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  • 11
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 21 (1983), S. 1557-1557 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 12
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 20 (1982), S. 3271-3283 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A commercially available densimeter with a vibrating stainless steel tube was used as a detector in the GPC analysis of styrene/methyl methacrylate copolymers under normal GPC operational conditions. The densimeter was thermostated to ±0.001°C and sample injection concentrations were 4.0 mg/mL. The copolymer samples were polydisperse in molecular weight but uniform in composition. A refractive index detector and the densimeter detector produced comparable estimates of the parameters of the molecular weight distributions. The densimeter is less sensitive to the effects of variations in copolymer composition than differential refractive index or ultraviolet detectors. The only serious drawback to the densimeter is a relative lack of sensitivity. Variations in composition of styrene/methyl methacrylate copolymers over a fairly wide range have no signficant effect on the relation between gel permeation chromatographic elution volume and copolymer molecular weight. In general, however, conventional means of summarizing these data are not applicable to compositionally heterogeneous mixtures. Instrumental and data-handling solutions to this problem are discussed.
    Additional Material: 1 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 19 (1981), S. 1799-1800 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 14
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 1443-1451 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of data imprecision and baseline uncertainties have been investigated by computer simulation of GPC data from a polymer sample with a truncated log-normal molecular weight distribution. If the data are very accurate, as few as five data points can be sampled without serious error in computed molecular weight averages. The number of data points required is much larger, however, if these are taken at equal increments of molecular weight rather than elution volume. The effects of noise can be counteracted by increasing the sampling frequency. Baseline uncertainties present a more serious problem, especially for broad-distribution samples. If the detected signal is too noisy to permit accurate location of the baseline, errors can be minimized by using a second, more sensitive detector to determine the peak start and end. It is very difficult to estimate M̄z and higher molecular weight averages accurately if the noise level is greater than 0.5%.
    Additional Material: 8 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 14 (1976), S. 37-44 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Styrene was polymerized in emulsion with initiation by γ-rays at a dose rate of 0.6 Mrad/hr. Polymerization rates were as expected from previous reports by others. No branching or crosslinking was detectable, and the Mw/Mn ratio of the polystyrene did not change significantly during the course of the polymerization reaction. The molecular weight of the product polymer decreased with increasing conversion, in contrast to the behavior of chemically initiated emulsion polymerizations. Monomer-free polystyrene does not degrade under the same radiation conditions, and the progressive decrease of polymer molecular weight with conversion is shown to result from the presence of monomer.
    Additional Material: 7 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 493-502 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Radical chain-transfer constants can be deduced from corresponding measurements of rates and degrees of polymerization in copolymerization experiments. It is particularly useful to carry out such copolymerization in emulsion systems where the normal termination reactions are relatively less important and chain-transfer processes are significant in determining the number-average degree of polymerization. The method is illustrated for copolymerization of styrene and α-methylstyrene at three temperatures. Rate constants for transfer of styryl and α-methylstyryl radicals to either monomer were measured. All the rate constants are consistent with the relative stabilities of the product radicals which could be formed by the various transfer reactions. The procedure described here can be extended for measurements of rate constants for reactions of other potential transfer agents.
    Additional Material: 4 Tab.
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  • 17
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 9 (1971), S. 3009-3025 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The free-radical copolymerization of styrene and methacrylonitrile was studied in toluene solution at 60, 90, and 120°C. Copolymer composition was estimated from gas-chromatographic measurement of unreacted monomer concentrations. Reactions were carried to about 20% conversion to minimize analytical errors. Reactivity ratios were calculated by using an integrated form of the Mayo-Lewis simple copolymerization equation. Reactivity ratios were not sensitive to reaction temperature. The values at 90°C are r1 = 0.41 (methacrylonitrile) and r2 = 0.37 (styrene). The r1 values are higher than those reported by other workers, presumably because of advantages in the present analytical technique and calculation method. The negligible temperature dependence of reactivity ratios is in accord with theory. If monomer pairs exhibit pronounced dependence of reactivity ratios on polymerization temperature, this may indicate a change in mode of placement of units in the polymer chain.
    Additional Material: 7 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 10 (1972), S. 217-235 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The M[η]-elution volume calibration curve for gel-permeation chromatography (GPC) is based on the implicit assumption that the hydrodynamic volume of a solvated polymer species in the GPC columns is that which pertains at infinite dilution. This is not true of highly solvated high molecular weight fractions and results in apparent failure of this calibration in some instances. A model is presented to estimate hydrodynamic volumes of polymers at finite concentrations. The parameters required are polymer concentration, molecular weight, amorphous density, and the Mark-Houwink constants for the particular polymer-solvent combination. The calculated log (hydrodynamic volume)-elution volume relation provides a universal GPC calibration. The model accounts for the occasional shortcomings of the infinite dilution calibration and is essentially equivalent to it in noncritical cases. The use of the proposed calibration method is illustrated.
    Additional Material: 12 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 10 (1972), S. 3589-3603 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Aqueous polystyrene emulsions were subjected to γ-irradiation at 30°C and 0.6 Mrad/hr dose rate. Analogy with water-soluble systems suggests that such conditions might suppress chain scission and favor crosslinking. The (extrapolated) infinite-dose gel content and gel-permeation analysis of the polymer in the pre-gel region indicate that the extent of chain scission was negligible. The G (crosslink) value obtained from the dose for incipient gelation and molecular weight variations in the pre-gel region is 0.051. Charlesby-Pinner plots were linear, but linearity cannot be construed as indicating that chain scission has produced an effective random molecular weight distribution. Our results are consistent with the conclusions that crosslinking events are random and directly proportional to dose. The probability that a given crosslink is effective in increasing the gel content decreases with dose past the incipient gel point, however, because of cyclization on preformed gel. The crosslink density/dose ratio is a decreasing function of dose in this range. Attempts to predict dose-gel relations with assumptions of various initial molecular weight distributions were unsuccessful, possibly because of the neglected influence of cyclization on the measured gel content.
    Additional Material: 4 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science Part A-1: Polymer Chemistry 9 (1971), S. 2587-2604 
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Peak elution volume in gel-permeation analysis of polymers depends on sample concentration as well as molecular weight. Elution volume is related to the logarithm of the hydrodynamic volume of the solvated polymer species. The hydrodynamic volume of a given species is, in turn, inversely related to the concentration. Since molecular weight and concentration are interacting variables, the elution volume-molecular weight relation is not uniquely determined. A model is presented which accounts quantitatively for concentration effects, using parameters which are available a priori. The data required are polymer molecular weight, concentration, and density and the Mark-Houwink relation for the particular polymer-solvent combination.
    Additional Material: 7 Ill.
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