Polylactic acid (PLA) is a promising biodegradable polymer whose widespread application is hindered by inherent brittleness. Polyethylene glycol (PEG) is a common plasticizer, but the effects of intermediate molecular weights, such as 4000 g/mol, on the coupled thermal, mechanical, and rheological properties of PLA remain insufficiently understood. This study presents a comprehensive analysis of PLA plasticized with 0–20 wt% PEG 4000, employing differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and rheology. DSC confirmed excellent miscibility and a significant glass transition temperature (T_g) depression exceeding 19 °C for the highest concentration. A complex, non-monotonic evolution of crystallinity was observed, associated with the formation of different crystalline forms (α′ and α). Critically, DMA revealed that the material’s thermo-mechanical response is dominated by its thermal history: while the plasticizing effect is masked in highly crystalline, as-cast films, it is unequivocally demonstrated in quenched amorphous samples. The core finding emerges from a targeted rheological investigation. An anomalous increase in melt viscosity and elasticity at intermediate PEG concentrations (5–15 wt%), observed at 180 °C, was systematically shown to vanish at 190 °C and in amorphous samples. This proves that the anomaly stems from residual crystalline domains (α′ precursors) persisting near the melting point, not from a transient molecular network. These results establish that PEG 4000 is a highly effective PLA plasticizer whose impact is profoundly mediated by processing-induced crystallinity. This work provides essential guidelines for tailoring PLA properties by controlling thermal history to optimize flexibility and processability for advanced applications, specifically in melt-processing for flexible packaging.

The thermal degradation behavior of Poly(2-ethyl hexyl hcrylate) (Poly(2-EHA)), blended with a commercially available nematic liquid crystal (LC) mixture, was investigated by thermal gravimetric analysis (TGA). Different heating rates, ranging from 5 to 200 °C/min, were applied under an inert atmosphere. Based on the TGA results, activation energies (E_α) at different conversion rates (α) were determined using three integral isoconversion methods: Flynn-Wall-Ozawa (FWO), Tang, and Kissinger-Akahira-Sunose (KAS). It can be noticed that the global evolution of these activation energies was the same for the three models. The coefficient of determination R² presented values generally higher than 0.97. Using these models, the E_α value for the LC remains constant at 64 kJ/mol for all conversions rates. For the polymer Poly(2-EHA), applying the Tang and FWO models, the activation energy presents a variation ranging from 80 kJ/mol, for conversion α = 0.1, to 170 kJ/mol, for α = 0.9. For the third model (KAS), this energy varies between 80 and 220 kJ/mol in the same range of α.