Whitfield, Richard (2018) The controlled radical polymerisation of hydrophobic and cationic monomers via Cu(0)-RDRP. PhD thesis, University of Warwick.

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Abstract

Cu(0)-RDRP can utilise significantly lower catalyst loadings than conventional ATRP methodologies, yielding high conversions and low dispersities. This technique has a simple set-up with reactions typically carried out in glass vials and deoxygenation simply via a short period of nitrogen bubbling. The synthesis of polyacrylates and polyacrylamides has resulted in many successes with a wide scope of materials previously prepared, but the polymerisation of low kp monomers, for example methacrylates and styrene has resulted in significant challenges. Polymerisation conditions that are successful for one monomer or monomer class typically fail for others, so there is no means of knowing the optimal conditions for carrying out a particular polymerisation. Therefore the selection of appropriate conditions for successful polymerisation can be a time consuming and arduous task for both “experts” and non-experts. In chapter 2 of this thesis, one set of conditions are optimised to yield well-defined polyacrylate, polymethacrylate and polystyrene homo and block copolymers. There are very limited reports of the polymerisation of styrene via Cu(0)-RDRP, so further optimisation of this synthesis is provided in Chapter 3, yielding higher molecular weights while maintaining both a high initiator efficiency and a narrow dispersity.

A further notable area of challenge within the polymer community is the controlled polymerisation of cationic monomers with reported protocols observing many side reactions and termination events. PDMAEA has many ideal properties making it a good candidate for RNA interference, so this polymer has many potential applications. Chapter 4 illustrates the optimisation of the synthesis of linear and star polymers of DMAEA and the ability of these materials to bind and subsequently release dsRNA in both aqueous solution and in soil is subsequently investigated in chapter 5. This is part of an industrial project funded by Syngenta.

Item Type:	Thesis or Dissertation (PhD)
Subjects:	Q Science > QD Chemistry
Library of Congress Subject Headings (LCSH):	Polymerization -- Testing, Addition polymerization, Acrylates, RNA interference
Official Date:	July 2018
Dates:	Date Event July 2018 UNSPECIFIED
Institution:	University of Warwick
Theses Department:	Department of Chemistry
Thesis Type:	PhD
Publication Status:	Unpublished
Supervisor(s)/Advisor:	Haddleton, David M.
Sponsors:	Syngenta Seeds Ltd.
Extent:	xxiv, 193 leaves
Language:	eng

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