Abstract
An attempt was made to establish a theoretical method for calculating the cloud point curve (CPC) and critical point of solutions of polydisperse polymers in a single solvent (i.e., quasi-binary system) on the basis of the polydispersity of the polymer and concentration- and molecular weight-dependences of the polymer–solvent thermodynamic interaction parameter χ. Expressions giving the cloud point curve were derived and a computer simulation technique, based on the theory, was developed. The effects of the average molecular weight, polydispersity of polymer and concentration dependence of χ-parameter on CPC, threshold cloud point and critical point were clarified. In order to represent accurately the CPC for the entire concentration range from the molecular characteristics of the original polymer and operating conditions, such as polymer–volume fraction and χ-parameter, the concentration dependence parameters p1 and p2, in the relation χ=χ0(1+p1vp+P2νp2) (χ0; concentration-independent parameter, vp, polymer volume fraction) should be adequately taken into account. Very delicate changes in p1 and p2 cause significant variation in CPC and none of the literature data on p1 and p2 for polystyrene/ cyclohexane adequately represent the experimental CPC. From an actual CPC experiment, p1=0.643 and p2=0.200 were evaluated. The effective role of the molecular weight dependence of χ in CPC was shown in the lower vp region.
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J. N. Bronsted and K. Volquartz, Trans. Faraday Soc., 35, 576 (1939).
R. B. Richards, Trans. Faraday Soc., 42, 10 (1946).
R. B. Richards, Trans. Faraday Soc., 42, 20 (1946).
A. R. Shultz and P. J. Flory, J. Am. Chem. Soc., 74, 4760 (1952).
K. Kamide and K. Sugamiya, Makromol. Chem., 139, 197 (1970).
K. Kamide and K. Sugamiya, Makromol. Chem., 156, 259 (1972).
K. Kamide, Y. Miyazaki, and K. Yamaguchi, Makromol. Chem., 173, 157 (1973).
K. Kamide, Y. Miyazaki, and K. Yamaguchi, Makromol. Chem., 173, 175 (1973).
K. Kamide and Y. Miyazaki, Makromol. Chem., 176, 1447 (1975).
K. Kamide, Y. Miyazaki and T. Abe, Makromol. Chem., 177, 485 (1976).
K. Kamide, Y. Miyazaki, and T. Abe, Polym. J., 9, 395 (1977).
K. Kamide and Y. Miyazaki, Polym. J., 13, 325 (1981).
K. Kamide, T. Abe, and Y. Miyazaki, Polym. J., 14, 355 (1982).
G. Rehage, D. Moller, and O. Ernst, Makromol. Chem., 38, 232 (1965).
N. Kuwahara, M. Nakata, and M. Kaneko, Polymer, 14, 415 (1973).
R. Koningsveld and A. J. Staverman, Kolloid Z. Z. Polym., 218, 114 (1967).
R. Koningsveld and A. J. Staverman, J. Polym. Sci., A-2, 6, 305 (1968).
R. Koningsveld and A. J. Staverman, J. Polym. Sci., A-2, 6, 349 (1968).
M. Gordon, H. A. G. Chermin, and R. Koningsveld, Macromolecules, 2, 107 (1969).
R. Koningsveld, W. H. Stockmayer, J. W. Kennedy, and L. A. Kleintjens, Macromolecules, 7, 73 (1974).
K. Kamide, T. Ogawa, and M. Matsumoto, Kobunshi Kagaku, 25, 788 (1968).
K. Kamide, T. Ogawa, M. Sanada, and M. Matsumoto, Kobunshi Kagaku, 25, 440 (1968).
R. Koningsveld and A. J. Staverman, J. Polym. Sci., A-2, 6, 325 (1968).
R. Koningsveld and L. A. Kleintjens, Macromolecules, 4, 637 (1971).
See, for example, M. Kurata, “Thermodynamics of Polymer Solution,” Harwood Academic Pubs., Chur, London, New York, 1982, Chapter 2.
W. H. Stockmayer, J. Chem. Phys., 17, 588 (1949).
K. Kamide, K. Sugamiya, T. Ogawa, C. Nakayama, and N. Baba, Makromol. Chem., 135, 23 (1970).
T. Dobashi, M. Nakata, and M. Kaneko, J. Chem. Phys., 72, 6685 (1970).
S. Saeki, N. Kuwahara, S. Konno, and M. Kaneko, Macromolecules, 6, 246 (1973).
K. Kamide, S. Matsuda, and Y. Miyazaki, Polym. J., 16, 479 (1984).
K. Kamide and S. Matsuda, Polym. J., 16, 515 (1984).
K. Kamide and S. Matsuda, Polym. J., 16, 591 (1984).
W. R. Krigbaum and D. Q. Geymer, J. Am. Chem. Soc., 81, 1859 (1959).
T. G. Scholte, J. Polym. Sci., A-2, 8, 841 (1970).
R. Koningsveld, L. A. Kleintjens, and A. R. Shultz, J. Polym. Sci., A-2, 8, 1261 (1970).
K. Kamide and S. Matsuda, Polym. J., 16, 807 (1984).
See, for example, P. J. Flory, “Principle of Polymer Chemistry,” Cornell Univ. Press, Ithaca, N.Y., 1953.
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Kamide, K., Matsuda, S., Dobashi, T. et al. Cloud Point Curve and Critical Point of Multicomponent Polymer/Single Solvent System. Polym J 16, 839–855 (1984). https://doi.org/10.1295/polymj.16.839
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DOI: https://doi.org/10.1295/polymj.16.839