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Prediction of Propagation Rate Coefficients in Free Radical Solution Polymerization Based on Accurate Quantum Chemical Methods: Vinylic and Related Monomers, Including Acrylates and Acrylic Acid
Author(s) -
Deglmann Peter,
Müller Imke,
Becker Florian,
Schäfer Ansgar,
Hungenberg KlausDieter,
Weiß Horst
Publication year - 2009
Publication title -
macromolecular reaction engineering
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 32
eISSN - 1862-8338
pISSN - 1862-832X
DOI - 10.1002/mren.200900034
Subject(s) - monomer , polymerization , solvation , radical polymerization , solution polymerization , acrylic acid , aqueous solution , solvent effects , polymer chemistry , quantum chemistry , chemistry , materials science , computational chemistry , solvent , polymer , reaction mechanism , organic chemistry , catalysis
The simulation of polymerization processes is of enormous industrial importance. A quantum chemical method based on density functional theory is developed and validated that provides almost chemical accuracy for radical polymerization propagation of industrially relevant monomers in aqueous solution. The necessary corrections are computed using the CC level of theory. Solvent effects are accounted for by the solvation model COSMO‐RS. The method is capable of reproducing and rationalizing, for example, monomer concentration effects on the propagation rate for NVP. A comparison is performed with recent PLP experimental data. The method does not rely on error compensation effects or empiric corrections and is suitable for industrially relevant systems.