Abstract
Designing high-performance crosslinked polymers requires overcoming the inherent stiffness-toughness trade-off through precise control of the network topology. Using epoxy resin as a model system, we establish a multiscale simulation framework to investigate curing reaction kinetics, network evolution, and structure-property relationships. By employing m-phenylenediamine (mPDA) and 1,3-bis(3-aminophenoxy)benzene (DABPB) as competing short- and long-chain curing agents, we demonstrate how network architecture dictates mechanical performance. Simulations reveal that mPDA produces a dense, heterogeneous network with enhanced stiffness, whereas DABPB forms a more uniform structure with greater chain mobility, leading to improved toughness. Through stoichiometric tuning, we achieve fine control over crosslink density and mechanical properties. Furthermore, we decouple cavity formation mechanisms into pendant chain slippage and bond rupture, offering molecular-level insights for the rational design of epoxy resins with programmable mechanical behavior.