Probing into the nucleation and reinforcing effects of poly (vinyl acetate) grafted cellulose nanocrystals in melt-processed poly (lactic acid) nanocomposites

Blending poly (lactic acid) (PLA) with cellulose nanocrystals (CNCs) to fabricate nanocomposites is a valuable strategy to improve the properties of PLA without sacrificing its biodegradability. However, the nucleation and reinforcing mechanisms of CNCs for semi-crystalline PLA matrix are still elusive in melt-processed PLA/CNC nanocomposites. Herein, poly (vinyl acetate) (PVAc) chains were grafted onto the surface of CNCs via an efficient radical polymerization in an aqueous medium, making CNCs suitable for conventional melting processing techniques. It is found that the dispersion state of CNCs in the PLA matrix and the interface interaction between PLA and CNCs can be tailored by varying the PVAc grafting density. Further studies show that well-dispersed CNCs play a positive role in reinforcing PLA. But unexpectedly, the nucleation effect is suppressed even though the homogeneous dispersion of CNCs is achieved with higher PVAc grafting density because the rich PVAc chains at the interface dilute the PLA chains, thus hindering the nucleation and spherulite growth of PLA. This research sheds light on the nucleation and reinforcing mechanisms of polymer grafted CNCs, and will provide theoretical guidance for the industrialization of high-performance bio-based nanocomposites.