Synthesis of Graft Polymer with Controlled Stereoregularities in the Main Chain and in the Side Chains by Stereospecific Copolymerization of Isotactic Poly(methyl methacrylate) Macromonomer with Methacrylate Monomer

Abstract

Highly isotactic poly(methyl methacrylate) (PMMA) macromonomer having methacryloyl group as a polymerizable function was synthesized from PMMA Iiving anion prepared with t-C4H9MgBr in toluene at −78°C. Anionic copolymerizations of the PMMA macromonomer with methyl or ethyl methacrylate were carried out to obtain stereoregular graft polymers. Copolymerizations by 1,1-diphenylhexyllithium in tetrahydrofuran at −78°C and by t-C4H9MgBr in toluene at −78°C gave graft polymers with syndiotactic and isotactic main chains, respectively, as confirmed by 13C NMR spectroscopy. Some of solution properties of the stereoregular graft polymers were investigated. The graft polymers with isotactic and syndiotactic PMMA chains were found to exhibit peculiar viscosity behavior due to stereocomplex formation.