Toward understanding the cross‐linking from molecular chains to aggregates by engineering terminals of supramolecular hyperbranched polysiloxane

Abstract Crosslinking thermosets with hyperbranched polymers confers them superior comprehensive performance. However, it still remains a further understanding of polymer crosslinking from the molecular chains to role aggregates. In this study, three polysiloxane structures (HBPSi‐R) are synthesized as model macromolecules, each featuring distinct terminal groups (R denotes amino, epoxy, and vinyl groups) while similar backbone (Si‐O‐C). These were subsequently copolymerized epoxy monomers construct interpenetrating HBPSi‐R/epoxy/anhydride co‐polymer systems. The spatial configuration flexible Si‐O‐C branches HBPSi‐R endow remarkable reinforcement toughening effects. Notably, an optimum impact strength 28.9 kJ mol −1 is achieved mere 3% loading HBPSi‐V, nearly times that native (12.9 ). By contrasting effects, aggregation states modes proposed, thus clarifying supramolecular‐dominant mechanism covalent‐dominant dispersion mechanism, which influences resulting material properties. This work underscores significance aggregate science in comprehending provides theoretical insights for tailoring properties at refined level field science.