Abstract
Two butadiene polymers were used in this investigation, one with 98.5% cis-1,4 units and the other with an approximately equibinary mixture of cis and trans units. Elastomeric networks prepared from these polymers were studied in elongation, in both the swollen and unswollen states over the temperature range −30 to 95°C. There is evidence for crystallization in these networks, particularly as manifested by marked increases in birefringence at relatively low elongations and at temperatures as high as 40°C. As expected, the birefringence and related quantities were found to be more sensitive to crystallization than the force, with the optical-configuration parameter and the stress-optical coefficient showing the greatest sensitivity. In the case of the cis–trans copolymer, the crystallization involves trans sequences, which are of relatively high melting point, and thus occurs at a temperature higher than for the lower melting cis sequences in the high-cis networks. The results which were free from the effects of network crystallization were used to calculate values of the temperature coefficient of the unperturbed dimensions of the chains, and values of the optical-configuration parameter. These configuration-dependent properties were found to be in satisfactory agreement with previously published theoretical results based on a rotational isomeric state model of these chain molecules.
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R. S. Hanmer and H. E. Railsback, in “Rubber Technology,” 2nd ed, M. Morton, Ed., Van Nostrand Reinhold, New York, 1973, Chapter 8.
R. W. Lenz, “Organic Chemistry of Synthetic High Polymers,” Interscience, New York, 1967.
D. H. Richards, Chem. Soc. Rev., 6, 235 (1977).
J. E. Mark, J. Am. Chem. Soc., 88, 4354 (1966).
J. E. Mark, J. Am. Chem. Soc., 89, 6829 (1967).
Y. Abe and P. J. Flory, Macromolecules, 4, 219 (1971).
P. J. Flory, “Statistical Mechanics of Chain Molecules,” Interscience, New York, 1969.
G. Natta and G. Moraglio, Makromol. Chem., 66, 218 (1963).
L. Mandelkern, “Crystallization of Polymers,” McGraw-Hill, New York, 1964.
B. Wunderlich, “Macromolecular Physics, Vol. 1,” Academic Press, New York, 1973.
“Polymer Handbook,” 2nd ed, by J. Brandrup and E. H. Immergut, Ed., Wiley-Interscience, New York, 1975.
Y. Akana and R. S. Stein, J. Polym. Sci., Polym. Phys. Ed., 13, 2195 (1975).
P. J. Flory, Trans. Faraday. Soc., 51, 848 (1955).
L. M. Dossin and W. W. Graessley, Macromolecules, 12, 123 (1979).
B. Erman, W. Wagner, and P. J. Flory, Macromolecules, 13, 1554 (1980).
It seems relevant in this regard that less protracted stress-strain experiments on very similar cis–trans polybutadiene networks [ G. Kraus and G. A. Moczvgemba, J. Polym. Sci., A, 2, 277 (1964)] give values of the elongation modulus which are much lower than those reported in ref 13. They are in fact inconsistent with large contributions from interchain entanglements.
P. J. Flory, J. Am. Chem. Soc., 78, 5222 (1956).
J. E. Mark, Polym. Eng. Sci., 19, 254 (1979).
J. E. Mark, Polym. Eng. Sci., 19, 409 (1979).
T. J. Hammack and R. D. Andrews, J. Appl. Phys., 38, 5182 (1967).
N. J. Mills, “Polymer Science,” A. D. Jenkins, Ed., North-Holland, 1972, Chapter 7.
J. Durisin and H. L. Williams, J. Appl. Polym. Sci., 17, 709 (1973).
M. Fukuda, G. L. Wilkes, and R. S. Stein, J. Polym. Sci., A-2, 9, 1417 (1971).
R. S. Stein, Rubber Chem. Technol., 49, 458 (1976).
R. S. Stein and S. D. Hong, J. Macromol. Sci., Phys., B12, 125 (1976).
M. A. Llorente and J. E. Mark, J. Polym. Sci., Polym. Phys. Ed., 19, 000 (1981).
P. J. Flory, Proc R. Soc. London, Ser. A, 351, 351 (1976).
P. J. Flory, Polymer, 20, 1317 (1979).
D. S. Pearson and W. W. Graessley, Macromolecules, 13, 1001 (1980).
M. Bruzzone, A. Mazzei, and G. Giuliani, Rubber Chem. Technol., 47, 1175 (1974).
G. Lugli, A. Mazzei, and S. Poggio, Makromol. Chem., 175, 2021 (1974).
S. Cesca, private communications.
G. Kraus, private communications.
“Handbook, of Chemistry and Physics,” 58th ed, CRC Press, Cleveland, 1977.
K. Nagai, J. Chem. Phys., 47, 4690 (1967).
A. N. Gent, Macromolecules, 2, 262 (1969).
T. Ishikawa and K. Nagai, Polym. J., 1, 116 (1970).
A. N. Gent and T. H. Kuan, J. Polym. Sci., A-2, 9, 927 (1971).
M. H. Liberman, Y. Abe, and P. J. Flory, Macromolecules, 5, 550 (1972).
T. Ishikawa, Polym. J., 5, 227 (1973).
M. A. Sharaf, Ph.D. Thesis in Chemistry, The University of Michigan, 1979.
T. Ishikawa and K. Nagai, J. Polym. Sci., A-2, 7, 1123 (1969).
R. J. Morgan and L. R. G. Treloar, J. Polym. Sci., A-2, 10, 51 (1972).
R. H. Valentine, J. D. Ferry, T. Homma, and K. Ninomiya, J. Polym. Sci., A-2, 6, 479 (1968).
L. R. G. Treloar, “The Physics of Rubber Elasticity,” 3rd Ed., Clarendon Press, Oxford, 1975.
A. De Chirico, P. C. Lanzani, E. Raggi, and M. Bruzzone, Makromol. Chem., 175, 2029 (1974).
G. P. Giuliani, E. Sorta, and M. Bruzzone, Angew. Makromol. Chem., 50, 87 (1976).
L. Gargani, G. P. Giuliani, F. Mistrali, and M. Bruzzone, Angew. Makromol. Chem., 50, 101 (1976).
K. J. Smith, Jr., A. Greene, and A. Ciferri, Kolloid Z. Z. Polym., 194, 49 (1964).
T.-K. Su and J. E. Mark, Macromolecules, 10, 120 (1977).
D. S. Chiu, T.-K. Su, and J. E. Mark, Macromolecules, 10, 1110 (1977).
P. J. Flory, “Principles of Polymer Chemistry,” Cornell University Press, Ithaca, N.Y., 1953.
P. J. Flory, A. Ciferri, and C. A. J. Hoeve, J. Polym. Sci., 45, 235 (1960).
A. Ciferri, C. A. J. Hoeve, and P. J. Flory, J. Am. Chem. Soc., 83, 1015 (1961).
J. E. Mark, J. Polym. Sci., Macromol. Rev., 11, 135 (1976).
J. E. Mark, Rubber Chem. Technol., 46, 593 (1973).
R. H. Becker, C. U. Yu, and J. E. Mark, Polym. J., 7, 234 (1975).
M. H. Liberman, L. C. DeBolt, and P. J. Flory, J. Polym. Sci., Polym. Phys. Ed., 12, 187 (1974).
There are also serious difficulties in the Dossin-Graessley assumption (ref 13) that the decreased values of the low deformation modulus 2C1+2C2 observed for a polybutadiene network cross-linked in solution and studied in the swollen state are due to a decrease in the number of inter-chain entanglements. This assumption neglects the results of numerous studies which have shown that (i) a network prepared in solution has a greatly decreased value of the constant 2C2 (ref 57—59), (ii) swollen networks have diminished values of 2C2 (ref 42, 58, and 59), (iii) reinforcement from network crystallization would be diminished by swelling (ref 17 and 48), and (iv) cross-linking in solution can give a considerable number of wasted intra-molecular cross-links or chain “loops” (ref 60 and 61). It is also contradicted by the results of several studies of poly(dimethylsiloxane) networks prepared in solution (ref 62 and 63).
J. E. Mark, J. Am. Chem. Soc., 92, 7252 (1970).
C. Price, G. Allen, F. de Candia, M. C. Kirkham, and A. Subramaniam, Polymer, 11, 486 (1970).
J. E. Mark, Rubber Chem. Technol., 48, 495 (1975), and pertinent references cited therein.
A. E. Tonelli and E. Helfand, Macromolecules, 7, 59 (1974).
A. E. Tonelli and E. Helfand, Macromolecules, 8, 248 (1975).
A. E. Tonelli, Polymer, 15, 194 (1974).
M. A. Llorente and J. E. Mark, J. Chem. Phys., 71, 682 (1979).
J. E. Mark and M. A. Llorente, J. Am. Chem. Soc., 102, 632 (1980).
A. L. Andrady, M. A. Llorente, and J. E. Mark, J. Chem. Phys., 72, 2282 (1980).
M. Cesari, L. Gargani, G. P. Giuliani, G. Perego, and A. Zazzeta, J. Polym. Sci., B, 14, 107 (1976).
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Mark, J., Llorente, M. Photoelastic Studies of Some Polybutadiene Networks. Polym J 13, 543–553 (1981). https://doi.org/10.1295/polymj.13.543
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DOI: https://doi.org/10.1295/polymj.13.543