The initiation of polymerization of methyl methacrylate by the poly(methyl methacrylate) anion

Abstract Addition of methyl methacrylate monomer to poly(methyl methacrylate) which has been polymerized with fluorenyllithium or sodium‐naphthalene in tetrahydrofuran at −78°C. produces high conversion of monomer to polymer. By a comparison of the number‐average molecular weights before and after the addition of the second monomer, it is demonstrated that no new polymer chains are formed on polymerization of the second monomer, so that the polymerization is initiated by the poly(methyl methacrylate) anion. Styrene is shown to be an inert diluent in these systems. The technique is also applied to additions of styrene and of methyl methacrylate monomer to polystyrene initiated with sodium‐naphthalene; the new polymer is demonstrated to be initiated by the polystyrene anions.