Future biorefinery concepts are seriously entertaining the use of ionic liquids (ILs) as a platform media for the processing of woody material as a second-generation biomass feedstock.The main motivation is the demonstrated efficiency of some molten salts in the dissolution of cellulose, a major structural and solvolytically resistant component of lignocellulosic materials.The first report of the use of molten salts for the modification of cellulose came in the form of a patent by Graenacher, [1] where alkyl pyridinium chlorides were used to dissolve cellulose, thus allowing for efficient chemical modification from those media. The melting points of most alkyl pyridinium chloride salts are above 100 8C and, as such, these species do not fall under the common definition of ionic liquids. Nevertheless, the molten compounds solvated cellulose to such a state as to allow for acylation to a high degree. The next generational advance was the discovery by Rogers and co-workers [2] that dialkyl imidazolium based ionic liquids, with melting points below 100 8C, can dissolve cellulose. The most successful of these was 1-butyl-3-methylimidazolium chloride ([bmim]Cl]). This advance was further refined by Ohno et al.[ Despite the high efficiency for the solvation of cellulose, lignin, [5] and even wood [6] in an increasing range of dialkyl imidazolium based ionic liquids, sustainability of prospective processes will depend on the chemical stability of solutes and ionic liquids under process and recycling conditions. There are already some indications that ionic liquids such as [emim][OAc] react chemically with lignocellulosic solutes. [7] This reactivity may lower the recovery of the media upon recycling, although, in the case of the reaction of C2 imidazolium positions with C1 reducing end groups of cellulose, [7a,b] it is possible that this reaction is reversible under aqueous conditions, owing to the lability of the conjugate linkage.A bigger concern is the method of recycling to yield a pure ionic liquid. For most processes, high-purity ionic liquid will be required to maintain efficiency of dissolution and overall sustainability of the process. Decomposition of dialkyl imidazolium based ILs containing basic anions in the presence or absence of solutes proceeds according to three main pathways. From knowledge of the chemical stability of these cations, the pathways are most easily illustrated using a 1,3-diethylimidazolium cation ([eeim] + ) as countercation (Scheme 1).In relation to lignocellulose chemistry, pathway a, which involves formation of dialkyl imidazol-2-ylidene intermediates, has been demonstrated in the conjugation of cellulosic reducing end groups at C2 on the imidazolium ring. The publication by Liebert and Heinze, [7a] whereby the more basic [emim][OAc] reacts with oligocellulose reducing end groups to a much greater extent than [bmim]Cl or [emim]Cl, suggests that this reaction is likely dependent on the basicity of the anion. The initial step of this reaction is most likely deprotonation at C2, and t...
The accurate and reproducible determination of lignin molar mass by using size exclusion chromatography (SEC) is challenging. The lignin association effects, known to dominate underivatized lignins, have been thoroughly addressed by reaction with acetyl bromide in an excess of glacial acetic acid. The combination of a concerted acetylation with the introduction of bromine within the lignin alkyl side chains is thought to be responsible for the observed excellent solubilization characteristics acetobromination imparts to a variety of lignin samples. The proposed methodology was compared and contrasted to traditional lignin derivatization methods. In addition, side reactions that could possibly be induced under the acetobromination conditions were explored with native softwood (milled wood lignin, MWL) and technical (kraft) lignin. These efforts lend support toward the use of room temperature acetobromination being a facile, effective, and universal lignin derivatization medium proposed to be employed prior to SEC measurements.
Three wood species, eucalyptus grandis (E. grandis), southern pine (S. pine), and Norway spruce thermomechanical pulp (N. spruce TMP) were pretreated by dissolution in the ionic liquid (IL) 1-allyl-3-methylimidazolium chloride ([AMIM]Cl). The wood was regenerated from the ionic liquid in high yield and the recycling of the ionic liquid was nearly quantitative. The lignin contents and the efficiencies of cellulase enzymatic hydrolyses of the regenerated wood were examined offering an understanding into the IL pretreatment efficiency. The components that remained within the recycled ILs were qualitatively characterized by 31 P NMR spectroscopy. Wood density, pulverization intensity, and the nature of the regeneration nonsolvents were investigated as factors affecting the overall process. An increase in the wood density decreased the efficiency of the pretreatment, whereas extended pulverization periods decreased the yield of the regenerated wood after the IL pretreatment,with more glucose being released during the enzymatic hydrolysis. The yield of wood after IL pretreatment using water as the regeneration nonsolvent was found to be much higher than that of using methanol. As the reuse cycles of IL increased the wood regeneration yield increased, while certain wood components enriched within the recycled IL. The efficiency of cellulase enzymatic hydrolysis on the regenerated wood decreased with increasing reuse cycles of the IL.
Future biorefinery concepts are seriously entertaining the use of ionic liquids (ILs) as a platform media for the processing of woody material as a second-generation biomass feedstock. The main motivation is the demonstrated efficiency of some molten salts in the dissolution of cellulose, a major structural and solvolytically resistant component of lignocellulosic materials.The first report of the use of molten salts for the modification of cellulose came in the form of a patent by Graenacher, [1] where alkyl pyridinium chlorides were used to dissolve cellulose, thus allowing for efficient chemical modification from those media. The melting points of most alkyl pyridinium chloride salts are above 100 8C and, as such, these species do not fall under the common definition of ionic liquids. Nevertheless, the molten compounds solvated cellulose to such a state as to allow for acylation to a high degree. The next generational advance was the discovery by Rogers and co-workers [2] that dialkyl imidazolium based ionic liquids, with melting points below 100 8C, can dissolve cellulose. The most successful of these was 1-butyl-3-methylimidazolium chloride ([bmim]Cl]). This advance was further refined by Ohno et al. [3] into room-temperature ionic liquids capable of dissolving cellulose, such as 1-ethyl-3-methylimidazolium formate ([emim][CO 2 H]) [3a] or 1-ethyl-3-methylimidazolium dimethylphosphate ([emim][Me 2 PO 4 ]). [3b] From the structures listed in the claims of the Rogers patent, [2b] BASF have also refined this list down to room-temperature ionic liquids, such as 1-ethyl-3-methylimidazolium acetate ([emim]- [OAc]). It has been reported by BASF, by oral dissemination and unofficial reports, that [emim][OAc] has higher dissolving efficiency for cellulose and has lower toxicity than structures such as [bmim]Cl. However, no detailed studies comparing chlorides with carboxylates or other such structures have been published, although certainly their undeniable high efficiency for dissolution and chemoselectivity has been demonstrated for a number of cellulose modification applications. [4] Despite the high efficiency for the solvation of cellulose, lignin, [5] and even wood [6] in an increasing range of dialkyl imidazolium based ionic liquids, sustainability of prospective
Lignin, esterified with palmitic and lauric acid chloride, has been studied for the application as coating on fiber-based packaging material. The aim was to improve the barrier properties against water vapor and oxygen of paperboard. The esterification was followed by Fourier transform infrared spectroscopy, 31 P nuclear magnetic resonance spectroscopy, and gel permeation chromatography measurements. The lignin esters were applied on paperboard and formed a continuous film. The moisture barrier property of the coated paperboards was characterized by the water vapor transmission rate (WVTR). A significant decrease in WVTR was observed, for example, 40 g m -2 (for 24 h) for a paperboard coated with 10.4 g m -2 hardwood kraft lignin palmitate. The contact angle of water on the lignin ester coatings was high and stable. For all paperboard samples coated with lignin esters, a significant decrease in oxygen transmission rate was observed. Accordingly, lignin palmitate and laurate have a high potential as a barrier materials in packaging applications.
1-Butyl-2,3-dimethylimidazolium bromide {(bdmim)Br} (1) and iodide {(bdmim)I} (2) were prepared conveniently by the reaction of 1,2-dimethylimidazole and the corresponding 1-halobutane. The compounds were characterized by 1H and 13C{1H} NMR spectroscopy as well as by X-ray single crystal crystallography. 1 crystallizes in the monoclinic crystal system, space group P21/n, with Z = 4, and unit cell dimensions a = 8.588(2), b = 11.789(1), c = 10.737(2) Å, β = 91.62(3)°. Compound 2 crystallizes in the monoclinic crystal system, space group P21/c, with Z = 8, and unit cell dimensions a = 10.821(2), b = 14.221(3), c = 15.079(2) Å , β = 90.01(3)°. The lattices of the salts are built up of 1-butyl-2,3- dimethylimidazolium cations and halide anions. The cations of 1 form a double layer with the imidazolium rings stacked together due to π interactions. The Br− anions lie approximately in the plane of the imidazolium ring, and the closest interionic Br···H contacts span a range of 2.733(1) - 2.903(1) Å. Compound 2 shows no π stacking interactions. The closest interionic I···H contacts are 2.914(1) - 3.196(1) Å
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