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A Quantum Mechanical Study on the Propagation Kinetics of N ‐methylacrylamide: Comparison With N,N ‐Dimethylacrylamide in Free Radical Polymerization[Note 1. 1Experimental value: 0.66. (Ref. No.36). ...]
Author(s) -
Kayık Gülru,
Tüzün Nurcan Ş.
Publication year - 2015
Publication title -
macromolecular theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 56
eISSN - 1521-3919
pISSN - 1022-1344
DOI - 10.1002/mats.201400096
Subject(s) - steric effects , monomer , chemistry , kinetics , polymerization , reaction rate constant , radical polymerization , yield (engineering) , computational chemistry , quantum yield , basis set , density functional theory , polymer chemistry , thermodynamics , polymer , stereochemistry , organic chemistry , physics , quantum mechanics , fluorescence
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.