Grafting Diels-Alder moieties on cellulose nanocrystals through carbamation.

• Carbamation of cellulose nanocrystals with TDI obtained at various surface DS. • Efficiency of grafting different Diels-Alder moieties onto CNCs surface assessed. • Thorough spectroscopy characterization of functionalized CNCs. The Diels-Alder reaction is a promising click chemistry for the design of advanced materials from cellulose nanocrystals (CNCs). Transferring such chemistry to cellulose nanocrystals requires the precise grafting of reactive Diels-Alder moeities under heterogeneous conditions without compromising the nanocrystals morphology. In this study toluene diisocyanate is used as a spacer to graft Diels-Alder moieties viz the furyl and protected maleimido moieties onto cellulose nanocrystals. A factorial experimental design reveals that reaction time and reactant molar ratio positively affect the grafting efficiency, as evidenced by FTIR and CHNS elemental analysis. The surface degree of substitution was analyzed via CHNS elemental analysis and XPS and found to range between 0.05 to 0.30, with a good agreement between the two techniques. 13C CP/MAS NMR confirmed that the grafted moieties and CNCs are intact after reaction. Side reactions were also observed and their impact on performing controllable click chemistry between cellulose nanocrystals is discussed. [ABSTRACT FROM AUTHOR]