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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 15 (1977), S. 605-616 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Molecular motions in a series of linear aliphatic polyesters [poly(ethylene adipate), poly(ethylene sebacate), poly(hexamethylene sebacate), and poly(decamethylene 1,16-hexadecanedicarboxylate)] were studied by dielectric measurements. Two loss maxima were observed for each polymer in the temperature range from -196 to about 60°C and in the frequency range from 110 to 105 Hz. The loss maxima of these polyesters, lying between -17 and -38°C at 110 Hz (β-relaxation), are due to the micro-Brownian motions of amorphous main chains. It was found that these β-relaxations are well described by the WLF equation. The loss maxima in the range from -88 to -109°C at 110 Hz (γ-relaxation), are attributed both to local mode motions of main chains in the amorphous region and to motions of the polar groups involved at the chain ends. For the β-relaxation, no simple relation between the methylene sequence length and the loss peak temperature was found. Furthermore, as the methylene sequence length decreased, the effective dipole moment of the polyesters increased gradually. These facts were explained in terms of interchain dipole attraction.
    Additional Material: 11 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 2313-2320 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A study of the effect of drawing on the glass transition temperature Tg of amorphous polycarbonate was carried out. The Tg attains a maximum at a draw ratio in the range from 1.6 to 2.0. The relationship between the change of structure and Tg is discussed in terms of the configurational entropy and the rate of molecular motion in local mode relaxation. The variation of Tg with drawing may be explained by using the iso-entropy theory. The frequency of the maximum in the dielectric loss fmax and the dielectric relaxation strength Δε of the β mechanism changed with drawing in the same way as that of Tg. Based on the parallel behavior in these results, it is reasonable to consider that the β process of local mode relaxation of polyesters such as PC and PET reflects the structure of the glassy state.
    Additional Material: 4 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 13 (1975), S. 35-41 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Graessley's entanglement theory of viscosity modified by a frictional viscosity parameter ηfric is applied to data on solutions of polystyrene in diethyl phthalate at various concentrations and different temperatures. All the data modified give a single master curve over the entire rates of shear, as obtained previously with polydimethyl-siloxanes of various molecular weights and their solutions of various concentrations. The zero-shear viscosity η0, the upper Newtonian viscosity η∞, and ηfric are compared. Three activation energies for flow are estimated from η0, η∞ and ηfric, and are compared. The result suggests that the flow behavior in the upper Newtonian region is much more dependent on ηfric than on the entanglement viscosity term ηent. The ratio of zero-shear entanglement viscosity ηent,0 to ηfric can be used as a measure of the non-Newtonian behavior of the present solutions. Non-Newtonian behavior of the investigated polymer solution becomes appreciable at about ηent,0/ηfric = 2.5. These results are in agreement with previous conclusions based on comparison between η0, η∞ and ηfric for polydimethyl-siloxanes and their solutions.
    Additional Material: 5 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 725-734 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The non-Newtonian viscosity in steady flow was measured for solutions of polystyrene (M̄w/M̄n = 1.1) in diethyl phthalate at 30.0°C. In the moderately concentrated solutions, from 6.03 × 10-2 to 5.62 × 10-1g/cm3, the viscosity data modified by frictional parameters fit the Graessley theoretical curve for a narrow distribution polymer. The dilute solutions, from 3.26 × 10-3 to 1.57 × 10-2 g/cm3, were nonentangled systems whose non-Newtonian properties could be explained by the excluded volume effect as proposed by Fixman. On the basis of the non-Newtonian data, it was concluded that the solution of 3.30 × 10-2 g/cm3 was a lower critical entanglement concentration, which was distinguished from the usual higher critical concentration for entanglement. This lower critical concentration was also found in the concentration dependence of the activation energy of flow and the absorbance at 310 nm.
    Additional Material: 8 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 1435-1446 
    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 Chemical structure on the molecular motions in linear aliphatic polyesters have been investigated with a free-oscillation torsion pendulum. Broad-line NMR provided supplementary information. In the γ relaxation which corresponds to the local-mode motions of main chains in the noncrystalline region, the polyesters which are composed of two methylene units in the diol part of the chemical repeat unit showed an extremely asymmetric loss curve with a relatively high-loss peak temperature compared with that of the other polyesters. In addition to the two relaxations (β,γ) which have been observed in earlier dielectric measurements, a new relaxation (α) was found on the high-temperature side of the glass transition of the polyesters. The α relaxation was assigned to molecular motions of methylene segments in the crystalline region. The α and β relaxations of the two-dimensional series are situated close to the temperatures found for other polyesters with rather long methylene sequence in the chemical repeat unit. The results were explained in terms of a difference on the chain mobility in the noncrystalline regions which may be related to the difference of chemical structure of the polyesters.
    Additional Material: 7 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 401-413 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The dependence of the polymerization rate on initiator concentration over a wide range of conversion is analyzed by an equation derived on the assumption that the primary radical termination is important and another equation derived on the assumption of the chain length dependence of the termination. The analytical result by the former equation, is nearly equivalent to the result by the later when transfer predominates. Fujita-Doolittle theory is applicable to both results. In the apparent termination, small polymer radicals not exceeding the size of the segment play an important role.
    Additional Material: 12 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 17 (1979), S. 1565-1568 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 521-524 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 87-96 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the polymerization of diallyl phthalate in bulk at 60°C with azobisisobutyronitrile, extensive branching of the polymers obtained before gelation was ascertained from the enhanced broadening of the molecular weight distribution, coupled with the decrease of the residual unsaturation. Copolymerization of poly(diallyl phthalate) and styrene in bulk at 80°C with benzoyl peroxide was studied in detail with regard to the gel formation. The gel time increased with increasing fraction of styrene in feed. Both the gel yield and the conversion of styrene incorporated into the gel increased steadily with polymerization time, even after the total conversion of styrene exceeded 95%. The polystyrene recovered by saponification of the gel was found to carry hydroxyl groups, which should come from the copolymerized diallyl phthalate units. It was concluded that styrene behaved as a diluent in the early stage, and that the crosslinking after gelation of the system proceeded mainly through polymer-polymer reactions involving the occluded polystyryl radicals and poly(diallyl phthalate).
    Additional Material: 6 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 15 (1977), S. 2037-2040 
    ISSN: 0360-6376
    Keywords: Physics ; 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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