Focus on Gradientwise Control of the Surface Acetylation of Cellulose Nanocrystals to Optimize Mechanical Reinforcement for Hydrophobic Polyester-Based Nanocomposites

[Image: see text] Surface acetylation of cellulose nanocrystals (CNCs) imposes an important effect on CNC-related mechanical enhancement of hydrophobic polyester-based composites, of which interfacial properties still need optimization. In the present work, the surface acetylation of CNCs was adjusted as a gradient of above ca. 10%. Then, we found that the surface energy of acetylated CNCs (ACNs) decreased and thus their hydrophobicity increased as the surface acetylation degree increased. Hence, the ACNs with varied degrees of acetyl substitution (DS(surface-acetyl)) values were attempted to reinforce a kind of hydrophobic polyester, poly(3-hydroxybutyrate-co-4-hydroxybutyrate) (PHB). The results indicated that a smaller discrepancy in the surface energy between the CNC surface and the PHB matrix was obtained, as the surface acetylation degree increased, and then, the affinity and interaction between the two components increased, which improved the homogeneous distribution of ACNs in the PHB matrix. Besides, in comparison to the nanocomposites filled with 15 wt % unmodified CNCs, the tensile strength of those with ACNs of 62.9% DS(surface-acetyl) was 43.3% higher. This study was the first attempt to adjust the surface substitution degrees with a gradient profile for the surface modification of CNCs and prove that acetylation gradient control is an effective and facile strategy to optimize the mechanical properties.