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Title: Stereocontrol in the polymerisation of methyl methacrylate
Author: Horton, M. J.
Awarding Body: University of Cambridge
Current Institution: University of Cambridge
Date of Award: 2000
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This dissertation is concerned with an investigation into the control of relative stereochemistry, or tacticity, in the anionic polymerisation of methyl methacrylate. The emphasis is upon attaining a greater understanding of coordination phenomena at the propagating chain end, and the effect that such interactions have on the tacticity of the resulting polymer. In the work presented, initiators with both lithium and tetraalkylammonium counter-ions are used, in conjunction with various Lewis acids. It is hoped that stereocontrol will be induced by the interaction between the propagating enolate and the Lewis acid, and polymerisation results are discussed in this context. The nature of the complex between the two is further investigated by NMR spectroscopy, using model compounds. Of the Lewis acids used, titanium alkoxides and various organoaluminium compounds are selected for detailed investigation. It is found that a considerable range of tacticity may be produced, depending on the conditions used. In the case of titanium alkoxides, it is concluded that polymerisation occurs through the coordination sphere of the counter-ion of the initiating species. In the case of the organoaluminium compounds, it appears that polymerisation may occur through either the coordination sphere of aluminium or through that of the counter-ion, depending on the type of ligands used.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available