Use this URL to cite or link to this record in EThOS:
Title: Controlled radical polymerisation in aqueous media : new approaches
Author: Jones, Glen R.
Awarding Body: University of Warwick
Current Institution: University of Warwick
Date of Award: 2018
Availability of Full Text:
Access from EThOS:
Access from Institution:
The aim of this work was to develop methods of controlling radical polymerization in aqueous and polar media using copper catalysts. Water as a solvent is important as it is cheap, abundant and environmentally benign. Control of radical polymerization in water is desirable as it allows for the synthesis of functional hydrophilic macromolecules with wide ranging applications. As a starting point the aqueous Cu(0)-RDRP of acrylamide (Am) was optimized; yielding a process capable to controlling the polymerization of a monomer which has traditionally been seen as highly challenging. Reactions were found to proceed rapidly in aqueous media, with quantitative monomer conversion being attained in just a few minutes. High end group fidelity was proven via in-situ chain extensions to yield stimuli responsive block copolymers. Photopolymerization mediated by excess tertiary amine ligand and a Cu(II) complex is well reported in organic media and has been successfully employed to synthesize a wide range of complex functional macromolecular architectures. However, attempts at conducting these polymerizations in aqueous media had proved challenging. The second part of this thesis optimizes and approach to aqueous photopolymerization by offsetting a deleterious side reaction through addition of a halide salt. Controlled polymerization was achieved at ppm copper concentrations with excellent temporal control. Polymerization of methacrylates was then investigated in polar organic media. It was found that the stability of the initiating radical plays a significant role in the degree of control over the polymerization. This principle was also then applied in aqueous media, with limited success. Finally, Cu(0) mediated RDRP was utilized to synthesize a number of novel pigment dispersants for use in waterborne coatings, including a series of polymers with varied molecular weight distributions. In collaboration with industry sponsors, Lubrizol, these polymers were milled with carbon black pigments in order to test their efficacy.
Supervisor: Not available Sponsor: Lubrizol Corporation
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: QD Chemistry