Abstract: | The rate of homopolymerization of maleimide has been measured in dimethylformamide solution at 60°C. in the presence of azobisisobutyronitrile; it has been compared to that of N-n-butylmaleimide. The overall rates of polymerization are equal to Rp = kM]1.1–1.2 In]0.8 for maleimide, and Rp = k'M] In]0.5 for the N-substituted imide. The difference of behavior has been interpreted on the basis of an intramolecular tautomery of the terminal group of the maleimide growing chain and the formation of a resonance-stabilized succinimidyl radical. The relative ease of polymerization of these monomers and of maleic anhydride has been discussed. In the presence of sodium tert-butoxide at 20°C. in dimethylformamide solutions, maleimide polymerizes with hydrogen isomerization. The percentage of N-substituted isomerized units was evaluated at 70–75% by measurement of the rate of hydrolysis in 0.005N sodium hydroxide and comparison with succinimide and N-butylsuccinimide. N-n-butylmaleimide undergoes ring opening together with anionic polymerization in the presence of sodium tert-butoxide at 20°C. and butyllithium at -40°C. Unlike the radical-initiated polymerization, it was impossible to obtain anionic copolymers of maleimide and N-butylmaleimide with acrylonitrile and methyl methacrylate. |