Binary mixtures of ionic liquids-DMSO as solvents for the dissolution and derivatization of cellulose: Effects of alkyl and alkoxy side chains

Ferreira, Daniela Colevati; Oliveira, Mayara L. de; Bioni, Thaís de Almeida; Nawaz, Haq; King, Alistair W. T.; Kilpeläinen, Ilkka; Hummel, Michael; Sixta, Herbert; Seoud, Omar A. El

doi:10.1016/j.carbpol.2019.02.024

Cited by 30 publications

(25 citation statements)

References 45 publications

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“…An interesting observation was that the acylation with N-benzoylimidazole in these IL-DMSO mixtures produced appreciable amounts of cellulose acetate. The DS Acetate /DS Benzoate were 0.45 and 1.54, for BuMeImAcO-DMSO, and PrOMeImAcO-DMSO, respectively [74]. The only source of acetate is the IL, another manifestation that that ILs and their solutions in MSs are not always "spectators" [76].…”

Section: Binary Mixtures Of Ionic Liquids-molecular Solvents As Cellumentioning

confidence: 99%

Cellulose in Ionic Liquids and Alkaline Solutions: Advances in the Mechanisms of Biopolymer Dissolution and Regeneration

et al. 2019

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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.

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Section: Binary Mixtures Of Ionic Liquids-molecular Solvents As Cellumentioning

confidence: 99%

Cellulose in Ionic Liquids and Alkaline Solutions: Advances in the Mechanisms of Biopolymer Dissolution and Regeneration

et al. 2019

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“…Although ILs have demonstrated excellent capacity for cellulose dissolution, their use in the neat state often brings some drawbacks, mainly related to their high viscosity that hinders the mass transfer phenomena and requires the use of high temperatures [ 173 ]. Therefore, recent works in which ILs were used as co-solvents with dimethyl sulfoxide (DMSO), γ-valerolactone (GVL) or N,N -dimethylmethanamide (DMF) to dissolve cellulose have been reported [ 174 , 175 , 176 , 177 , 178 , 179 ]. The data compilation of the different works of cellulose dissolution with ILs and co-solvents is given in Table 5 .…”

Section: Cellulosementioning

confidence: 99%

“…The addition of GVL [ 175 ] and imidazole [ 176 ] as co-solvents of ILs increased the solubility of cellulose when compared with the pure ILs, namely [C 2 C 1 im][COO] and 1-butyl-3-methylimidazolium phosphonate. In the first case, 15 wt% of α-cellulose dissolution was achieved at 80 °C, while only 5 wt% of cotton fibers were dissolved at 90°C.…”

Section: Cellulosementioning

confidence: 99%

“…The addition of GVL to [C 2 C 1 im][COO] allowed an increase in solubility (15 wt% at 80 °C) when compared with the pure IL. Moreover, the addition of GVL decreased the dissolution activation energy, thus having a higher dissolution rate, whereas mixing imidazole with [C 4 C 1 im][(C 1 O)(H)PO 2 ] decreased the viscosity of the system without affecting the H bond acceptor capacity of the IL [ 175 , 176 ]. In another study, Sánchez et al [ 179 ] tested microwave irradiation for cellulose dissolution in 1:1 ( w/w ) mixtures of [C 2 C 1 im][COO] and DMSO, achieving an increase between 21% and 57% of cellulose dissolution rate compared to the pure IL [ 179 ].…”

Section: Cellulosementioning

confidence: 99%

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Use of Ionic Liquids and Deep Eutectic Solvents in Polysaccharides Dissolution and Extraction Processes towards Sustainable Biomass Valorization

et al. 2020

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A shift to a bioeconomy development model has been evolving, conducting the scientific community to investigate new ways of producing chemicals, materials and fuels from renewable resources, i.e., biomass. Specifically, technologies that provide high performance and maximal use of biomass feedstocks into commodities with reduced environmental impact have been highly pursued. A key example comprises the extraction and/or dissolution of polysaccharides, one of the most abundant fractions of biomass, which still need to be improved regarding these processes’ efficiency and selectivity parameters. In this context, the use of alternative solvents and the application of less energy-intensive processes in the extraction of polysaccharides might play an important role to reach higher efficiency and sustainability in biomass valorization. This review debates the latest achievements in sustainable processes for the extraction of polysaccharides from a myriad of biomass resources, including lignocellulosic materials and food residues. Particularly, the ability of ionic liquids (ILs) and deep eutectic solvents (DESs) to dissolve and extract the most abundant polysaccharides from natural sources, namely cellulose, chitin, starch, hemicelluloses and pectins, is scrutinized and the efficiencies between solvents are compared. The interaction mechanisms between solvent and polysaccharide are described, paving the way for the design of selective extraction processes. A detailed discussion of the work developed for each polysaccharide as well as the innovation degree and the development stage of dissolution and extraction technologies is presented. Their advantages and disadvantages are also identified, and possible synergies by integrating microwave- and ultrasound-assisted extraction (MAE and UAE) or a combination of both (UMAE) are briefly described. Overall, this review provides key information towards the design of more efficient, selective and sustainable extraction and dissolution processes of polysaccharides from biomass.

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“…In addition to carbamides, thiourea was investigated as thiocarbamide has been previously shown to improve the dissolution of cellulose (and other polysaccharides) in various solvents (Zhang et al 2002;Sharma et al 2013). Moreover, DMSO was studied as a reference as it has been widely used as a solvent to dissolve cellulose together with various salts (Ö stlund et al 2009;Chen et al 2018;Kostag and El Seoud 2019) and as a cosolvent to decrease the viscosity of cellulose solutions in ionic liquids (Rinaldi 2010;Ferreira et al 2019). The chemical formulas of all the studied chemicals are presented in Fig.…”

Section: Teaoh and Carbamide-based Solventsmentioning

confidence: 99%

Room-temperature dissolution and chemical modification of cellulose in aqueous tetraethylammonium hydroxide–carbamide solutions

Sirviö

Heiskanen

2019

Cellulose

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The room-temperature dissolution of cellulose in aqueous tetraethylammonium hydroxide (TEAOH) in the presence of carbamides (ureas) was investigated. Without carbamide, 35 wt% TEAOH was able to dissolve cellulose (microcrystalline cellulose) up to 3 wt%, whereas carbamides-such as urea, N-methylurea, N-ethylurea, 1,3-dimethylurea, and imidazolidone-were able to improve the dissolution of cellulose. At 5 wt% cellulose concentration, the highest carbamide contents in the solvent still able to dissolve cellulose within 1 h were 56 and 55 wt% of 1,3-dimethylurea and N-methylurea, respectively. When using urea, up to 15% of cellulose could be dissolved in a solution containing 22 wt% of urea. To demonstrate the possibility of the use of a carbamidebased solvent in cellulose modification, cationic cellulose was produced using glycidyltrimethylammonium chloride (GTAC). At a molar ratio of 1:3 of cellulose and GTAC, all the studied TEAOH-carbamide solvents produce cationic cellulose with higher charge density compared to the reference NaOH-urea solvent.

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Binary mixtures of ionic liquids-DMSO as solvents for the dissolution and derivatization of cellulose: Effects of alkyl and alkoxy side chains

Cited by 30 publications

References 45 publications

Cellulose in Ionic Liquids and Alkaline Solutions: Advances in the Mechanisms of Biopolymer Dissolution and Regeneration

Cellulose in Ionic Liquids and Alkaline Solutions: Advances in the Mechanisms of Biopolymer Dissolution and Regeneration

Use of Ionic Liquids and Deep Eutectic Solvents in Polysaccharides Dissolution and Extraction Processes towards Sustainable Biomass Valorization

Room-temperature dissolution and chemical modification of cellulose in aqueous tetraethylammonium hydroxide–carbamide solutions

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