Abstract

AbstractThe kinetics of the polymerization of methyl methacrylate initiated by lithium alkyls (tert‐butyllithium or ethyl α‐lithiobutyrate) was investigated in the presence of aluminium alkyls (triethylaluminium or triisobutylaluminium) in toluene at −78°C. The rate of polymerization decreases considerably once the living dimer is formed. This suggests that the aluminate end‐group coordinates with the penultimate ester group of the polymer chain, thus decreasing reactivity. The results are at variance with an activated monomer mechanism.

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