Bulky Quaternary Alkylammonium Counterions Enhance the Nanodispersibility of 2,2,6,6-Tetramethylpiperidine-1-oxyl-Oxidized Cellulose in Diverse Solvents

The degree of nanodispersion of cellulose in diverse solvents is a significant primary criterion for the preparation of bulk nanocelluloses and nanocellulose-containing composites. Here, high degrees of nanodispersion of fibrous 2,2,6,6-tetramethylpiperidine-1-oxyl-oxidized cellulose (TOC) were achieved in various solvents by efficiently incorporating quaternary alkylammoniums (QAs) as counterions of TOC carboxyl groups via simple ion-exchange treatment in water. Tetramethyl-, tetraethyl-, tetra-n-propyl-, and tetra-n-butylammoniums were used as the QAs. The TOC-QAs were converted to TOC nanofibrils (TOCN-QAs) with a high nanofibrillation yield via mechanical disintegration in not only water but also methanol and other organic solvents after solvent-exchange treatment. Fourier transform infrared spectra of cast TOCN-QA films and the electric conductivities of the TOCN-QA dispersions indicated that the TOCNs-QAs were dispersed primarily through dissociation of the bulky QA carboxylate groups. Moreover, the TOC-QAs were nanodispersible in water even after being oven dried at 105 degrees C, which is advantageous for their practical application.