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DFT study on the propagation kinetics of free-radical polymerization of alpha–substituted acrylates

Isa Değirmenci, Viktorya Aviyente, Veronique Van Speybroeck UGent and Michel Waroquier UGent (2009) MACROMOLECULES. 42(8). p.3033-3041
abstract
The kinetics of the free-radical propagation of methyl acrylate (MA), methyl methacrylate (MMA), ethyl alpha-fluoroacrylate (EFA), ethyl alpha-chloroacrylate (ECA), ethyl alpha-cyanoacrylate (ECNA), and methyl alpha-hydroxymethacrylate (MHMA) have been calculated using quantum chemical tools. Various DFT functionals such as BMK, BBIK, MPW1B95, MPW1K, and MPWB1K were used to model the relative propagation kinetics of the monomers. Among the methodologies used, MPWB1 K/6-311+G(3df,2p)//B3LYP/6-31+G(d) was found to yield the best qualitative agreement with experiment. We explored chain length effects by examining addition reactions of monomeric, dimeric, trimeric, and tetrameric radicals to the monomers. We have also modeled the tacticity of the widely used monomers MA and MMA by considering all of the alternatives of attack of the radical in the 3D space around the monomer. This study has qualitatively confirmed the experimental syndiotactic/isotactic ratio of 66/3 for MMA. Finally, the kinetics of the initiation to polymerization for MA and MMA is also successfully reproduced.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
STEREOSPECIFIC POLYMERIZATION, THERMOCHEMICAL KINETICS, AB-INITIO, CHAIN-LENGTH DEPENDENCE, EVALUATED RATE COEFFICIENTS, DENSITY-FUNCTIONAL THEORY, UNIMOLECULAR REACTIONS, METHYL-METHACRYLATE, REACTION-RATES, FLUOROALCOHOLS
journal title
MACROMOLECULES
Macromolecules
volume
42
issue
8
pages
3033 - 3041
publisher
AMER CHEMICAL SOC
place of publication
Washington, USA
Web of Science type
Article
Web of Science id
000265411400024
JCR category
POLYMER SCIENCE
JCR impact factor
4.539 (2009)
JCR rank
5/76 (2009)
JCR quartile
1 (2009)
ISSN
0024-9297
DOI
10.1021/ma802875z
project
HPC-UGent: the central High Performance Computing infrastructure of Ghent University
language
English
UGent publication?
yes
classification
A1
id
484422
handle
http://hdl.handle.net/1854/LU-484422
date created
2009-02-12 15:17:45
date last changed
2013-09-17 10:47:17
@article{484422,
  abstract     = {The kinetics of the free-radical propagation of methyl acrylate (MA), methyl methacrylate (MMA), ethyl alpha-fluoroacrylate (EFA), ethyl alpha-chloroacrylate (ECA), ethyl alpha-cyanoacrylate (ECNA), and methyl alpha-hydroxymethacrylate (MHMA) have been calculated using quantum chemical tools. Various DFT functionals such as BMK, BBIK, MPW1B95, MPW1K, and MPWB1K were used to model the relative propagation kinetics of the monomers. Among the methodologies used, MPWB1 K/6-311+G(3df,2p)//B3LYP/6-31+G(d) was found to yield the best qualitative agreement with experiment. We explored chain length effects by examining addition reactions of monomeric, dimeric, trimeric, and tetrameric radicals to the monomers. We have also modeled the tacticity of the widely used monomers MA and MMA by considering all of the alternatives of attack of the radical in the 3D space around the monomer. This study has qualitatively confirmed the experimental syndiotactic/isotactic ratio of 66/3 for MMA. Finally, the kinetics of the initiation to polymerization for MA and MMA is also successfully reproduced.},
  author       = {De\u{g}irmenci, Isa and Aviyente, Viktorya and Van Speybroeck, Veronique and Waroquier, Michel},
  issn         = {0024-9297},
  journal      = {MACROMOLECULES},
  keyword      = {STEREOSPECIFIC POLYMERIZATION,THERMOCHEMICAL KINETICS,AB-INITIO,CHAIN-LENGTH DEPENDENCE,EVALUATED RATE COEFFICIENTS,DENSITY-FUNCTIONAL THEORY,UNIMOLECULAR REACTIONS,METHYL-METHACRYLATE,REACTION-RATES,FLUOROALCOHOLS},
  language     = {eng},
  number       = {8},
  pages        = {3033--3041},
  publisher    = {AMER CHEMICAL SOC},
  title        = {DFT study on the propagation kinetics of free-radical polymerization of alpha--substituted acrylates},
  url          = {http://dx.doi.org/10.1021/ma802875z},
  volume       = {42},
  year         = {2009},
}

Chicago
Değirmenci, Isa, Viktorya Aviyente, Veronique Van Speybroeck, and Michel Waroquier. 2009. “DFT Study on the Propagation Kinetics of Free-radical Polymerization of Alpha–substituted Acrylates.” Macromolecules 42 (8): 3033–3041.
APA
Değirmenci, I., Aviyente, V., Van Speybroeck, V., & Waroquier, M. (2009). DFT study on the propagation kinetics of free-radical polymerization of alpha–substituted acrylates. MACROMOLECULES, 42(8), 3033–3041.
Vancouver
1.
Değirmenci I, Aviyente V, Van Speybroeck V, Waroquier M. DFT study on the propagation kinetics of free-radical polymerization of alpha–substituted acrylates. MACROMOLECULES. Washington, USA: AMER CHEMICAL SOC; 2009;42(8):3033–41.
MLA
Değirmenci, Isa, Viktorya Aviyente, Veronique Van Speybroeck, et al. “DFT Study on the Propagation Kinetics of Free-radical Polymerization of Alpha–substituted Acrylates.” MACROMOLECULES 42.8 (2009): 3033–3041. Print.