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

(2009) MACROMOLECULES. 42(8). p.3033-3041
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HPC-UGent: the central High Performance Computing infrastructure of Ghent University
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.
Keywords
STEREOSPECIFIC POLYMERIZATION, THERMOCHEMICAL KINETICS, AB-INITIO, CHAIN-LENGTH DEPENDENCE, EVALUATED RATE COEFFICIENTS, DENSITY-FUNCTIONAL THEORY, UNIMOLECULAR REACTIONS, METHYL-METHACRYLATE, REACTION-RATES, FLUOROALCOHOLS

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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.
@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},
}

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