An ionic liquid as polar phase in low-temperature-stable microemulsions [Elektronische Ressource] / vorgelegt von Agnes Harrar

Agnes Sapper

Informations

• Publié par: universitat_regensburg
• Publié le: 01 janvier 2011
• Nombre de lectures: 66
• Poids de l'ouvrage: 15 Mo

Extrait

An Ionic Liquid as Polar Phase in
Low-Temperature-Stable Microemulsions












Dissertation zur Erlangung des Doktorgrades der Naturwissenschaften
(Dr. rer. nat.)
der Fakultät IV der Universität Regensburg






vorgelegt von

Agnes Harrar
geb. Kolodziejski


aus
Regensburg

2011 Promotionsgesuch eingereicht am: 13.01.2011
Tag des Kolloquiums: 25.02.2011
Die Arbeit wurde angeleitet von: Prof. Dr. Werner Kunz
Prüfungsausschuss: Prof. Dr. Dr. h. c. Josef Barthel (Vorsitzender)
Prof. Dr. Werner Kunz
Prof. Dr. Richard Buchner
Prof. Dr. Henri Brunner

Meinem Mann Klaus,
meinen Eltern und meiner Schwester Table of Contents
Preface...................................................................................................v
Constants and Symbols .....................................................................vii
Introduction..........................................................................................1
I. Fundamentals ...................................................................................5
1. Ionic Liquids................................................................................................. 5
1.1 Definition and Classification ..................................................................................... 5
1.2 Properties .................................................................................................................... 7
1.2.1 Liquidus Range-Lower and Upper Limit .............................................................. 7
1.2.2 Viscosity and Conductivity ................................................................................. 11
1.2.3 Polarity & Solubility Properties .......................................................................... 13
1.3 Applications .............................................................................................................. 14
2. Microemulsions .......................................................................................... 17
2.1 Definition................................................................................................................... 17
2.2 Classification............................................................................................................. 17
2.3 Phase Diagrams ........................................................................................................ 20
2.4 Applications .............................................................................................................. 25
2.5 Ionic Liquids in Microemulsions ............................................................................ 26
3. Characterization of Microemulsions........................................................ 31
3.1 Electrical Conductivity and Viscosity .................................................................... 31
3.2 Small Angle Scattering............................................................................................. 34
II. Experimental Section ...................................................................45
1. Methods....................................................................................................... 45
1.1 Analytical Methods .................................................................................................. 45
1.2 Phase Diagrams ........................................................................................................ 46
1.3 Surface Tension Measurements .............................................................................. 47
1.4 Conductivity.............................................................................................................. 47
1.5 Viscosity..................................................................................................................... 48
1.6 Density....................................................................................................................... 49
1.7 Small Angle X-Ray Scattering (SAXS)................................................................... 49
2. Chemicals.................................................................................................... 50
i Table of Contents
3. Synthesis...................................................................................................... 51
III. Results and Discussion................................................................55
1. Critical Aggregation Concentrations of Non-Ionic Surfactants in
[emim][etSO ]................................................................................................. 55 4
1.1 Introduction .............................................................................................................. 55
1.2 Comparison of Cacs in Water and IL .................................................................... 56
1.3 Conclusion................................................................................................................. 59
2. [emim][etSO ] as Polar Phase for Low-Temperature-Stable 4
Microemulsions Including Triton X-100 as Surfactant ............................. 61
2.1 Introduction .............................................................................................................. 61
2.2 Results and Discussion............................................................................................. 63
2.2.1 Phase Diagrams and Phase Behaviour at 25 °C .................................................. 63
2.2.2 Lower Segregation Temperatures and Viscosity Measurements as a Function of
Temperature ................................................................................................................. 68
2.2.3 Small Angle X-Ray Scattering............................................................................ 71
2.3 Conclusion................................................................................................................. 79
3. Microemulsions with Triton X-114 - Effect of Surfactant
Hydrophobicity on the Phase Behaviour of Ionic Liquid Based
Microemulsions .............................................................................................. 81
3.1 Introduction .............................................................................................................. 81
3.2 Results and Discussion............................................................................................. 82
3.2.1 Structural Changes along the Dilution Line at Ambient Temperature................ 82
3.2.2 Structural Changes of o/IL Microstructure as a Function of Temperature ......... 88
3.2.3 “Fish”-Cut at = 0.5........................................................................................... 91
3.3 Conclusion................................................................................................................. 93
4. Microemulsions with C E - Formulation of Microemulsions Suitable 10 4
for Applications as Reaction Media ............................................................. 95
4.1 Introduction .............................................................................................................. 95
4.2 Results and Discussion............................................................................................. 96
4.2.1 Ternary Phase Diagram....................................................................................... 96
4.2.2 Characterisation along the Experimental Path .................................................... 97
4.2.3 SAXS Investigations ......................................................................................... 103
4.3 Preliminary Experiments for Applications of Low-Temperature-Stable
Microemulsions as Nanoreactor ................................................................................. 106
4.4. Conclusion.............................................................................................................. 111
ii
aTable of Contents
V. Conclusions and Outlook ...........................................................113
Summary...........................................................................................117
VI. Appendix ....................................................................................119
1. List of Publications .................................................................................. 119
2. List of Figures........................................................................................... 120
3. List of Tables ............................................................................................ 124
4. List of Schemes......................................................................................... 125
References.........................................................................................127
iii
iv
Preface
The work presented in this PhD thesis was carried out at the Institute of Physical and
Theoretical Chemistry, University of Regensburg, Germany, under the supervision of Prof.
Dr. W. Kunz in the period from 10/2007 to 12/2010. This work would not have been possible
without the help and support of many people whom I am deeply grateful.
First of all I would like to express my since