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Access to the β-scission rate coefficient in acrylate radical polymerization by careful scanning of pulse laser frequencies at elevated temperature

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Abstract
A novel method to estimate the β-scission rate coefficient (kβ) in radical polymerization of acrylates is introduced, provided that the backbiting and tertiary propagation rate coefficient have already been determined at sufficiently low temperatures at which β-scission is negligible (≪350 K). The method relies on the sensitivity of kβ upon a change of the pulse laser frequency (≪200 Hz) under isothermal pulsed laser polymerization (PLP) conditions in the temperature range between ca. 350 and 415 K, leading to a sufficient variation of the times scales of the radicals involved. These observations are not significantly influenced by macropropagation and thermal self-initiation, as respectively confirmed by in silico testing and experimental data. Solution inflection point data (e.g. solvent butyl propionate) are needed in the lower temperature range (350–410 K), whereas bulk inflection point data suffice in the higher temperature range (410–415 K). The proposed method leads to an estimated kβ value of (4.26 ± 1.8) × 102 s −1 at 413 K with bulk PLP data, suggesting a high propensity of macromonomer formation in acrylate polymerization under high temperature radical polymerization conditions, exceeding the previously suggested levels (kβ = 6 × 100 –1.45 × 102 s −1 ).

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Chicago
Vir, Anil, Yoshi Marien, Paul Van Steenberge, Christopher Barner-Kowollik, Marie-Françoise Reyniers, Guy Marin, and Dagmar D’hooge. 2018. “Access to the Β-scission Rate Coefficient in Acrylate Radical Polymerization by Careful Scanning of Pulse Laser Frequencies at Elevated Temperature.” Reaction Chemistry & Engineering 3 (5): 807–815.
APA
Vir, A., Marien, Y., Van Steenberge, P., Barner-Kowollik, C., Reyniers, M.-F., Marin, G., & D’hooge, D. (2018). Access to the β-scission rate coefficient in acrylate radical polymerization by careful scanning of pulse laser frequencies at elevated temperature. REACTION CHEMISTRY & ENGINEERING, 3(5), 807–815.
Vancouver
1.
Vir A, Marien Y, Van Steenberge P, Barner-Kowollik C, Reyniers M-F, Marin G, et al. Access to the β-scission rate coefficient in acrylate radical polymerization by careful scanning of pulse laser frequencies at elevated temperature. REACTION CHEMISTRY & ENGINEERING. 2018;3(5):807–15.
MLA
Vir, Anil et al. “Access to the Β-scission Rate Coefficient in Acrylate Radical Polymerization by Careful Scanning of Pulse Laser Frequencies at Elevated Temperature.” REACTION CHEMISTRY & ENGINEERING 3.5 (2018): 807–815. Print.
@article{8579171,
  abstract     = {A novel method to estimate the \ensuremath{\beta}-scission rate coefficient (k\ensuremath{\beta}) in radical polymerization of acrylates is introduced,
provided that the backbiting and tertiary propagation rate coefficient have already been determined
at sufficiently low temperatures at which \ensuremath{\beta}-scission is negligible (\unmatched{226a}350 K). The method relies on
the sensitivity of k\ensuremath{\beta} upon a change of the pulse laser frequency (\unmatched{226a}200 Hz) under isothermal pulsed laser
polymerization (PLP) conditions in the temperature range between ca. 350 and 415 K, leading to a sufficient
variation of the times scales of the radicals involved. These observations are not significantly
influenced by macropropagation and thermal self-initiation, as respectively confirmed by in silico testing
and experimental data. Solution inflection point data (e.g. solvent butyl propionate) are needed in the
lower temperature range (350--410 K), whereas bulk inflection point data suffice in the higher temperature
range (410--415 K). The proposed method leads to an estimated k\ensuremath{\beta} value of (4.26 {\textpm} 1.8) {\texttimes} 102 s
\ensuremath{-}1 at
413 K with bulk PLP data, suggesting a high propensity of macromonomer formation in acrylate polymerization
under high temperature radical polymerization conditions, exceeding the previously suggested
levels (k\ensuremath{\beta} = 6 {\texttimes} 100
--1.45 {\texttimes} 102 s
\ensuremath{-}1
).},
  author       = {Vir, Anil and Marien, Yoshi and Van Steenberge, Paul and  Barner-Kowollik, Christopher and Reyniers, Marie-Fran\c{c}oise and Marin, Guy and D'hooge, Dagmar},
  issn         = {2058-9883 },
  journal      = {REACTION CHEMISTRY \& ENGINEERING},
  language     = {eng},
  number       = {5},
  pages        = {807--815},
  title        = {Access to the \ensuremath{\beta}-scission rate coefficient in acrylate radical polymerization by careful scanning of pulse laser frequencies at elevated temperature},
  url          = {http://dx.doi.org/10.1039/C8RE00171E},
  volume       = {3},
  year         = {2018},
}

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