Chinese Journal of Polymer Science

, Volume 29, Issue 3, pp 360–367

Synthesis of highly reactive polyisobutylenes with BF3·cyclohexanol initiating system

  • Lai-bao Zhang
  • Yi-xian Wu (吴一弦)
  • Peng Zhou
  • Guan-ying Wu
  • Wan-tai Yang
  • Ding-sheng Yu


The selective cationic polymerization of isobutylene (IB) initiated by a BF3·cyclohexanol (CL) complex was carried out from the mixed C4 fraction feed containing the 4C saturated and unsaturated hydrocarbons at −20°C. The effects of CL concentration, BF3 concentration, solvent for preparing BF3·CL complex and polymerization time on the chemical structure of end groups, number-average molecular weight (Mn) and molecular weight distribution (MWD, Mw/Mn) of the resulting polymers were investigated. The experimental results indicate that the BF3·CL complex initiating system exhibited an extremely high selectivity toward the cationic polymerization of IB in the mixed C4 fraction feed and low molecular weight (Mn = 900–3600) polyisobutylenes (PIBs) with large proportion of exo-double bond end groups were obtained. The exo-double bond content in PIB chain ends increased by increasing CL concentration or by decreasing solvent polarity in initiating system, BF3 concentration and polymerization time. The Mn and MWD of the resulting PIBs were dependent on the concentrations of CL and BF3. Highly reactive PIBs with around 90 mol% of exo-double bonds were successfully synthesized by the selective polymerization of IB from the mixed C4 fraction feed, providing a potentially practical process for its simplicity and low costs.


Reactivity Polyisobutylene Initiator Cationic polymerization 


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Kresge, E.N., Schatz, R.H. and Wang, H.C., “Encyclopedia of polymer science and engineering, Vol. 8”, Wiley, New York, 1985, p. 423Google Scholar
  2. 2.
    Boerzel, P., Bronstert, K. and Hovemann, F., 1978, DE. Pat., 2,702,604Google Scholar
  3. 3.
    Edward, B. Jr, Gilbert, V. Christopher, L. and Timothy, L., 2004, US. Pat., 6,683,138Google Scholar
  4. 4.
    Maxwell, K.J., McMahon, J. and Mann, S.J., 1995, EP. Pat., 0,671,419Google Scholar
  5. 5.
    Tokumoto, Y., Ohashi, K., Okada, T. and Takashima, T., 1999, EP. Pat., 1,026,175Google Scholar
  6. 6.
    Rath, H.P., Kanne, U. and Deyck, F., 2002, US. Pat., 6,407,186Google Scholar
  7. 7.
    Rath, H.P., 1994, US. Pat., 5,408,018Google Scholar
  8. 8.
    Rath, H.P., Perner, T.H. and March, H., 2004, WO. Pat., 065,432Google Scholar
  9. 9.
    Li, H.C., Wang, G.Y., Nan, C.M., Jiang, M. and Shi, C.Y., 2003, CN. Pat., 1,415,634Google Scholar
  10. 10.
    Vierle, M., Zhang, Y.M., Herdtweck, E., Bohnenpoll, M., Nuyken, O. and Kuhn, F.E., Angew. Chem. Int. Ed., 2003, 42: 1307CrossRefGoogle Scholar
  11. 11.
    Hijazi, A.K., Yeong, H., Zhang, Y.M., Herdtweck, E., Nuyken, O. and Kuhn, F.E., Macromol. Rapid. Commun., 2007, 28: 670CrossRefGoogle Scholar
  12. 12.
    Vierle, M., Schon, D., Bohnenpoll, M., Kuhn, F.E. and Nuyken, O., 2003, CA. Pat., 2,421,688Google Scholar
  13. 13.
    Vierle, M., Zhang, Y.M., Santos, A.M., Kohler, K., Haessner, C., Herdtweck, E., Bohnenpoll, M., Nuyken, O. and Kuhn, F.E., Chem. Eur. J., 2004, 10: 6323CrossRefGoogle Scholar
  14. 14.
    Guerrero, A., Kulbaba, K. and Bochmann, M., Macromolecules, 2007, 40: 4124CrossRefGoogle Scholar
  15. 15.
    Lin, T., Wu, Y.X., Ye, X.L., Zhang, L.B., Huang, Q.G. and Wu, G.Y., Acta Polymerica Sinica(in Chinese), 2008, (2): 130Google Scholar
  16. 16.
    Qiu, Y.X., Wu, Y.X., Gu, X.L., Xu, X. and Wu, G.Y., Eur. Polym. J., 2005, 41: 349CrossRefGoogle Scholar
  17. 17.
    Gunther, W., Maenz, K. and Stadermann, D., Macromol. Mater. Eng., 1996, 234: 71Google Scholar
  18. 18.
    Toman, L., Spevacek, J., Vlcek, P. and Holler, P., J. Polym. Sci., Part A: Polym. Chem., 2000, 38: 1568CrossRefGoogle Scholar
  19. 19.
    Sipos, L., De, P. and Faust, R., Macromolecules, 2003, 36: 8282CrossRefGoogle Scholar
  20. 20.
    Puskas, I. and Meyerson, S.J., Org. Chem., 1984, 49: 258CrossRefGoogle Scholar
  21. 21.
    Puskas, I., Banas, E.M., Nerheim, A.G. and Ray, G.J., Macromolecules, 1979, 12: 1024CrossRefGoogle Scholar
  22. 22.
    De, P. and Faust, R., Macromolecules, 2006, 39: 6861CrossRefGoogle Scholar
  23. 23.
    Storey, R.F., Curry, C.L. and Brister, L.B., Macromolecules, 1998, 31: 1058CrossRefGoogle Scholar

Copyright information

© Chinese Chemical Society, Institute of Chemistry, Chinese Academy of Sciences and Springer-Verlag Berlin Heidelberg 2011

Authors and Affiliations

  • Lai-bao Zhang
    • 1
  • Yi-xian Wu (吴一弦)
    • 1
  • Peng Zhou
    • 1
  • Guan-ying Wu
    • 1
  • Wan-tai Yang
    • 1
  • Ding-sheng Yu
    • 1
  1. 1.State Key Laboratory of Chemical Resource Engineering, Key Laboratory of Carbon Fiber and Functional Polymers (Ministry of Education)Beijing University of Chemical TechnologyBeijingChina

Personalised recommendations