Kilbride, Siobhan Gemma (2020). Ring-opening polymerisation of ε-substituted-ε-caprolactones towards novel, semi-crystalline functional polyesters. University of Birmingham. Ph.D.
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Kilbride2020PhD.pdf
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Abstract
This thesis investigates the synthesis of stereoenriched poly(ε-substituted-ε- caprolactones) based on organocatalytic methods. Moreover, the investigation into orthogonally controlled switchable catalysis for ring-opening polymerisation (ROP) is also explored.
Chapter one reviews how substituent placement on a cyclic monomer effects the thermodynamics of the polymerisation. Moreover, an overview of organocatalysts for ROP, including those that display stereoselectivity during the polymerisation, is presented.
Chapter two describes the enantioenriched synthesis and subsequent functionalisation of a ε-substituted-ε-caprolactone (εSεL) monomer. The effect of functionality on the polymerisation is then reviewed. Following this, the thermal properties of the resulting polymer was then analysed.
Chapter three describes the screening of a range of chiral binaphthol-based phosphoric acids as stereoselective catalysts for the ROP of a variety of racemic εSεLs. The steric and electronic properties of the catalysts are investigated to understand how these influence the polymerisation. Moreover, the microstructure of the polymer is evaluated by 13C NMR spectroscopy, and the thermal properties of the resulting polymers are analysed.
Chapter four summarises donor-acceptor Stenhouse adducts as switchable catalysts for the ROP of cyclic esters using light and heat to control the ON and OFF states of the polymerisation.
Chapter five describes the key findings of chapters two to four and presents opportunities for future investigations in the area of research of this thesis.
Chapter six provides the experimental protocols and characterisation data of the compounds and materials prepared in this thesis.
| Type of Work: | Thesis (Doctorates > Ph.D.) | ||||||
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| Award Type: | Doctorates > Ph.D. | ||||||
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| Licence: | All rights reserved | ||||||
| College/Faculty: | Colleges (2008 onwards) > College of Engineering & Physical Sciences | ||||||
| School or Department: | School of Chemistry | ||||||
| Funders: | European Research Council | ||||||
| Subjects: | Q Science > QD Chemistry | ||||||
| URI: | http://etheses.bham.ac.uk/id/eprint/11024 |
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