Surface Modification of Nanocellulose towards Composite Applications

Abstract: Nanocelluloses have attracted great interest during recent decades owing to their renewability, abundancy and remarkable physical and mechanical properties. The aim of this work was to investigate new strategies for surface modification and functionalization of nanocelluloses and their subsequent incorporation in polymer-host matrices.Nanocomposites of cellulose nanofibrils (CNF) and polycaprolactone (PCL) were produced by employing CNF nanopaper (NP) as a template and surface-initiated ring-opening polymerization (SI-ROP) of ε-caprolactone (ε-CL). SI-ROP of ε-CL from filter paper (FP) was also carried out for comparison. A larger amount of PCL was grafted from NP than from FP. The grafted NP had stronger mechanical properties than neat PCL.Cellulose nanocrystal (CNC)-reinforced polyvinyl acetate (PVAc) nanocomposites were also investigated. CNC were modified via “SI-reversible addition-fragmentation chain transfer and macromolecular design via the interchange of xanthate” (SI-RAFT/MADIX) polymerization of vinyl acetate (VAc). The resulting nanocomposites exhibited improved mechanical performance than the unmodified CNC.It is generally agreed that covalent grafting is superior to physical adsorption for the modification of a reinforcing agent. However, this hypothesis has never been thoroughly investigated. CNC was modified either through covalent grafting or through physical adsorption of poly(butyl methacrylate) (PBMA). Both methods resulted in improved mechanical performance than that of pure PCL or PCL containing unmodified CNC. However, covalent grafting gave the best mechanical performance even at high relative humidity.Functionalized CNC (F-CNC) were obtained through a versatile methodology employing organic acids bearing a functional group were employed for the simultaneous acid hydrolysis and esterification of cellulose fibers. This provided a facile route for the preparation of F-CNC.