Ionic LiquidsIonic Liquids from Exotic to designer molecules for Chemical Processesfrom Exotic to designer molecules for Chemical Processes
Jelliarko Palgunadi Ph.D
1Presented 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.
Cation Anion
1. http://www.electrochem.org/dl/interface/spr/spr07/spr07_p38.pdf
Ionic Liquids (ILs) are… Ionic Liquids (ILs) are…
• Composed entirely of ions (organic cation and anion)• Induced largely by packing frustration of asymmetric cations)• But liquid at low temperature (<100 )℃
• Composed entirely of ions (organic cation and anion)• Induced largely by packing frustration of asymmetric cations)• But liquid at low temperature (<100 )℃
milestonesmilestones
1914 First reported by Walden, ethylammonium nitrate (m.p. 12 )℃Gained no interest at all at that time
1967 Swain, tetra-n-hexylammonium benzoateAs a solvent for electrochemical reactions
1970s Osteryoung, WilkesOpened 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
IL's structure can be tailored for specific applications.
Outstanding FeaturesOutstanding Features
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
Properties of Imidazolium-based ILsProperties of Imidazolium-based ILs
6
ApplicationsApplicationsApplicationsApplications
Synthesis of Imidazolium-based ILsSynthesis of Imidazolium-based ILs
NNMe
NNMe R
NNMe R
R-Cl
Cl
KPF6 or
HPF6 / NaOH
PF6
Alkyl HalideAlkyl Halide
Dialkyl CarbonateDialkyl Carbonate
NNEt
NNEt Me
in CH3OH
+ CH3OCOCH3
OOCOCH3
O
Trifluoroalkyl EsterTrifluoroalkyl Ester
NNEt
NNEt Me
in CH3OH
OY
+ CH3OY
Y = SCF3
O
O
CCF3
O
,
1,3-dibutylimidazolium (41%), 1-butyl-3-methylimidazolium (50%), 1,3-dimethylimidazolium (9%)
HCHOO O
MeNH2
i) HBF4
ii) n-BuNH2 NNMe n-Bu
BF4
One pot synthesisOne pot synthesis
Fluorinated Ionic Liquids - CationFluorinated Ionic Liquids - Cation
NNMe (CF2)xCF3
PF6
Thermally stable, water insolubleHigh density New surfactants
J. H. Davis, et al. Chem. Comm.. 2000, 2051
Fluorinated ILsAnionFluorinated ILsAnion
[emim]Cl + (n+1)HF [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)
NN NNMF5 (M =Nb, Ta)
- HFHnFn+1 (n = 2,3) MF6
[emim]NbF6 [emim]TaF6
m.p (℃) 1 2Conductivity (mScm-1) 8.5 7.1Viscosity (cP). 49 51
R. Hagiwara, et al. J. Fluorine Chem 2000, 105, 221; 2002, 115, 133
11
Natural product ILNatural product IL
Letters in Organic Chemistry, Volume 6, 2009, 264
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
Sweet Success of ILsSweet Success of ILsSweet Success of ILsSweet Success of ILs
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
Applications of ILs in Chemical Reaction and Separationstate of the art
Applications of ILs in Chemical Reaction and Separationstate of the art
Reaction MediaReaction Media
Immobilization of precious catalyst & recycling Biphasic reaction Enhancement of reaction rates Selectivity improvement Stabilization of catalysts
Immobilization of precious catalyst & recycling Biphasic reaction Enhancement of reaction rates Selectivity improvement Stabilization of catalysts
PurposesPurposes
Ionic liquid
Starting material
Catalyst
Starting material Product Catalyst
Productmixture
Catalyst
heating cooling
ProductsCatalystCatalyst recycle
Immobilization of Precious Catalyst & RecyclingImmobilization of Precious Catalyst & Recycling
OH
NHAc
Rh[(cod)( )-diop]PF6
[bmim]SbF6/i-PrOH+ H2
OH
NHAc
¥á-acetamidocinnamic acid (S)-phenylalanine, 64% ee
Y. Chauvin et al., Angew. Chem., Int. Ed. 1995, 34, 2698
HydrogenationHydrogenation
+ H2, [Rh(nbd)(PPh3)2]
in [bmim][A-]
[A-] = BF4, PF6, SbF6
5 times faster than in acetone
83%
Biphasic reaction, higher ee, easy catalyst separation
OxidationOxidation
C. E. Song, et al. Chem. Comm. 2000, 837
N N
O O
Mn
But But
But But
Cl
H H
(R,R)-1
Run 1 2 3 4 5
Yield (%) 86 73 73 60 53
% ee 96 90 90 89 88
O O(R,R)-1 4mol%, NaOCl
[bmim]PF6 CH2Cl2(1:4, v/v), 0oC, 2 h
O2,2-dimethylchromene
Higher reaction rate (6 h in conventional solvent), higher ee
HydroformylationHydroformylation
H
O
H
O
+ CO/H2, [PtCl2(PPh3)2]
in [bmim]Cl / SnCl2, [x(SnCl2) = 0.51]
120oC, 90 bar CO/H2
+
n : iso = 19 : 1
P. Wasserscheid, et al. J. Mol. Catal. A: Chemical 2000, 164, 61
TOF = 126 h-1
1-octene
Higher n/iso ratioBiphasic reactionEasy catalyst/product separation
n-nonanal
Dimerization “Difasol Process” by IFP (France)Dimerization “Difasol Process” by IFP (France)
butenes isooctenes[bmim]Cl-AlCl3-EtAlCl2
NiCl2L2
(L = PPh3 or pyridine)
Y. Chauvin et al., French Patent, FR 2,611,700
97% selectivity
The first commercial biphasic process in ionic liquidImproved yield, Lower catalyst consumption
N
N
H3C
i) 3-phenylpropyl chloride, 70¡É, 1dii) NaPF6, acetone, rt, 2d
N
N
H3CPF6
M-J. Kim, et al., J. Org. Chem. 2002, 67, 6845
BiocatalysisBiocatalysis
Ionic liquid-coated Enzyme (ILCE)
[pmim]PF6, m.p. 53℃
Lipase + [pmim]PF6 i) mixing at 60℃ii) cooling
Enhanced enantioselectivity (2-fold compared to the conventional lipase) Easy catalyst recycling
R
+[emim]Cl/AlCl3 (1:2)
CH3COCl
R
O
CatalystsCatalysts
K. R. Seddon et al., Chem. Comm. 1998, 2097
Chloroaluminate Ionic Liquid System: Friedel-Crafts Alkylation and Acylation
Chloroaluminate Ionic Liquid System: Friedel-Crafts Alkylation and Acylation
para isomer 99%
Enhanced regioselectivity (4-fold compared to the conventional catalyst)
-10~0 , 0.25~ 1 h℃
R = OMe, Me, Cl
RNH2 + CO +12
(RNH)2CO + H2OCatalyst
Catalyst:
N
N
R1
CH3
Se
O
O
OR2 or [R34P][SeO2(OCH3)]
R2: CH3, C2H5, CH2CF3, Ph; R3: C2H5, n-C4H9
R: aliphatic, alicyclic, aromatic; R1: CH3, C2H5, n-C4H9;
O2CH3OH
H. S. Kim, Y. J. Kim, et al. Angew. Chem., Int. Ed. 2002, 41, 4300
Imidazolium and Phosphonium Alkylselenite Ionic Liquids SystemImidazolium and Phosphonium Alkylselenite Ionic Liquids System
Non-phosgene processNon-phosgene process
Imidazolium Zinc Tetrahalides Ionic Liquids SystemImidazolium Zinc Tetrahalides Ionic Liquids System
ZnX2Y2X ZnY22
+2
1: R = CH3; 2: R = C2H5; 3: R = n-C4H9; 4: R = CH2C6H5a: X = Y = Cl; b: X = Cl, Y = Br; c: X = Y = Br
NNR CH3
NNR CH3
(1,3-dimethylimidazolium)2ZnCl2Br2 ,1b
TOF = 2700-3400 h-1
O O
R
OO
R
+ CO2
catalyst: 1b
H. S. Kim, et al. J. Catal..2003
10 h-1 for (MePh3)P+I-
J.H. Davis, et al., J. Am. Chem. Soc., 2002, 124, 926
Gas Extraction – CO2Gas Extraction – CO2
Separation MediaSeparation Media
Olefin/Paraffin Separation Olefin/Paraffin Separation
butane /1-butene= 50/50 (mol %)
Ag+ / [bmim]BF4Ag+(1-butene)
/ [bmim]BF4
butane >1-butene
C. L. Munson, et al. US Patent Number 6,339,182
Porous Membrane Support
PoreFTC/Ionic Liquid
Facilitated Transport MembranFacilitated Transport Membran
Supported Ionic Liquid Membrane (SILM) Supported Ionic Liquid Membrane (SILM)
Porous Membrane Support
Pore FTC/H2O
Supported Liquid Membrane (SLM) Supported Liquid Membrane (SLM)
Drawback: vaporization of H2O Non-volatile
FTC: Facilitated Transport Carrier
diisopropylamine/triethylamine/hexylamine Mixture
[bmim]PF6/PVDF diisopropylamine
C. A. M. Afonso, et al. Angew. Chem., Int. Ed. 2002, 41, 2771
Liquid-Liquid ExtractionLiquid-Liquid Extraction
SILM SystemSILM System
Extraction of actinides (Am3+, UO22+, Pu4+) from wastewater
at nuclear processing site
Extraction of actinides (Am3+, UO22+, Pu4+) from wastewater
at nuclear processing site
Metal Ion Extraction TSILs Metal Ion Extraction TSILs
R. D. Rogers, K. R. ACS Symposium Series 818. 2002
NN NH
NH
CH3O
BF4
NN NH
P
PhPh
O
PF6
Extraction of heavy metals (Hg2+ or Cd2+) from aqueous wasteExtraction of heavy metals (Hg2+ or Cd2+) from aqueous waste
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=inocajwww.iolitec.dehttp://pubs.rsc.org/en/content/articlelanding/2010/cp/b920568n
Dispersion & Preparation of NanoparticlesDispersion & Preparation of Nanoparticles
S. Dai, et al. Chem. Comm. 2000, 243
NanoparticlesNanoparticles
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 ILReduce a gelation time: 30min < 1minElimination of risky super critical drying step
H2, [IrCl(cod)]2
[bmim]PF6
Nano CatalysisNano Catalysis
J. Dupont, et al. J. Am. Chem. Soc. 2002, 124, 4228
TOF: 6,000 h-1
Biphasic reaction, Higher turnoversEasy catalyst/product separationFormation of stable Ir0 nanoparticles as an active hydrogenation catalystCatalyst reuse (7 times) without loss of initial activities
Product was extracted out of ionic liquid by scCO2 and recycled several timesProduct was extracted out of ionic liquid by scCO2 and recycled several times
D. J. Cole-Hamilton, et al. Chem.Comm. 2001, 781
scCO2 – IL Hybrid SystemscCO2 – IL Hybrid System
Problems to be SolvedProblems to be Solved
• Difficulty in purification (halides, H2O)• High cost ($ 10/g $ 40 ~ 80/L)• Toxicity• Insufficient long-term stability to hydrolysis
• Difficulty in purification (halides, H2O)• High cost ($ 10/g $ 40 ~ 80/L)• Toxicity• Insufficient long-term stability to hydrolysis
… and many more.
From Academia to MarketFrom Academia to Market
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