Synthesis of Glycerol-Based Biopolyesters as Toughness Enhancers for Polylactic Acid Bioplastic through Reactive Extrusion

[Image: see text] The synthesis of polyesters based on glycerol, succinic acid [poly(glycerol succinate), PGS] and/or maleic anhydride [poly(glycerol succinate-co-maleate), PGSMA] was investigated aiming to produce a green product suitable for toughening of polylactic acid (PLA) using melt blending technologies. The molar ratio of reactants and the synthesis temperature were screened to find optimum synthesis conditions leading to the highest toughness enhancement of PLA. It was found that a molar ratio of reactants of 1:1 glycerol/succinic acid increases the effectiveness of PGS as a toughening agent for PLA, which correlates with the achievement of a higher molecular weight on the synthesis of PGS. The introduction of maleic anhydride as a comonomer for the synthesis of the partial replacement of succinic acid was advantageous for making PGS suitable for reactive extrusion (REX) mediated by free radical initiators. The tensile toughness of the REX PLA/PGSMA blends was improved by 392% compared with that of neat PLA, which was caused by the simultaneous cross-linking of PGSMA within the PLA matrix, and the in situ formation of PLA-g-PGSMA graft copolymers acting as interfacial compatibilizers. Two-dimensional nuclear magnetic resonance and Fourier transform infrared analysis confirmed the formation of PLA-g-PGSMA species on REX experiments. This in turn caused a decrease in the diameter of the PGS particles dispersed within the PLA matrix from >10 μm to approximately 2 μm as observed using scanning electron microscopy. A further increase of 1600% in the toughness of the blends was achieved by lowering the synthesis temperature of PGSMA from 180 to 150 °C. The optimum synthesis conditions for PGSMA leading to the highest increase in the toughness of 80/20 PLA/PGSMA blends were found to be 1:0.5:0.5 mol glycerol/succinic acid/maleic anhydride synthesized at a temperature of 150 °C for 5 h.