AbstractA combination oftert‐butyllithium (t‐BuLi) and bis(2,6‐di‐t‐butylphenoxy)methylaluminium (MeAI(ODBP)2) was found to be an efficient initiator for heterotactic living polymerization of certain alkyl methacrylates in toluene at low temperatures. The polymerization of methyl methacrylate (MMA) witht‐BuLi/MeAI(ODBP)2(AI/Li=5 mol/mol) in toluene at −78°C gave heterotactic‐rich poly(methyl methacrylate) (PMMA) with narrow molecular weight distributions (MWDs) (heterotactic triad fractionmr= 68, ratio of weight‐ to number‐average molecular weightsM̄w/M̄n =1.06‐1.17). Other alkyl methacrylates also gave heterotactic polymers under the same conditions; in particular, ethyl and butyl methacrylates gave polymers with heterotactic triad fractions of 87. The highest triad heterotacticity of 91.6 was obtained for the polymerization of ethyl methacrylate at −95°C. Some characteristic features of this stereospecific polymerization were discussed based on the polymerization results combined with other structural information of the polymer such as chain‐end stereostructure and stereosequence d
展开▼
