Serse, Francesco;
Salvalaglio, Matteo;
Pelucchi, Matteo;
(2025)
First principles assessment of solvent induced cage effects on intramolecular hydrogen transfer in the free radical polymerization of acrylates.
Physical Chemistry Chemical Physics
, 27
(10)
pp. 5271-5284.
10.1039/D4CP04415K.
Preview |
Text
d4cp04415k.pdf - Published Version Download (1MB) | Preview |
Abstract
We investigate the rate constant of poly-butyl acrylate backbiting between 310 and 510 K using semi-empirical metadynamics in the gas phase, bulk and solution. The simulations in the condensed phase are performed through a hybrid quantum mechanics/molecular mechanics approach. The free energy landscape associated with the reactive events under vacuum and in the condensed phase is used to correct harmonic transition state theory (TST) rate constants. The Arrhenius parameters so determined are introduced in a semi-detailed mechanistic kinetic mechanism of butyl acrylate polymerization in bulk and in solution, allowing it to test how the butyl acrylate polymerization rate is affected by solvent-induced cage effects on backbiting. The results show that the backbiting rate constant is higher in the condensed phase than in the gas phase. In addition, a twofold increase is observed in xylene compared to the bulk. These results differ significantly from previous theoretical calculations, especially at high temperatures, aligning better with experimental rate measurements. The semi-detailed model, incorporating our calculated rate coefficients, is validated against monomer concentration profiles from bulk and solution polymerizations in various reactor configurations, demonstrating good agreement with experimental data. This study paves the way for developing detailed kinetic models in the condensed phase using a priori kinetic parameters derived from molecular simulations, thus widening their range of applicability beyond the one experimentally accessible.
| Type: | Article |
|---|---|
| Title: | First principles assessment of solvent induced cage effects on intramolecular hydrogen transfer in the free radical polymerization of acrylates |
| Location: | England |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1039/D4CP04415K |
| Publisher version: | https://doi.org/10.1039/D4CP04415K |
| Language: | English |
| Additional information: | © The Author(s), 2025. This is an open access article distributed in accordance with the Creative Commons Attribution Non Commercial (CC BY-NC 4.0) license, which permits others to distribute, remix, adapt, build upon this work non-commercially, and license their derivative works on different terms, provided the original work is properly cited, appropriate credit is given, any changes made indicated, and the use is non-commercial. See: http://creativecommons.org/licenses/by-nc/4.0/. |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Engineering Science > Dept of Chemical Engineering |
| URI: | https://discovery.ucl.ac.uk/id/eprint/10206386 |
Loading...
Loading...Loading...Loading...Archive Staff Only
 |
View Item |
