A series of polylactic acid (PLA)/polyethylene glycol (PEG) blends was prepared by melt blending using PEG as a plasticizer to address the disadvantages of PLA brittleness. PEG can weaken the intermolecular chain interactions of PLA and improve its processing properties. PLA-grafted maleic anhydride (GPLA) was reactively blended with PLA/PEG to obtain a high tenacity PLA/PEG/GPLA blend. GPLA was prepared by melt grafting using diisopropyl peroxide as the initiator and maleic anhydride as the graft. The effects of different PEG molecular weights (1000–10 000 g mol⁻¹) on the properties of PLA/PEG/GPLA blends were investigated. GPLA reacted with PEG1000 (M_w = 1000 g mol⁻¹) to form short PLA branched chains and reacted with PEG10000 (M_w = 10 000 g mol⁻¹) to form a small number of PLA branched chains, which was unconducive to increasing the intermolecular chain entanglement. The branched PLA formed by the reaction between PEG6000 (M_w = 6000 g mol⁻¹) and GPLA had a remarkable effect on increasing intermolecular chain entanglement. The complex viscosity, modulus, and melt strength values of PLA/PEG6000/GPLA blends were relatively large. The elongation at break of the blends reached 526.9%, and the tensile strength was 30.91 MPa. It provides an effective way to prepare PLA materials with excellent comprehensive properties.

In this study, poly(lactic acid) (PLA)/starch blends were prepared through reactive melt blending by using PLA and starch as raw materials and vegetable oil polyols, polyethylene glycol (PEG), and citric acid (CA) as additives. The effects of CA and PEG on the toughness of PLA/starch blends were analyzed using a mechanical performance test, scanning electron microscope analysis, differential scanning calorimetry, Fourier-transform infrared spectroscopy, X-ray diffraction, rheological analysis, and hydrophilicity test. Results showed that the elongation at break and impact strength of the PLA/premixed starch (PSt)/PEG/CA blend were 140.51% and 3.56 kJ·m⁻², which were 13.4 and 1.8 times higher than those of pure PLA, respectively. The essence of the improvement in the toughness of the PLA/PSt/PEG/CA blend was the esterification reaction among CA, PEG, and starch. During the melt-blending process, the CA with abundant carboxyl groups reacted in the amorphous region of the starch. The shape and crystal form of the starch did not change, but the surface activity of the starch improved and consequently increased the adhesion between starch and PLA. As a plasticizer for PLA and starch, PEG effectively enhanced the mobility of the molecular chains. After PEG was dispersed, it participated in the esterification reaction of CA and starch at the interface and formed a branched/crosslinked copolymer that was embedded in the interface of PLA and starch. This copolymer further improved the compatibility of the PLA/starch blends. PEGs with small molecules and CA were used as compatibilizers to reduce the effect on PLA biodegradability. The esterification reaction on the starch surface improved the compatibilization and toughness of the PLA/starch blend materials and broadens their application prospects in the fields of medicine and high-fill packaging.