Enhanced Mechanical and Thermal Properties of Epoxy Resins Through Hard–Soft Biphasic Synergistic Toughening with Modified POSS/Polysulfide Rubber

Toughening modification of epoxy resin (EP) matrices is important for advancing high-performance fiber-reinforced composites. A promising strategy involves the use of multi-component additive systems. However, synergistic effects in such additive systems are difficult to achieve for multidimensional performance optimization due to insufficient interfacial interactions and competing toughening mechanisms. Herein, a "hard-soft" biphasic synergistic toughening system was engineered for epoxy resin, composed of furan-ring-grafted polyhedral oligomeric silsesquioxane (FPOSS) and liquid polysulfide rubber. The hybrid toughening agent significantly enhanced the integrated performance of the epoxy system: Young's modulus, tensile strength, and elongation at break increased by 13%, 56%, and 101%, respectively. These improvements are attributed to the formation of enriched molecular chain entanglement sites and optimized dispersion, facilitated by nucleophilic addition reactions between flexible rubber segments and rigid FPOSS units with the epoxy matrix. The marked enhancement in toughness primarily stems from the synergistic toughening mechanism involving "crazing pinning" and "crazing-shear band". Concurrently, FPOSS incorporation effectively modulated the curing reaction kinetics, rendering the process more gradual while substantially elevating the glass transition temperature (T_g) of the cured system by 16.82 °C and endowing it with superior thermal degradation stability. This work provides a simple and unique strategy to leverage multi-scale mechanisms for the construction of epoxy-based composites with good toughness and strength, and enhanced heat resistance.