Living Anionic Polymerization of N ‐Methacryloyl‐2‐methylaziridine

Anionic polymerization of N ‐methacryloyl‐2‐methylaziridine ( 1 ) proceeded with 1,1‐diphenyl‐3‐methylpentyllithium (DMPLi) in the presence of LiCl or Et 2 Zn to give the polymers possessing predicted molecular weights and narrow molecular weight distributions ( M w / M n  < 1.1) at −78 ∼ −40 °C in THF. In each polymerization initiated with DMPLi/LiCl at the various temperatures ranging from −40 to −60 °C, the linear relationship between polymerization time and conversion of monomer was obtained from the GLC analysis. The rate constant and the activation energy of the anionic polymerization for 1 were determined as follows: ln k   p ap  = −5.85 × 10 3 /T + 23.3 L mol −1 s −1 and 49 ± 4 kJ mol −1 , respectively. Poly( 1 ) showed the glass transition temperature at 98 °C, and gave the insoluble product at higher temperature around 150 °C through the thermal cross‐linking of highly strained N ‐acyl‐aziridine moiety.