Effect of the cation structure on cellulose dissolution in aqueous solutions of organic onium hydroxides

The solubility of cellulose was systematically assessed in organic onium/inium hydroxide aqueous solutions (OHAS) having assorted cations, such as phosphonium, ammonium, piperidinium, morpholinium, pyrrolidinium, and cholinium. From a dissolution test of cellulose in OHAS, it was confirmed that the single most important factor in the dissolution is the high concentration of OHAS. In addition, having a weaker hydrogen bond network around OH and H2O was found to be important to facilitate the cellulose dissolution. In NMR analysis, the OHAS with an excellent cellulose solubility, such as tetrabutylphosphonium hydroxide ([P4444]OH), exhibited a chemical shift of water (δH2O) integrated with that of OH in the low frequency region (∼4.9 ppm), while choline hydroxide ([Ch]OH) with poor cellulose solubility showed δH2O higher than 5.2 ppm. A higher δH2O means that the protons are deshielded due to a stronger hydrogen bond network around H2O and OH, which indicates a strong self-associating property of OHAS that is unfavourable for the cellulose dissolution. Assuming that the strong self-associating property can be reduced by improving the hydrophobicity of organic cations, the methyl group in N-butyl-N-methylmorpholinium hydroxide ([Mor14]OH) was replaced by a butyl chain to shield the positive charge. While [Mor14]OH dissolved only 5 wt% of cellulose, the solubility in the synthesised OHAS, N,N-dibutylmorpholinium hydroxide ([Mor44]OH), was successfully improved to 20 wt%. In the present paper, cellulose solubility was also analysed in relation to the Kamlet-Taft parameters.