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  • 1
    Publication Date: 1961-04-01
    Print ISSN: 0003-2700
    Electronic ISSN: 1520-6882
    Topics: Chemistry and Pharmacology
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  • 2
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Analytical chemistry 33 (1961), S. 577-579 
    ISSN: 1520-6882
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 17 (1955), S. 391-401 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A polymethyl methacrylate polymer, prepared by the emulsion technique, was fractionated three times to obtain essentially homogeneous fractions. The intrinsic viscosities and weight average molecular weights were determined in an ideal solvent at 23°C. and in nonideal solvents at 25°C. The constants K and a in the conventional modified equation [η] = KMa were determined. The intrinsic viscosity in an ideal solvent was found to fit closely over the molecular range studied with the relation [η]θ = KM1/2. Light scattering measurements giving root-mean-square distance between ends of a polymer chain were carried out. It was shown that these results support both Kuhn's relation (r̄2)1/2 ≍ M0.50 and Flory's relation (r̄2)3/2 = M[η]/2.1 × 1021 in an ideal solvent. In a nonideal solvent only Flory's relation was found to be in agreement with the experimental results. The values of volume expansion factor α3 ratios A2Mw2/(r̄2)3/2 and A2Mw/[η] in a nonideal solvent and the value of the ratio [η]/M1/2 in an ideal solvent showed that the polymer molecules were expanded beyond their random flight dimensions in a nonideal solvent.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 31 (1958), S. 45-52 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The complex dielectric constant of a pure molecular weight fraction of poly-n-hexyl methacrylate and of poly-n-octyl methacrylate was determined over a frequency range of 30 to 3 × 105 cycles/sec. and a temperature range of -66 to 106°C. and -61 to 81°C., respectively. The data indicate the presence of two transition regions, with the transitions being further apart with increasing side chain length. Examination of the data showed that superposition was not possible using the usual superposition schemes.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly-n-lauryl methacrylate, prepared by the emulsion technique, was fractionally precipitated to obtain nine sharp fractions. These fractions were studied in an ideal solvent, isopropyl acetate at 13°C., and in a nonideal solvent, n-butyl acetate at 23°C., by the light scattering and viscosity methods. The principal relationships obtained are: in isopropyl acetate at 13°C. (theta solvent); [η]θ = 3.22 × 10-4 Mw0.50, (r02)½ = 0.49 Mw0.50; and the the good solvent, n-butyl acetate at 23°C.; [η] = 8.46 × 10-5 Mw0.64, (r2)½ = 0.35 Mw0.54; for λ = 5460 A., A2 = 9.782 × 10-3 Mw-0.348 and for λ = 4360A., A2 = 9.778 × 10-3 Mw-0.353. The effect of the size of the pendent groups on the degree of chain extension in ideal solvents is discussed. It was found that the degree of chain extension of the polymers thus far studied follows the order poly-n-lauryl methacrylate 〉 poly-n-hexyl methacrylate 〉 poly-n-octyl methacrylate 〉 poly-n-butyl methacrylate 〉 poly ethyl methacrylate ≥ polymethyl methacrylate.
    Additional Material: 6 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 33 (1958), S. 471-485 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly-n-octyl methacrylate, prepared by the emulsion technique, was fractionated three times by the fractional precipitation procedure to obtain eight fractions. Relationships between viscosity and weight-average molecular weight were obtained in both an ideal solvent, n-butanol, and a nonideal solvent, methyl ethyl ketone. These relationships are represented by the equations, [η]16.8Θ = 2.68 × 10-4M0.50w [η]23 = 4.47 × 10-5M0.69w, respectively. The effect of the size of the pendant groups (-methyl, -ethyl, n-butyl, -n-hexyl, and -n-octyl ester) on the degree of extension of macromolecules in ideal solvents is discussed. It was found that, initially, as we progress from polymethyl to poly-n-butyl methacrylate, the degree of flexibility of the macromolecule increases as the size of the pendant group increases. These results are believed to be due to the short-range interference effect of the solvent molecule on the degree of free rotation of the macromolecule. However, it was found that poly-n-hexyl methacrylate chains have considerably greater chain extension than any of the other three polymers. This expansion of poly-n-hexyl methacrylate chains is a result of the steric effect of large pendant units. From the results obtained for n-octyl polymer, it is evident that, in spite of further increase in the size of the pendant group by —(CH2)2—, there is a substantial contraction in the n-octyl polymer chain. The reason for this reversal in the polymer chain expansion is not clearly understood at present.
    Additional Material: 8 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 43 (1960), S. 557-565 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Poly(2-ethylbutyl methacrylate) was prepared by emulsion polymerization and fractionated. Light-scattering and viscosity techniques were used to study eight fractions in a good solvent, methyl ethyl ketone, and in an ideal solvent, isopropanol. Relations between viscosity and molecular weight are shown. The effect of the size of pendant groups on the degree of chain extension of a series of alkyl methacrylate polymers in ideal solvents is discussed. It was found that the degree of chain extension of the polymers thus far studied follows the order: poly(n-lauryl methacrylate) 〉 poly(n-hexyl methacrylate) 〉 poly(2-ethylbutyl methacrylate) ≥ poly(n-octyl methacrylate) 〉 poly(n-butyl methacrylate) 〉 poly(ethyl methacrylate) ≥ poly(methyl methacrylate).
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 17 (1955), S. 117-124 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A viscosity-weight average molecular weight relationship was obtained for fractionated polyvinyl acetate in a thermodynamically “good” solvent acetone at 30°C. This relationship is represented by [η] = 8.6 × 10-5Mw0.74. The value of the root-meansquare end-to-end distance is approximately three times as large as the theoretical value for a chain with completely free rotation. The values of the osmotic second virial coefficient indicate the polymer molecules are expanded beyond their random flight dimensions. Consideration of the thermodynamic interactions in “good” solvent results in approximately constant values for A2M/[η] and A2M2/(r2)3/2. The average value obtained for the Flory universal constant is 1.98 × 1021.
    Additional Material: 4 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 22 (1956), S. 527-534 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Polystyrene was fractionated and refractionated to obtain essentially homogeneous fractions. The constants K and a in the conventional equation [η] = KMa were determined. The intrinsic viscosity in an ideal solvent fitted the relation [η]θ = KM1/2 over the molecular weight range 0.04 × 106 to 1.46 × 106. The degree of flexibility of polystyrene chains in solution is compared with those of polymethyl and polyethyl methacrylates.
    Additional Material: 5 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    Hoboken, NJ : Wiley-Blackwell
    Journal of Polymer Science 49 (1961), S. 533-541 
    ISSN: 0022-3832
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The preparation of a completely isopropylated polystyrene by polymerization of p-isopropylstyrene monomer is described. This polymer was autoxidized in cyclohexane with lauroyl peroxide to give a material of good reproducibility and high purity. Methyl methacrylate was successfully grafted to the polymeric hydroperoxide by using a sugar-containing recipe. Homopolymer was separated from the graft copolymer by extraction. Evidence for grafting was obtained from solubility and fractionation behavior, as well as from light-scattering and viscosity measurements.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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