Synthesis of new crosslinkable polymers by chemoselective polymerizations of 2‐(1‐aziridinyl)ethyl methacrylate

The anionic vinyl polymerization of 2-(1-aziridinyl)ethyl methacrylate (1) quantitatively proceeded with diphenylmethylpotassium in the presence of diethylzinc in tetrahydrofuran at −78 °C for 12 h to form a polymethacrylate (2) with an aziridine ring in each repeating unit. The resulting polymer 2 possessed the predicted molecular weight and narrow molecular weight distribution (weight-average molecular/number-average molecular weight < 1.1) and became readily insoluble by treatment with adipic acid via the crosslinking of the pendant aziridinyl moiety. A poly(ethylene imine) bearing methacryloyl pendant groups was obtained with triethyloxonium tetrafluoroborate via the cationic ring-opening polymerization of 1 in heptane/dichloromethane at 0 °C for 2 h.