SEPARATION OF VOCl 3 F R O M T I C l 4 USINGSOYAOIL jared h crane Doctor of Philosophy Department of Chemistry University College London 2014 I, Jared H Crane, confirm that the work presented in this thesis is my own. Where information has been derived from other sources, I confirm that this has been indicated in the thesis. This thesis is dedicated to my family, new and old. The support of everyone over the years has allowed me to reach this point and I am eternally grateful for that 3 ABSTRACT This thesis investigated the reactivity of the metal chlorides TiCl4, VOCl3 and VCl4 with different organic ligands. The chosen ligands were based around the chemical structure of soya oil due to its relevance to the industrial chlorine process used to manufacture TiO2. This thesis primarily used nuclear magnetic resonance (NMR)spectroscopy to characterise the reactions of the metal chlorides with soya oil and component parts, namely the glycerol and the alkene. This thesis goes on to investigate the coordination chemistry of the metal chlorides with ligands including diester groups. The chemical properties of the metal chlorides are known to be similar and hence hard to separate, the reactions studied provide a mechanism for their separation using diesters. It will be shown that TiCl4 coordinates with the ligands without the loss of any chlorine atoms and without disrupting the ligand. The VOCl3 reacted with the ligands, releasing a chlorine atom to produce a VOCl2 adduct. The difference in reactivity provides a removal mechanism. In the industrial process TiCl4 is present in very high concentrations and the coordination of TiCl4 can be seen as reversible and in equilibrium. Whereas, the VOCl3 converts VOCl3 into VOCl2, VOCl2 has a higher boiling point and can therefore be removed by distillation. 4 ACKOWLEDGMENTS I would like to thank the following people for their help and support throughout the last 4 years during the completion of this thesis: Professors Claire Carmalt and Ivan Parkin for supervising me throughout the last 4 years. It is their regular discussions which has allowed this thesis to develop from an industrial question into an academic research project. Huntsman Pigments, in particular Steve Sutcliffe, Andrew Brown and Neil Richmond for their assistance in all the industrial areas within this investigation. Dr Abil Aliev for all the NMR analysis work, his insight into the spectroscopy was invaluable throughout this thesis. Ben Blackburn, Dr Caroline Knapp and Dr Peter Marchand for all their help working through synthetic routes, growing crystals and analysing them. Dr Rachael Hazael for her love and support and help proof reading this piece of work on numerous occasions. 5 CONTENTS 1 introduction 14 1.1 Overview . 14 1.2 Titanium Dioxide . 15 1.3 Titanium Dioxide Pigment . 17 1.4 Titanium Tetrachloride . 26 1.5 Vanadium Oxychloride . 31 1.6 Vanadium Tetrachloride . 34 1.7 Separation of Vanadium Oxychloride and Titanium Tetrachloride . 35 2 initial nmr based analysis of soya oil 38 2.1 NMR ............................. 38 2.2 Oil Analysis . 40 2.3 Experimental . 46 2.4 Results . 48 2.5 Conclusions . 55 3 reactions of ticl4 with diesters 57 3.1 Introduction . 57 3.2 Results . 63 3.3 Titanium complexes . 63 3.3.1 Synthesis of tetrachloro(diethyl malonate)-titanium(IV) [1] ............. 63 3.3.2 Synthesis of tetrachloro(bis isopropyl malonate)-titanium(IV) [2] ............. 66 3.3.3 Synthesis of tetrachloro(di-tBu malonate)-titanium(IV) . 74 3.3.4 Synthesis of tetrachloro(di-Benzyl malonate)- titanium(IV) [3] ................... 74 3.3.5 Synthesis of tetrachloro(diethyl succinate)-titanium(IV) [4] ............. 81 3.3.6 Synthesis of tris titanium tetrachloro di-glyceroltribenzoate [5] ............. 83 3.3.7 Synthesis of tetrachloro(acac)-titanium(IV) [6] . 91 3.4 Conclusion . 93 6 contents 7 3.5 Experimental . 95 3.5.1 Synthesis of tetrachloro(diethyl malonate)-titanium(IV) [1] ............. 95 3.5.2 Synthesis of tetrachloro(bis isopropyl malonate)-titanium(IV) [2] ............. 96 3.5.3 Synthesis of bis t-Bu Malonate-titanium(IV) chloride . 96 3.5.4 Synthesis of tetrachloro(dibenzyl malonate)-titanium(IV) [3] ............. 97 3.5.5 Synthesis of tetrachloro(diethyl succinate)-titanium(IV) [4] ............. 97 3.5.6 Synthesis of glycerol tribenzoate TiCl4 [5] .... 98 3.5.7 Synthesis of tetrachloro(acac)-titanium(IV) [6] . 98 4 reactions of vanadium chlorides with diesters 100 4.1 Vanadium Oxychloride complexes . 100 4.1.1 Reaction of VOCl3 with diethyl malonate [7] .. 101 4.1.2 Reaction of VOCl3 with bis-isopropyl malonate [8] ..................... 105 4.1.3 Reaction of VOCl3 with di-ethyl succinate [9] .. 107 4.1.4 Reaction of VOCl3 with glycerol tribenzoate [10]112 4.1.5 The reaction of VOCl3 acacH [11] ........ 114 4.2 Vanadium Tetrachloride complexes . 118 4.2.1 Reaction of VCl4 with di-ethyl malonate [12] .. 119 4.2.2 Reaction of VCl4 with di-ethyl succinate [13] .. 121 4.2.3 Reaction of VCl4 with gycerol tribenzoate . 124 4.2.4 Reaction of VCl4 with acacH [14] ......... 125 4.3 Conclusion . 129 4.4 Experimental . 130 4.4.1 Reaction of VOCl3 with ethyl malonate [7] ... 131 4.4.2 Reaction of VOCl3 with bis-isopropyl malonate [8] ..................... 131 4.4.3 Reaction of VOCl3 with di-ethyl succinate [9] .. 132 4.4.4 Reaction of VOCl3 with glycerol tribenzoate[10] 132 4.4.5 Reaction of VOCl3 with acacH [11] ........ 133 4.4.6 Reaction of VCl4 with di-ethyl malonate[12] .. 133 4.4.7 Reaction of VCl4 with di-ethyl succinate [13] .. 134 4.4.8 Reaction of VCl4 with glycerol tribenzoate . 135 contents 8 4.4.9 Reaction of VCl4 with acacH[14] ......... 135 5 designofuv-vis flow cell 136 6 conclusions 146 bibliography 150 LISTOFFIGURES Figure 1 Unit cell of rutile TiO2 on the left and anatase TiO2 on the right. 16 Figure 2 Photo of the spiral heat exchange . 18 Figure 3 Simplified Schematic of the TiO2 production plant showing the steps in creating pure TiO2 pigment . 22 Figure 4 Structure of monomeric TiCl4 compared to polymeric ZrCl4 .................. 26 Figure 5 Structure of [TiCl4(C4H8S)2 ............ 27 Figure 6 Crystal structure of 2,7-bis(1,1-dimethylethylflouorene)-1,8- tricholortitanium phenoxide) showing an alkoxide synthesised from TiCl4 ......... 29 Figure 7 Reaction scheme for the polymerisation of ethene to polyethene via the Cossee mechanism. 30 Figure 8 Scheme to show the bonding of a metal centre to an alkene through the Dewar-Chatt-Duncanson model . 31 Figure 9 Structure to show VOCl3 bound to a neutral N-donor ligand . 32 Figure 10 Structure to show VOCl3 bound to a neutral N-donor ligand with a bridging oxygen . 33 Figure 11 NMR of Soya Oil . 41 Figure 12 Chemical Structure Soya Oil . 41 Figure 13 NMR of Soya Oil . 43 Figure 14 COSY spectrum to show proton-proton coupling in soya oil. 47 Figure 15 NMR of soya oil with metal chlorides . 50 Figure 16 NMR of linseed oil with metal chlorides . 50 Figure 17 Molecular structure of octadecene . 51 Figure 18 Molecular structure of tristearin . 51 9 List of Figures 10 Figure 19 Molecular structure of trimyristrin . 52 Figure 20 NMR of trimyristrin with metal chlorides . 53 Figure 21 NMR of octene with metal chlorides . 54 Figure 22 NMR of octene with metal chlorides after 48 hours . 54 Figure 23 Structure of [CH2(COOCH2CH3)2TiCl4 ..... 58 Figure 24 Figure to show TiCl4 bound to acac . 58 Figure 25 TiCl4 bonded to 3,3-dimethyl-2 4- pentanedione 59 Figure 26 Scheme to show the addition of acacH to TiCl4 in differing solvents . 59 Figure 27 Structure of malonate where R = ethyl, benzyl, isopropyl and t- Bu. 61 Figure 28 Structure of glycerol tribenzoate. 61 Figure 29 Structure of acacH. 61 Figure 30 Representation of the structure of soya oil . 62 Figure 31 Figure to show crystal structure of tetrachloro(diethyl malonate)-titanium(IV) [1] . 63 Figure 32 Scheme to show the reaction of TiCl4 with the malonate ligands . 66 Figure 33 Crystal structure of tetrachloro(bis isopropyl malonate)-titanium(IV) [2a] ........... 67 Figure 34 Figure to show crystal structure of trichloro-O-(bis isopropyl malonate)-titanium(IV) dimer [2b] ....... 71 Figure 35 NMR spectra to show iso-propyl malonate coordinated to TiCl4 and then dissociated, both are compared to the starting material shown at the bottom . 73 Figure 36 Figure to show crystal structure of [3] ..... 76 Figure 37 Chemical structure of diethyl succinate . 78 Figure 38 1H NMR of diethyl succinate shown in blue compared to tetrachloro(diethyl succinate)-titanium(IV)[4] shown in red . 79 Figure 39 Crystal structure of tetrachloro(diethyl succinate)-titanium(IV)[4]............ 80 Figure 40 Structure of cis-C2H2(CO2CH2CH3)2 ...... 82 Figure 41 Structure of [Cis − C2H2(CO2CH2CH3)2TiCl4] 82 List of Figures 11 Figure 42 Structure of glycerol tribenzoate. 84 Figure 43 1H NMR spectra of glycerol tribenzoate (red) and compound [5] (blue). The top spectra shows the entire range where peaks are present with labels to show where the protons are on the molecule. The bottom two spectra show areas B and P zoomed in to show coordination shifts. 85 Figure 44 Crystal structure of [5]. Two dichloromethane molecules were observed in the unit cell but have been removed for clarity . 86 Figure 45 Chemical structure of compound 5 shown as a simple chemical structure to aid understanding of bonding positions . 88 Figure 46 Scheme to show the different reported reactions of TiCl4 and acacH with compound [6] shown on the final row . 92 Figure 47 Crystal structure of [7], one malonate ligand is shown for clarity, O17 and O18 are part of a malonate as are O13,O14,O9 and O10....