ILSEPT, Sitges, Spain, September 6 - IoLiTec Ionic Liquids ... · Most publications target only a few ILs (in particular BMIM PF 6 and BMIM BF 4) and use specific solvents or solvent

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


4 Company Information

1 Introduction


1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide

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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


& 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


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


BMIM Bu3Pic DEP DMP

N

Bu

N N

Me BuPMeO

O

OMe PEtO

O

OEt

S C NI

2 Solubility Tests



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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


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


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


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


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


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


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


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


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


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


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


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



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


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



0

5

ETHYL ACETATE TOLUENE HEXANE OCTANE

Org

an

ic s

ub

sta

nce's

co

nte

nt

3 Conclusions



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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


� 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


N-Butyl-N-methylpyrrolidinium dicyanamide

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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


~ 130 Nanomaterials2011: New Dyes for DSSCs

Customers: > 1’400 worldwide

Employees: 20(8 PhD Chemists)

IOLITEC Inc.Tuscaloosa



Heilbronn, Germany

Foundation: 2003





Tuscaloosa, Alabama, USA






Heilbronn, Germany

Foundation: 2003





Heilbronn, Germany




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Documents

ILSEPT, Sitges, Spain, September 6 - IoLiTec Ionic Liquids ... · Most publications target only a few ILs (in particular BMIM PF 6 and BMIM BF 4) and use specific solvents or solvent