dc.contributor.author | Groombridge, Benjamin John | |
dc.date.accessioned | 2016-04-11T12:53:44Z | |
dc.date.available | 2016-04-11T12:53:44Z | |
dc.date.issued | 2015-09-14 | |
dc.date.submitted | 2015-12-02T13:16:30.128Z | |
dc.identifier.citation | Groombrudge, BJ. 2015. Investigation of PEPPSI precatalysts for controlled polymerization of -conjugated polymers from cheap starting materials. Queen Mary University of London | en_US |
dc.identifier.uri | http://qmro.qmul.ac.uk/xmlui/handle/123456789/11750 | |
dc.description.abstract | Since the discovery of catalyst-transfer polymerization in 2004 there has been significant
research into expanding the scope from Kumada couplings of poly-thiophenes mediated
by nickel initiators. This thesis presents an investigation toward the synthesis of
-conjugated polymers by the elusive pseudo-living polymerization of chloroarene
monomers.
Chapter 1 sets the scene with an in-depth review of chain-growth polymerizations
mediated by palladium catalysts. In chapter 2, we report the first examples of exhaustive
substitution of poly-chloroarenes in the presence of a deficit of nucleophile in the sp3-sp2
Negishi coupling mediated by PEPPSI-IPr. These experiments demonstrated
intramolecular transfer of the active catalyst which is essential for catalyst-transfer
polymerization.
Chapter 3 describes the synthesis of the highly active PEPPSI-IPent precatalyst from
cheap commercially available starting materials with minimal purification. Subsequently
in chapter 4, it was demonstrated that PEPPSI-IPent undergoes exhaustive substitution of
poly-chloroarenes in the presence of a deficit of nucleophile in sp2-sp2 Kumada, Negishi
and Suzuki cross-couplings.
In chapter 5, optimization of current Kumada polymerization of bromo phenylene-based
monomer mediated by PEPPSI-IPr is described. Direct comparison of model reactions
and Kumada polycondensation confirmed high selectivity for exhaustive substitution is
required to achieve polycondensation in a chain-growth manner. Initial research into
catalyst-transfer polycondensation of chloroarene monomers did not achieve
polymerization in a chain-growth manner using modified conditions from bromoarene
monomers. | en_US |
dc.language.iso | en | en_US |
dc.publisher | Queen Mary University of London | en_US |
dc.subject | Biological & Chemical Sciences | en_US |
dc.subject | Polymerization | en_US |
dc.title | Investigation of PEPPSI precatalysts for controlled polymerization of -conjugated polymers from cheap starting materials | en_US |
dc.type | Thesis | en_US |
dc.rights.holder | The copyright of this thesis rests with the author and no quotation or information derived from it may be published without the prior written consent of the author | |