A Quantum Mechanical Study on the Propagation Kinetics of N-methylacrylamide: Comparison With N,N-Dimethylacrylamide in Free Radical Polymerization

作者：Kayik Gulru; Tuzun Nurcan S^*

来源：Macromolecular Theory and Simulations, 2015, 24(3): 218-231.

DOI：10.1002/mats.201400096

• acrylamides
• B3LYP
• density functional theory
• propagation kinetics
• quantum mechanical modeling

In this study propagation kinetics of free radical polymerization of N-methylacrylamide (NMAAm) is studied with density functional theory calculations. The propagation rate constant ratio of N,N-dimethylacrylamide (DMAAm) and NMAAm (k(NMAAm)/k(DMAAm)) is evaluated via model reactions at dimeric stage. The most favorable modes of addition is shown to be determined by the steric effects and hydrogen bonding interactions between the reactive fragments. Gauche and trans orientations are preferred as the least energetic additions in pro-meso and pro-racemo attacks, respectively. Benchmark studies with various density functionals (M05-2X, M06-2X, MPWB1K, BMK) combined with 6-311+G(3df,2p) basis set assess the calculations. The k(NMAAm)/k(DMAAm) ratio obtained in this study is in line with the experimental value. The addition reaction barrier via dimeric associates in case of NMAAm does not yield significant difference than the barrier via monomeric species.

• 出版日期2015-5