Anionic Polymerization of N ‐Methacryloyl‐2‐methylaziridine and N ‐Methacryloylazetidine

Anionic polymerizations of N ‐methacryloyl‐2‐methylaziridine ( 1 ) and N ‐methacryloylazetidine ( 2 ) were carried out in THF with 1,1‐diphenyl‐3‐methylpentyllithium (DMPLi) and with diphenylmethylpotassium (Ph 2 CHK) in the presence of LiCl or Et 2 Zn. Poly( 1 ) and poly( 2 ) possessing predicted M n s based on the molar ratios between monomer to initiators and narrow molecular weight distributions (MWD, M w / M n  < 1.1) were quantitatively obtained at −40 °C within 24 h. The stability of the propagating chain end of poly( 1 ) was confirmed by the quantitative initiation efficiency in the postpolymerization. The radical polymerizations of 1 and 2 with AIBN gave the polymers in 77 and 40% yields, respectively. These are first examples demonstrating the positive polymerizability of N , N ‐dialkylmethacrylamide derivatives, while N , N ‐dimethylmethacrylamide showed the negative polymerizability under the radical and anionic polymerization conditions.