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Title: Advanced materials prepared by ring-opening (co)polymerisations of an alkene-functional cyclic carbonate
Author: Thomas, Anthony W.
ISNI:       0000 0004 6348 7901
Awarding Body: University of Warwick
Current Institution: University of Warwick
Date of Award: 2016
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This thesis describes the synthesis of functional materials based on homo- and copolymers of an alkene-functional cyclic carbonate, 2-allyloxymethyl-2-ethyltrimethylene carbonate (AOMEC), prepared via organocatalysed ring-opening polymerisations (ROP). Chapter 1 provides a general introduction to the main concepts which are applied throughout this thesis, and surveys the reported applications of alkene-functional polycarbonates prepared by ROP in the published literature. Chapter 2 details the synthesis of poly(2-allyloxymethyl-2-ethyltrimethylene carbonate) (PAOMEC) via organocatalysed ROP, and subsequent post-polymerisation modifications of this material through radical thiol-ene addition chemistry. In addition, the grafting of poly(ethylene glycol) (PEG) to the polycarbonate backbone to generate thermoresponsive materials is described. Chapter 3 describes the synthesis of statistical copolymers of AOMEC and δ-valerolactone (VL), and the synthesis of terpolymers of AOMEC, VL and an alkylfunctional carbonate, 2-propyloxymethyl-2-ethyltrimethylene carbonate (POMEC) in order to provide materials with independently modifiable functional group density and ester:carbonate composition. Chapter 4 explores the use of thiol-ene addition chemistry to generate PAOMEC-based porous 3D structures via microstereolithography. The partial epoxidation of the pendent alkene groups of PAOMEC is also described, and initial results detailing the fabrication of epoxide-functional 3D constructs are presented. Chapter 5 details the use of homo- and copolymers of AOMEC and VL as macroinitiators for the ROP of L-lactide (LLA) in order to generate A-B-A triblock copolymers with thermoplastic elastomer character. In addition, this chapter describes the simple modification of the mechanical properties and elastomeric behaviour of these materials through variation of the midblock composition, and also by changing the ratio of hard to soft block segments. Chapter 6 provides a general summary of Chapters 2-5, and explores opportunities for further work that may be productively undertaken based on the results presented in this thesis. Chapter 7 lists experimental protocols and spectroscopic data for the materials presented in this thesis.
Supervisor: Not available Sponsor: University of Warwick ; University of Queensland
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: QD Chemistry