Journal of Polymer Science Part A: Polymer Chemistry, Vol.34, No.17, 3441-3463, 1996
Living Carbocationic Polymerization .4. Living Polymerization of Isobutylene (Reprinted from Journal of Polymer Science .A. Polymer Chemistry, Vol 25, Pg 1847-1869, 1987)
Truly living polymerization of isobutylene (IB) has been achieved for the first time by the use of new initiating systems comprising organic acetate-BCl3 complexes under conventional laboratory conditions in various solvents from -10 to -50 degrees C. The overall rates of polymerization are very high, which necessitated the development of the incremental monomer addition (IMA) technique to demonstrate living systems. The living nature of the polymerizations was demonstrated by linear <(M)over bar (n)> versus grams polyisobutylene (PIB) formed plots starting at the origin and horizontal number of polymer molecules formed versus amount of polymer formed plots. <(DP)over bar (n)> obeys [IB]/[CH(3)COOR(t) . BCl3]. Molecular weight distributions (MWD) are very narrow in homogeneous systems (<(M)over bar (w)>/<(M)over bar (n)> = 1.2-1.3) whereas somewhat broader values are obtained when the polymer precipitates out of solution (<(M)over bar (w)>/<(M)over bar (n)> = 1.4-3.0). The MWDs tend to narrow with increasing molecular weights, i.e., with the accumulation of precipitated polymer in the reactor. Traces of moisture do not affect the outcome of living polymerizations. In the presence of monomer both first and second order chain transfer to monomer are avoided even at -10 degrees C. The diagnosis of first and second order chain transfer has been accomplished, and the first order process seems to dominate. Forced termination can be effected either by thermally decomposing the propagating complexes or by nucleophiles. In either case the end groups will be tertiary chlorides. The living polymerization of isobutylene initiated by ester . BCl3 complexes most likely proceeds by a two-component group transfer polymerization.