Grafting novel and nature-inspired phenolic esters onto cellulose nanocrystals (CNCs) provides nanofibers with excellent protection against UV radiation when incorporated into a polymer matrix. In this work, CNCs decorated with a novel UVabsorbing phenolic diester (CNC-diethyl ferulate or CNC-DEF) obtained via a click-type copper-catalyzed azide/alkyne cycloaddition reaction were incorporated into a polyvinyl alcohol (PVA) matrix to produce transparent films with excellent photostability and UV-absorbing properties. PVA films filled with 20 wt % CNC-DEF exhibited complete UV protection (0% transmittance) and high transparency in the visible region (70− 90% transmittance). In contrast, PVA films loaded with the pristine CNCs do not show any UV-shielding properties. Importantly, the grafting of DEF moieties on CNCs significantly aids the dispersion of the phenolic diester in the aqueous PVA matrix, which was not achieved with DEF blended with PVA. Mechanical tests also show that the addition of 20 wt % CNC-DEF in PVA increases the tensile strength and modulus by 91 and 150%, respectively, relative to neat PVA. The oxygen barrier properties of the composite film also improve with CNC-DEF addition. This study shows the great potential of the phenolic-ester-decorated CNCs as dispersible, multifunctional UV-absorbing nanoreinforcements in PVA films for industrial and packaging applications.
New nature‐inspired and plant‐derived p‐hydroxycinnamate esters and p‐hydroxycinnamate diesters provide excellent protection against UV radiation when incorporated into a matrix. Herein, an efficient and sustainable pathway is reported to graft these phenolic compounds onto cellulose nanocrystals (CNCs) via click‐type copper‐catalyzed azide/alkyne cycloaddition (CuAAC) reaction. The successful grafting of the phenolic esters on CNC surface was evidenced by a range of chemical analyses, and the degrees of substitution (DS) of the CNC were found to depend on the structure of the phenolic ester grafted. Moreover, aqueous suspensions of the phenolic ester‐grafted CNCs not only strongly absorb in both the UVA and UVB regions, but they also exhibit average to very high photostability. Their wide spectrum UV‐absorbing properties and their stability upon exposure to UV are highly influenced by the structure of the phenolic ester, particularly by the extra ester group in p‐hydroxycinnamate diesters. These findings demonstrate that cellulose nanocrystals decorated with such plant‐derived and nature‐inspired phenolic esters are promising sustainable nanomaterials for anti‐UV applications.
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