Group Transfer Polymerization of N-Substituted Maleimides

Group transfer polymerization (GTP) of N-phenylmaleimide (NPM), N-phenylcitraconimide (NPC), and N-(4-dimethylaminophenyl)maleimide (NAPM) was investigated with methyl trimethylsilyl dimethylketene acetal (MTDA) as initiator and tetrabutylammonium bibenzoate (TBAB) as catalyst. NPM can be polymerized by GTP initiators and can be incorporated into statistical copolymers with methyl methacrylate (MMA). These reactions do not exhibit the characteristics of living polymerization. NPM is more reactive than MMA in GTP-initiated copolymerizations, and at low concentration effectively inhibits the polymerization of MMA. Poly(MMA-block-NPM) can be obtained by adding NPM to living poly(MMA), but the block copolymer is polydisperse in size and composition. NAPM can also be polymerized, but NPC gave no polymers via GTP. Poly(NPM) and poly(MMA-co-NPM) prepared by GTP show excellent thermal stability.