Intrinsic Viscosity of Polystyrene in Toluene-Supercritical Carbon Dioxide Mixtures

Abstract

Intrinsic viscosities [η] were determined for five polystyrene samples ranging in molecular weight Mw from 9.0 × 104 to 1.2 × 106 in toluene-supercritical carbon dioxide mixtures with different weight fractions of CO2 (denoted as w(CO2)) at 40 °C in a pressure range P = 7.0–10.0 MPa using a rolling-ball viscometer. For every sample [η] was a gradually increasing function of P, indicating that the polystyrene coil expands with increasing P. At fixed P and w(CO2), the molecular weight dependence of [η] was expressed in the form [η] α Mwa. The exponent a remarkably changed with w(CO2) at constant P; for example, it decreased from 0.68 (a good solvent value) to 0.42 (a poor solvent value below the theta point where a = 0:5) with an increase in w(CO2) from 15 to 31% at P = 7.0 MPa. The solvent goodness was quantified in terms of the binarycluster integral determined by analyzing the [η] data according to the two-parameter theory.

References

  1. 1

    M. A. McHugh and T. L. Guckes, Macromolecules, 18, 674 (1985).

  2. 2

    A. A. Kiamos and M. D. Donohue, Macromolecules, 27, 357 (1994).

  3. 3

    S. N. Joung, J.-U. Park, S. Y. Kim, and K.-P. Yoo, J. Chem. Eng. Data, 47, 270 (2002).

  4. 4

    S. Kim, Y.-S. Kim, and S.-B. Lee, J. Supercrit. Fluids, 13, 99 (1998).

  5. 5

    K. Liu and E. Kiran, Polymer, 49, 1555 (2008).

  6. 6

    S.-D. Yeo and E. Kiran, Macromolecules, 32, 7325 (1999).

  7. 7

    S.-D. Yeo and E. Kiran, J. Appl. Polym. Sci., 75, 306 (2000).

  8. 8

    H. Yamakawa, “Modern Theory of Polymer Solutions”, Harper & Row, New York, 1971.

    Google Scholar 

  9. 9

    R. M. Hubbard and G. G. Brown, Ind. Eng. Chem., Anal. Ed., 15, 212 (1943).

  10. 10

    L. T. Carmichael and B. H. Sage, Ind. Eng. Chem., 44, 2728 (1952).

  11. 11

    K. Kubota and K. Ogino, Macromolecules, 12, 74 (1979).

  12. 12

    J. R. Schmidt and B. A. Wolf, Macromolecules, 15, 1192 (1982).

  13. 13

    S. Sawamura, N. Takeuchi, K. Kitamura, and Y. Taniguchi, Rev. Sci. Instrum., 61, 871 (1990).

  14. 14

    M. Lechner and G. V. Schulz, Eur. Polym. J., 6, 945 (1970).

  15. 15

    G. V. Schulz and M. Lechner, J. Polym. Sci., Part A-2, 8, 1885 (1970).

  16. 16

    D. Gaeckle and D. Patterson, Macromolecules, 5, 136 (1972).

  17. 17

    K. Kubota and K. Ogino, Polymer, 20, 175 (1979).

  18. 18

    J. F. Skinner, E. L. Cussler, and R. M. Fuoss, J. Phys. Chem., 72, 1057 (1968).

  19. 19

    D. Li, B. Han, Z. Liu, J. Liu, X. Zhang, S. Wang, X. Zhang, J. Wang, and B. Dong, Macromolecules, 34, 2195 (2001).

  20. 20

    Y. Einaga, Y. Miyaki, and H. Fujita, J. Polym. Sci., Polym. Phys. Ed., 17, 2103 (1979).

  21. 21

    F. Abe, Y. Einaga, and H. Yamakawa, Macromolecules, 26, 1891 (1993).

  22. 22

    A. J. Barrett, Macromolecules, 17, 1566 (1984).

  23. 23

    J. Shimada and H. Yamakawa, J. Polym. Sci., Polym. Phys. Ed., 16, 1927 (1978).

  24. 24

    Y. Miyaki, Y. Einaga, and H. Fujita, Macromolecules, 11, 1180 (1978).

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Correspondence to Yo Nakamura.

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Onishi, M., Nakamura, Y. & Norisuye, T. Intrinsic Viscosity of Polystyrene in Toluene-Supercritical Carbon Dioxide Mixtures. Polym J 41, 477–481 (2009). https://doi.org/10.1295/polymj.PJ2008319

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Keywords

  • Intrinsic Viscosity
  • High Pressure
  • Supercritical Liquid
  • Carbon Dioxide
  • Excluded-Volume Effect
  • Binary-Cluster Integral

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