Novel blends of polylactide with ethylene glycol derivatives of POSS

Polylactide (PLA), a main biodegradable and biobased candidate for the replacement of petrochemical polymers, is stiff and brittle at room conditions. It is therefore of high interest to formulate new PLA-based materials suitable for applications demanding flexibility and toughness. In this work, novel blends of PLA with polyhedral oligomeric silsesquioxanes (POSS) grafted with longer (P1) and shorter (P2) arms of ethylene glycol derivatives were prepared and studied. It was hypothesized that, owing to their architecture with the central POSS cage grafted with arms, miscibility and stability of the blends could be improved. Indeed, PLA/P1 blends were homogeneous despite P1 relatively high M_w of 9,500 g mol^-1. The blend with 20 wt% of P1, having T_g at 16 °C, was transparent and flexible, elastomer-like material with excellent drawability. The blend remained homogeneous and retained its good drawability as well as flexibility during 6 months of aging at room temperature: a 2 % secant modulus of elasticity well below 100 MPa, a low yield stress below 2 MPa, and and a large strain at break of 8 (800 %). Contary to that, PLA/P2 blends were only partially miscible. Nevertheless, owing to the liquid state of the dispersed phase, the blend with 15 wt% of P2 was transparent and ductile, with T_g at 49 °C, a relatively high yield strength of 29 MPa, and a large strain at break of 2.3 (230 %). The toughening mechanism involved the initiation of crazes and facilitation of their propagation by the liquid inclusions via the local plasticization effect.