Abstract
Eleven samples of cellulose tris(3,5-dimethylphenylcarbamate) ranging in weight-average molecular weight Mw from 2×104 to 4×106 have been prepared by extensive fractionation and studied by static light scattering, sedimentation equilibrium, and viscometry with 1-methyl-2-pyrrolidone at 25°C as the solvent. This polymer is found to exhibit pronounced optical anisotropy differing from other cellulose derivatives, and light scattering data are corrected for the anisotropy effect on the basis of the Nagai theory for the Kratky–Porod wormlike chain with cylindrically symmetric polarizabilities. It is shown that the molecular weight dependences of 〈S2〉z (the z-average mean-square radius of gyration), δ (the optical anisotropy factor), and [η] (the intrinsic viscosity) for Mw below 106 are explained consistently by the known theories for the unperturbed wormlike chain. From the comparison between theory and experiment the persistence length and the monomeric length along the chain contour are estimated to be 7.8 and 0.52 nm, respectively. It is also shown that excluded-volume effects on 〈S2〉z and [η] are experimentally visible for Mw above 106 but remain small even at the highest Mw studied.
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Y. Okamoto, M. Kawashima, and K. Hatada, J. Am. Chem. Soc., 106, 5357 (1984).
Y. Okamoto, M. Kawashima, and K. Hatada, J. Chromatogr., 363, 173 (1986).
Y. Okamoto, R. Aburatani, Y. Kaida, and K. Hatada, Chem. Lett., 1125 (1988).
Y. Okamoto and R. Aburatani, Polym. News, 14, 295 (1989).
W. Burchard and E. Husemann, Makromol. Chem., 44–46, 358 (1961).
V. P. Shanbhag, Ark. Kemi, 29, 1 (1968).
W. Burchard, Polymer, 11, 467 (1969).
J. T. Guthrie, M. B. Huglin, R. W. Richards, V. I. Shah, and A. H. Simpson, Eur. Polym. J., 11, 527 (1975).
O. Kratky and G. Porod, Rec. Trav. Chim., 68, 1106 (1949).
D. Henley, Ark. Kemi, 18, 327 (1961).
Dj. Deželić and J. Vavra, Croat. Chem. Acta, 38, 35 (1966).
D. N. Rubingh and H. Yu, Macromolecules, 9, 681 (1976).
G. C. Berry, J. Chem. Phys., 44, 4550 (1966).
H. Yamakawa, “Modern Theory of Polymer Solutions,” Harper & Row, New York, N.Y., 1971.
K. Nagai, Polym. J., 3, 67 (1972).
H. Fujita, “Foundations of Ultracentrifugal Analysis,” Wiley, New York, N.Y., 1975.
T. Norisuye, T. Yanaki, and H. Fujita, J. Polym. Sci., Polym. Phys. Ed., 18, 547 (1980).
H. Benoit and P. Doty, J. Phys. Chem., 57, 958 (1953).
H. Murakami, T. Norisuye, and H. Fujita, Macromolecules, 13, 345 (1980).
K. Sakurai, K. Ochi, T. Norisuye, and H. Fujita, Polym. J., 16, 559 (1984).
C. W. Carlson and P. J. Flory, J. Chem. Soc., Farady Trans. 2, 73, 1505 (1977).
U. W. Suter and P. J. Flory, J. Chem. Soc., Farady Trans. 2, 73, 1521 (1977).
T. Konishi, T. Yoshizaki, J. Shimada, and H. Yamakawa, Macromolecules, 22, 1921 (1989).
P. J. Flory, “Statistical Mechanics of Chain Molecules,” Wiley, New York, N.Y., 1969.
H. Yamakawa, M. Fujii, and J. Shimada, J. Chem. Phys., 71, 1611 (1979).
J. W. M. Noordermeer, R. Daryanani, and H. Janeschitz-Kriegl, Polymer, 16, 359 (1975).
V. N. Tsvetkov and L. N. Andreeva, Adv. Polym. Sci., 39, 95 (1981).
T. Yoshizaki, I. Nitta, and H. Yamakawa, Macromolecules, 21, 165 (1988).
T. Norisuye and H. Fujita, Polym. J., 14, 143 (1982).
K. Hayashi, K. Tsutsumi, F. Nakajima, T. Norisuye, and A. Teramoto, Macromolecules, 28, 3824 (1995).
H. Yamakawa and W. H. Stockmayer, J. Chem. Phys., 57, 2843 (1972).
H. Yamakawa and J. Shimada, J. Chem. Phys., 83, 2607 (1985).
J. Shimada and H. Yamakawa, J. Chem. Phys., 85, 591 (1986).
P. Zugenmaier and U. Vogt, Makromol. Chem., 184, 1749 (1983).
Y. Takahashi, Macromolecules, 24, 3968 (1991).
H. Steinmeier and P. Zugenmaier, Carbohydr. Res., 164, 97 (1987).
J. Daňhelka, M. Netopilík, and M. Bohdanecký, J. Polym. Sci., B: Polym. Phys., 25, 1801 (1987).
T. Norisuye, Prog. Polym. Sci., 18, 543 (1993).
H. Yamakawa and M. Fujii, Macromolecules, 7, 128 (1974).
A. Takada, T. Fukuda, J. Watanabe, and T. Miyamoto, Macromolecules, 28, 3394 (1995).
G. Conio, E. Bianchi, A. Ciferri, A. Tealdi, and M. A. Aden, Macromolecules, 16, 1264 (1983).
G. V. Laivins and G. D. Gray, Macromolecules, 18, 1746 (1985).
P. Sixou and A. Ten Bosh, “Cellulose: Structure, Modification and Hydrolysis,” R. A. Young and R. M. Rowell, Ed., Wiley, New York, N.Y., 1986.
A. K. Gupta, E. Marchal, and W. Burchard, Macromolecules, 8, 843 (1975).
W. Sutter and W. Burchard, Makromol. Chem., 179, 1961 (1978).
F. Fried, G. M. Searby, M. J. Seurin-Vellutini, S. Dayan, and P. Sixou, Polymer, 23, 1755 (1982).
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Tsuboi, A., Yamasaki, M., Norisuye, T. et al. Dilute-Solution Behavior of Cellulose Tris(3,5-dimethylphenylcarbamate). Polym J 27, 1219–1229 (1995). https://doi.org/10.1295/polymj.27.1219
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DOI: https://doi.org/10.1295/polymj.27.1219