ANIONIC-POLYMERIZATION OF ALKYL METHACRYLATES IN THE PRESENCE OF DIETHYLZINC

The anionic polymerizations of methyl methacrylate (MMA), isopropyl methacrylate (IPMA), and tert-butyl methacrylate (TBMA) in THF in the presence of diethylzinc were investigated. The addition of diethylzinc to the reaction mixture remarkably lowers the polymerization rates of the methacrylates initiated with potassium diphenylmethanide to afford polymers with the predicted molecular weights and very narrow molecular weight distributions, while PMMA and poly(IPMA) produced with potassium diphenylmethanide in the absence of diethylzinc have rather broad molecular weight distributions. The stereospecificities of PMMA, poly(IPMA) and poly(TBMA) are not affected by diethylzinc. From the result of the block copolymerization of MMA with TBMA, it was found that the presistency of the anionic propagating end of PMMA is significantly enhanced by the addition of diethylzinc. The retardation of the polymerization rates and the enhancement of the persistency of the propagating end in the presence of diethylzinc may be caused by the weak coordination of diethylzinc toward the enolate anions at the propagating end groups.