There is a sustained interest in developing solvents for physically dissolving cellulose, i.e., without covalent bond formation. The use of ionic liquids, ILs, has generated much interest because of their structural versatility that results in efficiency as cellulose solvents. Despite some limitations, imidazole-based ILs have received most of the scientific community’s attention. The objective of the present review is to show the advantages of using quaternary ammonium electrolytes, QAEs, including salts of super bases, as solvents for cellulose dissolution, shaping, and derivatization, and as a result, increase the interest in further investigation of these important solvents. QAEs share with ILs structural versatility; many are liquids at room temperature or are soluble in water and molecular solvents (MSs), in particular dimethyl sulfoxide. In this review we first give a historical background on the use of QAEs in cellulose chemistry, and then discuss the common, relatively simple strategies for their synthesis. We discuss the mechanism of cellulose dissolution by QAEs, neat or as solutions in MSs and water, with emphasis on the relevance to cellulose dissolution efficiency of the charge and structure of the cation and. We then discuss the use of cellulose solutions in these solvents for its derivatization under homogeneous and heterogeneous conditions. The products of interest are cellulose esters and ethers; our emphasis is on the role of solvent and possible side reactions. The final part is concerned with the use of cellulose dopes in these solvents for its shaping as fibers, a field with potential commercial application.
This review is focused on assessment of solvents for cellulose dissolution and the mechanism of regeneration of the dissolved biopolymer. The solvents of interest are imidazole-based ionic liquids, quaternary ammonium electrolytes, salts of super-bases, and their binary mixtures with molecular solvents. We briefly discuss the mechanism of cellulose dissolution and address the strategies for assessing solvent efficiency, as inferred from its physico-chemical properties. In addition to the favorable effect of lower cellulose solution rheology, microscopic solvent/solution properties, including empirical polarity, Lewis acidity, Lewis basicity, and dipolarity/polarizability are determinants of cellulose dissolution. We discuss how these microscopic properties are calculated from the UV-Vis spectra of solvatochromic probes, and their use to explain the observed solvent efficiency order. We dwell briefly on use of other techniques, in particular NMR and theoretical calculations for the same purpose. Once dissolved, cellulose is either regenerated in different physical shapes, or derivatized under homogeneous conditions. We discuss the mechanism of, and the steps involved in cellulose regeneration, via formation of mini-sheets, association into "mini-crystals", and convergence into larger crystalline and amorphous regions. We discuss the use of different techniques, including FTIR, X-ray diffraction, and theoretical calculations to probe the forces involved in cellulose regeneration.
Pure quaternary tetraalkylammonium chlorides with one long alkyl chain dissolved in various organic solvents constitute a new class of cellulose solvents. The electrolytes are prepared in high yields and purity by Menshutkin quaternization, an inexpensive and easy synthesis route. The pure molten tetraalkylammonium chlorides dissolve up to 15 wt% of cellulose. Cosolvents, including N,N-dimethylacetamide (DMA), may be added in large excess, leading to a system of decreased viscosity. Contrary to the well-established solvent DMA/LiCl, cellulose dissolves in DMA/quaternary ammonium chlorides without any pretreatment. Thus, the use of the new solvent avoids some disadvantages of DMA/LiCl and ionic liquids, the most extensively employed solvents for homogeneous cellulose chemistry.
matched by synthetic fibers. Therefore, the demand on natural and fabricated cellulosic fibers is expected to continue and rise. The production of cotton, however, is not expected to meet this demand because of restrictions on farmland use and availability of irrigation water. [3] Anticipating the so-called "the cellulosic fiber gap," [1] the textile industry currently leads several initiatives for developing fibers that can complement cotton. [3] Consequently, there is incitement and opportunities for an increase in use of cellulose from other sources, in particular wood, and increased interest in physical (i.e., mechanical) and chemical recycling (CR) of biopolymers. [4] Production of fibers and other artifacts from cellulose extracted from wood involves chemical or physical dissolution of the biopolymer, followed by its regeneration in the desired physical form in an appropriate bath. The most important example of cellulose chemical dissolution (i.e., via covalent bond formation) is the viscose rayon fiber, produced by regeneration of cellulose from its xanthate in acid bath. The Lyocell fiber process involves, however, physical dissolution of cellulose in N-methylmorpholine-N-oxide (NMMO) hydrate, followed by regeneration in an aqueous bath. [5] Cellulose regeneration is not restricted to formation of fibers. The biopolymer and its derivatives, in particular esters, can be "shaped" into other physical forms including spheres of different diameters (down to the nanoscale), films produced by casting and spin coating, and nonwoven mats produced by electrospinning or solution blowing. This review covers some recent advances of the regeneration of cellulose from alkali solutions and ionic solvents, in particular those based on imidazole, quaternary ammonium electrolytes (QAEs), and salts of heterocyclic super-bases. We refer to these ionic solvents collectively as ionic liquids (ILs). Representative examples of the ILs employed for cellulose dissolution are shown in Figure 1. These solvents dissolve cellulose samples of a wide range of degrees of polymerization (DPs) and indices of crystallinity (Ics). For practical reasons, binary mixtures of ILs with molecular solvents (MSs) are used alongside pure ILs. This use is advantageous because of the concomitant decrease in solution viscosity; there are many examples where the binary solvent mixture dissolves more cellulose than the parent pure IL. [5] Strategies to mitigate the expected "cellulose gap" include increased use of wood cellulose, fabric reuse, and recycling. Ionic liquids (ILs) are employed for cellulose physical dissolution and shaping in different forms. This review focuses on the regeneration of dissolved cellulose as nanoparticles, membranes, nonwoven materials, and fibers. The solvents employed in these applications include ILs and alkali solutions without and with additives. Cellulose fibers obtained via the carbonate and carbamate processes are included. Chemical recycling (CR) of polycotton (cellulose plus poly(ethylene terephthalate)) is addressed...
Pure, perfectly spherical cellulose nanoparticles with sizes of ≈80-260 nm can be prepared by dialysis starting from trimethylsilylcellulose (TMSC). The aqueous suspensions obtained are storable for several months. Subsequent covalent labeling of the cellulose nanoparticles with FITC has no influence on particle size, shape, and stability. The particles can be sterilized and suspended in biological media without structural changes. Incorporation of FITC-labeled cellulose nanoparticles into living human fibroblasts is studied using confocal LSM. In contrast to cellulose nanocrystals, fast cellular uptake is found for the nanospheres without transfection reagents or attachment of a receptor molecule. This suggests an influence of the geometry of biocompatible nanomaterials on endocytosis.
Silyl ethers of cellulose are promising derivatives of the biopolymer because they exhibit thermoplastic behavior at higher functionalization, may be applied as intermediate in subsequent reactions and have a high tendency to form defined supramolecular structures. Trimethylsilylation can be carried out by applying ionic liquids (ILs) such as 1‐ethyl‐3‐methylimidazolium acetate (EMIMAc) as reaction medium. Pure trimethylsilyl cellulose (TMSC) can be efficiently synthesized with 1,1,1,3,3,3‐hexamethyldisilazane (HMDS) yielding products with degrees of substitution (DS) up to 2.89. During the synthesis of highly functionalized derivatives, precipitation of the TMSC occurred, which simplifies the recycling of the IL. The tendency of TMSC toward the formation of supermolecular structures was exploited for the formation of pure cellulose nanospheres by a simple dialysis process. FTIR spectroscopy confirmed the complete removal of the TMS functions during this process. Scanning electron microscopy, dynamic light scattering, atomic force microscopy, and particle size distribution analysis showed that cellulose particles with a size of 100 to 200 nm are accessible in this simple manner.
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