Polylactic Acid and Polylactic Acid-Based Nanocomposite Photooxidation

The importance of photooxidation in promoting formation of anhydride functional groups and thus promoting hydrolysis/biodegradation of polylactic acid and PLA nanocomposites were elucidated. PLA-based nanocomposites were prepared by adding 5% wt filler content of sodium montmorillonite (ClNa), sodium montmorillonite partially exchanged with Fe(III) (ClFe), organically modified montmorillonite (Cl20A), unmodified sepiolite (SEP), and fumed silica (SiO2). The pure PLA and nanocomposites were UV-light irradiated in artificial accelerated conditions representative of solar irradiation (λ > 300 nm) at 60 °C in air. The chemical modifications resulting from photooxidation were followed by IR and UV−visible spectroscopies. The infrared analyses of PLA photooxidation show the formation of a band at 1845 cm−1 due to the formation of anhydrides. A photooxidation mechanism based on hydroperoxide decomposition is proposed. The mechanism proposed is confirmed by an increase in anhydride formation rate: the main responsible for this acceleration was identified as transition metals contained in the nanofillers as impurities and involved in the catalytic hydroperoxide decomposition.