Abstract
The Flory–Huggins interaction parameter (χ12) between poly(vinylidene fluoride) (PVdF) and organic solvent was estimated experimentally over wide range of temperature by an inverse gas chromatography (IGC) using many kinds of solvents such as alkane, alkene, ketone, lactone, and nitrogen-containing solvent. The thermoreversible gelation of PVdF solution was discussed from the magnitude of interaction parameter χ12 between PVdF and solvent. The parameter χ12 was measured for a concentrated PVdF solution by the usual IGC technique. The parameter χ12 obtained for each PVdF/solvent system increased slowly with decreasing temperature. The present systems were divided broadly into three groups according to the magnitude of χ12 in the vicinity of room temperature, i.e., group (a) with χ12»0.5, group (b) with χ12≍0.5, and group (c) with χ12«0.5. The group (b), to which ketone and lactone belong, converted to thermoreversible gels accompanying with crystallization of polymer. The gelation process of PVdF solution was investigated through measurement of in situ Fourier transform infrared (FT-IR) spectroscopy. The time-resolved FT-IR spectra suggested that the gelation took place taking the conformation T3GT3G̅ for the system where the parameter χ12 was nearly equal to 0.5 such as PVdF in γ-butyrolactone. For the system where the parameter χ12 became larger than 0.5 such as PVdF in cyclohexanone, 3-pentanone, 3-hexanone, 3-heptanone, or 3-octanone, the gelation occurred taking the conformation TGTG̅.
Similar content being viewed by others
Article PDF
References
K. Tashiro, “Ferroelectric Polymers: Chemistry, Physics, and Applications”, H. S. Nalwa, Ed., Marcel Dekker, Inc., New York, N.Y., 1995, p 63.
K. Tashiro, H. Tadokoro, and M. Kobayashi, Ferroelectrics, 32, 167 (1981).
W. W. Doll and J. B. Lando, J. Macromol. Sci., Phys., B4(2), 309 (1970).
R. Hasegawa, M. Kobayashi, and H. Tadokoro, Polym. J., 3, 591 (1972).
A. J. Lovinger, Macromolecules, 15, 40 (1982).
L. J. Fina, J. L. Koenig, and W. L. Gordon, J. Polym. Sci., Part B: Polym. Phys., 24, 2541 (1986).
D. Geiss and D. Hofmann, Prog. Polym. Sci., 15, 57 (1990).
A. Takahashi, T. Nakamura, and I. Kagawa, Polym. J., 3, 207 (1972).
M. Tazaki, A. Onodera, and T. Homma, Kobunshi Ronbunshu, 50, 533 (1993).
M. Tazaki and T. Homma, Kobunshi Ronbunshu, 53, 482 (1996).
J. W. Cho, H. Y. Song, and S. Y. Kim, Polymer, 34, 1024 (1993).
S. Mal, P. Maiti, and A. K. Nandi, Macromolecules, 28, 2371 (1995).
A. K. Dikshit and A. K. Nandi, Macromolecules, 33, 2616 (2000).
M. Tazaki, R. Wada, M. Okabe, and T. Homma, J. Appl. Polym. Sci., 65, 1517 (1997).
Y. Sato, R. Wada, M. Tazaki, and M. Okabe, Nippon Kagaku Kaishi, 481 (1998).
R. Wada, Y. Sato, M. Tazaki, and M. Okabe, Nippon Kagaku Kaishi, 253 (1999).
R. Wada, K. Aihara, H. Nomoto, M. Tazaki, and M. Okabe, Nippon Kagaku Kaishi, 797 (2000).
K. Tashiro, F. Joubert, K. Fukuda, and F. Kaneko, Polym. Prepr. Jpn., 47, 3811 (1998).
P.-D. Hong and C.-M. Chou, Polymer, 41, 8311 (2000).
For example, Y. Rosenberg, A. Siegmann, M. Narkis, and S. Shkolnik, J. Appl. Polym. Sci., 43, 535 (1991).
C.-T. Chen and Z. Y. Al-Saigh, Polymer, 31, 1170 (1990).
P. Munk, P. Hattam, Q. Du, and A. A. Adbel-Azim, J. Appl. Polym. Sci., Appl. Polym. Symp., 45, 289 (1990).
A. Takahashi, M. Sakai, and T. Kato, Polym. J., 12, 335 (1980).
J. R. Conder and C. L. Young, “Physicochemical Measurement by Gas Chromatography”, John Wiley & Sons, Inc., New York, N.Y., 1979.
For example, J. F. Rabek, “Inverse Gas Chromatography”, in “Experimental Methods in Polymer Chemistry”, Wiley-Interscience, New York, N.Y., 1980, chapt. 24.
T. E. Daubert and R. P. Danner, Eds., “Physical and Thermodynamic Properties of Pure Chemicals, Data Compilation”, Hemisphere Publishing, Corp., New York, N.Y., 1989.
E. Benedetti, A. D’Alessio, C. Bertolutti, P. Vergamini, N. D. Fanti, M. Pianca, and G. Moggi, Polym. Bull., 22, 645 (1989).
H. Matsuda, T. Inoue, M. Okabe, and T. Ukaji, Polym. J., 19, 323 (1987).
M. Okabe and A. Takahashi, Polym. J., 30, 883 (1998).
M. Okabe, K. Mitsui, F. Sasai, and H. Matsuda, Polym. J., 21, 313 (1989).
M. Ohkura, T. Kanaya, and K. Kaji, Polymer, 33, 3686 (1992).
G. J. Welch, Polymer, 15, 429 (1974).
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Okabe, M., Wada, R., Tazaki, M. et al. The Flory-Huggins Interaction Parameter and Thermoreversible Gelation of Poly(vinylidene fluoride) in Organic Solvents. Polym J 35, 798–803 (2003). https://doi.org/10.1295/polymj.35.798
Issue Date:
DOI: https://doi.org/10.1295/polymj.35.798
Keywords
This article is cited by
-
Structural color of polymeric physical gels
Journal of Polymer Research (2016)
-
Sol-gel transitions of poly(vinylidene fluoride) in organic solvents containing LiBF4
Polymer Journal (2011)