Polyglycerol-Based Polymers for Additive Manufacturing: Thermomechanical Design for Structural Applications

Additive manufacturing (AM) is revolutionizing the fabrication of structural compo-nents, demanding materials that balance printability with superior thermal and me-chanical performance. Polyglycerol-based macromolecular systems have emerged as promising candidates due to their highly tunable chemical architecture. Variations such as linear, hyperbranched, and dendritic topologies significantly influence thermal behavior, elasticity, and mechanical strength. Functional strategies including cross-linking, copolymerization, and additive incorporation enable property enhancement tailored to diverse AM platforms like stereolithography (SLA), digital light processing (DLP), and fused deposition modeling (FDM). While native polyglycerol systems ex-hibit low thermal stability, chemical modifications and hybridization with fillers like carbon nanotubes, cellulose nanofibers, or graphene oxide improve decomposition temperatures, flame retardancy, and thermal conductivity. Crosslinked derivatives also show increased glass transition and melting points, suitable for moder-ate-temperature printing and structural applications. However, trade-offs such as brittleness from excessive crosslinking and dispersion challenges with nanofillers re-main unresolved. This review critically evaluates the structure–property-processing relationships in polyglycerol-based systems, emphasizing their role in the development of next-generation, multifunctional materials for AM. Emphasis is placed on thermal performance, mechanical optimization, and the integration of environmentally friendly processing strategies.