Modeling and moisture uptake analysis of transition metal-catalyzed thermosetting resins via hybrid quantum chemistry and molecular dynamics simulations

Catalysts play a critical role in polymer synthesis by enhancing formation selectivity, accelerating crosslinking, and influencing final polymer properties. However, consider the catalysts effect in materials simulation research is still lack . However, consideration of the catalysts' effect in materials simulation research is still lacking. Here, we introduce a multistep Global Reaction Route Mapping/Monte Carlo/MD (GRRM/MC/MD) simulation approach that considers the catalytic crosslinking of bisphenol A dicyanate ester (BPACN) under transition metal catalysis. Two catalytic crosslinking pathways were identified and incorporated into our crosslinking algorithm to create polymer models. The predicted thermophysical properties, gel point, and glass transition temperature ( T g ), resulting from the polymer models, aligned with the experiment. With the catalyst concentration increased, the T g value increased and reached a plateau under high catalyst concentration. Grand canonical MC/MD simulations and radial distribution function analyses indicate that catalysts promote water aggregation to the ether O near the triazine structure. The coordination number peaks at moderate catalyst concentrations, explaining the varying hydrolysis rates under different catalytic conditions. This integrated approach enables the rational design of high-performance materials with desirable physicochemical properties, including elevated T g value and enhanced corrosion resistance. • Two reaction pathways for cyanate resin formation with transition metal catalysts were identified using the Global Reaction Route Mapping method. • Quantum chemistry calculations and molecular dynamics (MD) simulations were combined to construct realistic cyanate resin models with varying catalyst concentrations and sizes, enabling prediction of resin properties that align with experimental data. • Water adsorption values and adsorption sites were analyzed using Grand Canonical Monte Carlo/MD simulations and radial distribution functions, revealing a strong dependence on catalysts size.