Investigation of the Mechanism of Formation of Overbased Detergents

This thesis describes an experimental study of calixarate overbased detergent oil additives, used to neutralise acidic by-products of engine combustion. Aspects of interest in this study include experimental synthesis of calixarenes and overbased detergents, physical and structural characterisation and monitoring of the synthesis process. Two types of calixarenes were prepared (6 and 8 phenolic units). A synthesis procedure of the calixarate overbased detergent was set up, based on adaptation of existing procedures used for other classes of overbased detergents. The procedure was also modified to suit a lab-scale. 13C NMR and UV-Vis spectroscopy have provided strong evidence for a precursor of the overbased detergent. The ionisation of the surfactants (stearic acid carboxylic group, and phenolic units) was clearly established. The synthesis process was monitored at the molecular and macroscopic level. The use of 13 C-labelled compounds enabled a semi-quantitative study of the concentration evolution of each chemical during the synthesis. Langmuirtrough measurements and dynamic light scattering showed a decrease of particle size during the synthesis of the overbased detergent. The final calixarate overbased detergent was then fully characterised by these two methods. Based on the various information gathered (starting and final material characterisation, monitoring of the process), a mechanism was suggested. This involved a progressive solvation of calcium hydroxide, and breakdown of mixed calcium hydroxide and calcium carbonate.