Summary
Rapid truly living carbocationic polymerization of 2,4,6-trimethylstyrene (TMeSt) has been achieved by the use of the cumyl acetate (CumOAc)/BCl3 initiating system in CH3Cl at −30°C. The ¯Mn of the polymer is determined by the ratio [TMe]/[CumOAc]and ¯Mw/¯Mns are 1.1–1.2. Below about 2.5×10−3 mole/L CumOAc adventitious initiation most likely by “H2O”. BCl3 is nonnegligible. Forced termination with pyridine or by heating to ambient temperature yields benzylic chlorine end groups whereas with methanol both −Cl and −OCH3 end groups are obtained in the ratio ∼60/40.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Carbocationic Polymerization, J. P. Kennedy and E. Maréchal, John Wiley Interscience, New York 1982
D. C. Pepper and P. J. Reilly, Proc. Roy. Soc. Ser. A291, 41 (1966)
R. Faust, A. Fehérvári, and J. P. Kennedy, J. Macromol. Sci. Chem. A18(9), 1229 (1982)
V. S. C. Chang, J. P. Kennedy and B. Iván, Polym. Bull. 3, 339 (1980)
V. S. C. Chang and J. P. Kennedy, Polym. Bull. 4, 513 (1981)
See paper XVI in this series, R. Faust and J. P. Kennedy, Polym. Bull., in this issue
Polymer Handbook, J. Brandrup, E. H. Immergut, John Wiley Interscience 1975
M. Győr, J. P. Kennedy, T. Kelen and F. Tüdős, J. Macromol. Sci. Chem. A21(10), 1295 (1984)
R. Faust and J. P. Kennedy, J. Polym. Sci., Polym. Chem. A25, 11847 (1987)
C. G. Swain, T. E. C. Knee and A. MacLachlan, J. Am. Chem. Soc. 82, 6101 (1960)
J. P. Kennedy and R. T. Chou, J. Macromol. Sci. Chem. A18(1) 47 (1982)
J. C. Charlton and E. D. Hughes, J. Chem. Soc. 56, 850