Studies on PLA grafting onto graphene oxide and its effect on the ensuing composite films

Polylactide (PLA) with a terminal triple bond was synthesized by organocatalyzed ring-opening polymerization and coupled with azide-functionalized graphene oxide (GO) through an azide-alkyne cycloaddition "click" reaction. The functionalized graphenic species involved were analyzed by spectroscopic techniques (FT-IR, solid state ¹³C NMR, Raman), which confirmed the coupling of PLA and GO. Additionally, an in depth study of the prepared GO, intermediates and GO-g-PLA hybrid was carried out that sheds light on the mechanisms involved in the functionalization path. The obtained GO-g-PLA hybrid, containing at least 20% of biopolymer, presented an exfoliated graphenic structure, as established by XRD. The conditions used in the grafting of the PLA chains inhibited the crystallization and melting observed for the free polymer. Furthermore, the graphene oxide seems to be reduced during functionalization, which can also be an advantage. Nanocomposites were obtained as solvent-cast films, prepared by dispersion of the GO-g-PLA hybrid in commercial PLA. Preliminary results regarding the performance of these nanocomposites, obtained by DSC and DMA, highlighted the effect of functionalization. Loading values as low as 0.5% suffice to improve the mechanical properties over a broad temperature range due to the high surface area resulting from the good dispersibility of polymer functionalized nanofillers and/or their effect on the polymer chain organization. - Highlights: • A graphene oxide/PLA (GO-g-PLA) hybrid was obtained by a grafting-to method. • Grafting of PLA chains onto the surface of GO inhibited polymer crystallization. • The GO-g-PLA material was used in the reinforcement of PLA, as nanocomposite films. • GO-g-PLA provides more homogeneously reinforced nanocomposite films, than neat GO. • Nanocomposite films with 0.5% loading present high storage modulus even above T_g.