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Title: Novel polymers and dendrimers of intrinsic microporosity derived from triptycene and other monomers of high internal free volume
Author: Walker, Jonathan Keith Earl
ISNI:       0000 0004 2732 5913
Awarding Body: Cardiff University
Current Institution: Cardiff University
Date of Award: 2011
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The research described in this thesis is largely focused on monomers derived from the triptycene moiety, and their potential to form polymers of intrinsic microporosity (PIMs), organic molecules of intrinsic microporosity (OMIMs) and dendrimers of intrinsic microporosity (DIMs). Triptycene is of particular interest here due to its high internal molecular free volume (IMFV) and previously reported success in the formation of microporous materials - triptycene is in fact the basis of the most microporous PIM reported to date, and the basis of the only reported example of an amorphous molecular microporous material. The work later extends to incorporate other presumed high IMFV moieties based on spirobifluorene and propellane. The research begins by focusing on the synthesis of potentially soluble polymers. They are of interest due to their processability, which when coupled with microporosity, can potentially yield permeable membranes suitable for selective gas separation. There has been much research into PIMs and their corresponding membranes, with particular interest surrounding PIM-1, a polymer formed between a spirobisindane based monomer, and 2,3,5,6-tetrafluoroterephthalonitrile.1 The same nucleophilic aromatic substitution reaction (SNAr) as is used to make PIM-1 is employed throughout this thesis for the formation of final products. The second section of this project focused on the synthesis of network polymers based around triptycene, introducing bitriptycenes, triptycene side groups, and unsymmetrical triptycenes with new functional groups, the main focus on increased surface area. Although highly microporous materials were prepared, no enhancement over previously obtained triptycene polymers was obtained. The third section of the thesis focuses on the synthesis of novel microporous materials termed Organic Molecules of Intrinsic Microporosity (OMIMs) and Dendrimers of Intrinsic Microporosity (DIMs). These are discrete molecules lacking any long range order that cannot pack space efficiently due to their rigid structures, composed of monomer subunits with high IMFV. All materials were analysed for their apparent BET surface areas (N2 adsorption at 77 K), which were in the range 0-700 m2 g"1.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available