Non-covalently cationized nanocellulose from hemp: Kinetics, key properties, and paper strengthening

Abstract

Cationic cellulose, despite its long history, has yet to find a place in the paper industry. However, recent research is evaluating the potential of its nanoscale forms. Likewise, the processes of Western manufacturers are optimized for wood pulps, relegating non-wood crops to specific products that, as also proposed by current research, could include nanocellulose. We combined these trends with the existing knowledge of the strong adsorption of poly(diallyldimethylammonium chloride) (polyDADMAC) on cellulosic fibers, which can be deemed a non-covalent kind of cationization. For that, polyDADMAC was first anchored to refined hemp pulps, under conditions that allowed the deprotonation of the primary hydroxyl groups of cellulose. The fiber surface remained positively-charged even after thoroughly washing the samples, owing not only to the small proportions of acidic hemicelluloses and lignin, but also to stable ion-dipole interactions. This non-covalent cationization was found to follow pseudo-second order kinetics, indicating that diffusion through the fiber was the rate-controlling step. PolyDADMAC-containing fibers were then fibrillated by high-pressure homogenization. The surface charge of cationic nanocellulose was greater than that of the starting fibers, as the specific surface area increased. Nonetheless, polyDADMAC caused agglomeration of fibrils to a certain extent. As a drawback, when applied in papermaking, cationic nanocellulose lowered air permeability to a lesser extent than non-cationized nanofibers. As an advantage, the tensile index increased by up to 57% in the absence of any retention agent. • Adsorption of polyDADMAC to hemp pulp fibers follows pseudo-second order kinetics. • Both refining and fibrillation increase the absolute value of the surface charge. • Strong binding of polyDADMAC: ionic in alkaline media, ion-dipole after neutralization. • The resulting nanofibers improve paper strength without the need of retention aids.