Anionic polymerization of methyl methacrylate by initiating systems based on lithium amides of various secondary amines

The anionic polymerization of methyl methacrylate in toluene at −78 °C with lithium amides of various secondary amines (diisopropylamine, N‐isopropylaniline, N‐n‐butylaniline, indoline, and N‐ethyl‐o‐toluidine) as initiators was studied. The tacticity of the resulting poly(methyl methacrylate)s (PMMAs) was dependent on the kind of secondary amine, and highly isotactic PMMAs (91–93% mm) were obtained when lithium amides of N‐isopropylaniline and N‐n‐butylaniline were employed. The isotacticity of the PMMAs further increased up to 98% mm with initiating systems composed of the lithium amides, n‐butyllithium, and transition‐metal halides (WCl₆, MoCl₅, and NbCl₅). © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4405–4411, 2005