Polylactide (PLA) was blended by conventional and reactive extrusion with limonene (LM) or myrcene (My) as bio-based plasticizers. As-processed blends were carefully analyzed by a multiscale and multidisciplinary approach to tentatively determine their chemical structure, microstructure, thermal properties, tensile and impact behaviors, and hydrothermal stability. The main results indicated that LM and My were efficient plasticizers for PLA, since compared to neat PLA, the glass transition temperature was reduced, the ultimate tensile strain was increased, and the impact strength was increased, independently of the type of extrusion. The addition of a free radical initiator during the extrusion of PLA/LM was beneficial for the mechanical properties. Indeed, the probable formation of local branched/crosslinked regions in the PLA matrix enhanced the matrix crystallinity, the tensile yield stress, and the tensile ultimate stress compared to the non-reactive blend PLA/LM, while the other properties were retained. For PLA/My blends, reactive extrusion was detrimental for the mechanical properties since My polymerization was accelerated resulting in a drop of the tensile ultimate strain and impact strength, and an increase of the glass transition temperature. Indeed, large inclusions of polymerized My were formed, decreasing the available content of My for the plasticization and enhancing cavitation from inclusion-matrix debonding.
Keywords: limonene; mechanical properties; myrcene; plasticization; polylactide; reactive extrusion; structure.