Sulfur‐Rich Vitrimers From Oligosulfides and Epoxy Cross‐Linkers With Tunable Mechanical Properties and Adhesive Performance

ABSTRACT Sulfur‐rich vitrimers have attracted increasing interest due to their dynamic covalent networks and potential in sustainable materials. In this work, sulfur‐based vitrimer networks were constructed via a two‐step strategy by combining hydroxyl‐functionalized oligosulfides with epoxy cross‐linkers. The oligosulfides, containing dynamic oligosulfide (–Sx–) linkages, were synthesized through the oligomerization of elemental sulfur with cyclic disulfides, followed by cross‐linking with bisphenol A diglycidyl ether or diethylene glycol diglycidyl ether in the presence of imidazole. By tuning the type and loading of epoxy cross‐linkers, the resulting networks exhibit a wide range of mechanical properties, from rigid thermosets to soft and extensible materials, with tensile strengths up to 12.85 ± 2.73 MPa and elongations at break up to 44.40% ± 5.01%. In addition, these vitrimers demonstrate effective adhesive performance, achieving lap‐shear strengths of up to 6.05 ± 0.99 MPa on steel substrates. This work provides a straightforward and versatile strategy for designing sulfur‐rich vitrimer materials with tunable mechanical behavior and promising potential in structural adhesive applications.