Fractionated samples of poly(phthaloyl-trans-2,5-dimethylpiperazine) in various organic solvents at 25°C were studied by light scattering, viscosity, and sedimentation velocity. The data obtained for z-average mean-square radii of gyration ‹S2›z, intrinsic viscosities [η], and sedimentation coefficients s0 exhibited features predictable for stiff or semiflexible chains. Thus an attempt was made to analyze the data by combination of the Yamakawa—Fujii theory for intrinsic viscosity and the Benoit—Doty expression for mean-square radius of gyration of unperturbed wormlike chains with a reasonable assumption for the partial specific volume. In this way, three parameters q, ML, and d characterizing the wormlike cylinder were estimated for each solvent; for example, q=33 Å, ML=33 daltons/Å, and d=7.4 Å in N-methyl-2-pyrrolidone. Here q is the persistence length, ML is the molecular weight per unit length of the wormlike cylinder, and d is the its diameter. The estimated parameter values were found to reproduce quite closely the observed molecular weight dependence of ‹S2›z, [η], and s0.
P. W. Morgan, “Condensation Polymers: By Interfacial and Solution Methods,” Interscience, New York, N.Y., 1965.
P. W. Morgan and S. L. Kwolek, J. Polym. Sci., Part A-2, 181 (1964).
M. Katz, J. Polym. Sci., Part A-2, 40, 337 (1959).
E. M. Hodnet and D. A. Holmer, J. Polym. Sci., Part A-2, 58, 1415 (1962).
T. Tsuji, T. Norisuye, and H. Fujita, Polym. J., 7, 558 (1975).
Gj. Dezelic and J. Vavra, Croat. Chim. Acta, 38, 35 (1966).
J. P. Kratohvil, Gj. Dezelic, M. Kerker, and E. Matijevic, J. Polym. Sci., 57, 59 (1962).
G. C. Berry, J. Chem. Phys., 44 4550 (1966).
M. L. Huggins, J. Am. Chem. Soc., 64, 2716 (1942).
D. F. Mead and R. M. Fuoss, J. Am. Chem. Soc., 64, 277 (1942).
J. W. Williams, R. L. Baldwin, K. E. Van Holde, and H. Fujita, Chem. Rev., 58, 715 (1958).
H. Fujita, “Foundations of Ultracentrifugal Analysis,” Interscience, New York, N.Y., 1975.
R. L. Baldwin, Biochem. J., 55, 644 (1953).
H. Yamakawa, “Modern Theory of Polymer Solutions,” Harper & Row, New York, N.Y. 1971.
G. V. Schulz and E. Penzel, Makromol. Chem., 112, 260 (1968).
E. Penzel and G. V. Schulz, Makromol. Chem., 113, 64 (1968).
H. Yamakawa, Pure Appl. Chem., 46, 135 (1976).
H. Benoit and P. Doty, J. Phys. Chem., 57, 958 (1953).
H. Yamakawa and M. Fujii, Macromolecules, 6, 407 (1973).
H. Yamakawa and M. Fujii, Macromolecules, 7, 128 (1974).
O. Kratky and G. Porod, Rec. Trav. Chim., 68, 1106 (1949).
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Motowoka, M., Norisuye, T. & Fujita, H. Stiff Chain Behavior of Poly(phthaloyl-trans-2,5-dimethyIpiperazine) in Dilute Solution. Polym J 9, 613–624 (1977). https://doi.org/10.1295/polymj.9.613
- Wormlike Chain
- Persistence Length
- Dilute Solution
- Refractive-Index Increment
- Light Scattering
- Intrinsic Viscosity
- Sedimentation Coefficient
- Yamakawa—Fujii Theory
- Benoit—Doty Theory
Crossover effects and molecular mass regions in solutions of worm-like polymers: a new relation for the determination of their statistical segment length, based on the blob model
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