Accelerated living cationic ring-opening polymerization of a methyl ester functionalized 2-oxazoline monomer

dietmar — Wed, 19 Nov 2014 15:41:28 +0000

P.J.M. Bouten, D. Hertsen, M. Vergaelen, B. Monnery, M.A. Boerman, H. Goossens, S. Catak, J.C.M. van Hest, V. Van Speybroeck, R. Hoogenboom

Polymer Chemistry

6, 514-518

2015

Abstract

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.

Open Access version available at UGent repository

DOI

http://dx.doi.org/10.1039/C4PY01373E

Private attachment

14_Polym-Chem_2015_6_514_Bouten.pdf

Theoretical Rationalization of the Cationic Ring-opening Polymerization of a Methyl Ester Functionalized 2-Oxazoline Monomer

dietmar — Wed, 19 Nov 2014 15:28:06 +0000

D. Hertsen, H. Goossens, S. Catak, P.J.M. Bouten, M. Vergaelen, B. Monnery, J.C.M. van Hest, R. Hoogenboom, V. Van Speybroeck

ISBN/ISSN:

Poster

Conference / event / venue

Annual IAP Meeting (P7/05)

Louvain-La-Neuve, Belgium

Friday, 19 September, 2014

Abstract (private)

poster_abstract.pdf

Center for Molecular Modeling - J.C.M. van Hest