Abstract
Stress, strain, and birefringence measurements have been carried out on swollen and unswollen networks of trans-1,4-polybutadiene (trans-PBE) and trans-1,4-polyisoprene (trans-PIP), gutta percha. The average values of the optical anisotropy ΔΓ of Kuhn’s random link for specimens swollen with solvents of optically and geometrically nearly isotropic molecules (simply, isotropic solvents) are 6.1 Å3 for trans-PBE and 5.8 Å3 for trans-PIP, while for unswollen specimens they are 8.6 Å3 and 9.2 Å3, respectively. For comparison, some measurements on swollen networks of cis-1,4-polyisoprene are included. The decrease in ΔΓ upon swelling with isotropic solvents, observed previously also for polyethylene and cis dienic polymers, is ascribed to the short-range orientational (parallel) order among polymer segments and solvent molecules, caused by the excluded volume and space-filling requirement. The unperturbed dimension ‹r2›, ΔΓ, and their temperature coefficients have been calculated for both trans-PBE and PIP, on the basis of conformational models explored by Mark and of theories developed previously by us. Alternative models for trans- and cis-PIP are presented from certain structure-geometric considerations. Theoretical values of ΔΓ are in close agreement with observed values obtained with isotropic solvents, provided statistical weight parameters adjusted to ‹r2› are combined with the anisotropic bond polarizabilities given by Clément and Bothorel, just as in the case of cis dienic polymers previously discussed.
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Ishikawa, T., Nagai, K. Stress-Optical Coefficient of trans-1, 4-Polybutadiene and trans-1, 4-Polyisoprene Networks. Measurements and Theoretical Interpretation. Polym J 1, 116–129 (1970). https://doi.org/10.1295/polymj.1.116
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DOI: https://doi.org/10.1295/polymj.1.116
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