Abstract
New solvents based on DMSO in combination with alkylammonium fluorides, in particular TBAF · 3H~2~O and BTMAF · H~2~O, were established as media for homogeneous functionalization of cellulose. Even DMSO in combination with freshly prepared, anhydrous TBAF, obtained by the reaction of tetrabutylammonium cyanide and hexafluorobenzene, dissolves cellulose. In contrast, a mixture of DMSO and tetramethylammonium fluoride does not dissolve cellulose. The solvents were characterized by capillary viscosity, which showed that a cellulose solution of DMSO/BTMAF · H~2~O possesses a lower viscosity at comparable cellulose concentrations compared with DMSO/TBAF · 3H~2~O. The determination of the degree of polymerization of the starting cellulose (microcrystalline cellulose, spruce sulfite pulp, and cotton linters), and of the regenerated samples, shows that degradation of the polymer depends on the dissolution time, temperature and on the ammonium fluoride used. The results of different homogeneous reactions including acylation and carbanilation of cellulose in the solvents were compared with those of the most‐commonly‐applied solvent N,N‐dimethylacetamide/LiCl. The products were characterized by elemental analysis, ^1^H‐ and ^13^C NMR spectroscopy (additionally after perpropionylation) and FTIR spectroscopy.
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