N,N-dimethylmorpholinium hydroxide was synthesized and its ability to dissolve microcrystalline cellulose and pulp was assessed for the first time. Microscopy and UV-Vis measurements showed that dissolution occurred over a range of 1-2 M concentration of the solvent and a maximum solubility of 7 wt% microcrystalline cellulose could be achieved. The stability of cellulose solutions was evaluated by size exclusion chromatography, which did not detect degradation to any noticeable extent. This observation was further confirmed by 13C NMR measurements. Finally, DLS studies confirmed that most of the cellulose was molecularly dissolved, with intrinsic viscosity values indicating cellulose chains expansion in this solvent.

The direct reaction between carbohydrates and CO2 has recently attracted attention in the context of cellulose dissolution and derivatization as well as carbon capture applications. We have directly demonstrated the formation of cellulose carbonate upon the introduction of CO2 into a non-aqueous cellulose solution by nuclear magnetic resonance spectroscopy. Comparison of the observed spectra with accurate electronic structure calculations of the changes in chemical shifts upon reaction allowed us to confirm the expectation that CO2 reacts with the hydroxyl group on carbon 6 of the cellulose but not exclusively this hydroxyl group. We found good agreement between predicted and measured chemical shifts using a simple computational method.

Autohydrolysis-based pretreatments enable extraction of hemicellulose from wood tissue prior to the paper pulp cooking processes enabling their further use as platform chemicals and in material applications. In this study, hot water extraction of birch meal was conducted in a small flow-through system. The combination of high surface area of the milled material with increased driving force induced by constant flow of freshwater, together with fast evacuation of extract, enabled a detailed study of the dissolution process. Based on the findings, deeper insight into acidification and autohydrolysis progress was obtained.

Gaining insight into the oxidation of hardwood kraft fibres using hydrogen peroxide at mildly acidic conditions was the main aim of this study. The oxidized hardwood pulp had an increased number of carbonyl groups and, when formed into sheets, an enhanced durability in water was seen due to the formation of cross-links, known as hemiacetals. The carbonyl groups formed were found to be mainly ketones with the exception of the case with longer reaction times (60-90 minutes) at 85 degrees C, where aldehydes were detected. Through compositional analysis it was found that mainly xylan was oxidized, likely due to the higher amount of xylan close to the surface of the fibre wall. The influence of xylan on the oxidation process was investigated using cold caustic extraction (CCE) performed prior to oxidation. When the CCE pulp was oxidized, there was an increased rate of introduced carbonyl groups and degradation was more pronounced. This is likely due to the accessible surface area being increased, caused by the formation of pores when the lower molecular weight xylan was being extracted during CCE.

The CO2/CO32− chemistry of the cellulose/NaOH(aq) solutions has been recently reported to comprise a CO2 incorporation through formation of a transient cellulose carbonate intermediate along with cellulose – CO32− interactions. This work explores on molecular interactions arising when this chemistry is brought together with urea, the most common stabiliser of these solutions. 1H, 13C and steady-state heteronuclear Overhauser effect NMR studies on the cellulose analogues (methyl-β-glucopyranoside (β-MeO-Glcp) and microcrystalline cellulose), combined with pH and ATR-FTIR measurements, reveal concurrent interactions of urea with both CO2 and CO32−– leading to increased uptake of CO2 and a buffering effect. Yet, regardless of the presence of urea, the route of conversion from CO2 to CO32-, whether going through reaction with the carbohydrate alkoxides or OH−, is likely to determine the chemical environment of the formed CO32-. These findings shed a new light on rather overlooked, albeit prominent, interactions in these solutions with the readily absorbed air CO2, essential for further development and implementation, whether towards regenerated and modified cellulose or CO2-capturing concepts. 

Combining NaOH with other hydroxide bases with superior dissolution properties can be a means of improving dissolution of cellulose. However, this raises questions about how the size and structure of cellulose vary when dissolved in different hydroxide bases. Here, cellulose in aqueous solutions of NaOH, Tetramethylammonium hydroxide (TMAH), Benzyltrimethylammonium hydroxide (Triton B) and previously studied equimolar solutions of NaOH/TMAH and NaOH/Triton B were investigated using small angle X-ray scattering, static and dynamic light scattering. The results show that cellulose in NaOH(aq) is largely aggregated and that the more hydrophobic TMAH and Triton are capable of molecularly dissolving cellulose into worm-like conformations, stiffer than in NaOH. The dissolution properties of mixtures are highly dependent on the compatibility of the individual bases; in line with previous observations of the properties of the solutions which now could be correlated to the structure of the cellulose on a nano- and microscale.

In order to further understand the role of the cation when dissolving cellulose in aqueous solutions of hydroxide bases, different bases were combined in solution. Up to 5 wt.% of microcrystalline cellulose was dissolved using a combination of NaOH and the organic base tetramethylammonium hydroxide (TMAH) in water at low temperatures. Thermoscans of solutions containing both NaOH(aq) and TMAH(aq) indicated that cellulose interaction with TMAH seems to be favoured over NaOH. Dynamic rheology measurements of the solutions revealed that combining the two bases delayed gelation significantly when compared to cellulose dissolved in NaOH(aq) or TMAH(aq) alone. Intrinsic viscosity of cellulose in the combined NaOH- and TMAH(aq) solutions was slightly higher than that of the single-base solutions, indicating a slight increase in solvent quality. This shows that combining bases may lead to synergies that improve solvent stability without requiring the use of other additives.

The aim of this work was to provide softwood kraft pulp fibres with new functionalities by the introduction of carbonyl groups. Carbonyl groups are known to affect properties such as wet strength through the formation of covalent bonds, i.e. hemiacetals. The method developed involves oxidation using hydrogen peroxide at mildly acidic conditions. It was found that the carbonyl group content increased with both increasing temperature and residence time when oxidized at acidic conditions. The number of carboxylic groups, however, remained approximately constant. There was virtually no increase in carbonyl groups when oxidation was performed at alkaline conditions. The maximum increase in carbonyl groups was found at a residence time of 90 min, a reaction temperature of 85 degrees C and a pH of 4. These conditions resulted in an increase in carbonyl groups from 30 to 122 mu mol/g. When formed into a sheet, the pulp oxidized at acidic conditions proved to maintain its structural integrity at aqueous conditions. This indicates the formation of hemiacetal bonds between the introduced carbonyl groups and the hydroxyl groups on the carbohydrate chains. Thus, a possible application for the method could be fibre modification during the final bleaching stage of softwood kraft pulp, where the wet strength of the pulp could be increased.

To further understand cellulose-solvent interactions in aqueous hydroxide solutions, cellulose behavior in aqueous solutions of NaOH combined with tetramethylammonium hydroxide (TMAH) or benzyltrimethylammonium hydroxide (Triton B), as well as urea, was investigated. The rheological properties of the solutions were assessed through flow sweeps at different temperatures, and the intermolecular interactions were probed using solvatochromic dyes. The results showed that NaOH combined with TMAH had synergistic effects on cellulose dissolution and was a better solvent for cellulose than the combination of NaOH with Triton B, in spite of the superior dissolution ability of Triton B alone. This somewhat unexpected finding shows that the base pair needs to be selected with care. Interestingly, addition of urea had no significant effect on the solvatochromic parameters or dissolution capacity of solutions of Triton B but rendered improved stability of solutions containing NaOH and/or TMAH. It seems that both urea and Triton B weaken the hydrophobic assembly effect of these solutions, but urea is excluded from interacting with cellulose in the presence of Triton B. This study provides further insight into dissolution of cellulose and the possibility of utilizing combinations of hydroxide bases to achieve improved solution properties.