Anionic polymerization of acrylates. II. Polymerization of 2-ethylhexyl acrylate initiated by butyllithium/lithium-tert-butoxide system in tetrahydrofuran and its mixtures with toluene

The anionic polymerization of 2-ethylhexyl acrylate (EtHA) initiated with the complex butyllithium/lithium-tert-butoxide (BuLi/t-BuOLi) was investigated at ?60°C in a medium of various solvating power, i.e., in mixtures of toluene and tetrahydrofuran and in neat tetrahydrofuran. With increasing amount of THF in the mixture the attainable limiting conversion of polymerization decreases; the monomer can be polymerized quantitatively only in a toluene/THF mixture (9/1). Molecular weights of the polymers thus obtained, their distribution, and initiator efficiency are not appreciably affected by the polymerization medium. The molecular weight distribution of the products is medium-broad (M_w/M_n = 2–2.4), with a hint of bimodality. The ¹H-¹³C-NMR, and IR spectra suggest that during the polymerization there is neither any perceptible reesterification of the polymer with the alkoxide nor transmetalation of the monomer with the initiator. In a suitable medium, autotermination of propagation proceeds to a limited extent only, predominantly via intramolecular cyclization of propagating chains; in a medium with a higher content of polar THF, it prevails and terminates propagation before the polymerization of the monomer has been completed. © 1992 John Wiley & Sons, Inc.