| Abstract: | The reactivity of n‐butyllithium (n‐BuLi) toward pyridine derivatives (pyridine, pyridazine, pyrimidine, and 1,3,5‐triazine) was subjected to a computational study to determine the most suitable n‐BuLi/heterocyclic ring system as an initiator for the anionic polymerization of methyl methacrylate (MMA). These systems were suggested to prevent side reactions occurring through n‐BuLi attack on the carbonyl carbon of MMA by sterically blocking the initiator. The initiation reaction was modeled with the B3LYP methodology 6‐31+G*. Activation barriers were used to analyze the reactivity of each n‐BuLi/heterocyclic ring system. Computational results showed that n‐BuLi/triazine had a significantly lower activation barrier. Therefore, n‐BuLi/triazine was the suggested initiator system for the anionic polymerization of poly(methyl methacrylate). © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 455–467, 2005 |
