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Kinetic Monte Carlo generation of complete electron spray ionization mass spectra for acrylate macromonomer synthesis

(2017) MACROMOLECULES. 50(7). p.2625-2636
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Abstract
Absolute electron spray ionization mass spectrometry (ESI-MS) data are reported, for the first time, over the complete chain length range for the synthesis of welldefined macromonomers (MMs) obtained via activation of bromine-capped poly(n-butyl acrylate) (0.1 mass %; solvent: anisole; 140 °C) with CuBr2/Me6TREN (Me6TREN: tris(2 (dimethylamino)ethyl)amine) and tin ethylhexanoate. These data are generated based on bivariate kinetic Monte Carlo simulations, tracking the chain lengths and the positions of radicals/characteristic groups along the chains (>100 reactions, 12 radical/dormant species types, and 7 characteristic end/ mid-groups). Based on qualitative tuning to experimental data, migration is found to be 50 times slower than backbiting but 15 times faster than βC-scission, making it a dominant reaction. Benefiting from the absence of monomer, the chain transfer to polymer rate coefficient is assessed as 6 × 102 L mol−1 s −1 (140 °C). Model analysis shows that consecutive backbiting/migration/βC-scission leads to a favoring of MMs with even chain lengths and a hydrogen chain end over MMs with the nonreactive chain end originating from the initial dormant polymer. The obtained insights contribute to a better fundamental understanding of hydrogen abstractions in acrylate radical polymerization and open the path for a more detailed polymer product characterization in general.
Keywords
TRANSFER RADICAL POLYMERIZATION, N-BUTYL ACRYLATE, BIVARIATE MOLECULAR-WEIGHT, CHAIN TRANSFER, ICAR ATRP, POLY(BUTYL ACRYLATE), RAFT POLYMERIZATION, HIGH-TEMPERATURES, METHYL ACRYLATE, RATE CONSTANTS

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MLA
Van Steenberge, Paul, et al. “Kinetic Monte Carlo Generation of Complete Electron Spray Ionization Mass Spectra for Acrylate Macromonomer Synthesis.” MACROMOLECULES, vol. 50, no. 7, 2017, pp. 2625–36, doi:10.1021/acs.macromol.7b00333.
APA
Van Steenberge, P., Vandenbergh, J., Reyniers, M.-F., Junkers, T., D’hooge, D., & Marin, G. (2017). Kinetic Monte Carlo generation of complete electron spray ionization mass spectra for acrylate macromonomer synthesis. MACROMOLECULES, 50(7), 2625–2636. https://doi.org/10.1021/acs.macromol.7b00333
Chicago author-date
Van Steenberge, Paul, Joke Vandenbergh, Marie-Françoise Reyniers, Thomas Junkers, Dagmar D’hooge, and Guy Marin. 2017. “Kinetic Monte Carlo Generation of Complete Electron Spray Ionization Mass Spectra for Acrylate Macromonomer Synthesis.” MACROMOLECULES 50 (7): 2625–36. https://doi.org/10.1021/acs.macromol.7b00333.
Chicago author-date (all authors)
Van Steenberge, Paul, Joke Vandenbergh, Marie-Françoise Reyniers, Thomas Junkers, Dagmar D’hooge, and Guy Marin. 2017. “Kinetic Monte Carlo Generation of Complete Electron Spray Ionization Mass Spectra for Acrylate Macromonomer Synthesis.” MACROMOLECULES 50 (7): 2625–2636. doi:10.1021/acs.macromol.7b00333.
Vancouver
1.
Van Steenberge P, Vandenbergh J, Reyniers M-F, Junkers T, D’hooge D, Marin G. Kinetic Monte Carlo generation of complete electron spray ionization mass spectra for acrylate macromonomer synthesis. MACROMOLECULES. 2017;50(7):2625–36.
IEEE
[1]
P. Van Steenberge, J. Vandenbergh, M.-F. Reyniers, T. Junkers, D. D’hooge, and G. Marin, “Kinetic Monte Carlo generation of complete electron spray ionization mass spectra for acrylate macromonomer synthesis,” MACROMOLECULES, vol. 50, no. 7, pp. 2625–2636, 2017.
@article{8536541,
  abstract     = {{Absolute electron spray ionization mass spectrometry (ESI-MS) data are reported, for the first time, over the complete chain length range for the synthesis of welldefined macromonomers (MMs) obtained via activation of bromine-capped poly(n-butyl acrylate) (0.1 mass %; solvent: anisole; 140 °C) with CuBr2/Me6TREN (Me6TREN: tris(2 (dimethylamino)ethyl)amine) and tin ethylhexanoate. These data are generated based on bivariate kinetic Monte Carlo
simulations, tracking the chain lengths and the positions of radicals/characteristic groups along the chains (>100 reactions, 12 radical/dormant species types, and 7 characteristic end/ mid-groups). Based on qualitative tuning to experimental data, migration is found to be 50 times slower than backbiting but 15 times faster than βC-scission, making it a dominant reaction. Benefiting from the absence of monomer, the chain transfer to polymer rate coefficient is assessed as 6 × 102 L mol−1 s −1 (140 °C). Model analysis shows that consecutive backbiting/migration/βC-scission leads to a favoring of MMs with even chain lengths and a hydrogen chain end over MMs with the nonreactive chain end originating from the initial dormant polymer. The obtained insights contribute to a better fundamental understanding of hydrogen abstractions in acrylate radical polymerization and open the path for a more detailed polymer product characterization in general.}},
  author       = {{Van Steenberge, Paul and Vandenbergh, Joke and Reyniers, Marie-Françoise and Junkers, Thomas and D'hooge, Dagmar and Marin, Guy}},
  issn         = {{0024-9297}},
  journal      = {{MACROMOLECULES}},
  keywords     = {{TRANSFER RADICAL POLYMERIZATION,N-BUTYL ACRYLATE,BIVARIATE MOLECULAR-WEIGHT,CHAIN TRANSFER,ICAR ATRP,POLY(BUTYL ACRYLATE),RAFT POLYMERIZATION,HIGH-TEMPERATURES,METHYL ACRYLATE,RATE CONSTANTS}},
  language     = {{eng}},
  number       = {{7}},
  pages        = {{2625--2636}},
  title        = {{Kinetic Monte Carlo generation of complete electron spray ionization mass spectra for acrylate macromonomer synthesis}},
  url          = {{http://dx.doi.org/10.1021/acs.macromol.7b00333}},
  volume       = {{50}},
  year         = {{2017}},
}

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