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High chi polymers from hydrophobic initiators for ultra-small microphase separation
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Hancox, Ellis (2022) High chi polymers from hydrophobic initiators for ultra-small microphase separation. PhD thesis, University of Warwick.
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Official URL: http://webcat.warwick.ac.uk/record=b3884068
Abstract
This work focuses on the use of copper-mediated polymerisation as a versatile method to produce low molecular weight polymers with narrow dispersity (< 3000 Da, Đ < 1.20) for the specific aim of studying their self-assembly in the solid state via microphase separation. By exploiting the theory of microphase separation of block copolymers, separated polymer phases have been achieved by maximising the Flory-Huggins interaction parameter () and minimising the total degree of polymerisation (molecular weight, N).
The study of block copolymer behaviour has grown in prominence and academic interest due to applications in the microelectronics industry, which has become a significant driving force for obtaining smaller domains, as it can lead to higher density data storage. This work focusses on the synthesis of highly amphiphilic polymers produced by copper-mediated polymerisations and studying their self-assembly in the solid state.
Initially an F13 initiator (perfluorooctyl bromoisobutyrate) was used as a pseudo block to minimise N and maintain high . The conditions of the polymerisation of poly(acrylic acid) using this initiator were optimised and polymer morphologies and domain sizes were inferred from Small-angle X-ray scattering (SAXS). The use of both solvent and temperature annealing show different assemblies, and thermal annealing was shown to alter the structures.
The work moved onto the investigation of an F17 and F21 pseudo block (perfluorodecyl bromoisobutyrate and perfluorododecyl bromoisobutyrate), While domain sizes were found to be larger than those in F13-PAA films, F17/F21 polymers exhibited longer range order and more crystallinity. Block copolymer models were used to predict the phase behaviour of these polymers and a phase diagram was developed.
Finally, the scope of hydrophobic initiators and hydrophilic monomers possible for use in the synthesis and microphase separation of high low N polymers was investigated. The polymerisation conditions were optimised for targeting low degree of polymerisation with both acrylates and methacrylates and included incorporation of additional photo-responsive properties via an anthracene end group.
Item Type: | Thesis (PhD) | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Library of Congress Subject Headings (LCSH): | Polymerization, Polymers, Copper catalysts, Self-assembly (Chemistry), Block copolymers, Amphiphiles, Small-angle x-ray scattering | ||||
Official Date: | July 2022 | ||||
Dates: |
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Institution: | University of Warwick | ||||
Theses Department: | Department of Chemistry | ||||
Thesis Type: | PhD | ||||
Publication Status: | Unpublished | ||||
Supervisor(s)/Advisor: | Haddleton, David M. ; Davis, Thomas P. (Thomas Paul), 1960- ; Whittaker, Michael | ||||
Sponsors: | Monash Warwick Alliance | ||||
Format of File: | |||||
Language: | eng |
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