Structural and functional modification of cellulose nanofibrils using graft copolymerization with glycidyl methacrylate by Fe²⁺–thiourea dioxide–H₂O₂ redox system

To graft epoxy and ester functional groups onto cellulose nanofibrils (CNFs) and to overcome their poor hydrophobicity, we studied the modification of CNFs using graft copolymerization with glycidyl methacrylate (GMA) by a Fe²⁺–thiourea dioxide–H₂O₂ initiator system (Fe²⁺–TD–H₂O₂) in aqueous solution. The synthesized poly (GMA)-grafted CNF (CNF-g-PGMA) was characterized by FTIR, AFM, XRD, water contact angle, and TGA. GMA was successfully grafted onto the CNFs by Fe²⁺–TD–H₂O₂, the epoxy groups and ester groups of GMA were clearly present and intact in the CNF-g-PGMA, and TD is an important component of the initiator system under relatively mild graft conditions. CNF-g-PGMA may be an important intermediate because of its epoxy and ester functional groups. The main nanostructure of the CNFs was retained after graft copolymerization, and there were no obvious effects of graft copolymerization on the crystalline structure of the CNF backbone, although the crystalline index slightly decreased with the increased percentage of grafting. Graft copolymerization significantly modifies the CNF hydrophobicity. This strategy could extend the applications of CNFs into many areas.