The Development and Evaluation of Novel Techniques for the Study of Polymerisation and Degradation Reactions

Abstract

The work described in this thesis has been divided into two sections, designated I and II. Section I deals with the feasibility of utilising the known chemistry of cationically initiated olefinic polymerisation reactions in a metal coating application. The ultimate aim of this work is to harness reactions of this type, which are potentially very fast, to obtain a polymer system capable of undergoing rapid cross linking reactions in thin film. The development and application of a novel technique is described by means of which rapid rates of polymerisation and cross linking can be measured in thin film. In addition the results of synthetic work are presented showing how the more promising homopolymerisation systems based on cyclic dienes can be utilised in cross linking reactions. Section II describes the development and application of equipment, incorporating some novel features, for use in thermal degradation studies of polymers. The technique combines thermo-gravimetric, gas evolution and gas liquid chromatographic analyses, the latter being coupled to in-line filament and Curie point pyrolysis techniques. A further technique is incorporated which enables rheological studies of residual polymer in the melt state to be carried out during degradation processes. The potential applicability of the above equipment to the study of the thermal degradation of cross linked polymers in the context of work described in Section I is referred to. In order to demonstrate the scope of application of the equipment the detailed study of the thermal degradation of a series of poly-α-esters in the melt state is described.