsic viscosity measurements. It was found that these data plotted versus elution volume could be represented by a common curve for both polymer types. The elution volumes of the polyisobutene series were determined at three additional temperatures, 35, 70, and 110°C. It could be shown that elution volume is again determined by polymer coil size at the temperature of measurement.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A series of new aromatic polyethers have been prepared by solution condensation polymerization. The synthesis involves the condensation of a dialkali metal salt of a dihydric phenol with an “activated” or negatively substituted aromatic dihalide in an anhydrous dipolar aprotic solvent at elevated temperatures. The reaction is rapid, free of side reactions, and yields polymers of excellent color. Bakelite polysulfone can be prepared in this manner by reaction of the disodium salt of bisphenol A with 4,4′-dichlorodiphenyl sulfone in dimethyl sulfoxide (DMSO). Only dipolar aprotic solvents are useful for conducting the polymerization. Of these, DMSO and Sulfolane (tetrahydrothiophene 1,1-dioxide) are the most effective. Water or other competing nucleophiles must be absent if high molecular weight is to be obtained. Besides providing the necessary solubility, this highly polar solvent is believed to be essential in providing the rapid polymerization rates observed. The rates are further found to depend on the basicity of the bisphenol salt and upon the electron-withdrawing power of the activating group in the dihalide. As is usual for this type of reaction, the difluorides are found to be more reactive than the corresponding dichlorides. Most of the polyethers are amorphous, rigid, tough thermoplastics with high second-order transitions (Tg). Thermal stability and electrical properties are noteworthy. These and other properties are described for polysulfone, and glass transitions are given for a selected list of the other polyethers.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The molecular weight of polysulfone, i.e., the aryl polyether that is prepared by the reaction of the disodium salt of bisphenol A with 4,4′-dichlorodiphenyl sulfone in dimethyl sulfoxide (DMSO) solvent is shown to depend, among other things, on the moisture content of the polymerizing system. In the presence of water, hydrolysis of the sulfone monomer occurs concomitant with the polymerization. This leads to a deviation from the desired 1:1 ratio of coreactant groupings and therefore in attendant reduction in possible molecular weight. The hydrolysis is shown to lead to the formation of the sodium salt of 4-chloro-4′-hydroxydiphenyl sulfone and to a lesser extent polymer derived from self-condensation of this salt. At low levels this salt is essentially inert towards the principal polymerization at hand but in somewhat greater amounts functions as an effective chain terminator. Similar hydrolysis of polysulfone chloro endgroups is believed to occur under the aqueous conditions of polymerization but to a lesser extent than for the sulfone monomer. It is shown that polysulfone or similar polyethers are subject to chain cleavage by bases in DMSO solvent. The base attacks the activated position para to the sulfonyl group with the formation of a chain terminating in a bisphenol A type phenolic group and a chain terminating in a phenolic group of the bisphenol S (p-hydroxyphenyl sulfonyl) type. It is shown that cleavage is probably not important under normal conditions of polymer formation. The effect of these hydrolytic side reactions on the attainment of high molecular weight under conditions of imperfect reaction stoichiometry is shown to be consistent with the above conclusions.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 419-430 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pure liquid styrene, carefully purified and exhaustively dried, exhibits kinetic behavior under γ-irradiation that can best be described in terms of an ionic mechanism. This is based on the observed linear dependence of the rate of polymerization on the dose rate, the independence of molecular weight on the same parameter, and comparison with the thermal and ultraviolet initiated polymerization of monomer prepared under the same stringent conditions. The highest rate of conversion to polymer is 400%/hr. at a dose rate of 106 rads/hr., corresponding to a G(-monomer) ≈ 40,000.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 5 (1967), S. 1391-1394 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Column systems for gel permeation chromatography are usually calibrated by eluting a series of sharp polymer fractions of known molecular weights and by correlating their elution volumes with molecular size or weight. A different method for calibration is proposed in which only one polymer sample, with a broad, well-characterized molecular weight distribution, is used. The cumulative distribution and the integrated, normalized GPC chromatogram are successively superimposed, and molecular weights and corresponding elution volumes are correlated. It is found that calibration curves obtained in this manner show a definite curvature. A possible explanation and correction for this behavior is given, based on the concentration dependence of elution volumes.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 5 (1967), S. 2835-2841 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pore-size distributions of various grades of porous glass were determined by gas desorption and mercury porosimeter measurements. This allowed the calculation of elution volumes as a function of pore diameters. The coil sizes of polystyrenes in toluene were obtained for a series of molecular weights from hydrodynamic theory and matched with pore diameters. In this manner, expected calibration curves for gel permeation chromatography could be calculated. Good agreement was found with experimental data.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 4 (1966), S. 1791-1798 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It has been shown that the rates of polymerization of individual monomers in a mixture of monomers can be followed by means of an NMR technique. The technique is rapid and simple and requires very little sample. The system MMA-MA-VIBE was investigated by the technique. From the data obtained it was concluded that the polymer formed in a mixture of the three monomers is a block copolymer made up of (MMA)m and (MA-VIBE)n units, the lengths of which depend on the monomer concentrations.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 5 (1967), S. 2091-2098 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The results of quantitative studies of the rates of free-radical polymerization of vinyl ferrocene indicate that the latter has polymerization characteristics similar to those of styrene. The rates of homopolymerization of these two monomers in benzene at 70°C. were measured with the use of azobisisobutyronitrile as catalyst. The rate constants (k = Rp/[M][I]1/2) are kVF = (1.1 - 1.8) × 10-4, kSTY = 1.65 × 10-4. Small amounts of vinyl ferrocene and styrene have similar effects on the rates of polymerizations of methyl methacrylate and ethyl acrylate and on the molecular weights of the resulting polymer. Polystyrene and poly(vinyl ferrocene) with similar molecular weights are isolated from polymerizations carried out under identical conditions. The rates of copolymerization of vinyl ferrocene - methyl methacrylate, vinyl ferrocene - styrene, and styrene - methyl methacrylate were determined by following the disappearance of monomers by means of gas chromatographic analyses. The relative reactivity for vinyl ferrocene is slightly lower than that for styrene.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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