Stereochemical Aspects of the Cationic Polymerization of Chiral Alkyl Vinyl Ethers

  • Emo Chiellini
  • Roberto Solaro
  • Francesco Masi
Part of the Polymer Science and Technology book series (POLS, volume 19)

Synopsis

A survey of the stereochemical aspects relevant to the cationic polymerization of chiral alkyl vinyl ethers has been presented. Accordingly the routes to the preparation of optically active poly(alkyl vinyl ether)s by starting both from optically active monomers and racemic ones have been presented. In particular, to approach the mechanistic aspects of the stereospecific heterogeneous catalytic systems based on alkyl or alkoxy aluminum and sulphuric acid, the activity of soluble organoaluminum sulphates has been investigated. The kinetic trend of the polymerization of some optically active vinyl ethers has been determined simply by optical rotation measurements. On the basis of the presented data a coordinate polymerization mechanism has been proposed for the multicomponent catalyst introduced by Vandenberg.

Keywords

Toluene Hydrocarbon Fractionation Vinyl Macromolecule 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    G. Natta, J. Polymer Sci., 16:143(1955); G. Natta, P. Pino, F. Danusso, E. Mantica, G. Mazzanti, and G. Moraglio, J. Am. Chem. Soc., 77: 1708 (1955).CrossRefGoogle Scholar
  2. 2.
    C.E. Schildknecht, A.O. Zoss, and C. McKinley, Ind. Eng. Chem., 39: 180 (1947).CrossRefGoogle Scholar
  3. 3.
    A.D. Ketley, “The Stereochemistry of Macromolecules”, A.D. Ketley Ed., M. Dekker Inc., New York, N.Y., 1967, vol. 2, p. 37.Google Scholar
  4. 4.
    R.F. Heck, (Hercules Incorporated), U.S. Pat. 3,014,013, Dec. 1961; Chem. Abstr., 57: 1080e (1962).Google Scholar
  5. 5.
    R. Chiang, (Hercules Incorporated) U.S. Pat. 3,025,281, March 1962; Chem. Abstr., 57: 4884h (1962).Google Scholar
  6. 6.
    D.L. Christman and E.J. Vandenberg, (Hercules Incorporated), U.S. Pat. 3,025,282, March 1962; Chem. Abstr., 57: 2415d (1962).Google Scholar
  7. 7.
    R.F. Heck, (Hercules Incorporated), U.S. Pat. 3,098,061, July 1963; Chem. Abstr., 59: 10314b (1963).Google Scholar
  8. 8.
    R.F. Heck and E.J. Vandenberg, (Hercules Incorporated), U.S. Pat. 3,025,283, March 1962; Chem. Abstr., 57: 20415f (1962).Google Scholar
  9. 9.
    P. Pino, G.P. Lorenzi, and E. Previtera, Rend. Acc. Naz. Lincei, 29: 562 (1960).Google Scholar
  10. 10.
    P. Pino, G.P. Lorenzi, and E. Chiellini, Ric. Sci., 7: 193 (1964)Google Scholar
  11. 11.
    G.P. Lorenzi, E. Benedetti, and E. Chiellini, Chim. Ind. (Milan), 46: 1474 (1964).Google Scholar
  12. 12.
    P. Pino, G.P. Lorenzi, and E. Chiellini, J. Polymer Sci., C, 16: 3279 (1968).Google Scholar
  13. 13.
    P. Pino, Adv. Polymer Sai., 4: 393 (1965).CrossRefGoogle Scholar
  14. 14.
    P. Pino, P. Salvadori, E. Chiellini, and P.L. Luisi, Pure Appi. Chem., 16: 469 (1968).CrossRefGoogle Scholar
  15. 15.
    P. Pino, F. Ciardelli, and M. Zandomeneghi, Ann. Rev. Phys. Chem., 21: 561 (1970).CrossRefGoogle Scholar
  16. 16.
    P. Pino, P. Salvadori, G.P. Lorenzi, E. Chiellini, L. Lardicci, G. Consiglio, O. Bonsignori, and L. Lepri, Chim. Ind. (Milan), 55: 182 (1973).Google Scholar
  17. 17.
    F. Ciardelli, E. Chiellini, and C. Carlini, in “Charged and Reactive Polymers”, E. Selegny Ed., D. Reidei Publisher, Dordrecht Holland, 1979, vol. 5, p. 83.Google Scholar
  18. 18.
    A.M. Liquori and B. Pispisa, Chim. Ind. (Milan), 48: 1045 (1966).Google Scholar
  19. 19.
    A. Ledwith, E. Chiellini, and R. Solaro, Macromolecules, 12: 240 (1979).CrossRefGoogle Scholar
  20. 20.
    E. Chiellini, Macromolecules, 3: 527 (1970).CrossRefGoogle Scholar
  21. 21.
    E. Chiellini, G. Montagnoli, and P. Pino, J. Polymer Sci., B, 7: 121 (1969).CrossRefGoogle Scholar
  22. 22.
    P. Pino, A. Oschwald, F. Ciardelli, C. Carlini, and E. Chiellini, in “Coordination Polymerization”, J.W. Chien Ed., Acad. Press, New YorK, N.Y., 1975, p. 25.Google Scholar
  23. 23.
    E. Zucchi, Thesis, University of Pisa, 1971.Google Scholar
  24. 24.
    T. Higashimura and Y. Hirokawa, J. Polymer Sci., Polymer Chem. Ed., 15: 1137 (1977).CrossRefGoogle Scholar
  25. 25.
    F. Ciardelli, E. Benedetti, G. Montagnoli, L. Lucarini, and P. Pino, Chem. Comm., 285 (1965).Google Scholar
  26. 26.
    C. Carlini, F. Ciardelli, and P. Pino, Makromol. Chem., 119: 244 (1968).CrossRefGoogle Scholar
  27. 27.
    H. Yuki, K. Ohta, and N. Yajima, Polymer J., 1: 164 (1970).CrossRefGoogle Scholar
  28. 28.
    R. Solaro and E. Chiellini, Gazz. Chim. Ital., 106: 1037 (1976).Google Scholar
  29. 29.
    G. Natta, G. Allegra, I.W. Bassi, C. Carlini, E. Chiellini, and G. Montagnoli, Macromolecules, 2: 311 (1969).CrossRefGoogle Scholar
  30. 30.
    E. Chiellini and R. Solaro, unpublished results.Google Scholar
  31. 31.
    H. Yuki, K. Ohta, Y.Okamoto, and K. Hatada, J. Polymer Sci., Polymer Lett. Ed., 15: 589 (1977).CrossRefGoogle Scholar
  32. 32.
    K. Ohta, K. Hatada, Y. Okamoto, and H. Yuki, J. Polymer Sci., Polymer Lett. Ed., 16: 545 (1978).CrossRefGoogle Scholar
  33. 33.
    Y. Okamoto, K. Suzuki, K. Ohta, K. Hatada, and H. Yuki, J. Am. Chem. Soc., 101: 4763 (1979).CrossRefGoogle Scholar
  34. 34.
    C. Carlini and E. Chiellini, Makromol. Chem., 176: 519 (1975).CrossRefGoogle Scholar
  35. 35.
    E. Chiellini and C. Carlini, Makromol. Chem., 178: 2545 (1977).CrossRefGoogle Scholar
  36. 36.
    E. Chiellini, R. Solaro, M. Palmieri, and A. Ledwith, Polymer, 17: 641 (1976).CrossRefGoogle Scholar
  37. 37.
    E. Chiellini, R. Solaro, O. Colella, and A. Ledwith, Europ. Polym. J., 14: 489 (1978).CrossRefGoogle Scholar
  38. 38.
    E. Chiellini, R. Solaro, and F. Ciardelli, Makromol. Chem., in press.Google Scholar
  39. 39.
    T. Higashimura, H. Teranishi, and M. Sawamoto, Polymer J. 12: 393 (1980).CrossRefGoogle Scholar
  40. 40.
    E.J. Vandenberg, J. Polymer Soi., C, 1: 207 (1963).Google Scholar
  41. 41.
    J. Furukawa, Polymer, 3: 487 (1962).CrossRefGoogle Scholar

Copyright information

© Plenum Press, New York 1983

Authors and Affiliations

  • Emo Chiellini
    • 1
  • Roberto Solaro
    • 1
  • Francesco Masi
    • 1
  1. 1.CNR Center of Stereordered Optically Active Macromolecules, Institute of Industrial Organic ChemistryUniversity of PisaItaly

Personalised recommendations