Hierarchically Structured Vitrimer Biocomposites for Sustainable Manufacturing

Abstract Polymers containing dynamic covalent bonds (DCBs) exhibit thermoplastic‐like flow above their topology freezing temperature ( T _v ) while maintaining thermoset‐like properties below it, making them promising for sustainable manufacturing. However, their large‐scale adoption remains limited due to challenges in accurately determining T _v and achieving efficient fiber‐matrix bonding in composite applications. Here, hierarchically structured epoxy‐anhydride‐based polyester vitrimer composites reinforced with cellulosic filaments is demonstrated, where hydroxyl groups on fiber surfaces participate directly in transesterification with the matrix. This dynamic interfacial bonding delivers exceptional mechanical properties, including ≈70 MPa shear strength and >10% strain‐to‐failure, while enabling thermal malleability. Using a combination of nuclear magnetic resonance and nano‐infrared spectroscopies, direct evidence is provided that chemical bond exchange begins well below the conventionally measured T _v , supporting the hypothesis that rheologically determined T _v reflects a combination of chemical exchange and frictional dynamics rather than a discrete transition. The composites demonstrate excellent processability through vacuum‐assisted resin transfer molding and maintain >90% of their mechanical properties after multiple thermal reforming cycles. These findings advance both the fundamental understanding of vitrimeric transitions and the practical development of sustainable, high‐performance composite materials.