Green and versatile: catalytic production of recyclable co-polymers from epoxides and anhydrides

Shaw, Matthew 2023. Green and versatile: catalytic production of recyclable co-polymers from epoxides and anhydrides. PhD Thesis, Cardiff University. Item availability restricted.

Preview	PDF - Accepted Post-Print Version Download (11MB) | Preview
	PDF (Cardiff University Electronic Publication Form) - Supplemental Material Restricted to Repository staff only Download (1MB)

Abstract

The Ring-Opening Copolymerisation (ROCOP) of epoxides and cyclic anhydrides is a versatile, atom economical and controllable way of synthesising a broad range of chemically recyclable polyesters. Throughout this work, the synthesis and material properties of ROCOP polyesters will be investigated, including the development of metal catalysts and their coordination chemistry, experimental and theoretical mechanistic investigations into both the initiation and propagation cycles of the polymerisation, and analysis of the resultant novel polymers. The following is a summary of the research undertaken in each of the following chapters: Chapter 1: Introduces Ring-Opening Copolymerisation and describes some of its core concepts as well as key achievements within the field. Experimental techniques pertaining to polymers which are used in the subsequent chapters are also introduced. Chapter 2: Features the synthesis and full characterisation of a series of novel aluminium complexes based on the “Salpy” ligand framework. These complexes will then be investigated for use as catalysts in ROCOP both experimentally and computationally. Chapter 3: Features the catalytic screening of a series of Group 4 metallocene complexes as precatalysts for ROCOP, including the synthesis of partially bio-derived poly(LO-alt-PA) and its subsequent scale up to produce over 200 g of polymer. The mechanism of action for the Group 4 complexes, which are underrepresented in the ROCOP literature, will be examined using a variety of approaches. Chapter 4: Details the material properties of the poly(LO-alt-PA) made on a large scale in chapter 3, and its subsequent post-polymerisation modification by the thiol-ene click reaction. This modification also includes cross-linking, performed both post-polymerisation and in situ, and how it can influence a polymer’s properties. Modification by phosphorylation will be performed to examine the effect of binding chemical functionality possessing flame retardant behaviour has on the resulting polymer, Chapter 5: Details investigations into the doping of an epoxide containing a bipyridine-like unit into ROCOP reactions, meaning the resultant polymer is able to chelate metals. Metal-doped polymers of Ir, Ru, Cu, Fe and Zn will be synthesised and extensively characterised, including examination of the photophysical properties of the iridium polymer with a view to its use in electronic devices. Chapter 6: Features a summary of the above and avenues for further investigations. Chapter 7: Provides details of experimental procedures.

Item Type:	Thesis (PhD)
Date Type:	Completion
Status:	Unpublished
Schools:	Schools > Chemistry
Funders:	EPSCR Centre for Doctoral Training in Catalysis
Date of First Compliant Deposit:	21 February 2024
Last Modified:	21 Feb 2025 02:30
URI:	https://orca.cardiff.ac.uk/id/eprint/166421

Actions (repository staff only)

Edit Item