TY - JOUR
T1 - A Mechanism-Based Reaction-Diffusion Model for Accelerated Discovery of Thermoset Resins Frontally Polymerized by Olefin Metathesis
AU - Bistri, Donald
AU - Arretche, Ignacio
AU - Lessard, Jacob J.
AU - Zakoworotny, Michael
AU - Vyas, Sagar
AU - Rongy, Laurence
AU - Gómez-Bombarelli, Rafael
AU - Moore, Jeffrey S.
AU - Geubelle, Philippe
N1 - Publisher Copyright:
© 2024 American Chemical Society.
PY - 2024/8/7
Y1 - 2024/8/7
N2 - Frontal ring-opening metathesis polymerization (FROMP) involves a self-perpetuating exothermic reaction, which enables the rapid and energy-efficient manufacturing of thermoset polymers and composites. Current state-of-the-art reaction-diffusion FROMP models rely on a phenomenological description of the olefin metathesis kinetics, limiting their ability to model the governing thermo-chemical FROMP processes. Furthermore, the existing models are unable to predict the variations in FROMP kinetics with changes in the resin composition and as a result are of limited utility toward accelerated discovery of new resin formulations. In this work, we formulate a chemically meaningful model grounded in the established mechanism of ring-opening metathesis polymerization (ROMP). Our study aims to validate the hypothesis that the ROMP mechanism, applicable to monomer-initiator solutions below 100 °C, remains valid under the nonideal conditions encountered in FROMP, including ambient to >200 °C temperatures, sharp temperature gradients, and neat monomer environments. Through extensive simulations, we demonstrate that our mechanism-based model accurately predicts the FROMP behavior across various resin compositions, including polymerization front velocities and thermal characteristics (e.g., Tmax). Additionally, we introduce a semi-inverse workflow that predicts FROMP behavior from a single experimental data point. Notably, the physiochemical parameters utilized in our model can be obtained through DFT calculations and minimal experiments, highlighting the model’s potential for rapid screening of new FROMP chemistries in pursuit of thermoset polymers with superior thermo-chemo-mechanical properties.
AB - Frontal ring-opening metathesis polymerization (FROMP) involves a self-perpetuating exothermic reaction, which enables the rapid and energy-efficient manufacturing of thermoset polymers and composites. Current state-of-the-art reaction-diffusion FROMP models rely on a phenomenological description of the olefin metathesis kinetics, limiting their ability to model the governing thermo-chemical FROMP processes. Furthermore, the existing models are unable to predict the variations in FROMP kinetics with changes in the resin composition and as a result are of limited utility toward accelerated discovery of new resin formulations. In this work, we formulate a chemically meaningful model grounded in the established mechanism of ring-opening metathesis polymerization (ROMP). Our study aims to validate the hypothesis that the ROMP mechanism, applicable to monomer-initiator solutions below 100 °C, remains valid under the nonideal conditions encountered in FROMP, including ambient to >200 °C temperatures, sharp temperature gradients, and neat monomer environments. Through extensive simulations, we demonstrate that our mechanism-based model accurately predicts the FROMP behavior across various resin compositions, including polymerization front velocities and thermal characteristics (e.g., Tmax). Additionally, we introduce a semi-inverse workflow that predicts FROMP behavior from a single experimental data point. Notably, the physiochemical parameters utilized in our model can be obtained through DFT calculations and minimal experiments, highlighting the model’s potential for rapid screening of new FROMP chemistries in pursuit of thermoset polymers with superior thermo-chemo-mechanical properties.
UR - http://www.scopus.com/inward/record.url?scp=85199943135&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85199943135&partnerID=8YFLogxK
U2 - 10.1021/jacs.4c06527
DO - 10.1021/jacs.4c06527
M3 - Article
C2 - 39075856
AN - SCOPUS:85199943135
SN - 0002-7863
VL - 146
SP - 21877
EP - 21888
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 31
ER -