Ionic Liquids as Solvents for Homogeneous Derivatization of Cellulose: Challenges and Opportunities

Heinze, Thomas; Gericke, Martin

doi:10.1007/978-94-007-7711-8_5

Cited by 8 publications

(6 citation statements)

References 124 publications

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“…A class of solvents that have attracted much interest during recent years is ionic liquids (IL) (Swatloski et al 2002;Zhang et al 2017). Some IL can dissolve technically relevant amounts of cellulose, and have also been used successfully in wood component separation (Kilpeläinen et al 2007), chemical derivatization of cellulose (Gericke et al 2012;Heinze and Gericke 2014), or in regeneration and cellulose fibre spinning (Sixta et al 2015). However, imidazolium based IL, a family that includes several of the most-studied IL cellulose solvents, have been shown to be reactive towards reducing sugars, including the reducing terminus of cellulose (Gericke et al 2012;Clough et al 2015).…”

Section: Introductionmentioning

confidence: 99%

On the dissolution of cellulose in tetrabutylammonium acetate/dimethyl sulfoxide: a frustrated solvent

Idström¹,

Gentile

Gubitosi

et al. 2017

Cellulose

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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.

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Section: Introductionmentioning

confidence: 99%

On the dissolution of cellulose in tetrabutylammonium acetate/dimethyl sulfoxide: a frustrated solvent

Idström¹,

Gentile

Gubitosi

et al. 2017

Cellulose

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“…Cellulose tosylation in ILs is usually performed in the presence of 1-allyl-3-methylimidazolium chloride (AMIMCl) or 1-butyl-3-methylimidazolium chloride (BMIMCl), at room temperature or below in order to avoid the tosyl reaction with chloride ions yielding in chlorodeoxycellulose as by-product, or the formation of insoluble cellulose derivatives by the cross-linking reaction between different hydroxyl groups [2,122]. However, cellulose tosylation in ILs at 10 • C yielded in a mixture of tosylated derivative (65%) and unmodified cellulose (45%) as result of the ineffective stirring of the reaction medium [117].…”

Section: Wood Surface Modification By Tosylation Reactionmentioning

confidence: 99%

Advances in Surface Modification and Treatment of Wood

2021

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“…In this context, ionic liquids (ILs) are promising media for lignocellulose processing owing to their excellent solubility − and organocatalytic abilities for various chemical modification reactions. − Recently, our group has demonstrated direct conversion of bagasse into lignocellulose-based thermoplastics via homogeneous transesterification using an IL, 1-ethyl-3-methylimidazolium acetate (EmimOAc), as both a solvent and catalyst. , Two kinds of vinyl esters were successively added to the homogeneous reaction system, and all the hydroxy (OH) groups in bagasse were substituted with long/short chain-mixed aliphatic acyl groups in the desired ratios. In particular, decanoylated and per-acetylated bagasse exhibited excellent thermal moldability; there was a sufficient gap between the temperatures of thermal decomposition and melt flow, and it was readily applied to hot pressing and injection molding.…”

Section: Introductionmentioning

confidence: 99%

Controlled Allocation of Aromatic/Aliphatic Substituents to Polysaccharides and Lignin in Sugarcane Bagasse via Successive Homogeneous Transesterification Using Ionic Liquid

et al. 2023

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Lignocellulosic agricultural waste is an abundant renewable feedstock that can be utilized as a sustainable source of biomass-based plastics. Ideally, it is used without discarding any components, including cellulose, hemicellulose, and lignin. However, their utilization as lignocellulose-based plastics has been limited because of the low compatibility between the polysaccharides and lignin derivatives and the resulting poor mechanical properties of the final products. Here, we demonstrate a facile but highly controllable conversion of sugarcane bagasse into valuable thermoplastics by utilizing the excellent solubility and unique organocatalytic abilities of an ionic liquid, 1-ethyl-3-methylimidazolium acetate. In a homogeneous and one-pot chemical modification reaction system, the substitution ratio of an aromatic benzoyl group to an aliphatic hexanoyl group in the bagasse derivative was adjusted by the ratio of acyl reagents used. Moreover, the allocation of these two acyl groups to polysaccharide and lignin components in bagasse was successfully controlled only by exchanging the order of the acyl reagents introduced into the reaction system. The controlled introduction of the acyl groups into bagasse achieved a homogeneous polymer phase in the resultant multicomponent hot-pressed film, resulting in enhanced mechanical properties such as sufficient tensile strength (∼20 MPa) and excellent ductility with a high strain energy density (∼5 MJ m–3).

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Ionic Liquids as Solvents for Homogeneous Derivatization of Cellulose: Challenges and Opportunities

Cited by 8 publications

References 124 publications

On the dissolution of cellulose in tetrabutylammonium acetate/dimethyl sulfoxide: a frustrated solvent

On the dissolution of cellulose in tetrabutylammonium acetate/dimethyl sulfoxide: a frustrated solvent

Advances in Surface Modification and Treatment of Wood

Controlled Allocation of Aromatic/Aliphatic Substituents to Polysaccharides and Lignin in Sugarcane Bagasse via Successive Homogeneous Transesterification Using Ionic Liquid

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