Living carbocationic polymerization of isobutylene by tert-amyl alcohol/BCl₃/1-methyl-2-pyrrolidinone initiating system

1-Methyl-2-pyrrolidinone has been investigated, for the first time, as an efficient electronpair donor in conjunction with tert-amyl alcohol and BCl₃ in CH₂Cl₂ diluent at −40°C for the living polymerization of isobutylene. The use of this new monofunctional initiator -trans fer (minifer) system has led to the synthesis of low molecular weight, living (near-monodisperse) polyisobutylenes carrying “ethyl” head group and “tert-chloro” end group (asymmetric telechelic polyisobutylenes). The nature of these groups was confirmed by ¹H-NMR spectroscopy. The living nature of the α-ethyl-ω-(tert-chloro)polyisobutylenes has been demonstrated by a linear plot, passing through the origin, of number-average molecular weight (M̄_n) vs. the amount of polymer formed (W_p) and a horizontal N (number of polyisobutylene molecules) vs. W_p plot. These results are further substantiated by gel permeation chromatography data of these polymers, and the molecular weight distributions of these polymers are narrow (low M̄_w/M̄_n = 1.1–1.2). The initiating efficiencies (I_eff) are close to 100% with this system. Dehydrochlorination of the prepolymer has yielded an isopropylidene (exo-olefin) end group. Structure of the end group in the resulting polymer, α-ethyl-ω-(isopropenyl)polyisobutylene, was confirmed by FTIR spectroscopy.