Green and sustainable polymers [Elektronische Ressource] : high-value aliphatic polycarbonates from CO_1tn2 and epoxides / vorgelegt von Gerhard Richard Haas

Informations

• Publié par: universitat_ulm
• Publié le: 01 janvier 2009
• Nombre de lectures: 19
• Poids de l'ouvrage: 2 Mo

Extrait

Green and Sustainable Polymers:
High-Value Aliphatic Polycarbonates
from CO and Epoxides 2



Dissertation zur Erlangung der Doktorwürde Dr. rer. nat.
der Fakultät für Naturwissenschaften
der Universität Ulm

vorgelegt von

Gerhard Richard Haas
aus Ellwangen/Jagst, Deutschland.

2009




















Amtierender Dekan: Prof. Dr. A. Groß
1. Gutachter: Prof. Dr. Dr. h.c. B. Rieger
2. Gutachter: Prof. Dr. N. Hüsing
Tag der Promotion: 12.02.2010 INDEX
CHAPTER 1 INTRODUCTION - 1 -
1.1 SYNTHETIC POLYMERS ...................................................................- 2 -
1.2 COMMERCIAL PROCESSES USING CARBON DIOXIDE.................- 4 -
1.3 BARRIERS TO FURTHER DEVELOPMENT ......................................- 5 -
1.4 NEW APPLICATIONS .........................................................................- 7 -
1.5 SUSTAINABILITY..............................................................................- 11 -
1.6 THEME AND CONTENT OF THE THESIS .......................................- 12 -
1.7 REFERENCES..................................................................................- 13 -
CHAPTER 2 MONOMERS - 17 -
2.1 CARBON DIOXIDE ...........................................................................- 18 -
2.2 EPOXIDES ........................................................................................- 19 -
2.3 HOMOPOLYMERISATION OF EPOXIDES ......................................- 22 -
2.3.1 Stereochemistry ........................................................................- 23 -
2.3.2 Regio Isomerism .......................................................................- 23 -
2.3.3 Stereo Isomerism......................................................................- 24 -
2.3.4 Coordination Mechanism...........................................................- 25 -
2.4 REFERENCES..................................................................................- 29 -
I INDEX
CHAPTER 3 POLYCARBONATES - 33 -
3.1 INTRODUCTION...............................................................................- 34 -
3.2 AROMATIC POLYCARBONATES ....................................................- 35 -
3.3 ALIPHATIC POLYCARBONATES.....................................................- 38 -
3.4 RING-OPENING POLYMERISATION OF CYCLIC CARBONATES .- 40 -
3.4.1 Synthesis of Aliphatic Cyclic Carbonates..................................- 40 -
3.4.2 ROP of 5-Membered Cyclic Carbonates...................................- 41 -
3.4.3 ROP of 6-Membered Cyclic Carbonates...................................- 42 -
3.5 ALTERNATING COPOLYMERISATION OF CO AND EPOXIDES..- 49 - 2
3.5.1 Early Discoveries and Background ...........................................- 49 -
3.5.2 General Mechanistic Considerations of the Copolymerisation
of CO and Epoxides ................................................................- 50 - 2
3.6 REFERENCES..................................................................................- 55 -
CHAPTER 4 METAL-SALOPHEN CATALYSTS - 61 -
4.1 INTRODUCTION...............................................................................- 62 -
4.2 EXPERIMENTAL PART....................................................................- 64 -
4.2.1 Complex Synthesis ...................................................................- 64 -
4.2.2 Copolymerisation of Carbon Dioxide and Propylene Oxide ......- 66 -
4.3 RESULTS..........................................................................................- 69 -
4.3.1 Effect of trans Ligand................................................................- 86 -
4.3.2 Effect of Temperature ...............................................................- 88 -
4.3.3 Effect of Catalyst/Co-Catalyst Ratio..........................................- 90 -
II INDEX
4.3.4 Effect of CO Pressure..............................................................- 93 - 2
4.4 SPECIAL CATALYSTS .....................................................................- 95 -
4.4.1 Binuclear Chromium(III)- and Aluminium(III)-Salophen
Complexes ................................................................................- 95 -
4.5 REFERENCES................................................................................- 100 -
CHAPTER 5 SYNTHESIS - 103 -
5.1 INTRODUCTION.............................................................................- 104 -
5.2 SYNTHESIS OF LIGANDS AND COMPLEXES..............................- 105 -
5.3 REFERENCES................................................................................- 131 -
SUMMARY.............................................................................. - 133 -
ZUSAMMENFASSUNG .......................................................... - 139 -

III

IV ABBREVIATIONS AND SYMBOLS


Abbreviation or Symbol Signification
13 C-NMR 13-Carbon Nuclear Magnetic Resonance
1H-NMR Proton Nuclear Magnetic Resonance
Cat. Catalyst
Cyclohexene Oxide CHO
CO Carbon Dioxide 2
cPC Cyclic Propylene Carbonate
D Polydispersity
DMAP 4-(N,N-dimethyl)aminopyridine
DSC Differential Scanning Calorimetry
EO Ethylene Oxide
HH Head-to-Head Sequence Arrangement
HT Head-to-Tail Sequence Arrangement
IR Infrared Spectroscopy
M Number Average Molecular Weight n
mol-% Molar Percentage
M Weight Average Molecular Weight w
V ABBREVIATIONS AND SYMBOLS
NMR Nuclear Magnetic Resonance
OAc Acetate Group [CH -(C=O)-O] 3
PCHC Poly(cyclohexene carbonate)
PO Propylene Oxide
PPC Poly(propylene carbonate)
PPO Poly(propylene oxide)
ROP Ring-Opening Polymerisation
Salophen General Class of Bis(salicylaldimine) Ligands
and Complexes
TBA Tetrabutyl Ammonium
TBA-Cl Tetrabutyl Ammonium Chloride
TBA-OAc Tetrabutyl Ammonium Acetate
T Glass Transition Temperature g
THF Tetrahydrofuran
T Melting Temperature m
TOF Turnover Frequency
TON Turnover Number
TT Tail-to-Tail Sequence Arrangement


VI