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Ligand frameworks for olefin polymerisation catalysts

Baghurst, Rebecca Elizabeth 2005. Ligand frameworks for olefin polymerisation catalysts. PhD Thesis, Cardiff University.

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Abstract

The synthesis and characterisation of ligands which have the potential to support olefin polymerisation catalysts has been investigated. The syntheses are presented of a range of mixed tertiary amine/alkoxide donor ligands formed by the ring opening of (+/-)-3,3-dimethyl-l,2-epoxybutane by linear and cyclic amines, including N,N'-c/nnethylethylenediamine, 1,4-diazacycloheptane, 1,4-diazacyclohexane, monoazacyclohexane, 1,4,7,10-tetraazacyclododecane and 1,4,7-triazacyclononane. A series of ligands derived from rraw5-l,2-uiaminocyclohexane, 1,4-diazacyclohexane and 1,4-diazacycloheptane has also been synthesised via substitution chemistry. The coordination chemistry of 7V A'-bis(2-hydroxy-3,3-dimethylbutyl)-1,4-diazacycloheptane has been investigated. Monometallic complexes with nickel and aluminium have been characterised. Two examples of bimetallic titanium complexes with Ar,7-bis(2-hydroxy-3,3-dimemylbutyl)-l,4-diazacycloheptan synthesised from titanium ethoxide and titanium isopropoxide are also reported the structure of each has been determined by X-ray crystallography. A discussion of how the choice of titanium alkoxide starting material affects the outcome of the ligand substitution chemistry is presented. The syntheses of related complexes containing the more flexible ligand N,7V-6w(2-hydroxy-3,3-& in conjunction with zirconium and titanium are presented and the crystal structures reported. Furthermore, complexes of the macrocyclic ligands Ar,A',A'-(2-hydroxy- 3,3-dimethylbutyl)- 1,4,7-triazacyclononane with titanium and N,N',N',N''-(2- hydroxy-3,3-dimethylbutyl)-1,4,7,10-tetraazacyclododecane with zirconium are reported. The activity of selected complexes towards olefins including ethylene and 1-hexene using methylaluminoxane as an activator has been determined. Investigation into the nature of the reaction products has been undertaken using gel permeation chromatography and GC-MS. In general the complexes synthesized during the course of this study show low activities towards olefin polymerisation

Item Type: Thesis (PhD)
Status: Unpublished
Schools: Chemistry
Subjects: Q Science > QD Chemistry
ISBN: 9781303166037
Date of First Compliant Deposit: 30 March 2016
Last Modified: 09 Jan 2018 20:13
URI: http://orca.cardiff.ac.uk/id/eprint/55566

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