Anionic Polymerization of Monomers Containing Functional Groups. 8. Anionic Living Polymerization of 4-Cyano-α-methylstyrene

The anionic polymerization of 4-cyano-α-methylstyrene ( 1 ) was carried out in THF at −78 °C with (1,1,4,4-tetraphenylbutanediyl)dipotassium and -dilithium, (diphenylmethyl)potassium, and (triphenylmethyl)potassium and -cesium. All the polymerizations of 1 quantitatively proceeded with each initiator, although the rates of polymerization were quite slow, especially in the case of organolithium initiator. The resulting poly( 1 )s always possessed narrow molecular weight distributions ( M w / M n < 1.13) and predicted molecular weights based on the molar ratios of monomer to initiators. The living nature of the propagating carbanion derived from 1 was demonstrated by the postpolymerization. Novel well-defined block copolymers poly( 1 - b -styrene- b - 1 ) and poly( 1 - b - tert -butyl methacrylate- b - 1 ) were successfully synthesized by the sequential addition of 1 and styrene or tert -butyl methacrylate.