An investigation into the synthesis and properties of some fluorinated polycarbonates

This thesis describes the synthesis and characterisation of several fluorinated aliphatic, aliphatic and aliphatic ether polycarbonates. The thesis is divided into four sections. In the first section the origins and motivation for the work are discussed, essentially the work forms part of a long term project concerned with the development of a predictively useful correlation between the structure of a polymer repeat unit and its glass transition temperature (Tg). In the second section the various methods for aliphatic polycarbonate synthesis are critically discussed together with the reason for selecting the method used in this work. The third section describes the progressive development of the eventually successful synthetic method and its application to the preparation of ten polycarbonates. The final section is concerned with the detailed characterisation of the polymers obtained, in particular with establishing that they were high polymers of the correct structure, and the measurement of their glass transition temperatures and thermal stabilities. The results of this work suggest that the theoretical oasis for the prediction of the glass transition temperatures of polymers is not presently particularly reliable. Part of the difficulty in developing a more predictively useful theory arises from the uncertainties associated with published values for Tg and a useful contribution of this work is to provide a further ten reliable data points for well characterised materials.