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Advancements in organocatalyzed atom transfer radical polymerization by investigation of key mechanistic steps

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dc.contributor.authorCorbin, Daniel Andreas, author
dc.contributor.authorMiyake, Garret, advisor
dc.contributor.authorFinke, Richard, committee member
dc.contributor.authorRappé, Anthony, committee member
dc.contributor.authorKipper, Matt, committee member
dc.date.accessioned2022-05-30T10:22:32Z
dc.date.available2022-05-30T10:22:32Z
dc.date.issued2022
dc.description.abstractOrganocatalyzed atom transfer radical polymerization (O-ATRP) is a controlled radical polymerization method employing organic photoredox catalysts to mediate the synthesis of well-defined polymers. The success of this method derives from its reversible-deactivation mechanism, where polymers are activated by reduction of a chain-end C-Br bond to generate a reactive radical for chain growth, followed by deactivation of the polymer by reinstallation of the dormant bromide chain-end group. As a result, the polymer chain can be grown by reaction of the polymer radical with alkene-based monomers, but undesirable termination and side reactions can be suppressed by minimization of the radical concentration through deactivation. In this work, key mechanistic steps of O-ATRP are investigated to understand the fundamental limitations of this method and improve upon them. When N,N-diaryl dihydrophenazines were investigated, side reactions were identified in which alkyl radicals add to the phenazine core, leading to new core-substituted PC derivatives with non-equivalent catalytic properties. Employing these core-substituted PCs in O-ATRP showed these side reactions can be eliminated to improve polymerization control. In addition, the deactivation step of O-ATRP and related intermediates were studied, which revealed new side reactions that can limit polymerization efficiency as well as influences on the rate of deactivation. Finally, methods to exert control over the deactivation process were developed as a means of improving polymerization outcomes in challenging systems. For example, the intermediate responsible for deactivation was isolated and added to a polymerization to increase the rate of deactivation and limit side reactions in O-ATRP. Alternatively, a similar outcome could be achieved through in-situ electrolysis to increase the concentration of the desired intermediate during the polymerization. Ultimately, this work has yielded insight into important mechanistic processes in O-ATRP that will continue to benefit the development of this method.
dc.format.mediumborn digital
dc.format.mediumdoctoral dissertations
dc.identifierCorbin_colostate_0053A_17061.pdf
dc.identifier.urihttps://hdl.handle.net/10217/235285
dc.languageEnglish
dc.language.isoeng
dc.publisherColorado State University. Libraries
dc.relation.ispartof2020-
dc.rightsCopyright and other restrictions may apply. User is responsible for compliance with all applicable laws. For information about copyright law, please see https://libguides.colostate.edu/copyright.
dc.subjectcatalysis
dc.subjectpersistent radical
dc.subjectpolymerization
dc.subjectO-ATRP
dc.subjectATRP
dc.subjectphotoredox
dc.titleAdvancements in organocatalyzed atom transfer radical polymerization by investigation of key mechanistic steps
dc.typeText
dcterms.rights.dplaThis Item is protected by copyright and/or related rights (https://rightsstatements.org/vocab/InC/1.0/). You are free to use this Item in any way that is permitted by the copyright and related rights legislation that applies to your use. For other uses you need to obtain permission from the rights-holder(s).
thesis.degree.disciplineChemistry
thesis.degree.grantorColorado State University
thesis.degree.levelDoctoral
thesis.degree.nameDoctor of Philosophy (Ph.D.)

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