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Title: Magnesium ring-opening polymerisation catalysts
Author: Yin, Xinning
ISNI:       0000 0004 6497 9860
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2016
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This Thesis describes the synthesis and characterisation of new magnesium borohydride, alkoxide and amide complexes, and their uses as catalysts for the ringopening polymerisation (ROP) of rac-, L-, D-, meso-lactide and ?-caprolactone. Chapter One introduces cyclic esters and possible mechanistic pathways leading to polyesters by ROP. Common techniques for polymer characterisation are described and an overview of ROP from an industrial perspective is also given. Chapter Two describes the synthesis and characterisation of a series of magnesium alkyl, halide, borohydride and alkoxide complexes supported by the 3-tert-butyl, 5- methyl tris(pyrazolyl)methane ligand. Computational analysis will be discussed to gain further understanding from the viewpoint of bonding and structures. Chapter Three describes the activities of magnesium borohydride and benzyloxide catalysts in the ROP of cyclic esters. Detailed mechanistic studies for the ROP of LA using a magnesium borohydride catalyst are discussed. Chapter Four describes the use of borate ester species as chain transfer agents in the immortal ROP of rac-LA and ?-CL. The effect of non-activated catalysts and borate ester species on the occurrence of transesterification side reactions is also discussed. Chapter Five describes the synthesis and characterisation of a series of magnesium amide, borohydride and halide complexes supported by the chiral bis(oxazolinylphenyl)amine ligand. The catalytic activities of the magnesium borohydride complex in the living and immortal ROP of LA are also discussed. Chapter Six contains experimental details and characterising data for the new complexes reported in this Thesis. CD Appendix contains .CIF files for all the new crystallographically-characterised complexes and .xyz files containing the coordinates of the geometrically optimised structures.
Supervisor: Mountford, Philip Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available