Living Anionic Polymerization of 1,4-Divinylbenzene

We have successfully realized for the first time the living anionic polymerization of 1,4-divinylbenzene (1) with the use of a specially designed initiator system prepared from oligo(alpha-methylstyryl)lithium and a 11-fold or more excess of potassium tert-butoxide. The polymerization was very fast and complete at -78 degrees C for 1 min. Soluble polymers having a pendant vinyl group in each monomer unit were always quantitatively obtained under such conditions. The resulting poly(1)s possessed predictable molecular weights (M-n = 11 000-26 400 g/mol) and narrow molecular weight distributions (M-w/M-n < 1.05). Furthermore, a new well-defined diblock copolymer, poly(1)-block-poly(tert-butyl methacrylate), was also successfully synthesized with the same initiator system by the anionic block copolymerization where 1 and tert-butyl methacrylate were sequentially added in this order.