Development of a toughened and antibacterial Poly(lactide acid) (PLA) with preserved strength by elemental sulfur-based bio-renewable dynamically crosslinked elastomers

The toughening of PLA is usually realized by blending with elastomers or plasticizers, but often conflicted with lowered mechanical strength and complicated preparation steps. In the current study, inverse vulcanization was used to synthesize a series of dynamically cross-linked polysulfide (SOA) elastomers based on refining by-product elemental sulfur, soybean oil (SO) and allyl glyceryl ether (AGE), which provides dynamically reversible S-S bonds, flexible triglyceride segments and reactive epoxy functions. Melt blended with PLA, the SOAs exhibit great toughening effects and produce droplet-matrix typed blends with good interfacial compatibilization verified by rheology. SOA composition was decisive in dictating toughening efficiency. A high AGE content induces self-polymerization of epoxy groups, resulting in dominance of permanent crosslinking in SOA, giving rise to rigid SOA particles with bad processability and dispersity in PLA, hence poor toughener cavitations under external forces with unsatisfying toughening effect. A high sulfur and low AGE content results in dominance of dynamic crosslinking, providing soft SOA particles in favor of processing and dispersion in PLA matrix with small domains and thin ligament thickness, thus favoring internal cavitation of SOA particles to achieve good toughness. However, the presence of unreacted sulfur with a too high sulfur content can mitigate the toughening effect. In particular, a highly toughened blend with optimized SOA composition (PLA-S50O25A25) was obtained with excellent toughness (elongation at break 235.7% and tensile toughness 76.5 MJ/m3) balanced by only slightly impaired strength (tensile strength 50–60 MPa and modulus ∼ 900 Mpa). Moreover, the PLA-SOA exhibits excellent broad-spectrum anti-bacterial effects. This study reported the unprecedented use of fully sustainable dynamically-crosslinked elastomers as tougheners of PLA, paving new ways for PLA modification with balanced stiffness-toughness and antibacterial activity.