Sustainable hemp-based bioplastics with tunable properties via reversible thermal crosslinking of cellulose

Modern bioplastics and biocomposites frequently contain non-biodegradable or non-sustainable components and require complex recycling routes. Sustainable materials require integrating bio-based, cheap, widely available, recycled, or waste components. In order to incorporate these concepts, we selected hemp stalk waste, the industrial byproducts glycerol and xylan (hemicellulose), and citric acid as key components. Hemp stalks were processed into cast papers using only mechanical processes and no chemical modifications or pre-treatments. Cast papers were impregnated with a crosslinking mixture of glycerol, xylan, citric acid, and the plasticizer polyethylene glycol (PEG). Thermal crosslinking was performed as a single-step reaction by curing materials at 140 °C. All prepared bioplastics were washed in water for 48 h and extensively tested for water resistance and water absorption. A recycling route with depolymerization (for pulp recovery) in sodium hydroxide is demonstrated. A comprehensive analysis of crosslinking reaction is provided via FTIR and rheology, supplemented by structure analysis via SEM. A 7-fold reduction in water uptake was achieved compared to cast hemp paper. Obtained bioplastics, after washing in water, show elastic modulus up to 2.9 GPa, tensile strength up to 70 MPa, and elongation up to 4.3 %. As a result of component ratio variation, bioplastics achieve a high tuneability of properties ranging from brittle to ductile. Dielectric analysis indicates that bioplastics have the potential for application in electric insulation. A three-layer laminate is demonstrated as a concept for potential application as an adhesive for bio-based composites.