Abstract
The solubilities of poly(p-chlorostyrene) (PPCS) were examined for about ninety solvents. The solvents employed were aliphatic, aromatic and chlorinated hydrocarbons, ethers, esters, ketones, alcohols, and others. The solubilities were successfully interpreted by the three dimensional plots according to Crowley, Teague, and Lowe, in which the solubility parameter, dipole moment, and hydrogen bonding parameter were used as three components, and to Hansen, who devided the solubility parameter into dispersion, polar and hydrogen bonding components. It can be seen that the soluble region is found to be inside the closed surface in the three-dimensional plots. The present systems involve some with either LCST or UCST. The difference between the PPCS–solvent system with LCST and that with UCST is reflected in the relative contribution of the three components rather than in the structure of the solvent. Furthermore, the phase relationships of PPCS were investigated. The eleven theta solvents found in this work contain both the four theta solvent with LCST, i.e., isopropyl acetate (θ=75.7°C), t-butyl acetate (θ=65.4°C), ethylcarbitol (θ=27.8°C) and n-butylcarbitol (θ=50.1°C), and the seven theta solvents with UCST, i.e., ethylbenzene (θ=−14.7°C), isopropylbenzene (θ=59.0°C), carbon tetrachloride (θ=50.7°C), tetrachloroethylene (θ=44.4°C), methyl chloroacetate (θ=64.6°C), ethyl chloroacetate (θ=−1.8°C), and isopropyl chloroacetate (θ=−8.2°C). It is considered from these phase relationships and from calorimetric measurements in the corresponding monomer solutions for esters that the theta solvent with LCST corresponds to an exothermic solvent and that characterized by UCST to an endothermic one.
Similar content being viewed by others
Article PDF
References
G. Müh, Makromol. Chem., 54, 222 (1962).
N. Kuwahara, K. Ogino, M. Konuma, N. Iida, and M. Kaneko, J. Polym. Sci., Part A, 4, 173 (1966).
K. Matsumura, Makromol. Chem., 124, 204 (1969).
K. Matsumura, Bull. Chem. Soc. Jpn., 42, 1874 (1969).
K. Matsumura, Polym. J., 1, 322 (1970).
J. E. Davis, Ph. D. Thesis, M. I. T. Cambridge, Mass., 1960.
T. Saito, Bull. Chem. Soc. Jpn., 35, 1580 (1962).
N. Kuwahara, K. Ogino, A. Kasai, S. Ueno, and M. Kaneko, J. Polym. Sci., Part A, 3, 985 (1965).
K. Takamizawa, Bull. Chem. Soc. Jpn., 39, 1186 (1966).
K. Kubo, K. Ogino, and T. Nakagawa, Nippon Kagaku Zasshi (J. Chem. Soc. Japan, Pure. Chem. Sect.), 88, 1254 (1967) (in Japanese).
R. B. Mohite, S. Gundiah, and S. L. Kapur, Makromol. Chem., 116, 280 (1968).
Y. Noguchi, A. Aoki, G. Tanaka, and H. Yamakawa, J. Chem. Phys., 52, 2651 (1970).
K. Matsumura, M. Fukaya, and K. Mizuno, Bull. Chem. Soc. Jpn., 43, 1881 (1970).
K. Matsumura, M. Fukaya, and K. Mizuno, Bull. Chem. Soc. Jpn., 43, 1303 (1970).
J. Hildebrand and R. Scott, “The Solubility of Nonelectrolytes”, 3rd ed, Renhold, New York, N. Y., 1949.
J. H. Hildebrand and R. L. Scott, “Regular Solutions”, Pretence-Hall, Inc., Englewood, Cliffs, N.J., 1962.
J. D. Crowley, G. S. Teague, Jr., and J. W. Lowe, Jr., J. Paint Technol., 38, 269 (1966).
H. Burrel, Official Digest, 27, 726 (1955).
E. P. Lieberman, Official Digest, 34, 30 (1962).
J. L. Gardon, J. Paint Technol., 38, 43 (1966).
C. M. Hansen, J. Paint Technol., 39, 104 (1967).
C. M. Hansen, J. Paint Technol., 39, 505 (1967).
C. M. Hansen, J. Paint Technol., 39, 511 (1967).
G. Delmas and D. Patterson, Preprint, IUPAC, Toronto, 1968, I, Al, 22.
E. Matsui, Kogyo Kagaku Zasshi (J. Chem. Soc. Chem. Ind. Sect.), 45, 1094 (1942) (in Japanese).
L. C. Rubens, J. Appl. Polym. Sci., 9, 1473 (1965).
D. Hümmel and E. Lunebach, Spectrochim. Acta, 18, 823 (1962).
M. K. Seikel, Ind. Eng. Chem., Anal. Ed, 13, 388 (1941).
A. Weissberger, E. S. Proskaver, J. A. Riddick, and E. E. Toops, Jr., “Organic Solvents,” Interscience, New York, N. Y. 1955.
M. R. Lipkin, J. A. Davison, W. T. Harvey, and S. S. Kurtz, Jr., Ind. Eng. Chem., Anal. Ed, 16, 55 (1944).
J. P. Kratohvil, G. Dezelic, M. Kerker, and E. Matijevic, J. Polym. Sci., 57, 59 (1962).
P. A. Small, J. Appl. Chem., 3, 71 (1953).
“International Critical Tables,” MacGraw Hill, New York, N. Y.-London and see also ref 25.
P. J. Flory, “Principles of Polymer Chemistry,” Cornell Univ. Press, Ithaca, N.Y., 1953.
R. F. Blanks and J. M. Prausnitz, Ind. Eng. Chem. Fund., 3, 1 (1964).
J. K. Craver, J. Appl. Polym. Sci., 14, 1755 (1970).
C. J. Böttcher, “Theory of Electric Polarizazation,” Elsevier, N. Y., 1952 and see also ref. 19.
J. W. Breitenbach and E. L. Forster, Monatsch. Chem., 82, 443 (1951).
M. L. Huggins, J. Am. Chem. Soc., 64, 2712 (1942).
M. L. Huggins, Ind. Eng. Chem., 35, 980 (1943).
D. F. Mead and R. M. Fuoss, J. Am. Chem. Soc., 64, 277 (1942).
E. O. Kraemer, Ind. Eng. Chem., 30, 1200 (1938).
D. Patterson, Macromolecules, 2, 672 (1969).
I. Prigogine, “The Molecular Theory of Solutions,” North Holland Publ. Co., Amsterdam, 1957.
P. J. Flory, J. L. Ellenson, and B. E. Eichinger, Macromolecules, 1, 279 (1968).
B. E. Eichinger and P. J. Flory, Trans. Faraday Soc., 64, 2035 (1968).
B. E. Eichinger and P. J. Flory, Trans. Faraday Soc., 64, 2053 (1968).
B. E. Eichinger and P. J. Flory, Trans. Faraday Soc., 64, 2061 (1968).
B. E. Eichinger and P. J. Flory, Trans. Faraday Soc., 64, 2066 (1968).
D. Patterson and G. Delmas, Trans. Faraday Soc., 65, 708 (1969).
D. Patterson, G. Delmas, and T. Somcynsky, Polymer, 8, 503 (1968).
J. Biroš, L. Zeman, and D. Patterson, Macromolecules, 4, 30 (1971).
J. H. Hildebrand, J. M. Prausnitz, and R. L. Scott, “Regular and Related Solutions,” Van Nostrand Reinhold Co., New York, N. Y., 1970.
A. R. Shultz and P. J. Flory, J. Am. Chem. Soc., 75, 3888 (1953).
S. Newman, W. R. Krigbaum, C. Laugier, and P. J. Flory, J. Polym. Sci., 14, 451 (1954).
H. C. Brown, et al., J. Am. Chem. Soc., 75, 1 (1953).
H. Cramér, “Mathematical Methods of Statistics,” Princeton University Press, Overseas Publishers Ltd., Tokyo, 1966.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Izumi, Y., Miyake, Y. Study of Linear Poly(p-chlorostyrene)–Diluent Systems. I. Solubilities, Phase Relationships, and Thermodynamic Interactions. Polym J 3, 647–662 (1972). https://doi.org/10.1295/polymj.3.647
Issue Date:
DOI: https://doi.org/10.1295/polymj.3.647