This work examines the potential of tetrabutylammonium acetate: dimethyl sulfoxide (TBAAc:DMSO) as a solvent used in a process for producing man-made cellulose fibers. The tolerance towards nonsolvents is an important step to evaluate the recyclability of the solvent. TBAAc:DMSO was in this work further confirmed to be an efficient solvent for cellulose. Non-solvent tolerance depended on cellulose concentration, TBAAc:DMSO ratio and type of non-solvent. There was no significant change in mechanical properties for filaments regenerated from solutions containing 2 wt% non-solvent compared to those spun from virgin solvent. With 4 wt% ethanol present in solution very brittle filaments were produced, not suitable for use as textile fibers.

The dissolution of cellulose in tetrabutylammonium acetate (TBAAc)/dimethyl sulfoxide (DMSO) was studied combining experimental and simulation techniques. It was found that the dissolution limit at 40 °C corresponded to a molar ratio close to one acetate per cellulose anhydroglucose units. MD simulations suggested that the acetate ions bind to cellulose by dual hydrogen bonds. This effectively turns cellulose into a polyelectrolyte, attracting the bulky tetrabutylammonium (TBA+ ) counter ions, which prevent close contact between chains in the dissolved state. This hypothesis was tested by 1 Hand 13C-NMR spectroscopy, which confirmed that acetate forms hydrogen bonds to cellulose, and by diffusion NMR spectroscopy, which demonstrated a strong dynamic correlation between bound acetate and tetrabutylammonium in near-quantitative agreement with simulation. The present results suggest that offering hydrogen bonding to the acetate ions is the main driving force for dissolving cellulose and that the TBA+ counter ions form a diffuse layer around the acetate-decorated cellulose chains.

We have found that the dissolution of cellulose in the binary mixed solvent tetrabutylammonium acetate/dimethyl sulfoxide follows a previously overlooked near-stoichiometric relationship such that one dissolved acetate ion is able to dissolve an amount of cellulose corresponding to about one glucose residue. The structure and dynamics of the resulting cellulose solutions were investigated using small-angle X-ray scattering (SAXS) and nuclear magnetic resonance techniques as well as molecular dynamics simulation. This yielded a detailed picture of the dissolution mechanism in which acetate ions form hydrogen bonds to cellulose and causes a diffuse solvation sheath of bulky tetrabutylammonium counterions to form. In turn, this leads to a steric repulsion that helps to keep the cellulose chains apart. Structural similarities to previously investigated cellulose solutions in aqueous tetrabutylammonium hydroxide were revealed by SAXS measurement. To what extent this corresponds to similarities in dissolution mechanism is discussed.

The demand for nonwoven materials has increased during the last few years and is expected to increase further due to its use in a broad range of new application areas. Today, the majority of nonwovens are from petroleum-based resources but there is a desideratum to develop sustainable and competitive materials from renewable feedstock. In this work, renewable nonwovens are produced by solution blowing of dissolved cellulose using 1-ethyl-3-methylimidazolium acetate (EMIMAc) as solvent. Properties of cellulose solutions and process parameters, such as temperature, flow rate, air pressure, and distance to collector, are evaluated in respect to spinnability and material structural properties. Nonwovens with fiber diameters mainly in the micrometer range were successfully produced and it was shown that high temperature or low flow rate resulted in thinner fibers. The produced materials were stiffer (higher effective stress and lower strain) compared to commercial polypropylene nonwoven. © 2019 The Authors. Journal of Applied Polymer Science published by Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 48339. © 2019 The Authors.

Cellulose, especially wood-based cellulose, is increasingly important for making everyday materials such as man-made-regenerated textile fibers, produced via dissolution and subsequent precipitation. In this paper, the effect of cosolvents in ionic liquid-facilitated cellulose dissolution is discussed. Both microcrystalline cellulose and dissolving grade hardwood pulp were studied. Three different cosolvents in combination with ionic liquid were evaluated using turbidity measurements and viscosity. The ionic liquid precursor N-methylimidazole proved to be a promising cosolvent candidate and was thus selected for further studies together with the ionic liquid 1-ethyl-3- methylimidazolium acetate. Results show that dissolution rate can be increased by cosolvent addition, and the viscosity can be significantly reduced. The solutions were stable over time at room temperature and could be converted to regenerated textile fibers with good mechanical properties via airgap spinning and traditional wet spinning. Fibers spun from binary solvents exhibited significantly higher crystallinity than the fibers from neat ionic liquid.

In this study the effects of altering the coagulation medium during regeneration of cellulose dissolved in the ionic liquid 1-ethyl-3-methylimidazolium acetate, were investigated using solid-state NMR spectroscopy and NMR cryoporometry. In addition, the influence of drying procedure on the structure of regenerated cellulose was studied. Complete conversion of the starting material into regenerated cellulose was seen regardless of the choice of coagulation medium. Coagulation in water predominantly formed cellulose II, whereas coagulation in alcohols mainly generated non-crystalline structures. Subsequent drying of the regenerated cellulose films, induced hornification effects in the form of irreversible aggregation. This was indicated by solid-state NMR as an increase in signal intensity originating from crystalline structures accompanied by a decrease of signal intensity originating from cellulose surfaces. This phenomenon was observed for all used coagulants in this study, but to various degrees with regard to the polarity of the coagulant. From NMR cryoporometry, it was concluded that drying induced hornification generates an increase of nano-sized pores. A bimodal pore size distribution with pore radius maxima of a few nanometers was observed, and this pattern increased as a function of drying. Additionally, cyclic drying and rewetting generated a narrow monomodal pore size pattern. This study implies that the porosity and crystallinity of regenerated cellulose can be manipulated by the choice of drying condition.