The research in this thesis is centred on the synthesis of novel organic molecules of intrinsic microporosity (OMIMs), dendrimers of intrinsic microporosity (DIMs) and sulfur-based polymers of intrinsic microporosity (sPIMs). OMIMs are a new class of discretely amorphous microporous materials, synthesised by the combination of functionalised cores and termini that share awkward molecular geometries exploited to generate microporosity in polymers of intrinsic microporosity (PIMs). OMIMs presented in this thesis are prepared by the combination of fluorinated biphenyl or terphenyl cores with dihydroxy (catechol) based benzene, naphthalene or triptycene termini. Through a systematic study of substituted termini, a structure-property relationship is established and applied to generate highly soluble OMIMs possessing apparent BET surface areas within the range of 7 – 726 m2 g-1, as measured by nitrogen sorption at 77 K. The second section on DIMs is an expansion of the work on OMIMs. By isolating tri-substituted biphenyl cores (branch units), first generation dendrimers are afforded by the reaction of a branch unit with a suitably functionalised core. DIMs in this thesis centre around the 9,10-diethyltriptycene-2,3,6,7,13,14-hexaol core, and give rise to apparent BET surface areas within the range of 300 – 722 m2 g-1, as measured by nitrogen sorption at 77 K. The final section of this thesis focuses around the monomer synthesis and subsequent polymerisations of three spirobisindane based sPIMs (sPIM-0, sPIM-1 and sPIM-2). Whereas typical PIMs exploit catechol containing monomers to generate dibenzodioxane containing polymers, sPIMs employ dithiol containing monomers to generate thianthrene containing polymers. These thianthrene units could lead to enhanced gas separation properties of the polymer before or after post-polymerisation oxidation to sulfones or sulfoxides. All three sPIMs were found to be microporous, possessing apparent BET surface areas within the range 438 – 510 m2 g-1, as measured by nitrogen sorption at 77 K.
| Identifer | oai:union.ndltd.org:bl.uk/oai:ethos.bl.uk:585300 |
| Date | January 2013 |
| Creators | Taylor, Rupert |
| Publisher | Cardiff University |
| Source Sets | Ethos UK |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Source | http://orca.cf.ac.uk/52947/ |
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