Sustainable One-Pot Cellulose Dissolution and Derivatization via a Tandem Reaction in the DMSO/DBU/CO2 Switchable Solvent System.

Abstract

New sustainable concepts have to be developed to overcome the increasing problems of resource availability. Cellulose derivatives with tunable material properties are promising biobased alternatives to existing petroleum-derived polymeric materials. However, the chemical modification of cellulose is very challenging, often requiring harsh conditions and complex solubilization or activation steps. More sustainable procedures toward novel cellulose derivatives are therefore of great interest. Herein, we describe a novel concept combining two approaches, (i) tandem catalysis and (ii) cellulose derivatization, by applying a single catalyst for three transformations in the DMSO/DBU/CO2 switchable solvent system. Cellulose was functionalized with four different biobased isothiocyanates, which were formed in situ via a catalytic sulfurization of isocyanides with elemental sulfur, preventing the exposure and handling of the isothiocyanates. The degree of substitution of the formed O-cellulose thiocarbamates was shown to be controllable in a range of 0.52-2.16 by varying the equivalents of the reactants. All obtained products were analyzed by ATR-IR, 1H, 13C, and 31P NMR spectroscopy as well as size exclusion chromatography, elemental analysis, differential scanning calorimetry, and thermal gravimetric analysis. Finally, the tandem reaction approach was shown to be beneficial in terms of efficiency as well as sustainability compared to a stepwise synthesis. Recycling ratios ranging from 79.1% to 95.6% were obtained for the employed components, resulting in an E-factor of 2.95 for the overall process.