Rheological Behavior and Mechanical Performance of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)/Natural Rubber Blends Modified with Coffee Oil Epoxide for Sustainable Packaging Applications.

The inherent brittleness of bio-based poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) significantly restricts its industrial applications despite its industrial compostability. Blending with elastomeric polymers addresses mechanical limitations; however, interfacial incompatibility compromises miscibility as our previous work established. Herein, we investigate coffee oil epoxide (COE) as a bio-based plasticizer for PHBV/natural rubber (NR) blends in sustainable packaging applications. COE, derived from spent coffee grounds, was incorporated into PHBV/NR/peroxide/coagent composites via twin-screw extrusion. FTIR spectroscopy with chemometric analysis confirmed successful COE incorporation (intensified CH stretching: 2847, 2920 cm; reduced crystallinity), with PCA and PLS-DA accounting for 67.9% and 54.4% of spectral variance. COE incorporation improved optical properties (7.73% increased lightness; 21.9% reduced yellowness). Rheological characterization through Cole-Cole and Han plots demonstrated enhanced phase compatibility in the PHBV/NR/COE blends. Mechanical testing showed characteristic reductions in flexural properties: strength decreased by 16.5% and modulus by 36.8%. Dynamic mechanical analysis revealed PHBV/NR/COE blends exhibited a single relaxation transition at 32 °C versus distinct glass transition temperatures in PHBV/NR blends. Tan δ deconvolution confirmed the transformation from bimodal distribution to a single broadened peak, indicating enhanced interfacial interactions and improved miscibility. These findings demonstrated COE's potential as a sustainable additive for biodegradable PHBV-based packaging while valorizing food waste.