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Title: Novel microporous polymers for gas separation membranes
Author: Felemban, Sarah Abdulhalim
ISNI:       0000 0004 8497 8988
Awarding Body: University of Edinburgh
Current Institution: University of Edinburgh
Date of Award: 2019
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Polymers of intrinsic microporosity (PIMs) owe their microporosity to their rigid and contorted structure which prevents efficient space packing. Their microporosity and processability make them attractive for many industrial applications, such as heterogeneous catalysis, gas separation membranes, hydrogen storage and adsorbents for organic compounds. Our goal in this project is to broaden the spectrum of PIM structures by preparing novel PIMs with potential for different industrial applications but focusing on gas separation membranes. Characterisation of the novel polymers was achieved to establish their chemical and physical properties including solubility, surface area, thermal stability and their molecular weight. In some cases, casting the resulting PIMs from solution enabled the formation of self-standing films which could then be analysed for their ability to separate different gas mixtures. Three different types of PIM were targeted during the PhD programme. Firstly, the preparation of Tröger's base (TB) containing hypercrosslinked polystyrene was attempted. The first step was the nitration of polystyrene by using different reaction conditions, with the aim to introduce the highest possible number of nitro groups, followed by the reduction of nitropolystyrene to the aminated polystyrene. Finally, hyper-crosslinking of the amino-polystyrene was attempted by formation of TB units between polymer chains. Secondly, new ladder and network PIMs derived from different catechols monomers with 2,3,7,8-tetrafluoro-5,5',10,10'- tetraoxidethianthrene were synthesised. This thiathrene-based rigid monomer increases the distances between two consecutive "sites of contortion" within the polymer chains and provides sulfonyl functional groups, which may influence the adsorption and gas separation properties of the resulting polymers. Thirdly, a series of novel microporous polyimides (PIMPIs) were prepared using different diamine monomers and thiathrene-based dianhydride monomers. All polymers were characterized by using NMR, IR spectrometers and their chemical and physical properties were measured using a variety of techniques. In addition, for some polymers successful film formation via casting from solution allowed the measurement of their gas permeability to assess their ability to separate gas mixture. All chemical procedures for the synthesis of monomers and polymers, properties of the resulting polymers and comparisons with existing polymers are described in this thesis.
Supervisor: McKeown, Neil ; Shaver, Michael Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: polymers of intrinsic microporosity ; PIMs ; novel PIMs ; gas separation membranes ; Tro¨ger's base ; hypercrosslinked polystyrene ; thiathrene-based rigid monomer