Abstract
Mutual- and self-diffusion coefficients of a semiflexible polymer, cellulose tris(phenyl carbamate) (CTC), in tetrahydrofuran were measured by dynamic light scattering and pulsed field gradient NMR, respectively, as functions of the polymer concentration and molecular weight. The mutual-diffusion coefficient after elimination of the effects of thermodynamic force and solvent back flow agrees with the self-diffusion coefficient for a low molecular weight CTC fraction with the number of Kuhn’s statistical segments N=1.8 up to high concentrations, but they disagree for a higher molecular weight CTC fraction with N=4.7 at the highest concentration investigated. The mutual diffusion coefficients for CTC fractions with N ranging from 1.8 to 10.6 after elimination of the above two effects were also compared with the fuzzy cylinder theory for the self-diffusion coefficient. Disagreements start at lower concentration for larger N, which form in a contrast with good agreements for a more stiff polymer, poly(n-hexyl isocyanate), previously studied.
Similar content being viewed by others
Article PDF
References
P.-G. de Gennes, “Scaling Concepts in Polymer Physics,” Cornell University Press, Ithaca, N.Y., 1979.
M. Doi and S. F. Edwards, “The Theory of Polymer Dynamics,” Clarendon Press, Oxford, U.K., 1986.
H. Fujita, “Polymer Solutions,” Elsevier, Amsterdam, 1990.
M. Tirrell, Rubber Chem. Technol., 57, 52 (1984).
R. G. Kitchen, B. N. Preston, and J. D. Wells, J. Polym. Sci., Polym. Symp., 55, 39 (1976).
C. Le Bon, T. Nicolai, M. E. Kuil, and J. G. Hollander, J. Phys. Chem. B, 103, 10294 (1999).
A. Ohshima, A. Yamagata, T. Sato, and A. Teramoto, Macromolecules, 32, 8645 (1999).
P. T. Callaghan and D. N. Pinder, Macromolecules, 14, 1334 (1981).
W. Brown, P. Stilbs, and R. M. Johnsen, J. Polym. Sci., Polym. Phys. Ed., 20, 1771 (1982).
W. Brown, P. Stilbs, and R. M. Johnsen, J. Polym. Sci., Polym. Phys. Ed., 21, 1029 (1983).
J. A. Marqusee and J. M. Deutch, J. Chem. Phys., 73, 5396 (1980).
F. Kasabo, T. Kanematsu, T. Nakagawa, T. Sato, and A. Teramoto, Macromolecules, 33, 2748 (2000).
T. Sato, Y. Takada, and A. Teramoto, Macromolecules, 24, 6220 (1991).
T. Sato and A. Teramoto, Adv. Polym. Sci., 126, 85 (1996).
T. Sato, M. Hamada, and A. Teramoto, Macromolecules, 36, 6840 (2003).
D. Wu, A. Chen, and C. S. Johnson Jr., J. Magn. Reson., Ser. A, 115, 260 (1995).
B. Antalek and W. Windig, J. Am. Chem. Soc., 118, 10331 (1996).
W. Windig and B. Antalek, Chemom. Intell. Lab. Syst., 37, 241 (1997).
S. W. Provencher, Comput. Phys. Commun., 27, 213 (1982).
M. A. Delsuc and T. M. Malliavin, Anal. Chem., 70, 2146 (1998).
P. S. Russo, F. E. Karasz, and K. H. Langley, J. Chem. Phys., 80, 5312 (1984).
M. Doi, T. Shimada, and K. Okano, J. Chem. Phys., 88, 4070 (1988).
J. Roots, B. Nystrom, L. O. Sundelof, and B. Posch, Polymer, 20, 337 (1979).
T. Sato, A. Ohshima, and A. Teramoto, Macromolecules, 31, 3094 (1998).
S. F. Edwards and K. E. Evans, J. Chem. Soc., Faraday Trans. 2, 78, 113 (1982).
I. Teraoka and R. Hayakawa, J. Chem. Phys., 89, 6989 (1988).
I. Teraoka, Ph. D. Thesis, University of Tokyo, 1988.
The previous paper indicated that a c2 term in the intermolecular HI is important in the zero-shear viscosity of THF solutions of fraction F19 with almost the same N as that of fraction F20 (cf. Table I) in a high c region. However, as shown in Figure 5 in ref 24, the c2 term is still minor at c ≲ 0.1 g/cm3, which is consistent with the use of eq 11 for Ds.
A. Ohshima, H. Kudo, T. Sato, and A. Teramoto, Macromolecules, 28, 6095 (1995).
In ref 7, both k′‖ and k′⊥ were assumed to be equal with k′HI estimated from the Huggins coefficient. The use of k′‖ and k′⊥ estimated by the same method as in this study provides better agreements between the theory and experiment of D̃ for PHIC solutions.
H. Benoit and P. M. Doty, J. Phys. Chem., 57, 958 (1953).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Kanematsu, T., Sato, T., Imai, Y. et al. Mutual- and Self-Diffusion Coefficients of a Semiflexible Polymer in Solution. Polym J 37, 65–73 (2005). https://doi.org/10.1295/polymj.37.65
Published:
Issue Date:
DOI: https://doi.org/10.1295/polymj.37.65
Keywords
This article is cited by
-
Optimization of a 3D-printed tubular reactor for free radical polymerization by CFD
Journal of Flow Chemistry (2021)