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Title: The development of amine-functionalised polymeric stars as dual-functional catalysts for polyurethane foam
Author: Rolph, Marianne S.
ISNI:       0000 0004 6348 740X
Awarding Body: University of Warwick
Current Institution: University of Warwick
Date of Award: 2016
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This Thesis explores the synthesis of amine-functionalised polymeric stars synthesised using Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerisation, and their applicability as dual functional catalysts for both the catalysis of polyurethane foam production, and for the deblocking of blocked isocyanates. Chapter 1 introduces polyurethane chemistry, and provides an in-depth summary of blocked isocyanates. Additionally, it introduces the RAFT polymerisation chemistry utilised for catalyst synthesis within this thesis. Chapter 2 investigates the use of RAFT polymerisation for the production of non-responsive crosslinked methacrylate polymeric stars. Evaluation of polymeric stars with different structural properties in the polyurethane foam formulation was carried out to assess the protection afforded to the catalytic amine when tethered within the star polymer. Chapter 3 utilises the RAFT synthesis of analogous acrylate based polymeric stars, the hydrolytic susceptibility of which is able to act as a model to those introduced in Chapter 2. Evaluation of the hydrolytic behaviour allowed for further probing of the effect of structural parameters on the protection of the amine. Chapter 4 describes the incorporation of responsive crosslinkers to produce stimuli responsive polymeric stars, including the incorporation of a furan-maleimide thermoresponsive crosslinker utilising Diels-Alder chemistry, in addition to a disulphide based crosslinker which is redox responsive. Chapter 5 explores the incorporation of a diisocyanate based crosslinker with a view towards the production of thermoresponsive polymeric stars using blocked isocyanate chemistries, and therefore minimising the addition of contaminants (e.g. other crosslinkers) to the polyurethane formulation. Chapter 6 discusses the determination of the deblocking temperature of isocyanates in order to understand any trends in the deblocking of both externally and internally blocked isocyanates, as well probing the effect of amines on the deblocking temperature. In the final Chapter, a summary of the work reported in Chapters 2- 6 is provided, with an outlook towards further applications of the polymeric stars reported in this thesis.
Supervisor: Not available Sponsor: Atomic Weapons Establishment
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: QD Chemistry