Use this URL to cite or link to this record in EThOS: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.606795
Title: Bespoke container molecules for fuel additives
Author: Webb, Oliver A.
Awarding Body: University of Surrey
Current Institution: University of Surrey
Date of Award: 2013
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Abstract:
The findings of the first reported guest centric encapsulation study are presented within. The guests were of interest as petrol and diesel (fuel) additives, with the focus on 2-ethylhexyl nitrate (2-EHN), di-tert-butyl peroxide (DTBP), aniline, N-methylaniline (NMA) and N,Ndimethylaniline CNNDMA). Complexation with 2-EHN and DTBP was achieved with the novel calix[4]arene derivative, 5, 11, 17, 23-tetra-tert-butyl, 25, 27-bis(oxyethylphenylurea), 26, 28-dihydroxycalix[4}arene, CA(III). This was confirmed in solution by the use of NMR techniques. The multi-step procedure to yield a tetrol cavitand. with recent updates to the procedures are fully described. A new carceplex system with aniline encapsulated, carceplex aniline (4, 24- 5,5'- 6,10- 11 , 11'- 12, 16- 17, 17'- 18, 22- 23, 23'- 4', 24'- 6',10'- 12', 16'- 18 ',22' dodecamethylenedioxy, 2, 8, 14,20, 2', 8' ,14', 20'-octapentyl-bis-calix[4]arene aniline) was produced in a pioneering pressure tube encapsulation follwing unsuccessful attempts under reflux conditions. A pyrogallol[4]arene with pentyl pendant group (2, 8, 14, 20-tetrapentylpyrogallol[4]arene) PA(I) was synthesised and successfully employed for self-assembled complex formation with aniline, NMA and NNDMA. These complexes were found to be stable in polar and apolar media at 313 K over a duration of 2 months. The complexes were of stoichiometry 10:1 (aniline: PA(I)), 12:1 (NMA : PA(I)), and 4:1 (NNDMA: PA(l)). Significant variation was observed when complexes were analysed by TGA in air up to 800 °C compared to control. PA(I) . aniline and PA(I) . NMA displayed solubilities in apolar media making them suitable for analysis in test engines as fuel additives. The first report of a (two-step) carcerand synthesised from pyrogallol[4]arene, PA(I) with the introduction of methylene dioxy spanning and bridging groups, yielding the novel carcerand 4,24- 5, 4'.- 6, 5' - 10, 1\ ' - 12, 16- 17, 16'- 18, 17'- 22, 23'- 23, 24' - 6', 10'- 18', 22' dodecamethylenedioxy, 2, 8, 14, 20, 2', 8', 14', 20' -octapentyl-bis-calix[4]arene is also presented.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.606795  DOI: Not available
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