Accelerated living cationic ring-opening polymerization of a methyl ester functionalized 2-oxazoline monomer
Polymer Chemistry, cilt.6, sa.4, ss.514-518, 2015 (SCI-Expanded, Scopus)
- Yayın Türü: Makale / Tam Makale
- Cilt numarası: 6 Sayı: 4
- Basım Tarihi: 2015
- Doi Numarası: 10.1039/c4py01373e
- Dergi Adı: Polymer Chemistry
- Derginin Tarandığı İndeksler: Science Citation Index Expanded (SCI-EXPANDED), Scopus
- Sayfa Sayıları: ss.514-518
- Açık Arşiv Koleksiyonu: AVESİS Açık Erişim Koleksiyonu
- Boğaziçi Üniversitesi Adresli: Evet
Özet
Kinetic studies on the homo- and copolymerization of 2-methoxycarboxyethyl-2-oxazoline (MestOx) with 2-methyl-2-oxazoline (MeOx) and 2-ethyl-2-oxazoline (EtOx) were performed. For the homopolymerisation of MestOx an increased propagation rate constant was observed compared to MeOx and EtOx while the copolymerization of MestOx with MeOx or EtOx unexpectedly revealed slower incorporation of MestOx. Density functional theory (DFT) calculations show that nearby MestOx residues in the living chain can activate both the oxazolinium chain end and the attacking monomer, stabilizing the propagation transition state, leading to faster homopolymerisation of MestOx. These effects also accelerate incorporation of both monomers in the copolymerisations. However, since MeOx is shown to be more nucleophilic than MestOx, the incorporation order is reversed in the copolymerisations.