Andrew Bryan Sellars

361 Pages·2015·9.26 MB·English

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A Thesis Submitted for the Degree of PhD at the University of Warwick
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New Materials from Waste and Renewable
Oils

By
Andrew Bryan Sellars
A thesis submitted for the degree of
Doctor of Philosophy

Supervised by Dr Andrew Clark
Department of Chemistry,
University of Warwick, UK
September 2014
Contents
List of Figures x
List of Equations xvii
List of Schemes xviii
List of Tables xx
Acknowledgements xxiii
Declaration xxiv
Abstract xxv
Abbreviations xxvii
1.0 Introduction 1
1.1 Carbohydrates 1
1.2 Waste Plastic Recycling 4
1.3 Wood and Agricultural Waste 6
1.4 Vegetable Oils 7
1.4.1 Reaction of the allylic carbon 9
1.4.2 Reactions at the carbonyl 9
1.4.3 Utilising the Alkene in Triglycerides 12
1.4.4 Polymers from epoxidised and dihydroxylated vegetable oil 22
1.5 Click Chemistry 28
1.5.1 Azide-alkyne cycloadditions 29
1.5.2 Nitrile oxide-alkyne cycloadditions 30
i
2.0 Wealth out of waste: Synthesis of Polyurethanes from Waste Cocoa
Butter 33
2.1 Introduction 33
2.2 Aims and objectives 38
2.3 Ring-opened cocoa butter synthesis 39
2.3.1 Optimising the ring-opening of epoxidised cocoa butter 39
2.3.2 Thermal analysis of cocoa butter based monomers 2.10 47
2.4 Cocoa butter based polyurethanes. 48
2.4.1 Polyurethane synthesis of PU 2.10(4%), PU 2.10(25%) and PU
2.10(100%), 48
2.4.2 Thermal analysis of cocoa butter based polyurethanes 51
2.4.3 Mechanical testing of PU2.10(4%) and PU2.10(25%) 53
2.5 Dyed cocoa butter based polyurethanes 54
2.5.1 Addition of dye to cocoa butter based polyurethanes 54
2.5.2 Thermal analysis of 2.16PU2.10(4%) and 2.16PU2.10(25%) 56
2.5.3 Discolouration of PU2.10 and leaching of dye form 2.16PU2.10
over time 58
2.5.4 Mechanical testing of 2.16PU2.10(4%) and 2.16PU2.10(25%) 60
2.6 Summary and conclusion 60
2.7 Future Work 62
3.0 Synthesis of Alkyne-Azide Click Polymers Derived from Renewable Oils 64
3.1 Introduction 64
ii
3.2 Aims and objectives 70
3.3 Synthesis of C2- linked Amide Click Polymers 72
3.3.1 Synthesis of C2- linked azido dioleamide (3.22) 72
3.3.2 Synthesis of C2 linked monomer C2-AzDLA 3.25 76
3.3.3 Thermal analysis of C2-ADOA 3.22 and C2-AzDLA 3.25 78
3.3.4 Synthesis of 1,4-bis(propynyloxy) butane linker 3.26. 79
3.3.5 Polymerisation of C2-AzDOA 3.22 and C2-AzDLA 3.25 with
dialkyne 3.26 via copper catalysed click reaction. 80
3.3.6 Thermal analysis of PCu(C2-AzDOA) 3.31 and PCu(C2-AzDLA)
3.32. 83
3.3.7 Synthesis of C2-monomers from rapeseed and soybean oils. 85
3.3.8 Thermal analysis of C2-AzDRSA 3.39 and C2-AzDSBA 3.40. 88
3.3.9 Copper catalysed polymerisation of C2-AzDRSA 3.39 and C2-
AzDSBA 3.40. 91
3.3.10 Thermal analysis of PCu(C2-AzDRSA) 3.41 and PCu(C2-
AzDSBA) 3.42. 92
3.3.11 Polymerisation of C2-monomers via a thermal approach. 94
3.3.12 Thermal analysis of C2 polymers prepared via the thermal
method. 95
3.3.13 Mechanical testing of C2-linked polymers prepared thermally. 98
3.4 Increasing the chain length of the monomers. 100
3.4.1 Synthesis of C4 and C6-series of monomers 101
iii
3.4.2 Thermal analysis of C4- and C6- derived monomers 3.63-3.70 102
3.4.3 Polymerisation of C4- and C6- monomers via copper catalysis. 106
3.4.4 Thermal analysis of C4- and C6- derived polymers 3.71-3.78, 107
3.4.5 Polymerisation of C4 and C6 monomers via a thermally. 109
3.4.6 Thermal analysis of C4- and C6- derived polymers 3.79-3.86. 110
3.4.7 Mechanical testing of C4- and C6-linked polymers prepared
thermally. 112
3.5 Summary and Conclusion 114
3.6 Future Work 115
4.0 Alkyne-Azide Click Homopolymers Derived from Renewable Oils 117
4.1 Introduction 117
4.2 Aims and objectives 118
4.3 Propargyl Derived Fatty Ester Based Homopolymers P4.7 121
4.3.1 Synthesis of OE 4.7, LE 4.7, RSE 4.7 and SBE 4.7. 121
4.3.2 Thermal analysis of OE 4.7, LE 4.7, RSE 4.7 and SBE 4.7
monomers. 124
4.3.3 Homopolymerisation of OE 4.7, LE 4.7, RSE 4.7 and SBE 4.7
monomers 126
4.3.4 Thermal analysis of POE 4.13, PLE 4.13, PRSE 4.13 and PSBE
4.13. 127
4.3.5 Mechanical testing of POE 4.13, PLE 4.13, PRSE 4.13 and PSBE
4.13 128
iv
4.4 Fatty Acid Extended Propargyl Ester Based Homopolymers 130
4.4.1 Synthesis of extended ester monomers 4.8. 130
4.4.2 Thermal analysis of extended monomers 4.8. 133
4.4.3 Polymerisation of extended monomers 4.8 134
4.4.4 Thermal analysis of extended polymers 4.16 134
4.4.5 Mechanical testing of extended polymers 4.16. 136
4.5 Fatty Acid Extended Propargyl Amide Based Homopolymers 137
4.5.1 Synthesis of extended amide monomers 4.9 137
4.5.2 Thermal analysis of extended amide monomers 4.9, and polymers
4.19. 140
4.5.3 Mechanical testing of extended amide polymers 4.19 143
4.6 Effect of branching and cross-linking in homopolymers. Synthesis of
monomers 4.10 and 4.11 derived from ethanolamine and
diethanolamine. 145
4.6.1 Synthesis of monomer series 4.10 and 4.11. 146
4.6.2 Thermal analysis of monomers and polymers derived from 4.10
and 4.11 150
4.6.3 Mechanical testing of polymers 4.24 and 4.25 152
4.7 Summary and Conclusion 154
4.8 Future Work 156
5.0 Synthesis of Renewable Alkyne-Nitrile Oxide Click Polymers 157
5.1 Introduction 157
v
5.2 Aims and Objectives 160
5.3 Synthesis of dialkyne monomers 5.11-5.14 163
5.4 Synthesis of polyalkynated soybean oil monomer PASBO 3.1 165
5.5 Synthesis of nitrile-oxide precursors 5.1 and 5.10. 166
5.6 Thermal analysis of alkyne monomers DAOA 5.11, DALA 5.12,
DARSA 5.13, DASBA 5.14, PASBO 3.1, and nitrile oxide precursors
5.1 and 5.10. 167
5.7 Base promoted polymerisation of fatty amide monomers 5.11-5.14 and
triglyceride monomer 3.1 with dihydroxymoyl dichlorides 5.1 and 5.10 169
5.8. Thermal analysis of PB (5.18-5.22) PB (5.23-5.27),
META PARA
PT (5.28-5.32) and PT (5.33-5.37). 173
META PARA
5.9 Summary and Conclusion 177
5.10 Future work 178
6.0 Experimental 179
6.1 General procedures and Information 179
6.2 General procedures in chapter 2 180
6.2.1 Synthesis of epoxidised cocoa butter using Venturello’s catalyst
(2.11) 180
6.2.2 Synthesis of epoxidised cocoa butter using Amberlite® method
(2.11) 181
6.2.3 Synthesis of ring opening of Cocoa butter (2.10(0%)) 182
6.2.4 Hydroxylation of Cocoa butter (2. 10(25%)) 183
vi
6.2.5 Ring-opening and hydrolysis of epoxidised cocoa butter (2.
10(100%)) 184
6.2.6 General procedure for the synthesis of polyurethanes 185
6.2.7 General procedure for the synthesis of dyed polyurethanes 186
6.3 General Procedures in Chapter 3 186
6.3.1 General Procedure for the synthesis of difatty amides 186
6.3.2 General Procedure for the epoxidation of difatty amides 197
6.3.3 General Procedure for the azidation of difatty amides 207
6.3.4 Synthesis of 1,4-bis(prop-2-ynyloxy) butane linker (3.26) 219
6.3.5 General Procedure for the copper catalysed 1,3-Huisgen
cycloaddition of difatty amides 220
6.3.6 General Procedure for Thermal 1,3 Huisgen cycloaddition of
difatty amides 225
6.3.7 GPC Data for diamide polymers 229
6.4 General Procedures in Chapter 4 229
6.4.1 General procedure for the synthesis of fatty acids from
triglycerides 229
6.4.2 General Procedure for the synthesis of epoxidised fatty acids 231
6.4.3 General Procedure for the synthesis of Azido fatty acids 234
6.4.4 General Procedure for the synthesis of azido propargyl fatty esters 238
6.4.5 Synthesis of prop-2-ynyl 6-bromohexanoate (4.15) 242
6.4.6 Synthesis of prop-2-ynyl 6-aminohexanoate (4.18) 248
vii
6.4.7 General Procedure for the synthesis of prop-2-ynyl 6-
aminohexanoate fatty amides 248
6.4.8 General Procedure for the synthesis of ethanolamine fatty amides 253
6.4.9 General Procedure for the synthesis of epoxidised ethanolamine
fatty amides 256
6.4.10 General Procedure for the synthesis of Azido ethanolamine fatty
amides 260
6.4.11 General Procedure for the synthesis of propargyl azido
ethanolamine fatty amides 264
6.4.12 General Procedure for the synthesis of diethanolamine fatty
amides 269
6.4.13 General Procedure for the synthesis of epoxidised
diethanolamine fatty amides 273
6.4.14 General Procedure for the synthesis of azido diethanolamine fatty
amides 277
6.4.15 General Procedure for the synthesis of propargyl azido
diethanolamine fatty amides 282
6.4.16 General Procedure for the Polymerisation of the Monomers 288
6.5 General Procedures in Chapter 5 291
6.5.1 General Procedure for the synthesis of propargyl unsaturated
diethanolamine fatty amides 291
6.5.2 Synthesis of epoxidised soybean oil (2.1) 295
6.5.3 Synthesis of propargyl ring-opened soybean oil (3.1) 296
viii