Evaluation and Modeling of Polylactide Photodegradation under Ultraviolet Irradiation: Bio-Based Polyester Photolysis Mechanism.

In our study, we investigated the accelerated aging process of PLA under 253.7 nm UV-C irradiation with the use of the GPC, NMR, FTIR, and DSC methods and formal kinetic analysis. The results of GPC and DSC indicated a significant degree of destructive changes in the PLA macromolecules, while spectroscopic methods NMR and FTIR showed maintenance of the PLA main structural elements even after a long time of UV exposure. In addition to that, the GPC method displayed the formation of a high molecular weight fraction starting from 24 h of irradiation, and an increase in its content after 144 h of irradiation. It has been shown for the first time that a distinctive feature of prolonged UV exposure is the occurrence of intra- and intermolecular radical recombination reactions, leading to the formation of a high molecular weight fraction of PLA decomposition products. This causes the observed slowdown of the photolysis process. It was concluded that photolysis of PLA is a complex physicochemical process, the mechanism of which depends on morphological changes in the solid phase of the polymer under UV radiation.

Hydrolysis, Biodegradation and Ion Sorption in Binary Biocomposites of Chitosan with Polyesters: Polylactide and Poly(3-Hydroxybutyrate).

The film binary composites polylactide (PLA)-chitosan and poly(3-hydroxybutyrate) (PHB)-chitosan have been fabricated and their functional characteristics, such as hydrolysis resistance, biodegradation in soil, and ion sorption behavior have been explored. It was established that hydrolysis temperature and acidity of solutions are differently affected by the weight loss of these two systems. Thus, in the HCl aqueous solutions, the stability of the PHB-chitosan composites is higher than the stability of the PLA-chitosan one, while the opposite situation was observed for biodegradation in soil. The sorption capacity of both composites to Fe3+ ions was investigated and it was shown that, for PHB-chitosan composites, the sorption is higher than for PLA-chitosan. It was established that kinetics of sorption obeys the pseudo-first-order equation and limiting values of sorption correspond to Henry's Law formalism. By scanning electron microscopy (SEM), the comparative investigation of initial films and films containing sorbed ions was made and the change of films surface after Fe3+ sorption is demonstrated. The findings presented could open a new horizon in the implementation of novel functional biodegradable composites.

Biodegradable Polylactide-Poly(3-Hydroxybutyrate) Compositions Obtained via Blending under Shear Deformations and Electrospinning: Characterization and Environmental Application.

Compositions of polylactide (PLA) and poly(3-hydroxybutyrate) (PHB) thermoplastic polyesters originated from the nature raw have been obtained by blending under shear deformations and electrospinning methods in the form of films and nanofibers as well as unwoven nanofibrous materials, respectively. The degrees of crystallinity calculated on the base of melting enthalpies and thermal transition temperatures for glassy state, cold crystallization, and melting point for individual biopolymers and ternary polymer blends PLA-PHB- poly(ethyleneglycol) (PEG) have been evaluated. It has been shown that the mechanical properties of compositions depend on the presence of plasticizers PEG with different molar masses in interval of 400-1000. The experiments on the action of mold fungi on the films have shown that PHB is a fully biodegradable polymer unlike PLA, whereas the biodegradability of the obtained composites is determined by their composition. The sorption activity of PLA-PHB nanofibers and unwoven nanofibrous PLA-PHB composites relative to water and oil has been studied and the possibility of their use as absorbents in wastewater treatment from petroleum products has been demonstrated.