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(α-methylstyryl)lithium and a 11-fold or more excess of potassium tert -butoxide. The polymerization was very fast and complete at −78 °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.