Effect of Temperature, Solvent Polarity, and Nature of Lewis Acid on the Rate Constants in the Carbocationic Polymerization of Isobutylene

The absolute rate constant of propagation for ion pairs ( k p ± ) was determined by the diffusion clock method in the living carbocationic polymerization of isobutylene at different solvent polarity and temperature in conjunction with TiCl 4, Me 2 AlCl, and BCl 3 as Lewis acids. The k p ± ((3.6−5.7) × 10 8 L mol -1 s -1 in hexanes/MeCl 60/40, v/v) was independent of temperature and nature of Lewis acid and increased moderately with increasing solvent polarity to a nearly diffusion-limited value (∼1.7 × 10 9 L mol -1 s -1 ) in pure MeCl. A similar k p ± (∼(5−6) × 10 8 L mol -1 s -1 ) value was obtained in the nonliving polymerization of isobutylene in conjunction with EtAlCl 2 in hexanes/MeCl 60/40 (v/v) at −80 °C, indicating that living and nonliving polymerizations proceed on identical propagating centers. The apparent equilibrium constant of ionization (activation) K i app (= K i K D0, where K i is the absolute equilibrium constant of ionization and K D0 is the equilibrium constant of TiCl 4 dimerization) was calculated from the apparent and absolute rate constant of propagation. The rate constant of deactivation, k - i was determined from the conversion vs polydispersity plots. From K i app and k - i, the apparent values of k i ( k i app = k i K D0, where k i is the absolute rate constant of ionization) were also calculated. On the basis of the results, the observed large differences in the overall polymerization rates with different solvent polarity and temperature can be attributed solely to the changes in the active center concentration, which decreases with decreasing solvent polarity and increasing temperature. From the temperature dependence of K i app, the apparent standard enthalpy (= Δ H i ° + Δ H D0 °) and entropy (= Δ S i ° + Δ S D0 °) of ionization, and from the temperature dependence of k i app and k - i, the apparent activation enthalpy and entropy of the activation/deactivation process were calculated.