Amine and amide containing novel polymers of intrinsic microporosity

Abstract

Polymers of Intrinsic Microporosity (PIMs) are a class of material that possess rigid and contorted structures so that their lack of flexibility and rotational freedom reduces the packing efficiency in the solid-state giving rise to microporosity and a large internal surface area. A great many combinations of functional groups can be introduced to the macromolecular structure of PIMs which helps to tune these polymers for application in heterogenous catalysis, gas storage electrochemistry, as well as gas separation. Importantly, owing to their solution processability, PIMs are suitable for membrane fabrication or electrospinning of fibres. Research reported in this thesis was focused on the incorporation of basic and nucleophilic sites within PIMs by introducing amide and amine functional groups into novel spirocyclic and propellane-based monomers that were suitable for polymerisation. In addition, these novel PIMs were further functionalised by converting nitrile groups into amidoximes. By increasing the basicity of the polymeric backbones of PIMs and introducing amidoxime groups, we aim to explore new applications, such as the catalytic destruction of organophosphate-based chemical warfare agents (CWAs) by amalgamating them into personal protective equipment (PPE). The effect of increasing the overall basicity of PIMs on gas separation, particularly on acidic gases such as carbon dioxide was investigated by analysing the gas permeability of the novel PIMs. Although these objectives were unfulfilled, as the combination of high porosity, super nucleophilic functionality and basis cut proved difficult to achieve, novel PIMs did have potential as gas separation membranes due to a combination of high permeability and moderate selectivity for a number of gas pairs.