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Effect of Intramolecular Transfer to Polymer on Stationary Free‐Radical Polymerization of Alkyl Acrylates, 5 – Consideration of Solution Polymerization up to High Temperatures
Author(s) -
Nikitin Anatoly N.,
Hutchinson Robin A.,
Wang Wei,
Kalfas George A.,
Richards John R.,
Bruni Christopher
Publication year - 2010
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.201000014
Subject(s) - polymerization , chain transfer , arrhenius equation , radical polymerization , chemistry , polymer chemistry , intramolecular force , acrylate , reaction rate constant , radical , macromonomer , monomer , butyl acrylate , polymer , thermodynamics , kinetics , activation energy , stereochemistry , physics , organic chemistry , quantum mechanics
Abstract Butyl acrylate solution polymerization has been studied at 80–170 °C over a range of monomer and initiator levels. A PREDICI model has been developed to describe the experiments, taking into account chain backbiting, β ‐scission, and addition of macromonomer. The model is used to estimate Arrhenius parameters for the rate coefficients of β ‐scission [ A ( k β ) = (1.49 ± 0.28) × 10 9 s −1 , E a ( k β ) = 63.9 ± 0.9 kJ · mol −1 ], for the ratio of the termination rate coefficients of secondary and midchain radicals ${\left[ {A(k_{{\rm t}} /k_{{\rm t}}^{{\rm t}} ) = 0.74\pm 0.08,\;\;\,E_{{\rm a}} (k_{{\rm t}} /k_{{\rm t}}^{{\rm t}} ) = {-} (11.2\pm 0.5){\rm kJ}\cdot {\rm mol}^{{-} 1} } \right]}$ and for the constant of chain transfer to xylene [ A ( C trS ) = 107 ± 13, E a ( C trS ) = 35.4 ± 0.8 kJ · mol −1 ] by fitting simulated dependencies to the experimental data.