Fundamental studies and instrumental methodology in the mass spectrometric analysis of low-mass polymeric systems

The analysis of polymer systems is a crucial field in modern petrochemicals and also other sectors of the chemical industry. This analysis stretches from simple mass measurement, to sample identification and structural studies. Mass spectrometry is one of a number of analytical fields that are used to investigate such samples, but it has been shown to have certain limitations for the routine analysis of polymers. Chapter one discusses the development of mass spectrometry and the progression that has led to the development of the methods of sample ionisation and separation that are most used today. It also discusses the field of polymer analysis and the other analytical techniques that are applied to such investigations in industry. Chapter two details the instrumentation used in this study and also the nature of the main samples that were investigated. Chapter three covers analysis by the technique of matrix-assisted laser desorption / ionisation which is the major mass spectrometric method currently for polymer analysis. Details of work investigating sample preparation arc given leading into a larger discussion of the mass biases that arise in such polymer analysis and a rationalisation of their causes. Chapter four details investigations of polymer analysis using an electrospray source on a Fourier-transform ion cyclotron resonance instrument. The added complexity of charge states is discussed leading to further study of the mass and charge variations given by instrumental conditions. Chapter five presents a small body of work in the field of structural analysis by the technique of collision-induced dissociation. Work with buckministerfullerene and a range of ethoxylate polymers is given to demonstrate the capabilities of such analysis. Chapter six concludes the thesis with a discussion of the topics raised in the previous chapters and how they affect the use of mass spectrometry as a routine tool for the industrial analysis of polymeric systems