Applicability of the Extended Flory-Huggins Equation for Molecular Weight Dependence of Liquid-liquid Equilibria in Binary Polymer Solutions

Young Chan Bae

Journal of Industrial and Engineering Chemistry, Vol.1, No.1, 18-27, December, 1995

Young Chan Bae

Dept. of Industrial Chem., Hanyang University, Seoul 133-791, Korea

A modified version of the extended Flory-Huggins equation is applicable to represent the chain-length dependence of liquid-liquid equilibria (LLE) for some binary polymer solutions, using the same universal parameters. Experimental results for polystyrene (PS)/tert-butyl acetate system agree well with the modified version of the extended Flory-Huggins equation. But those for poly(ethylene glycol) (PEG)/water system do not, probably because PEG/water system has a strong oriented interaction between polymer and solvent molecules. The extended Flory-Huggings equation ensures that excellent fits are obtained for PS/tert-butyl acetate (both lower critical solution temperature (LCST) and upper critical solution temperature (UCST)) and PEG/water (closed-loop).

[References]

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Madden WG, Pesci AI, Freed KF, Macromolecules, 23, 1181 (1990)
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[Related Articles]

[1] Flory PJ, "Principles of Polymer Chemistry," Cornell University Press, Ithaca, NY (1953)

[2] Freed KF, J. Phys. A: Mach. Gen., 18, 871 (1985)

[3] Bawendi MG, Freed KF, Mohanty U, J. Chem. Phys., 87, 5534 (1987)

[4] Bawendi MG, Freed KF, J. Chem. Phys., 88, 2741 (1988)

[5] Madden WG, Pesci AI, Freed KF, Macromolecules, 23, 1181 (1990)

[6] Madden WG, Dudowicz J, Freed KF, Macromolecules, 23, 4803 (1990)

[7] Dickman R, Hall C, J. Chem. Phys., 85, 4108 (1988)

[8] Hu Y, Liu H, Soane DS, Prausnitz JM, Fluid Phase Equilib., 67, 65 (1991)

[9] Hu Y, Lambert SM, Soane DS, Prausnitz JM, Macromolecules, 24, 4386 (1991)

[10] Flory PJ, J. Chem. Phys., 10, 51 (1942)

[11] Huggins ML, J. Phys. Chem., 46, 151 (1942)

[12] Eichinger BE, Flory PJ, Trans. Faraday Soc., 64, 2035 (1968)

[13] Flory PJ, Orwoll RA, Vrij A, J. Am. Chem. Soc., 86, 3515 (1964)

[14] Flory PJ, J. Am. Chem. Soc., 87, 1833 (1965)

[15] Flory PJ, Discuss. Faraday Soc., 49, 7 (1970)

[16] Patterson D, Macromolecules, 2, 672 (1969)

[17] Patterson D, Delmas G, Discuss. Faraday Soc., 49, 98 (1970)

[18] Sanchez IC, Lacombe RH, J. Phys. Chem., 21, 2352 (1976)

[19] Sanchez IC, Lacombe RH, J. Phys. Chem., 21, 2568 (1976)

[20] Sanchez IC, Lacombe RH, Macromolecules, 11, 1145 (1978)

[21] Kleintjens LA, Koningsveld R, Colloid Polym. Sci., 258, 711 (1980)

[22] Kleintjens LA, Koningsveld R, Sep. Sci. Technol., 17, 215 (1982)

[23] Sanchez IC, Balazs AC, Macromolecules, 22, 2325 (1989)

[24] Panayiotou C, Sanchez IC, Macromolecules, 24, 6231 (1991)

[25] Qian C, Mumby SJ, Eichinger BE, Macromolecules, 24, 1655 (1991)

[26] Qian C, Mumby SJ, Eichinger BE, J. Polym. Sci. B: Polym. Phys., 29, 635 (1991)

[27] Bae YC, Shim JJ, Soane DS, Prausnitz JM, J. Appl. Polym. Sci., 47, 1193 (1993)

[28] Bae YC, Lambert SM, Soane DS, Prausnitz JM, Macromolecules, 24, 4403 (1991)

[29] Koningsveld R, Starverman AJ, J. Polym. Sci. A: Polym. Chem., 6, 305 (1968)

[30] Koningsveld R, Starverman AJ, J. Polym. Sci. A: Polym. Chem., 6, 325 (1968)

[31] Koningsveld R, Starverman AJ, J. Polym. Sci. A: Polym. Chem., 6, 349 (1968)

[32] Koningsveld R, Kleintjens LA, Shultz AR, J. Polym. Sci. A: Polym. Chem., 8, 1261 (1970)

[33] Koningsveld R, Kleintjens LA, Macromolecules, 4, 637 (1971)

[34] Siow KS, Delmas G, Patterson D, Macromolecules, 5, 29 (1972)

[35] Orwoll RJ, Rubber Chem. Technol., 50, 452 (1977)

[36] Barton AFM, "Handbook of Solubility Parameters and Other Cohesion Parameters," CRC Press, Baton, FL (1983)