Computational study of alkyllithium/pyridine derivative systems as initiators for the living anionic polymerization of methyl methacrylates
Journal of Polymer Science, Part A: Polymer Chemistry, cilt.43, sa.2, ss.455-467, 2005 (SCI-Expanded, Scopus)
- Yayın Türü: Makale / Tam Makale
- Cilt numarası: 43 Sayı: 2
- Basım Tarihi: 2005
- Doi Numarası: 10.1002/pola.20506
- Dergi Adı: Journal of Polymer Science, Part A: Polymer Chemistry
- Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
- Sayfa Sayıları: ss.455-467
- Anahtar Kelimeler: Anionic polymerization, Density functional theory (DFT), Initiators, Molecular modeling, Poly(methyl methacrylate), Pyridine derivatives
- Boğaziçi Üniversitesi Adresli: Evet
Özet
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.