Colloidal Behavior of Cellulose Nanocrystals Grafted with Poly(2-alkyl-2-oxazoline)s

Polymer grafting onto cellulose nanocrystals (CNCs) has been used as a tool to improve CNC dispersion in nonpolar solvents or polymeric matrixes. The grafting of flexible polymer chains onto rigid particle surfaces leads to significant modifications in colloidal behavior. Here, poly(2-alkyl-2-oxazoline)s of well-defined molar mass and narrow molar mass distribution were synthesized by cationic ring-opening polymerization and grafted onto CNC surfaces, where the coupling reaction was favored when partially hydrolyzed polymers were used (reaching 64% reaction yield). The particles grafted with polymer chains could be redispersed in water after freeze-drying, producing stable dispersions, and they were not cell-toxic up to 10 wt % aqueous dispersion. Colloidal stability, nanostructure organization, and rheological behavior of grafted CNC and CNC-grafted CNC mixtures were evaluated. The rheological behavior of grafted nanoparticles, meanwhile, showed new features when compared to original CNC dispersions. Aqueous CNC dispersions showed a liquid crystal nematic organization and rheological behavior characteristic of true gel (at 5 wt %) prior to drying. On the other hand, nanoparticle dispersions behaved as weak gels upon the addition of 10 wt % of CNC-g-(PEtOx(95)-s-Ei(5)) under the same conditions. Dispersions of CNC-g-P(PEtOx-s-Ei) particles obtained by redispersion of freeze-dried particles behaved as a fluid, without the presence of the nematic organization. Through oscillatory rheology and time-domain NMR results, it can be concluded that polymer-water interactions are dominant over CNC-water interactions, being responsible for CNC nematic phase disruption. By introducing polymer chains, the introduction of isotropic character modifies water organization, changing the flow behavior of CNC-grafted with poly(oxazoline)s.