ilsept, sitges, spain, september 6 - iolitec ionic liquids ... · most publications target only a...
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ILSEPT, Sitges, Spain, September 6ILSEPT, Sitges, Spain, September 6thth
Boyan Iliev, Marcin Smiglak, Anna Świerczyńska,Thomas Schubert
IOLITEC
© IOLITEC GmbH, 2011.
Ionic Liquids Technologies GmbHSalzstraße 184D-74076 Heilbronn
OutlineOutline
1 Introduction
2 Solubility Tests
3 Conclusions
4 Company Information
© IOLITEC GmbH, 2011.
4 Company Information
1 Introduction
© IOLITEC GmbH, 2011.
1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
© C
OS
MO
LO
GIC
Ionic Liquids Ionic Liquids –– An Overview of ApplicationsAn Overview of Applications
PROCESS TECHNOLOGY█ Biomass Conversion█ Gas-Separation
█ Metal-Extraction
ANALYTICS█ Electrophoresis█ Solvents for GC-
Headspace
STATUS:
█ R&D█ Pilot█ Commercialized
ELECTROCHEMISTRY█ Fuel Cells█ Metal Deposition
& Electropolishing
█ Metal-Extraction█ Liquid-Liquid-Extraction
FUNCTIONAL FLUIDS& ADDITIVES█ Hydraulic Oils
█ Additives█ Lubricants█ Surfactants
Headspace█ Matrix-Materials
for MALDI-TOF-MS█ Karl-Fischer Titration
█ Protein-Crystallization█ GC-Materials
- Liquid over a Wide T-Range -Thermal Stability- Electrochemical Stability- Low Vapor Pressure- Non Volatility- Non Inflammability- Electric Conducting- Tunable Miscibility
IONIC LIQUIDS PROPERTIES
© IOLITEC GmbH, 2011.
& Electropolishing█ Batteries█ DSSCs█ Electrochromic
Windows█ Sensors█ Supercaps
SYNTHESIS & CATALYSIS█ Enzymatic Reactions█ Immobilization of
Catalysts (SILP)█ Nanoparticle-Synthesis█ Organic Synthesis
HEAT TRANSPORT& CONVERSION█ Thermal Fluids
█ Phase Changing Materials (PCM)
█ Sorption Cooling Media
� Most publications target only a few ILs (in particular BMIM PF6 and BMIM BF4) and use specific solvents or solvent mixtures
Solubility of ILs in Common Solvents Solubility of ILs in Common Solvents –– Why Bother ?Why Bother ?
� Recycling of ILs is usually associated with extraction
� Process optimization in extraction/separation processes
� Production scale-up
� Green process evaluation
© IOLITEC GmbH, 2011.
A more precise knowledge of the solubility of ILs in common organic solvents is needed to enable more applications in
organic synthesis
CationsCations, Anions and Abbreviations, Anions and Abbreviations
F
P
F F
F F
F
F
BF F
F
BMPyrr BuPy
PF6 BF4
DCA BTA
N
Me Bu
N
Bu
N
Me
N N
S
N
S
O
O
CF3O
O
F3C
F F
NC
N
CN
O
PMeO OMe
O
© IOLITEC GmbH, 2011.
BMIM Bu3Pic DEP DMP
N
Bu
N N
Me BuPMeO
O
OMe PEtO
O
OEt
S C NI
2 Solubility Tests
© IOLITEC GmbH, 2011.
1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
© C
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AcetoneChloro-
formEthyl
AcetateTolu-ene
Hex-ane
Water THFOct-ane
Octa-nol
1 DiMIM DMP
2 EMIM DEP
ILs Used in the StudyILs Used in the Study
2 EMIM DEP
3 EMIM OAc
4 EMIM SCN
5 PMIM I
6 BMIM PF6
7 HMIM PF6
© IOLITEC GmbH, 2011.
8 EMIM BF4
9 BMIM BF4
10 HMIM BF4
11 BuPy BF4
AcetoneChloro-
formEthyl
AcetateTolu-ene
Hex-ane
Water THFOct-ane
Octa-nol
12 Bu3Pic BF4
ILs Used in the Study (2)ILs Used in the Study (2)
13 EMIM BTA
14 BMIM BTA
15 BDiMIM BTA
16 HMIM BTA
17 BuPy BTA
18 Bu3Pic BTA
© IOLITEC GmbH, 2011.
19 PMPyrr BTA
20 BMPyrr BTA
21 BMIM DCA
22 EMIM DCA
Solubility in Hexane
Hexane concentration in IL Phase IL concentration in Hexane Phase
Solubility in HexaneSolubility in Hexane
5,00
10,00
15,00
20,00
25,00
Org
an
ic s
ub
sta
nce's
co
nte
nt
© IOLITEC GmbH, 2011.
0,00
5,00
DiM
IM D
MP
EM
IM D
CA
EM
IM O
Ac
EM
IM S
CN
PM
IM I
BM
IM P
F6
HM
IM P
F6
EM
IM B
F4
BM
IM B
F4
HM
IM B
F4
BuP
y B
F4
Bu3P
ic B
F4
EM
IM B
TA
BM
IM B
TA
BdiM
IM B
TA
HM
IM B
TA
BuP
y B
TA
Bu3P
ic B
TA
PM
Pyrr
BTA
BM
Pyrr
BTA
BM
IM D
CA
EM
IM D
EP
Solubility in Toluene
Toluene concentration in IL Phase IL concentration in Toluene Phase
Solubility in TolueneSolubility in Toluene
10
15
20
25
30
35
40
45
50
Org
an
ic s
ub
sta
nce's
co
nte
nt
© IOLITEC GmbH, 2011.
0
5
10
DiM
IM D
MP
EM
IM D
CA
EM
IM O
Ac
EM
IM S
CN
PM
IM I
BM
IM P
F6
HM
IM P
F6
EM
IM B
F4
BM
IM B
F4
HM
IM B
F4
BuP
y B
F4
Bu3P
ic B
F4
EM
IM B
TA
BM
IM B
TA
BdiM
IM B
TA
HM
IM B
TA
BuP
y B
TA
Bu3P
ic B
TA
PM
Pyrr
BTA
BM
Pyrr
BTA
BM
IM D
CA
EM
IM D
EP
Solubility in Ethyl Acetate
Ethyl Acetate concentration in IL Phase IL concentration in Ethyl Acetate Phase
Solubility in Ethyl AcetateSolubility in Ethyl Acetate
10
15
20
25
30
35
40
45
50
Org
an
ic s
ub
sta
nce's
co
nte
nt
Ethyl Acetate concentration in IL Phase IL concentration in Ethyl Acetate Phase
© IOLITEC GmbH, 2011.
0
5
10
DiM
IM D
MP
EM
IM D
CA
EM
IM O
Ac
EM
IM S
CN
PM
IM I
EM
IM B
F4
BM
IM B
F4
BuP
y B
F4
Bu3P
ic B
F4
BM
IM D
CA
EM
IM D
EP
Org
an
ic s
ub
sta
nce's
co
nte
nt
Researc
hed
su
bsta
nce's
co
nte
nt
Solubility in Water
Water concentration in IL Phase IL concentration in Water Phase
Solubility in WaterSolubility in Water
4
6
8
10
12
14
Researc
hed
su
bsta
nce's
co
nte
nt
© IOLITEC GmbH, 2011.
0
2
BM
IM P
F6
HM
IM P
F6
HM
IM B
F4
EM
IM B
TA
BM
IM B
TA
BdiM
IM B
TA
HM
IM B
TA
BuP
y B
TA
Bu3P
ic B
TA
PM
Pyrr
BTA
BM
Pyrr
BTA
Researc
hed
su
bsta
nce's
co
nte
nt
Solubility in THF
THF concentration in IL Phase IL concentration in THF Phase
Solubility in THFSolubility in THF
10
15
20
25
30
35
40
45
50
Org
an
ic s
ub
sta
nce's
co
nte
nt
© IOLITEC GmbH, 2011.
0
5
10
DiMIM DMP
EMIM DCA
EMIM OAc
EMIM SCN
PMIM I EMIM BF4
BMIM BF4
BuPy BF4
Bu3Pic BF4
EMIM DEP
Solubility in Octane
Octane concentration in IL IL concentration in Octane
Solubility in nSolubility in n--OctaneOctane
10
15
20
25
30
Org
an
ic s
ub
sta
nce's
co
nte
nt
© IOLITEC GmbH, 2011.
0
5
DiM
IM D
MP
EM
IM D
CA
EM
IM O
Ac
EM
IM S
CN
PM
IM I
BM
IM P
F6
HM
IM P
F6
EM
IM B
F4
BM
IM B
F4
HM
IM B
F4
BuP
y B
F4
Bu3P
ic B
F4
EM
IM B
TA
BM
IM B
TA
BdiM
IM B
TA
HM
IM B
TA
BuP
y B
TA
Bu3P
ic B
TA
PM
Pyrr
BTA
BM
Pyrr
BTA
BM
IM D
CA
EM
IM D
EP
Solubility of 1-Octanol
1-Octanol concentration in IL Phase IL concentration in Octanol Phase
Solubility in 1Solubility in 1--OctanolOctanol
10
15
20
25
30
35
40
Org
an
ic s
ub
sta
nce's
co
nte
nt
1-Octanol concentration in IL Phase IL concentration in Octanol Phase
© IOLITEC GmbH, 2011.
0
5
EM
IM S
CN
BM
IM P
F6
HM
IM P
F6
EM
IM B
F4
BM
IM B
F4
BuP
y B
F4
Bu3P
ic B
F4
EM
IM B
TA
BM
IM B
TA
BdiM
IM B
TA
HM
IM B
TA
BuP
y B
TA
Bu3P
ic B
TA
PM
Pyrr
BTA
BM
Pyrr
BTA
Solubility of 1,3-Dimethylimidazolium Dimethylphosphate
Solvent cocentration in IL Phase IL concentration in Solven Phase
Solubility of 1,3Solubility of 1,3--Dimethylimidazolium Dimethylimidazolium DimethylphosphateDimethylphosphate
10
15
20
25
30
35
40
Org
an
ic s
ub
sta
nce's
co
nte
nt
© IOLITEC GmbH, 2011.
0
5
ACETONE ETHYL ACETATE
TOLUENE HEXANE THF OCTANE
Solubility of 1-Ethyl-3-Methylimidazolium Diethylphosphate
Solubility of 1Solubility of 1--EthylEthyl--33--Methylimidazolium Methylimidazolium DiethylphosphateDiethylphosphate
15
20
25
30
35
40
Org
an
ic s
ub
sta
nce's
co
nte
nt
Solvent concentration in IL Phase IL concentration in Solvent Phase
© IOLITEC GmbH, 2011.
0
5
10
15
ETHYL ACETATE
TOLUENE HEXANE THF OCTANE
Org
an
ic s
ub
sta
nce's
co
nte
nt
Solubility of N-Butyl-N-Methylpyrrolidinium Bis(trifluormethylsulfonyl)imide
Solubility of BMPyrr Bis(trifluormethylsulfonyl)imide Solubility of BMPyrr Bis(trifluormethylsulfonyl)imide
10
15
20
25
30
35
40
Org
an
ic s
ub
sta
nce's
co
nte
nt
Solvent concentration in IL Phase IL concentration in Solvent Phase
© IOLITEC GmbH, 2011.
0
5
10
TOLUENE HEXANE WATER OCTANE 1-OCTANOL
Org
an
ic s
ub
sta
nce's
co
nte
nt
Solubility of 1-Butyl-3-Methylimidazolium Dicyanamide
Solvent concentration in IL Phase IL concentration in Solvent Phase
Solubility of 1Solubility of 1--ButylButyl--33--Methylimidazolium Methylimidazolium dicyanamidedicyanamide
10
15
20
25
30
35
40
Org
an
ic s
ub
sta
nce's
co
nte
nt
Solvent concentration in IL Phase IL concentration in Solvent Phase
© IOLITEC GmbH, 2011.
0
5
ETHYL ACETATE TOLUENE HEXANE OCTANE
Org
an
ic s
ub
sta
nce's
co
nte
nt
3 Conclusions
© IOLITEC GmbH, 2011.
1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
© C
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� ILs are not generally soluble in Acetone; why?
� Some PF6 ILs are well water soluble (!)
� ILs which are soluble in AcOEt are water insoluble, and vice versa
ConclusionsConclusions
� ILs which are soluble in AcOEt are water insoluble, and vice versa
� Imidazolium-based ILs are better soluble in AcOEt than Pyrrolidinium
or even Pyridinium ones
� BTA-based ILs are better soluble in Toluene than the corresponding
PF6 and BF4 ILs
� PF and BF - based ILs are better soluble in Hexane than the
© IOLITEC GmbH, 2011.
� PF6 and BF4 - based ILs are better soluble in Hexane than the
corresponding BTA ILs
We still do not understand enough in order to predict solubility.
IOLITEC –Enabling success in future Enabling success in future
technologies
© IOLITEC GmbH, 2011.
N-Butyl-N-methylpyrrolidinium dicyanamide
© C
OS
MO
LO
GIC
IOLITEC HQHeilbronn
IOLITEC since 01/2010 @ Heilbronn, Germanysince 02/2010 @ Tuscaloosa, USA(2003-2005 Freiburg)(2005-2009 Denzlingen)
Company FactsCompany Facts
HeilbronnFoundation: 2003
Branch: Chemistry / Material Science
Capacity: 10 mT (2010)fast Scale-Up2011: 25-100 to per year
Products: ~ 300 ionic liquids10 in bulk-quantity~ 130 Nanomaterials
© IOLITEC GmbH, 2011.
~ 130 Nanomaterials2011: New Dyes for DSSCs
Customers: > 1’400 worldwide
Employees: 20(8 PhD Chemists)
IOLITEC Inc.Tuscaloosa
Company FactsCompany Facts
IOLITEC since 01/2010 @ Heilbronn, Germanysince 02/2010 @ Tuscaloosa, USA(2003-2005 Freiburg)(2005-2009 Denzlingen)
Heilbronn, Germany
Foundation: 2003
Branch: Chemistry / Material Science
Capacity: 10 mT (2010)fast Scale-Up2011: 25-100 to per year
Products: ~ 300 ionic liquids10 in bulk-quantity~ 130 Nanomaterials
© IOLITEC GmbH, 2011.
Tuscaloosa, Alabama, USA
~ 130 Nanomaterials2011: New Dyes for DSSCs
Customers: > 1’400 worldwide
Employees: 20(8 PhD Chemists)
Company FactsCompany Facts
IOLITEC since 01/2010 @ Heilbronn, Germanysince 02/2010 @ Tuscaloosa, USA(2003-2005 Freiburg)(2005-2009 Denzlingen)
Heilbronn, Germany
Foundation: 2003
Branch: Chemistry / Material Science
Capacity: 10 mT (2010)fast Scale-Up2011: 25-100 to per year
Products: ~ 300 ionic liquids10 in bulk-quantity~ 130 Nanomaterials
© IOLITEC GmbH, 2011.
Heilbronn, Germany
~ 130 Nanomaterials2011: New Dyes for DSSCs
Customers: > 1’400 worldwide
Employees: 20(8 PhD Chemists)
Products @ IOLITECProducts @ IOLITEC
Ionic LiquidsIonic Liquids NanoNano--TechnologyTechnology Energy/CleantechEnergy/Cleantech
Available: Available: Available:Available:
� R&D-Chemicals:> 300 products& custom synthesis
� special-chemicals:10 products in bulk quantities availablebrands: IOLILyte®
IOLITive®
Available:
� Nanoparticles:125 productsmetals, metal oxides CNTs, carbides
� nanoparticle-dispersions& custom synthesis brand: IOLIDispers®
Available:
� Ready-to-useelectrolytes for dye sensitized solar cells (DSSCs)
� sensor-electrolytes
Market entry 2011/12:
� materials for
© IOLITEC GmbH, 2011.
IOLITive
Applications:
� solvents� process chemicals� functional fluids� Surfactants…
brand: IOLIDispers
Applications:
� coatings� abrasives� lubricants� additives…
� materials forheat storage and- transportBrand: IOLITherm®
� Electrolytes for bat-teries & Supercaps