Inverse-Vulcanized Sulfur-Soybean Oil Polymers as Renewable Materials with Tunable Thermal Insulation Properties: Effect of Formulation and Biochar Incorporation.

Sulfur-soybean oil polymers with tunable thermal insulation properties were synthesized via inverse vulcanization of elemental sulfur and soybean oil and reinforced with biochar (BC) derived from spent barley biomass. Biopolymer films (F-BPs) with sulfur contents ranging from 20 to 80 wt% were prepared, and biochar-filled biocomposites (F-BP-Cs) were obtained using different filler loadings and processing routes. Their structural, morphological, thermal, mechanical, and surface properties were systematically analyzed to establish structure-property relationships, with particular focus on thermal transport behavior. Differential scanning calorimetry (DSC) revealed that sulfur contents ≤ 50 wt% favored the chemical incorporation of elemental sulfur into the polymer network via covalent bonding, significantly reducing the presence of free crystalline sulfur in the material. SEM images and porosity analysis revealed that BC incorporation and processing conditions significantly affected microstructural connectivity and air-filled porosity. As a result, F-BP-C materials exhibited low thermal conductivities, reaching values of ~0.033-0.039 W/(m·K), comparable to commercial insulating materials such as cork and polymeric foams. This reduction was attributed to increased structural disorder, high interfacial density, and enhanced phonon scattering within the heterogeneous polymer-BC-air system. These findings demonstrate the potential of these biocomposites as sustainable thermal insulating materials derived from industrial and agricultural waste.