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Solid State NMR in the Study of Cellulose Ionic Liquid Interactions

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Title: Solid State NMR in the Study of Cellulose Ionic Liquid Interactions
Author(s): Haarman, Ties
Contributor: University of Helsinki, Faculty of Science, Department of Chemistry
Discipline: Polymer Chemistry
Language: English
Acceptance year: 2014
Recent years have seen an increasing interest in green chemistry and an emphasis on renewable resources. New methods for more efficient fractioning and processing of biomass have been explored as a potential replacement for the current pulping industry. It was found that a number of imidazolium based ionic liquids are capable of dissolving cellulose, lignin and even wood as a whole. Although many ionic liquids have been studied for their dissolution properties, the exact dissolution mechanism is not yet fully understood. In the current research, solid state NMR was applied to study the dissolution process of woodpulp in an ionic liquid. A set of spectral techniques, 13C CPMAS, HETCOR, 1H HRMAS and NOESY, was applied to partly dissolved softwood dissolving pulp. The ionic liquid 1-ethyl-3-methylimidazolium acetate (EMIMAc) was used as a solvent. The used samples were 66 wt%, 50 wt%, 33 wt% and 25 wt% pulp in EMIMAc. The CPMAS spectra proved useful in studying the breakdown of the cellulose crystalline structure. Cellulose fibril surfaces were effected already in the 66 wt% pulp sample. The in core crystallinity remained mainly intact up to 33 wt% pulp and then almost completely disappeared for the 25 wt% sample. The HETCOR experiments yielded no information on specific interactions between cellulose and EMIMAc because of too low signal intensities. The HRMAS spectra showed large changes in chemical shifts between the samples for EMIMAc and cellulose protons. The largest changes 0.3-0.7 ppm, were observed for the acidic EMIMAc protons and water. This means a change in hydrogen bonding interactions is taking place for both EMIMAc and cellulose upon increasing the EMIMAc concentration. The NOESY spectra showed that in the 50 wt% sample cellulose mainly interacts with water. In the 25 wt% sample water is largely replaced by acetate anions at the cellulose chains.

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