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Title: Investigating the self-assembly behavior of diblock copolymers via copolymer blending and fluorescence labelling
Author: Keogh, Robert
ISNI:       0000 0004 8510 0376
Awarding Body: University of Warwick
Current Institution: University of Warwick
Date of Award: 2018
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This thesis explores the use of copolymer blending and fluorescence labelling for investigating, understanding and controlling the self-assembly and stimuli-responsive behavior of amphiphilic block copolymers in solution. Chapter 1 provides an introduction to polymers and an overview of the various polymerization methodologies that exist, with a focus upon reversible addition-fragmentation chain transfer (RAFT) polymerization. The principles of block copolymer self-assembly in solution is discussed along with the numerous parameters and important factors that dictate solution state behavior. In Chapter 2 a range of novel RAFT agents are designed and synthesized for which the incorporation of an aminobromomaleimide (ABM) fluorophore into the chemical structure via both R and Z group functionalization is explored. In Chapter 3 the copolymer blending protocol is introduced as a method for predictably tuning the self-assembly and stimuli-responsive behavior of amphiphilic block copolymers. The limitations of this approach are examined through the blending of a series of pH-responsive micelles via two different mixing protocols. Core functionalized fluorescently-labelled polymer analogues are synthesized using an R group ABM-functionalized RAFT agent developed in Chapter 2, with their internal properties, self-assembly behavior and stimuli-responsiveness explored via fluorescence analysis. In Chapter 4 a series of thermoresponsive amphiphilic block copolymers are blended together in an attempt to modulate the cloud point transition in a controlled manner. A range of intermediate cloud points were measured for blended block copolymers with brush-like coronal chain architectures, in contrast to their homopolymeric analogues. In Chapter 5 fluorescently-labelled polymer nanostructures are prepared in solution via RAFT-mediated polymerization-induced self-assembly (PISA) using a Z group ABM-functionalized RAFT agent developed in Chapter 2. Pure phases of three different block copolymer morphologies are targeted and compared to literature predictions to determine the effect of ABM incorporation on the PISA mechanism.
Supervisor: Not available Sponsor: Engineering and Physical Sciences Research Council
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: QD Chemistry