Novel Aprotic Polar Polymers V. Synthesis of Poly(HMPA) by Ring-Opening Polymerization

The synthesis of a polymer homolog of hexamethylphosphoramide (HMPA) by ring-opening polymerization of the corresponding monomer (N-bis(dimethylamino)phosphorylpropylenimine) was conducted. Poly(HMPA) was obtained when polymerization was carried out with cationic initiators at 150°C. Both solution polymerization in 1,1,2,2-tetrachloroethane and bulk polymerization were successful, though anionic polymerization and cationic polymerization at lower temperature afforded no polymer. The obtained poly(HMPA) actually had properties as an aprotic polar polymer such as the amphiphilicity and the miscibility. Poly(HMPA) prepared by ring-opening polymerization showed better miscibility with polystyrene than poly(HMPA) having fewer phosphoryl groups (47%), synthesized by polymer reaction.