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Polymerization of methyl methacrylate (MMA) with metal acetylacetonates, especially vanadium (III) acetylacetonate [V(acac)3], in combination with AIEt3 was studied. V(acac)3–AIEt3 catalyst could initiate the polymerization of MMA, although other Mt(acac)xs are also effective. It was found that the polymerization of MMA with V(acac)3–AIEt3 catalyst proceeded through a coordination mechanism, from the results of copolymerization with styrene and polymerization in the presence of radical inhibitors. The resulting polymers were found to form stereocomplexes in acetone. Based on these results, it is concluded that multi‐active sites in the polymerization of MMA with V(acac)3–AIEt3 catalyst were produced.

The polymerization of methyl methacrylate (MMA) with V(acac), and VOCl, in combination with methylaluminoxane (MAO) was investigated. The obtained polymers have a relatively narrow molecular weight distribution (MJM,, < 13). It was found that the isotactic triad content of the polymers increases with increasing temperature and MAO/V and MAO/MMA mole ratios. The interaction between MMA and MA0 has an influence on the tacticity of radically (initiator AIBN) obained polymers: in presence of MA0 the fraction of isotactic triads (mm) is higher. The catalytic activity of MAOcontaining catalysts (V(acac),/MAO and VOCI,/MAO) was compared with that of AIEt,-containing catalysts (V(acac),/AlEt, and VOCI,/AIEt,). It was not much different, but for MA0 as cocatalyst the isotacticity of the resulting PMMA's was higher, and the polydispersity lower, than with AlEt, as cocatalyst.