Phase Transitions in Polymer Blends and Block Copolymers Induced by Selective Dilation with Supercritical CO2

  • J. J. Watkins
  • G. D. Brown
  • M. A. Pollard
  • V. S. Ramachandrarao
  • T. P. Russell
Part of the NATO Science Series book series (NSSE, volume 366)


Supercritical fluids (SCFs) offer a number of advantages for the synthesis and processing of polymeric materials. Early work in the field focused on the high-pressure polymerization of ethylene or exploited the adjustable physicochemical properties of SCFs, including density and dielectric constant, for the fractioeation, extraction and impregnation of polymers.1 Recently, the field has expanded to include polymer synthesis and modification by reactive processing in the presence of CO2. With few exceptions these are heterogeneous processes that are facilitated by enhanced transport within the SCF-swollen polymer and are sensitive to the partitioning of solutes between the fluid and polymer phases. Examples include heterogeneous dispersion polymerizations in CO2 2, condensation reactions in dilated melts3, and the preparation of composite materials by conducting chemical reactions directly within solid polymers swollen by CO2 4.


Block Copolymer Supercritical Fluid Lower Critical Solution Temperature Diblock Copolymer Vinyl Methyl Ether 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


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  1. 1.
    McHugh, M. A.; Krukonis, V. J. (1986) Supercritical Fluid Extraction: Principles and Practice; Butterworths: Boston.Google Scholar
  2. 2.
    DeSimone, J. M; Maury, E.E.; Menceloglu, Y.Z.; McClain, J.B.; Romack, T.J.; Combes, J.R. (1994) Dispersion Polymerizations in Supercritical Carbon Dioxide, Science 265, 356–359.CrossRefGoogle Scholar
  3. 3.
    Gross, S. M; Givens, R. D.; Jikei, M.; Royer, J. R.; Khan, S.; DeSimine, J. M.; Odell, P. G.; Hamer, G. K. (1998) Synthesis and Swelling of Poly(bisphenol A carbonate) Using Supercritical CO2; Macromolecules, 31, 9090–9092.CrossRefGoogle Scholar
  4. 4.
    Watkins, J. J. and McCarthy, T. J. (1995) Polymerization of Styrene in Supercritical CO2-Swoffen Poly(Chlorotrifluoroethylene), Macromolecules, 28, 4067–4074. Watkins, J. J. and McCarthy, T. J. (1995) Polymer/Metal Nanocomposite Synthesis in Supercritical CO2, Chem. Mater., 7, 1991–1994.CrossRefGoogle Scholar
  5. 5.
    Kiszka, M. B.; Meilchen, M. A,; McHugh, M. A. (I988) Modeling High-Pressure Gas-Polymer Mixtures Using the Sanchez-Lacombe Equation of State, J. Appl. Polym. Sci. 36, 583–587.Google Scholar
  6. 6.
    Garg, A.; Gulari, E.; Manke, C. W. (1994) Thermodynamics of Polymer Melts Swollen with Supercritical Fluids, Macromolecules 27, 5643–5653.CrossRefGoogle Scholar
  7. 7.
    Coedo, P. D.; Johnston, K. P. (1994) In Situ Measurement of the Glass Transition Temperature of Polymers with Compressed Fluid Diluents, J Polym. Sci Polym. Phys. 32, 523–533.CrossRefGoogle Scholar
  8. 8.
    Lecture presented at the NATO ASI on Supercritcal Fluids, Kemer, Turkey, 1998Google Scholar
  9. 9.
    Chapman, B. R.; Gochanour, C. R.; Paulaitis, M. E. (1996) CO2 -Enhanced Diffusion of Azobenzene in Glassy Polystyrene near the Glass Transition, Macromolecules, 29, 5635–5649.CrossRefGoogle Scholar
  10. 10.
    Berens, A. R.; Huvard, G. S.; Korsmeyer, R. W.; Kunig, F. W. (1992) Application of Compressed Carbon Dioxide in the Incorporation of Additives into Polymers, J. Appl. Polym. Sci. 46, 231.CrossRefGoogle Scholar
  11. 11.
    Watkins, J. J.; Brown. G. D.; RamachandraRao, V. S.; Pollard, M. A. Russell (1999)Phase Separation in Multi-Component Polymer Systems Induced by Compressible Solvents, submitted to Macromolecules. Google Scholar
  12. 12.
    Flory, P. J. (1970) Thermodynamics of Polymer Solutions, Discuss. Faraday. Soc., 49, 7–29.CrossRefGoogle Scholar
  13. 13.
    De Gennes, P.-G. (1979) Scaling Concepts in Polymer Physics; Cornell University Press: Ithaca, NY.Google Scholar
  14. 14.
    Sanchez, I. C. (1987) Polymer Phase Separation, in Encyclopedia of Physical Science and Technology; Academic Press: New York, Vol. XI 1–18.Google Scholar
  15. 15.
    Russell, T. P.; Karls, T. E.; Gallot, Y.; Mayes, A. M. (1994) A Lower Critical Ordering Transition in a Diblock Copolymer Melt, Nature 368, 729–731.CrossRefGoogle Scholar
  16. 16.
    Balsara, N. P.; Perahia, D.; Safinya, C. R.; Tirrell, M.; Lodge, T. P. (1992) Birefringence Detection of the Order-to-Disorder Transition in Block Copolymer Liquids, Macromolecules 25, 3896–3901.CrossRefGoogle Scholar
  17. 17.
    Lodge, T.P.; Pan, C.; Jin, X.; Liu, Z.; Zhao, J.; Maurer, W. W.; Bates, F. S. (1995) Failure of the Dilution Approximation in Block Copolymer Solutions, J. Polym. Sci, Polym. Phys. 33, 2289–2293.CrossRefGoogle Scholar
  18. 18.
    Tanaka, H.; Hashimoto, T. (1991) Thermal Concentration Fluctuations of Block Polymer/Homopolymer Mixtures in the Disordered State. 1.Binary Mixtures of SI/HS, Macromolecules 24, 5398–5407.CrossRefGoogle Scholar
  19. 18.
    Tanaka, H.; Hashimoto, T. (1991) Thermal Concentration Fluctuations of Block Polymer/Homopolymer Mixtures in the Disordered State. 1.Binary Mixtures of SI/HS, Macromolecules 24, 5398–5407.CrossRefGoogle Scholar
  20. 20.
    Janssen, S.; Schwahn, D.; Mortensen, K.; Springer, T. (1993) Pressure Dependence of the Flory-Huggins Interaction Parameter in Polymer Blends: A SANS study and a comparison to theFIory-Orwoll-Vrij Equation of State, Macromolecules, 26, 5587–5591.CrossRefGoogle Scholar
  21. 21.
    Hammouda, B.; Bauer, B. J. (1995) Compressibility of Two Polymer Blend MixturcsMocromolecules 28, 4505–4508.CrossRefGoogle Scholar
  22. 22.
    Hajduk, D. A.; Grüner, S. M.; Erramilli, S.; Register, R. A.; Fetters, L. J. (1996) High-Pressure Effects on the Order-Disorder Transition in Block Copolymer Melts, Macromolecules, 29, 1473–1481.CrossRefGoogle Scholar
  23. 23.
    Schwahn, D; Frielinghaus, H.; Mortensen, K.; Aimdal, K. (1996) Temperature and Pressure Dependence of the Order Parameter Fluctuations, Conformationsl Compressibility, and the Phase Diagram of the PEP-PDMS DIblock Copolymer, Phys. Rev. Lett. 77, 3153–3156.CrossRefGoogle Scholar
  24. 24.
    Steinhoff, B.; Rulimann, M.; Wenzel, M.; Junker, M.; Alig, I.; Oser, R.; Stuhn, B.; Meier, G.; Dial, O.; Bosecke, P.; Stanley, H. B. (1998) Pressure Dependence of the Ordcr-to-Disorder Transition in Polystyrene/Poly isoprene and Polystyrerte/Poly(methylphenyisiloxane) Diblock Copolymers, Macromolecules, 31, 36–40.CrossRefGoogle Scholar
  25. 25.
    An, L.; Horst, R.; Wolf, B. A.; (1997) Pressure Dependence of the Miscibility of Poly(vinyl methyl ether) and Polystyrene: Theoretical Representation, J. Chem. Phys., 107, 2597–2602.CrossRefGoogle Scholar
  26. 26.
    McHugh, M. A.; Guckes, T. L. (I985) Separating Polymer Solutions with Supercritical Fluids, Macromolecules, 18, 674–680.Google Scholar
  27. 27.
    McClellan, A. K.; Bauman, E. G.; McHugh, M. A. (1985) Polymer Solution-Supercritical Fluid Phase Behavior in Supercritical Fluid Technology, Penninger, J. M. L.; Radosz, M.; McHugh, M. A.; Krukonis, V. J. eds.; Elsevier Science Publishers B. V., Amsterdam, Netherlands.Google Scholar
  28. 28.
    Kiran, E.; Xiong, Y,; Zhuang, W. (1993) Modelling Polyethylene Solutions In Near and Supercritical Fly id Solutions Using the Sanchez-Lacombe Model, J. Supercrit. Fluids, 6, 193–203.CrossRefGoogle Scholar
  29. 29.
    McHugh, M. A.; Krukonis, V. J. (1989) Supercritical Fluids, in Encyclopedia of Polymer Science and Engineering; Mark, H. F.; Bikales, N. M.; Overberger, C. G.; Menges, G. eds.; John Wiley & Sons: New York, vol. 16.Google Scholar
  30. 30.
    Masson, J. C. (1989) in Polymer Handbook, 3rd. ed; Brandrup, J.; Immergut, E. H. Eds.; John Wiley and Sons: New York, p. II/1.Google Scholar
  31. 31.
    Wang, N.-H.; Takishima, S.; Masyoka, H. (1994) Measurement and Correlation of Solubility of a High Pressure Gas in a Polymer by Piezoelectric Quartz Sorption — CO2 + PVAC and CO2 + PBME Systems, Int. Chemical Eng., 34, 255–262.Google Scholar
  32. 32.
    Wissinger, R. G.; Paulaitis, M. E. (1987) Swelling and Sorption in Poiymer-CO2 Mixtures at Elevated Pressures, J. Polym. Sci. Polym. Phys., 25, 2497–2510.CrossRefGoogle Scholar
  33. 33.
    Mokdad, A.; Dubault, A.; Monnerie, L. (I996) Sorption and Diffusion of Carbon Dioxide in Single-Phase PoIystyrene/Poly(vinyimethylether) Blends, J. Polym. Sci. Polym. Phys., 34, 2723–2730.Google Scholar
  34. 34.
    Robard, A.; Patterson, D. (1977) Temperature Dependence of Polystyrene -PoJy(vinyl methyl ether) Compatibility in Trichloroethene, Macromolecules, 10, 1021–1025.CrossRefGoogle Scholar
  35. 35.
    Lodge, T. P.; Hamersky, M. W.; Hanfey, K. J.; Huang, C.-I (1997) Solvent Distribution in Weaklyordered Block Copoiymer Solutions, Macromolecules, 30, 6139–6149.CrossRefGoogle Scholar
  36. 36.
    Ruzette, A.-V. G.; Banerjee, P.; Mayes, A. M.; Pollard, M.; Russell, T.P.; Jerome, R.; Slawecki, T.; Hjelm, R.; Thiyagarajan, P. (1998) Phase Behavior of Diblock Copolymers between Styrene and n-Alkyl Methacrylates Macromolecules, 31, 8509–8516.CrossRefGoogle Scholar
  37. 37.
    Sanchez, I. C.; Lacombe, R. H. (1978) Statistical Mechanics of Polymer Solutions, Macromolecules 11, 1145–1156.CrossRefGoogle Scholar
  38. 38.
    Sanchez, I. C; Balasz, A. C. (1989) Generalization of the Lattice-Fluid Model for Specific Interactions, Macromolecules, 22, 2325–2331.CrossRefGoogle Scholar
  39. 39.
    Sanchez, I. C.; Lacombe, R. H. (1977) An Elementaiy Equation of State for Polymer Liquids, J. Polym. Sci. Polym. Lett. 15, 71–75.CrossRefGoogle Scholar
  40. 40.
    Haiary, J. L.; Ubrich, J. M.; Nunzi, J. M.; Monnerie, L.; Stein, R. S. (1984) Phase Separation in Polystyrene-Poly(vinylmethylether) Blends: A Fluorescence Emission Analysis, Polymer, 25, 956–962.CrossRefGoogle Scholar
  41. 41.
    Vogt, B.D.; Brown, G. D.; RamachandraRao, V. S.; Watkins, J. J. (1999) submitted to Macromolecules. Google Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2000

Authors and Affiliations

  • J. J. Watkins
    • 1
  • G. D. Brown
    • 1
  • M. A. Pollard
    • 2
  • V. S. Ramachandrarao
    • 1
  • T. P. Russell
    • 2
  1. 1.Departments of Chemical Engineering and Polymer Science and EngineeringUniversity of MassachusettsAmherstUSA
  2. 2.University of MassachusettsAmherstUSA

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