A Mechanism-Based Reaction–Diffusion Model for Accelerated Discovery of Thermoset Resins Frontally Polymerized by Olefin Metathesis

Bistri, Donald; Arretche, Ignacio; Lessard, Jacob J.; Zakoworotny, Michael; Vyas, Sagar; Rongy, Laurence; Gómez-Bombarelli, Rafael; Moore, Jeffrey S.; Geubelle, Philippe

doi:10.1021/jacs.4c06527

A Mechanism-Based Reaction–Diffusion Model for Accelerated Discovery of Thermoset Resins Frontally Polymerized by Olefin Metathesis

Journal Article · Mon Jul 29 00:00:00 EDT 2024 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.4c06527· OSTI ID:2427296

^[1]; Arretche, Ignacio ^[2]; ^[2]; Zakoworotny, Michael ^[2]; Vyas, Sagar ^[2]; ^[3]; ^[4]; ^[2]; ^[2]

University of Illinois Urbana-Champaign, IL (United States); EFRC REMAT, University of Illinois Urbana-Champaign
University of Illinois Urbana-Champaign, IL (United States)
Université libre de Bruxelles (Belgium)
Massachusetts Institute of Technology (MIT), Cambridge, MA (United States)

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., T_max). 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.

View Accepted Manuscript (DOE)

Research Organization:: University of Illinois Urbana-Champaign, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0023457

OSTI ID:: 2427296

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 31 Vol. 146; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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