Ionic Liquids — Promising but Challenging Solvents for Homogeneous Derivatization of Cellulose
Abstract
:1. Introduction
2. History
2.1. Dissolution of Cellulose in Molten Organic Salts
2.2. Ionic Liquids as Reaction Media for Cellulose Derivatization
Entry | Substituent (Cell-OR) | DS a | ILs b | Comments c | Ref. |
---|---|---|---|---|---|
carbamates | |||||
1 | | 0.5–3.0 | BMIMCl | [36] | |
0.3–3.0 | BMIMCl | - derivatization of bacterial cellulose | [37] | ||
2 | | 0.43, 2.95 | BMIMCl | - hydrolysis of ethoxysilyl groups directly after synthesis | [38] |
carboxylic acid esters | |||||
3 | | 0.9–2.8 | AMIMCl | [39,40] | |
1.9–3.0 | BMIMCl, EMIMCl, BDMIMCl, ADMIMBr | [36,41] | |||
0.7–3.0 | BMIMCl | - derivatization of bacterial cellulose | [37] | ||
4 | | ≈0.5–2.9 | ABIMCl, BMIMAc, DOHMIMAc, HMIMAc, MOEMIMAc | - cellulose esters and mixed esters prepared- microwave irradiation (partly)- also pentanoates and hexanoates prepared | [42,43,44] |
1.4–2.7(DSoverall) | AMIMCl | - acetate-butyrates and acetate-propionates prepared- derivatization of cellulose from sugarcane bagasse | [45] | ||
0.5–2.9(DSoverall) | BMIMAc, BMIMCl, BMIMDMP, BMIMPr, EMIMAc, TBMADMP | - cellulose esters and mixed esters prepared- co-solvents applied (partly)- also mixed esters with benzoate prepared | [16,17,18,19,20] | ||
0.2–2.5 | BMIMCl, EMIMAc | - heterogeneous conversion with gaseous ketenes- acetates, propionates, and pentanoates prepared | [21] | ||
5 | | 1.0–3.0 | AMIMCl | [46] | |
6 | | 0.5–3.0 | BMIMCl | - activation of carboxylic acid with N,N’-carbonyldiimidazole (partly) | [47] |
7 | | 0.3–1.5 | BMIMCl | - phase separation with increasing DS | [36] |
8 | | 2.2–2.6 | BMIMCl | [48] | |
9 | | 0.9–1.4 | AMIMCl | - comparison with DMA/LiCl and DMSO/TBAF | [49] |
10 | | 0.2–2.5 | AMIMCl, BMIMCl | - derivatization of cellulose from sugarcane bagasse- catalysts applied - co-solvents utilized (partly) | [50,51,52,53] |
11 | | 0.3–1.2 | BMIMCl | - ultrasound irradiation | [54] |
12 | | 0.1-1.2 | BMIMCl | - tosyl chloride used to form reactive intermediates- co-solvents utilized | [55,56] |
13 | | 0.1–3.0 | AMIMCl, BMIMCl, EMIMCl | - activation of oxy-carbonic acid with N,N’-carbonyldiimidazole- derivatization of bacterial cellulose (partly) | [57] |
14 | | 0.6–1.0 | AMIMCl | - co-solvents utilized- bromo compounds utilized | [58,59,60] |
0.3–1.9 | BMIMCl | - chloro compounds utilized | [61] | ||
15 | | 1.4–1.9 | BMIMBr | - catalyst applied | [62] |
16 | | 0.07 | AMIMCl | - activation of acid with N,N'-carbonyldiimidazole | [63] |
ethers | |||||
17 | | 0.1–2.2 | BMIMCl, BDMIMCl, BDTAC, EMIMAc | - co-solvents utilized | [64,65] |
18 | | 0.8, 1.8 | AMIMCl | - pyridine utilized as base and co-solvent | [66] |
0.8–1.4 | BMIMCl | - pyridine utilized as base and co-solvent | [67] | ||
19 | | 0.49 | BMIMCl | - co-solvents utilized- heterogeneous (solid NaOH used as base)- gel-like system formed | [36] |
n.a. | BMIMCl | - heterogeneous (solid NaOH used as base) | [68] | ||
20 | | 0.4–2.9 | BMIMCl, EMIMAc | - co-solvents utilized | [69] |
0.2–3.0 | BMIMCl, BMIMAc, BMIMBz, BMIMPr, EMIMAc, EMIMDEP | - heterogeneous derivatization (polar and non-polar liquid phase) | [70] | ||
sulfuric/sulfonic acid esters | |||||
21 | | 0.1–1.5 | AMIMCl, BMIMCl, EMIMCl | - co-solvents utilized | [71,72] |
1.3–1.7 | BMIMCl | - co-solvents utilized | [73] | ||
22 | | 0.1–1.1 | AMIMCl, BMIMCl | - co-solvents utilized, reaction at 25 °C | [74] |
0.84 | AMIMCl | - reaction at 10 °C | [63] | ||
deoxy cellulose derivatives | |||||
23 | | 0.8–1.l | BMIMCl | - co-solvent utilized- strong polymer degradation | [75] |
grafts | |||||
24 | | 0.7–2.7(1.4–4.5) d | AMIMCl | - grafting by ring-opening of L-lactide- 4-dimethylamino pyridine applied as catalyst | [76] |
25 | | n.a. | BMIMCl | - initiation by persulfate - microwave irradiation | [77] |
26 | | n.a. | BMIMCl | - initiation by γ-ray irradiation | [78] |
27 | | 0.3–1.9 | BMIMCl | - derived from 14 by atom transfer radical polymerization | [61] |
2.2.1. Esterification
2.2.2. Etherification
2.2.3. Other Reactions
3. Difficulties and Drawbacks
3.1. Purity of Ionic Liquids
3.2. Viscosity: A Matter of Kinetics vs. Thermodynamics
Ionic Liquid a | Temperature, | Viscosity, | Ref. | ||
---|---|---|---|---|---|
Cation | Anion | °C | mPa·s | ||
AMIM+ | Cl− | 50 | 120 | [112] | |
AMIM+ | Fo− | 25 | 66 | [113] | |
BMIM+ | Ac− | 25 | 485 | [114] | |
BMIM+ | Ac− | 80 | 26 | [114] | |
BMIM+ | Ac− | 100 | 15 | [114] | |
BMIM+ | Ac− | 120 | 9 | [114] | |
BMIM+ | Cl− | 80 | 142 | [114] | |
BMIM+ | Cl− | 100 | 68 | [114] | |
BMIM+ | Cl− | 120 | 31 | [114] | |
BMIM+ | Fo− | 25 | 38 | [112] | |
BMIM+ | DMP− | 20 | 696 | [115] | |
BMIM+ | DMP− | 80 | ≈30 | [115] | |
EMIM+ | Ac− | 21 | 180 | [116] | |
EMIM+ | Ac− | 25 | 162 | [114] | |
EMIM+ | Ac− | 80 | 17 | [114] | |
EMIM+ | Ac− | 100 | 6 | [114] | |
EMIM+ | Ac− | 120 | 5 | [114] | |
EMIM+ | Cl− | 80 | 65 | [114] | |
EMIM+ | Cl− | 100 | 27 | [114] | |
EMIM+ | Cl− | 120 | 13 | [114] | |
EMIM+ | DEP− | 20 | 394 | [115] | |
EMIM+ | DEP− | 21 | 460 | [116] | |
EMIM+ | DMP− | 20 | 457 | [115] | |
EMIM+ | DMP− | 25 | 265 | [117] | |
EMIM+ | DMP− | 80 | ≈27 | [115] | |
water | 25 | 0.9 | [118] | ||
water | 45 | 0.6 | [118] | ||
DMSO | 25 | 2.0 | [118] | ||
DMSO | 45 | 1.4 | [118] |
3.3. Hydrophobic Reagents in Hydrophilic Solvents—Homogeneous or Heterogeneous Derivatization
3.4. Ionic Liquids as Non-Innocent Solvents—Thermal Stability and Side Reactions
3.5. Toxicity and “Greenness” of Ionic Liquids
3.6. Recyclability of Ionic Liquids
4. Current Developments and Future Perspectives
4.1. Elucidation of the Dissolution Mechanism
Experimental Technique | Model Compound | Ref. |
---|---|---|
computational simulation | glucose, cellodextrins (DP = 2–12) | [174] |
computational simulation | glucose | [175,176] |
computational simulation | cellobiose | [177] |
computational simulation | cellodextrins (DP = 5–20) | [178] |
computational simulation | (1,4)-dimethoxy-β-D-glucopyranose | [179] |
computational simulation | cellulose microfibrils (36 glucan chains, DP = 16) | [180,181] |
computational simulation | cellodextrin (DP = 20) | [182] |
computational simulation | cellulose microfibrils (36 glucan chains, DP = 20) | [183] |
computational simulation | cellulose Iβ crystal | [184] |
computational simulation | cellobiose | [185] |
computational simulation | (1,4)-dimethoxy-β-D-glucopyranose | [186] |
IR spectroscopy(computational simulation) | pentaerythritol | [187] |
neutron diffraction(computational simulation)(NMR spectroscopy) | glucose | [188] |
NMR spectroscopy | glucose, cellobiose | [169,189,190] |
NMR spectroscopy | cellobiose | [170] |
NMR spectroscopy(solvatochromic parameters) | ethanol | [191] |
solvatochromic parameters | cellulose | [192] |
solvatochromic parameters | cellulose | [193] |
solvatochromic parameters | cellulose | [194] |
X-ray diffraction | cellulose | [195] |
Ionic liquid a | Solvatochromic parameters b | Dissolves cellulose | Ref. | |||||||
---|---|---|---|---|---|---|---|---|---|---|
Cation | Anion | ETN | α | β | π* | |||||
AMIM+ | Fo− | n.a. | 0.48 | 0.99 | 1.08 | yes | [198] | |||
AMIM+ | MPo− | n.a. | 0.51 | 0.99 | 1.06 | yes | [123] | |||
BMIM+ | Ac− | 0.611 | 0.43 | 1.05 | 1.04 | yes | [199] | |||
BMIM+ | Ac− | 0.892 | 0.57 | 0.99 | 0.97 | yes | [44] | |||
BMIM+ | Ac− | n.a. | 0.55 | 1.09 | 0.99 | yes | [113] | |||
BMIM+ | Ac− | n.a. | 0.43 | 1.20 | n.a. | yes | [193] | |||
BMIM+ | Ac− | n.a. | 0.36 | 0.85 | n.a. | yes | [200] | |||
BMIM+ | Ac− | n.a. | n.a. | 1.16 | n.a. | yes | [192] | |||
BMIM+ | Cl− | 0.901 | 0.51 | 0.84 | 1.08 | yes | [44] | |||
BMIM+ | Cl− | n.a. | 0.47 | 0.87 | 1.10 | yes | [113] | |||
BMIM+ | Cl− | n.a. | 0.49 | 0.83 | 1.03 | yes | [193] | |||
BMIM+ | Fo− | n.a. | 0.56 | 1.01 | 1.03 | yes | [113] | |||
BMIM+ | MPo− | n.a. | 0.52 | 1.02 | 1.01 | yes | [123] | |||
EDMIM+ | MPo− | n.a. | 0.33 | 1.01 | 1.11 | yes | [123] | |||
EMIM+ | DMP− | n.a. | 0.51 | 1.0 | 1.06 | yes | [117] | |||
EMIM+ | MPo− | n.a. | 0.52 | 1.0 | 1.06 | yes | [123] | |||
EMPIP+ | MPo− | n.a. | 0.29 | 1.08 | 1.08 | yes | [123] | |||
HEMIM+ | MPo− | n.a. | 0.63 | 0.91 | 1.06 | yes | [123] | |||
MOEMIM+ | Ac− | 0.912 | 0.59 | 1.06 | 1.01 | yes | [44] | |||
MOEMIM+ | MPo− | n.a. | 0.51 | 0.98 | 1.07 | yes | [123] | |||
TEMA+ | MPo− | n.a. | 0.29 | 1.04 | 1.14 | yes | [123] | |||
BMIM+ | CH3SO4− | n.a. | 0.54 | 0.67 | 1.05 | no | [193] | |||
BMIM+ | N(CN)2− | n.a. | 0.44 | 0.64 | n.a. | no | [193] | |||
BMIM+ | BF4− | 0.670 | 0.63 | 0.38 | 1.05 | no | [199] | |||
BMIM+ | TfO− | 0.630 | 0.62 | 0.46 | 1.0 | no | [199] | |||
Molecular solvents | ||||||||||
methanol | 0.762 | 0.98 | 0.66 | 0.60 | no | [201] | ||||
DMSO | 0.444 | 0.0 | 0.76 | 1.00 | no | [201] | ||||
Molecular solvents (cont.) | ||||||||||
pyridine | 0.302 | 0.0 | 0.64 | 0.87 | no | [201] | ||||
chloroform | 0.259 | 0.20 | 0.10 | 0.58 | no | [201] | ||||
toluene | 0.099 | 0.0 | 0.11 | 0.54 | no | [201] | ||||
hexane | 0.009 | 0.0 | 0.0 | −0.40 | no | [201] |
4.2. Ionic Liquid/Co-Solvent Mixtures as Tailored Reaction Media
4.3. Task Specific Cellulose Solvents for Dissolution, Sha**, and Chemical Modification of Cellulose
4.4. Combination of Derivatization and Sha** of Cellulose in Ionic Liquids
5. Conclusions
Acknowledgments
References and Notes
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Gericke, M.; Fardim, P.; Heinze, T. Ionic Liquids — Promising but Challenging Solvents for Homogeneous Derivatization of Cellulose. Molecules 2012, 17, 7458-7502. https://doi.org/10.3390/molecules17067458
Gericke M, Fardim P, Heinze T. Ionic Liquids — Promising but Challenging Solvents for Homogeneous Derivatization of Cellulose. Molecules. 2012; 17(6):7458-7502. https://doi.org/10.3390/molecules17067458
Chicago/Turabian StyleGericke, Martin, Pedro Fardim, and Thomas Heinze. 2012. "Ionic Liquids — Promising but Challenging Solvents for Homogeneous Derivatization of Cellulose" Molecules 17, no. 6: 7458-7502. https://doi.org/10.3390/molecules17067458