Invited Lecture material. Sharing Ionic Liquids to 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

6. Applications
Applications
6

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.