Ionic Liquids - Invited Lecture at the Dept. of Chemical Engineering Widya Mandala University
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The document presents an overview of ionic liquids (ILs), highlighting their unique properties, synthesis methods, and various applications in chemical processes. Key features of ILs include their liquid state at low temperatures, non-flammability, and ability to dissolve a wide range of compounds, which makes them valuable in catalytic and separation processes. The presentation discusses historical milestones, designer molecules, and commercial applications, emphasizing their potential in advancing chemical engineering.
![Fluorinated ILs−Anion
Fluorinated ILs−Anion
[emim]Cl + (n+1)HF
.
•
•
•
•
•
N
N
[emim] F·(HF)n + HCl
Air stable
Low melting point (-90 ℃)
Low viscosity (4.9 cP)
High conductivity (120 mScm-1)
Liquid range (350 ℃)
Wide electrochemical window (3.3 V)
HnFn+1 (n = 2,3)
MF5 (M =Nb, Ta)
- HF
[emim]NbF6
m.p (℃)
1
Conductivity (mScm-1)
8.5
Viscosity (cP).
49
N
N
MF6
[emim]TaF6
2
7.1
51
R. Hagiwara, et al. J. Fluorine Chem 2000, 105, 221; 2002, 115, 133](https://image.slidesharecdn.com/ionicliquids-wm-131025083004-phpapp02/85/Ionic-Liquids-Invited-Lecture-at-the-Dept-of-Chemical-Engineering-Widya-Mandala-University-10-320.jpg)
![Hydrogenation
Hydrogenation
+ H2, [Rh(nbd)(PPh3)2]
in [bmim][A-]
[A-] = BF4, PF6, SbF6
83%
5 times faster than in acetone
OH + H
2
NHAc
Rh[(cod)( )-diop]PF6
[bmim]SbF6/i-PrOH
¥á-acetamidocinnamic acid
OH
NHAc
(S)-phenylalanine, 64% ee
Biphasic reaction, higher ee, easy catalyst separation
Y. Chauvin et al., Angew. Chem., Int. Ed. 1995, 34, 2698](https://image.slidesharecdn.com/ionicliquids-wm-131025083004-phpapp02/85/Ionic-Liquids-Invited-Lecture-at-the-Dept-of-Chemical-Engineering-Widya-Mandala-University-16-320.jpg)
![Oxidation
Oxidation
H
H
N
N
Mn
t
O
Bu
But
O
Cl
But
But
(R,R)-1
O
O
(R,R)-1 4mol%, NaOCl
[bmim]PF6 CH2Cl2
(1:4, v/v), 0oC, 2 h
O
2,2-dimethylchromene
Run
1
2
3
4
5
Yield (%)
86
73
73
60
53
% ee
96
90
90
89
88
Higher reaction rate (6 h in conventional solvent), higher ee
C. E. Song, et al. Chem. Comm. 2000, 837](https://image.slidesharecdn.com/ionicliquids-wm-131025083004-phpapp02/85/Ionic-Liquids-Invited-Lecture-at-the-Dept-of-Chemical-Engineering-Widya-Mandala-University-17-320.jpg)
![Hydroformylation
Hydroformylation
+ CO/H2, [PtCl2(PPh3)2]
in [bmim]Cl / SnCl2, [x(SnCl2) = 0.51]
120oC, 90 bar CO/H2
1-octene
H
n-nonanal
O
O
+
n : iso = 19 : 1
H
TOF = 126 h-1
Higher n/iso ratio
Biphasic reaction
Easy catalyst/product separation
P. Wasserscheid, et al. J. Mol. Catal. A: Chemical 2000, 164, 61](https://image.slidesharecdn.com/ionicliquids-wm-131025083004-phpapp02/85/Ionic-Liquids-Invited-Lecture-at-the-Dept-of-Chemical-Engineering-Widya-Mandala-University-18-320.jpg)
![Dimerization − “Difasol Process” by IFP (France)
Dimerization − “Difasol Process” by IFP (France)
butenes
NiCl2L2
[bmim]Cl-AlCl3-EtAlCl2
isooctenes
97% selectivity
(L = PPh3 or pyridine)
The first commercial biphasic process in ionic liquid
Improved yield, Lower catalyst consumption
Y. Chauvin et al., French Patent, FR 2,611,700](https://image.slidesharecdn.com/ionicliquids-wm-131025083004-phpapp02/85/Ionic-Liquids-Invited-Lecture-at-the-Dept-of-Chemical-Engineering-Widya-Mandala-University-19-320.jpg)
![Biocatalysis
Biocatalysis
N
i) 3-phenylpropyl chloride, 70¡É, 1d
ii) NaPF6, acetone, rt, 2d
N
N
N
H 3C
H 3C
PF6
[pmim]PF6, m.p. 53℃
Lipase + [pmim]PF6
i) mixing at 60℃
ii) cooling
Ionic liquid-coated Enzyme (ILCE)
Enhanced enantioselectivity (2-fold compared to the conventional lipase)
Easy catalyst recycling
M-J. Kim, et al., J. Org. Chem. 2002, 67, 6845](https://image.slidesharecdn.com/ionicliquids-wm-131025083004-phpapp02/85/Ionic-Liquids-Invited-Lecture-at-the-Dept-of-Chemical-Engineering-Widya-Mandala-University-20-320.jpg)
![Catalysts
Catalysts
Chloroaluminate Ionic Liquid System
Chloroaluminate Ionic Liquid System
: :Friedel-Crafts Alkylation and Acylation
Friedel-Crafts Alkylation and Acylation
R
O
+
CH3COCl
[emim]Cl/AlCl3 (1:2)
-10~0℃, 0.25~ 1 h
R = OMe, Me, Cl
R
para isomer 99%
Enhanced regioselectivity (4-fold compared to the conventional catalyst)
K. R. Seddon et al., Chem. Comm. 1998, 2097](https://image.slidesharecdn.com/ionicliquids-wm-131025083004-phpapp02/85/Ionic-Liquids-Invited-Lecture-at-the-Dept-of-Chemical-Engineering-Widya-Mandala-University-21-320.jpg)
![Imidazolium and Phosphonium Alkylselenite Ionic Liquids System
Imidazolium and Phosphonium Alkylselenite Ionic Liquids System
Non-phosgene process
Non-phosgene process
RNH2
+
Catalyst
1
O
2 2
CO +
CH3OH
(RNH)2CO + H2O
R1
O
N
Se
Catalyst:
N
OR2
or
[R34P][SeO2(OCH3)]
O
CH3
R: aliphatic, alicyclic, aromatic; R1: CH3, C2H5, n-C4H9;
R2: CH3, C2H5, CH2CF3, Ph; R3: C2H5, n-C4H9
H. S. Kim, Y. J. Kim, et al. Angew. Chem., Int. Ed. 2002, 41, 4300](https://image.slidesharecdn.com/ionicliquids-wm-131025083004-phpapp02/85/Ionic-Liquids-Invited-Lecture-at-the-Dept-of-Chemical-Engineering-Widya-Mandala-University-22-320.jpg)
![Olefin/Paraffin Separation
Olefin/Paraffin Separation
butane /1-butene
= 50/50 (mol %)
butane >1-butene
Ag / [bmim]BF4
+
Ag+−(1-butene)
/ [bmim]BF4
C. L. Munson, et al. US Patent Number 6,339,182](https://image.slidesharecdn.com/ionicliquids-wm-131025083004-phpapp02/85/Ionic-Liquids-Invited-Lecture-at-the-Dept-of-Chemical-Engineering-Widya-Mandala-University-25-320.jpg)
![Liquid-Liquid Extraction
Liquid-Liquid Extraction
SILM System
SILM System
diisopropylamine/triethylamine
/hexylamine Mixture
[bmim]PF6/PVDF
diisopropylamine
C. A. M. Afonso, et al. Angew. Chem., Int. Ed. 2002, 41, 2771](https://image.slidesharecdn.com/ionicliquids-wm-131025083004-phpapp02/85/Ionic-Liquids-Invited-Lecture-at-the-Dept-of-Chemical-Engineering-Widya-Mandala-University-27-320.jpg)
![Nanoparticles
Nanoparticles
Ionic Liquid = [bmim]Tf2N (Tf2N = trifluoromethanesulfonylamide)
Allows a long aging process No shrinkage of the sol-gel network
due to the negligible vapor pressure of IL
Reduce a gelation time: 30min < 1min
Elimination of risky super critical drying step
S. Dai, et al. Chem. Comm. 2000, 243](https://image.slidesharecdn.com/ionicliquids-wm-131025083004-phpapp02/85/Ionic-Liquids-Invited-Lecture-at-the-Dept-of-Chemical-Engineering-Widya-Mandala-University-30-320.jpg)
![Nano Catalysis
Nano Catalysis
H2, [IrCl(cod)]2
[bmim]PF6
TOF: 6,000 h-1
Biphasic reaction, Higher turnovers
Easy catalyst/product separation
Formation of stable Ir0 nanoparticles as an active hydrogenation catalyst
Catalyst reuse (7 times) without loss of initial activities
J. Dupont, et al. J. Am. Chem. Soc. 2002, 124, 4228](https://image.slidesharecdn.com/ionicliquids-wm-131025083004-phpapp02/85/Ionic-Liquids-Invited-Lecture-at-the-Dept-of-Chemical-Engineering-Widya-Mandala-University-31-320.jpg)
Ionic Liquids - Invited Lecture at the Dept. of Chemical Engineering Widya Mandala University
- 1. Ionic Liquids from Exotic to designer molecules for Chemical Processes Jelliarko Palgunadi Ph.D Presented in the Dept. of Chemical Engineering, Widya Mandala University, October 26, 2013. Presented in the Dept. of Chemical Engineering, Widya Mandala University, October 26, 2013. 1
- 2. Ionic Liquids (ILs) are… Ionic Liquids (ILs) are… ••Composed entirely of ions (organic cation and anion) Composed entirely of ions (organic cation and anion) ••Induced largely by packing frustration of asymmetric cations) Induced largely by packing frustration of asymmetric cations) ••But liquid at low temperature (<100℃ )) But liquid at low temperature (<100℃ Cation 1. http://www.electrochem.org/dl/interface/spr/spr07/spr07_p38.pdf Anion
- 3. milestones milestones 1914 First reported by Walden, ethylammonium nitrate (m.p. 12℃ ) Gained no interest at all at that time 1967 Swain, tetra-n-hexylammonium benzoate As a solvent for electrochemical reactions 1970s Osteryoung, Wilkes Opened an area of room temperature ionic liquid 1980s Seddon and Chauvin, chloroaluminate ionic liquid Used as a solvent for biphasic catalysis 1992 Wilkes, a series of imidazolium salts "Designer solvent", "Innovative liquid", "Neoteric Solvent" A breakthrough, applied to a wide range of applications
- 4. Outstanding Features Outstanding Features IL's structure can be tailored for specific applications.
- 5. Properties of Imidazolium-based ILs Properties of Imidazolium-based ILs No effective vapor pressure Non-flammable High ionic conductivity Wide liquid range up to 300℃ Thermally stable up to 200 ºC Ability to dissolve a wide range of inorganic, organometallic compounds Ability to capture small molecules (H2, CO, CO2, and O2) Immiscibility with some organic solvents, e.g. alkanes, BTX Highly polar yet non-coordinating Polarity and hydrophilicity/lipophilicity can be easily tailored
- 7. Synthesis of Imidazolium-based ILs Synthesis of Imidazolium-based ILs Alkyl Halide Alkyl Halide PF6 Cl Me N N R-Cl Me R N N KPF6 or Me R N N HPF6 / NaOH Dialkyl Carbonate Dialkyl Carbonate O Et OCOCH3 O N N + CH3OCOCH3 Et in CH3OH N N Me
- 8. Trifluoroalkyl Ester Trifluoroalkyl Ester OY Et N N + Et CH3OY N N Me in CH3OH O Y = SCF3, CCF3 O O One pot synthesis One pot synthesis HCHO O O MeNH2 i) HBF4 ii) n-BuNH2 Me BF4 N N 1,3-dibutylimidazolium (41%), 1-butyl-3-methylimidazolium (50%), 1,3-dimethylimidazolium (9%) n-Bu
- 9. Fluorinated Ionic Liquids --Cation Fluorinated Ionic Liquids Cation Me N N (CF2)xCF3 PF6 Thermally stable, water insoluble High density New surfactants J. H. Davis, et al. Chem. Comm.. 2000, 2051
- 10. Fluorinated ILs−Anion Fluorinated ILs−Anion [emim]Cl + (n+1)HF . • • • • • N N [emim] F·(HF)n + HCl Air stable Low melting point (-90 ℃) Low viscosity (4.9 cP) High conductivity (120 mScm-1) Liquid range (350 ℃) Wide electrochemical window (3.3 V) HnFn+1 (n = 2,3) MF5 (M =Nb, Ta) - HF [emim]NbF6 m.p (℃) 1 Conductivity (mScm-1) 8.5 Viscosity (cP). 49 N N MF6 [emim]TaF6 2 7.1 51 R. Hagiwara, et al. J. Fluorine Chem 2000, 105, 221; 2002, 115, 133
- 11. Natural product IL Natural product IL Letters in Organic Chemistry, Volume 6, 2009, 264 11
- 12. Sweet Success of ILs Sweet Success of ILs BASILTM (Biphasic Acid Scavenging utilizing Ionic Liquids) is an auxiliary for acid scavenging – The first commercial process employing ILs by BASF BASIONICTM - A broad portfolio of Ionic Liquids by BASF BASF uses N-methylimidazolium chloride, which has a melting point of 75 °C. to scavenge acid that is formed in the process of alkoxyphenylphosphines production. Chemical & Engineering News, Volume 81, Number 13
- 13. Applications of ILs in Chemical Reaction and Separation Applications of ILs in Chemical Reaction and Separation state of the art state of the art
- 14. Reaction Media Reaction Media Purposes Purposes Immobilization of precious catalyst & recycling Immobilization of precious catalyst & recycling Biphasic reaction Biphasic reaction Enhancement of reaction rates Enhancement of reaction rates Selectivity improvement Selectivity improvement Stabilization of catalysts Stabilization of catalysts
- 15. Immobilization of Precious Catalyst & Recycling Immobilization of Precious Catalyst & Recycling Starting material heating Catalyst Starting material Product Catalyst cooling Product mixture Catalyst Ionic liquid Catalyst recycle Catalyst Products
- 16. Hydrogenation Hydrogenation + H2, [Rh(nbd)(PPh3)2] in [bmim][A-] [A-] = BF4, PF6, SbF6 83% 5 times faster than in acetone OH + H 2 NHAc Rh[(cod)( )-diop]PF6 [bmim]SbF6/i-PrOH ¥á-acetamidocinnamic acid OH NHAc (S)-phenylalanine, 64% ee Biphasic reaction, higher ee, easy catalyst separation Y. Chauvin et al., Angew. Chem., Int. Ed. 1995, 34, 2698
- 17. Oxidation Oxidation H H N N Mn t O Bu But O Cl But But (R,R)-1 O O (R,R)-1 4mol%, NaOCl [bmim]PF6 CH2Cl2 (1:4, v/v), 0oC, 2 h O 2,2-dimethylchromene Run 1 2 3 4 5 Yield (%) 86 73 73 60 53 % ee 96 90 90 89 88 Higher reaction rate (6 h in conventional solvent), higher ee C. E. Song, et al. Chem. Comm. 2000, 837
- 18. Hydroformylation Hydroformylation + CO/H2, [PtCl2(PPh3)2] in [bmim]Cl / SnCl2, [x(SnCl2) = 0.51] 120oC, 90 bar CO/H2 1-octene H n-nonanal O O + n : iso = 19 : 1 H TOF = 126 h-1 Higher n/iso ratio Biphasic reaction Easy catalyst/product separation P. Wasserscheid, et al. J. Mol. Catal. A: Chemical 2000, 164, 61
- 19. Dimerization − “Difasol Process” by IFP (France) Dimerization − “Difasol Process” by IFP (France) butenes NiCl2L2 [bmim]Cl-AlCl3-EtAlCl2 isooctenes 97% selectivity (L = PPh3 or pyridine) The first commercial biphasic process in ionic liquid Improved yield, Lower catalyst consumption Y. Chauvin et al., French Patent, FR 2,611,700
- 20. Biocatalysis Biocatalysis N i) 3-phenylpropyl chloride, 70¡É, 1d ii) NaPF6, acetone, rt, 2d N N N H 3C H 3C PF6 [pmim]PF6, m.p. 53℃ Lipase + [pmim]PF6 i) mixing at 60℃ ii) cooling Ionic liquid-coated Enzyme (ILCE) Enhanced enantioselectivity (2-fold compared to the conventional lipase) Easy catalyst recycling M-J. Kim, et al., J. Org. Chem. 2002, 67, 6845
- 21. Catalysts Catalysts Chloroaluminate Ionic Liquid System Chloroaluminate Ionic Liquid System : :Friedel-Crafts Alkylation and Acylation Friedel-Crafts Alkylation and Acylation R O + CH3COCl [emim]Cl/AlCl3 (1:2) -10~0℃, 0.25~ 1 h R = OMe, Me, Cl R para isomer 99% Enhanced regioselectivity (4-fold compared to the conventional catalyst) K. R. Seddon et al., Chem. Comm. 1998, 2097
- 22. Imidazolium and Phosphonium Alkylselenite Ionic Liquids System Imidazolium and Phosphonium Alkylselenite Ionic Liquids System Non-phosgene process Non-phosgene process RNH2 + Catalyst 1 O 2 2 CO + CH3OH (RNH)2CO + H2O R1 O N Se Catalyst: N OR2 or [R34P][SeO2(OCH3)] O CH3 R: aliphatic, alicyclic, aromatic; R1: CH3, C2H5, n-C4H9; R2: CH3, C2H5, CH2CF3, Ph; R3: C2H5, n-C4H9 H. S. Kim, Y. J. Kim, et al. Angew. Chem., Int. Ed. 2002, 41, 4300
- 23. Imidazolium Zinc Tetrahalides Ionic Liquids System Imidazolium Zinc Tetrahalides Ionic Liquids System 2 R N N CH3 X + R ZnY2 N N CH3 2 ZnX2Y2 1: R = CH3; 2: R = C2H5; 3: R = n-C4H9; 4: R = CH2C6H5 a: X = Y = Cl; b: X = Cl, Y = Br; c: X = Y = Br O O + CO2 R O catalyst: 1b TOF = 2700-3400 h-1 ∗ 10 h-1 for (MePh3)P+I- (1,3-dimethylimidazolium)2ZnCl2Br2 ,1b H. S. Kim, et al. J. Catal..2003 O R
- 24. Separation Media Separation Media Gas Extraction ––CO2 Gas Extraction CO2 J.H. Davis, et al., J. Am. Chem. Soc., 2002, 124, 926
- 25. Olefin/Paraffin Separation Olefin/Paraffin Separation butane /1-butene = 50/50 (mol %) butane >1-butene Ag / [bmim]BF4 + Ag+−(1-butene) / [bmim]BF4 C. L. Munson, et al. US Patent Number 6,339,182
- 26. Facilitated Transport Membran Facilitated Transport Membran Supported Liquid Membrane (SLM) Supported Liquid Membrane (SLM) Supported Ionic Liquid Membrane (SILM) Supported Ionic Liquid Membrane (SILM) Pore FTC/H2O Pore Porous Membrane Support FTC/Ionic Liquid Porous Membrane Support ∗ FTC: Facilitated Transport Carrier Drawback: vaporization of H2O Non-volatile
- 27. Liquid-Liquid Extraction Liquid-Liquid Extraction SILM System SILM System diisopropylamine/triethylamine /hexylamine Mixture [bmim]PF6/PVDF diisopropylamine C. A. M. Afonso, et al. Angew. Chem., Int. Ed. 2002, 41, 2771
- 28. Metal Ion Extraction −TSILs Metal Ion Extraction −TSILs CH3 O N N N H BF4 N H Extraction of heavy metals (Hg2+ or Cd2+))from aqueous waste Extraction of heavy metals (Hg2+ or Cd2+ from aqueous waste O N N N H P Ph Ph PF6 Extraction of actinides (Am3+, ,UO22+, ,Pu4+))from wastewater Extraction of actinides (Am3+ UO22+ Pu4+ from wastewater at nuclear processing site at nuclear processing site R. D. Rogers, K. R. ACS Symposium Series 818. 2002
- 29. Dispersion & Preparation of Nanoparticles Dispersion & Preparation of Nanoparticles Dispersion media for nanoparticles IL have been found as good synthesis and dispersion media for metal nanoparticles, carbon allotropes (CNTs, fullerenes, graphene). Plausible applications including coatings and nanoparticle incorporation into plastic resins. http://pubs.acs.org/doi/abs/10.1021/ic702071w?journalCode=inocaj www.iolitec.de http://pubs.rsc.org/en/content/articlelanding/2010/cp/b920568n
- 30. Nanoparticles Nanoparticles Ionic Liquid = [bmim]Tf2N (Tf2N = trifluoromethanesulfonylamide) Allows a long aging process No shrinkage of the sol-gel network due to the negligible vapor pressure of IL Reduce a gelation time: 30min < 1min Elimination of risky super critical drying step S. Dai, et al. Chem. Comm. 2000, 243
- 31. Nano Catalysis Nano Catalysis H2, [IrCl(cod)]2 [bmim]PF6 TOF: 6,000 h-1 Biphasic reaction, Higher turnovers Easy catalyst/product separation Formation of stable Ir0 nanoparticles as an active hydrogenation catalyst Catalyst reuse (7 times) without loss of initial activities J. Dupont, et al. J. Am. Chem. Soc. 2002, 124, 4228
- 32. scCO2 ––IL Hybrid System scCO2 IL Hybrid System Product was extracted out of ionic liquid by scCO2 and recycled several times Product was extracted out of ionic liquid by scCO2 and recycled several times D. J. Cole-Hamilton, et al. Chem.Comm. 2001, 781
- 33. Problems to be Solved Problems to be Solved •• •• •• •• Difficulty in purification (halides, H O) Difficulty in purification (halides, H O) High cost ($ 10/g $ 40 ~ 80/L) High cost ($ 10/g $ 40 ~ 80/L) Toxicity Toxicity Insufficient long-term stability to hydrolysis Insufficient long-term stability to hydrolysis 2 2
- 34. From Academia to Market From Academia to Market … and many more.
Editor's Notes
- #2: {"5":"Highly polar yet non-coordinating \nstrong rate-enhancing effect in reactions involving cationic intermediates\n","18":"In CH2Cl2 solvent: 130 h-1\n"}