Abstract
The unperturbed dimensions of poly-α-olefins are treated in consideration of the side chain configuration. Within the reasonable range of conformational energies, the root mean square end-to-end distance ‹r2›0/nl2 and its thermal coefficient dln‹r2›0/dT are evaluated and compared with those observed. The presence of several percent of heterotactic units in an allegedly isotactic poly-1-butene or poly-1-pentene is the primary requirement in finding the agreement between theory and experiments. The conclusion drawn in a previous paper is thus reconfirmed. When the pendant group is methyl, on the other hand, the experimental value of ‹r2›0/nl2 is found to be consistent with those calculated over a wider range of isotacticity (0.92–0.98), provided that the thermal coefficient is negative and large. The treatment is further extended to the polymer systems with bulky substituents. It is pointed out, finally, that the magnitude of ‹r2›0/nl2 cannot provide a good criterion to define the stiffness of the vinyl chain system except when the polymer possesses a stereoregular configuration.
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P. J. Flory, J. E. Mark, and A. Abe, J. Am. Chem. Soc., 88, 639 (1966).
A. Zambelli, A. L. Segre, M. Farina, and G. Natta, Makromol. Chem., 110, 1 (1967).
P. J. Flory and J. D. Baldeschwieler, J. Am. Chem. Soc., 88, 2873 (1966).
P. J. Flory and Y. Fujiwara, Macromolecules, 2, 315 (1969).
P. J. Flory and Y. Fujiwara, Macromolecules, 2, 327 (1969).
G. Moraglio and J. Brzezinski, J. Polym. Sci., Part B, 2, 1105 (1964).
K. S. Sastry and R. D. Patel, Eur. Polym. J., 5, 79 (1969).
J. E. Mark and P. J. Flory, J. Am. Chem. Soc., 87, 1423 (1965).
G. Natta and P. Corradini, Makromol. Chem., 110, 291 (1967).
A. Abe, J. Am. Chem. Soc., 90, 2205 (1968).
G. Allegra, Makromol. Chem., 117, 24 (1968).
A. Nakajima and A. Saijo, J. Polym. Sci., Part A-2, 6, 735 (1968).
P.J. Flory, Statistical Mechanics of Chain Molecules, Interscience Publishers, New York, 1969.
E. B. Wilson, Jr., Adv. Chem. Phys., 2, 367 (1959).
J. B. Hendrickson, J. Am. Chem. Soc., 83, 4537 (1961).
A. Abe, R. L. Jernigan, and P. J. Flory, J. Am. Chem. Soc., 88, 631 (1966).
D. W. Scott, J. P. McCullough, K. D. Williamson, and G. Waddington, J. Am. Chem. Soc., 73, 1707 (1951).
J. K. Brown and N. Sheppard, J. Chem. Phys., 19, 976 (1951).
E.L. Eliel, N.L. Allinger, S.L. Angyal, and G.A. Morrison, Conformational Analysis Interscience Publishers, New York, 1965, Chap. 2, p. 43.
A. Abe and T. Hama, J. Polym. Sci., Part B, 7, 427 (1969).
A. D. Williams and P. J. Flory, J. Am. Chem. Soc., 91, 3111 (1969).
R. L. Miller, "Crystalline and Spherulitic Properties" in Crystalline Olefin Polymers, Part I, R. A. V. Raff and K. W. Doak, Ed., Interscience Publishers, New York, 1965, p. 577.
P. Cossee, J. Catal., 3, 80 (1964).
E. J. Arlman, J. Catal., 3, 89 (1964).
E. J. Arlman and P. Cossee, J. Catal., 3, 99 (1964).
E. J. Arlman, J. Catal., 5, 178 (1966).
P. J. Flory, Private communication.
J. B. Kinsinger and R. E. Hughes, J. Phys. Chem., 67, 1922 (1963).
P. J. Flory and F. Hamada, unpublished results.
F. Danusso, G. Moraglio, V. Giannella, and G. Natta, Rend. Accad. Naz. Lincei, 25, 510 (1958).
H. Inagaki, T. Miyamoto, and S. Ohta, J. Phys. Chem., 70, 3420 (1966).
G. Moraglio, G. Gianotti, and F. Danusso, Eur. Polym. J., 3, 251 (1967).
G. Moraglio and G. Gianotti, Chim. Ind. (Milan), 49, 927 (1967).
H.-G. Elias and O. Etter, J. Macromol. Chem., 1, 431 (1966).
S. Brownstein, S. Bywater, and D. J. Worsfold, J. Phys. Chem., 66, 2067 (1962).
A. L. Segre, P. Ferruti, E. Toja, and F. Danusso, Macromolecules, 2, 35 (1969).
Y. Fujiwara and P. J. Flory, private communication.
W. R. Krigbaum, D. K. Carpenter, and S. Newman, J. Phys. Chem., 62, 1586 (1958).
T. A. Orofino and A. Ciferri, J. Phys. Chem., 68, 3136 (1964).
Y. Fujiwara and P. J. Flory, private communication.
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Abe, A. Unperturbed Dimensions of Vinyl Polymer Chains. Polym J 1, 232–244 (1970). https://doi.org/10.1295/polymj.1.232
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DOI: https://doi.org/10.1295/polymj.1.232
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