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Synthesis of Fluoropolymers in Liquid and Supercritical Carbon Dioxide Solvent Systems

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Fluoropolymers 1: Synthesis

Part of the book series: Topics in Applied Chemistry ((TAPP))

Conclusions

Unlike a large portion of the many billions of pounds of organic and halogenated solvents used in industry every year, CO2 is inexpensive, of low toxicity, and environmentally and chemically benign. The prime factors inhibiting the widespread use of this attractive solvent replacement have been the disappointingly low solubility of most materials in CO2 in both liquid and supercritical states, and a less than complete understanding of its physical properties. Discoveries made over the past decade identifying the solubility of siloxanes and many amorphous fluoropolymers in CO2 have facilitated a greater understanding of the solvency properties of this uniquely “tunable” solvent. The subsequent development of amphiphilic surfactants incorporating lyophilic fluorocarbon or siloxane segments with lipophilic or hydrophilic moieties opens the door for the synthesis of a broad range of hydrocarbons. Carbon dioxide technology is of particular significance with respect to the manufacture of many fluoropolymers that require nonaqueous synthesis. Reduction of unwanted side reactions such as β-scission and opportunities for unique separation and purification processes demonstrate that CO2 is not only an adequate replacement for chlorofluorocarbons, but in many cases a superior one.

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References

  1. M. McHugh and V. J. Krukonis, Supercritical Fluid Extraction: Principles and Practice, Butterworths, Boston (1986).

    Google Scholar 

  2. K. D. Bartle, A. A. Clifford, S. A. Jafar, and G. E Shilstone, J. Phys. Chem. Ref. Data 20, 713–778 (1991).

    CAS  Google Scholar 

  3. K. P. Johnson and J. M. L. Penninger (eds), Supercritical Fluid Science and Technology, American Chemical Society, Washington D.C. (1989).

    Google Scholar 

  4. C. L. Phelphs, N. G. Smart, and C. M. Wai, J. Chem. Ed. 73, 1163–1168 (1996).

    Google Scholar 

  5. J. M. Prausnitz, R. N. Lichtenthaler, and E. G. deAzevedo, Thermodynamics of Fluid Phase Equilibria, Prentice-Hall, Englewood Cliffs, N.J. (1986).

    Google Scholar 

  6. C. S. Murthy, K. Singer, and I. R. McDonald, Mol. Phys. 44, 135 (1981).

    CAS  Google Scholar 

  7. F. Rindfleisch, T. P. DiNoia, and M. A. McHugh, J. Phys. Chem. 28, 15581 (1996).

    Google Scholar 

  8. M. A. McHugh, V. J. Krukonis, and J. A. Pratt, TRIP 2, 301–307 (1994).

    CAS  Google Scholar 

  9. G. Odian, Principles of Polymerization, 3rd Ed., John Wiley and Sons, New York (1993), pp. 303–306.

    Google Scholar 

  10. V. Vesovic, W. A. Wakeham, G. A. Olchowy, J. V. Sangers, J. T. R. Watson, and J. Millat, J. Phys. Chem. Ref. Data 19, 763 (1990).

    CAS  Google Scholar 

  11. J. A. Hyatt, J. Org. Chem. 49, 5097 (1984).

    CAS  Google Scholar 

  12. M. McHugh and V. J. Krukonis, Supercritical Fluid Extraction: Principles and Practice, Butterworths, Boston (1986), Ch. 9.

    Google Scholar 

  13. Z. Guan, Homogeneous free radical polymerization in supercritical carbon dioxide, University of North Carolina, Dissertation, Ch. 2.

    Google Scholar 

  14. J. M. DeSimone, Z. Guan, and C. S. Eisbernd, Science 257, 945 (1992).

    CAS  Google Scholar 

  15. P. W. Moore, F. W. Ayscough, and J. G. Clouston, J. Polym. Sci: Polym. Chem. Ed. 15, 1291 (1977).

    Article  CAS  Google Scholar 

  16. Z. Guan, J. R. Combes, Y. Z. Menceloglu, and J. M. DeSimone, Macromolecules 26, 2663 (1993).

    CAS  Google Scholar 

  17. J. P. DeYoung, J. Kalda, and J. M. DeSimone, Decomposition kinetics of perfluoroalkyl acyl peroxides in liquid and supercritical carbon dioxide, in preparation.

    Google Scholar 

  18. K. E. O’Shea, J. R. Combes, M. A. Fox, and K. P. Johnson, Photochem. Photobiol. 54, 571 (1991).

    CAS  Google Scholar 

  19. J. M. DeSimone, and K. A. Shaffer, Trends Polym. Sci. 3, 146 (1995).

    Google Scholar 

  20. J. B. McClain, D. E. Belts, D. A. Canalas, E. T. Samulski, J. M. DeSimone, J. D. Londono, H. D. Cochran, G. D. Wignall, D. Chillura-Martino, and R. Trillo, Science 274, 2049 (1996).

    Article  CAS  Google Scholar 

  21. Y. Hsiao, E. E. Maury, J. M. DeSimone, S. Mawson, and K. P Johnson, Macromolecules 28, 8159 (1995).

    CAS  Google Scholar 

  22. J. M. DeSimone, E. E. Maury, Y. Z. Menceloglu, J. B. McClain, T. R. Romack and J. R. Combes, Science 265, 356–359 (1994).

    CAS  Google Scholar 

  23. A. E. Fiering, in Organofluorine Chemistry: Principles and Commercial Applications (R. E. Banks, B. E. Smart, and J. C. Tatlow, eds.), Plenum Press, New York (1994).

    Google Scholar 

  24. D. V. Avila, K. U. Ingold, J. Lusztyk, W. R. Dolbier, H. Q. Pan, and M. Muir, J. Am. Chem. Soc. 116, 99–104 (1994).

    Article  CAS  Google Scholar 

  25. A. E. Feiring, C. G. Krespan, P. R. Resnick, B. E. Smart, T. A. Treat, and R. C. Wheland, U.S. Patent 5182342 (1993).

    Google Scholar 

  26. C. G. Krespan and R. C. Wheland, U.S. Patent 5,286,822 (1994).

    Google Scholar 

  27. A. Funaki, K. Kato, and T. Takakura, Jpn. Patent 06,157,675 (1994).

    Google Scholar 

  28. D. J. Van Bramer, M. B. Shiflett, and A. Yokozeki, U.S. Patent 5,345,013 (1994).

    Google Scholar 

  29. J. R. Combes, Z. Guan, and J. M. DeSimone, Macromolecules 27, 865 (1994).

    Article  CAS  Google Scholar 

  30. T. J. Romack, J. R. Combes, and J. M. DeSimone, Macromolecules 28, 1724 (1995).

    CAS  Google Scholar 

  31. T. J. Romack and J. M. DeSimone, Macromolecules 28, 8429 (1995).

    CAS  Google Scholar 

  32. J. P. DeYoung, T. J. Romack, and J. M. DeSimone, Polym. Preprints 38(2), 424, (1997).

    CAS  Google Scholar 

  33. M. A. Harmer, W. E. Farneth, and Q. Sun, J. Am. Chem. Soc. 118(33), 7708 (1996).

    Article  CAS  Google Scholar 

  34. G. A. Olah, P. S. Iyer, and S. Prakash, Synthesis 1986, 513.

    Google Scholar 

  35. M. F. Vincent, S. G. Kazarian, and C. A. Eckert, AiChE J. 43(7), 1838 (1997).

    Article  CAS  Google Scholar 

  36. C. A. Mertdogan, T. P. DiNoia, and M. A. McHugh, Macromolecules 30, 7511 (1997).

    Article  CAS  Google Scholar 

  37. J. P. DeYoung, B. E. Kipp, and J. M. DiSimone, Solid acid catalysis using Nafion® in supercritical carbon dioxide: A quantitative kinetics study of α-methyl styrene dimerization, unpublished results.

    Google Scholar 

  38. K. P. Johnson, P. D. Condo, and D. R. Paul, Macromolecules 27, 365–371 (1994).

    Google Scholar 

  39. J. J. Watkins and T. J. McCarthy, Macromolecules 27, 4845–4847 (1994).

    Article  CAS  Google Scholar 

  40. T. J. Romack, Dissertation, University of North Carolina at Chapel Hill (1996).

    Google Scholar 

  41. R. E. Banks, B. E. Smart, and J. C. Tatlow, in Organofluorine Chemistry: Principles and Commercial Applications (R. E. Banks, B. E. Smart, and J. C. Tatlow, eds), Plenum Press, New York (1994).

    Google Scholar 

  42. G. Marchionni and P. Srinivasan, Proceedings of Fluoropolymer Conference (1992).

    Google Scholar 

  43. J. M. DeSimone, E. E. Maury, J. R. Combes, and Y. Z. Menceloglu, US. Patent 5,382,623 (1995).

    Google Scholar 

  44. W. C. Bunyard, T. J. Romack, and J. M. DeSimone, Polym. Preprints 38(2), 424, (1997).

    Google Scholar 

  45. T. J. Romack, B. E. Kipp, and J. M. DeSimone, Macromolecules 28, 8432 (1995).

    CAS  Google Scholar 

  46. D. J. Van Bramer, M. B. Shiflett, and A. Yokozeki, U.S. Patent 5,345,013, (1994).

    Google Scholar 

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Author information

Authors and Affiliations

  1. MICELL Technologies Inc., Raleigh, North Carolina, 27613

    James P. DeYoung & Timothy J. Romack

  2. Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina, 27599-3290

    Joseph M. DeSimone

Authors
  1. James P. DeYoung
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  2. Timothy J. Romack
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  3. Joseph M. DeSimone
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Editor information

Editors and Affiliations

  1. IBM T. J. Watson Research Center, Yorktown Heights, New York

    Gareth Hougham

  2. Southwest Texas State University, San Marcos, Texas

    Patrick E. Cassidy

  3. Chemical and Polymer, Windlesham, Surrey, England

    Ken Johns

  4. Princeton, New Jersey

    Theodore Davidson

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© 2002 Kluwer Academic Publishers

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DeYoung, J.P., Romack, T.J., DeSimone, J.M. (2002). Synthesis of Fluoropolymers in Liquid and Supercritical Carbon Dioxide Solvent Systems. In: Hougham, G., Cassidy, P.E., Johns, K., Davidson, T. (eds) Fluoropolymers 1: Synthesis. Topics in Applied Chemistry. Springer, Boston, MA. https://doi.org/10.1007/0-306-46918-9_13

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  • DOI: https://doi.org/10.1007/0-306-46918-9_13

  • Publisher Name: Springer, Boston, MA

  • Print ISBN: 978-0-306-46060-9

  • Online ISBN: 978-0-306-46918-3

  • eBook Packages: Springer Book Archive

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