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Polymerization catalysis for the precision synthesis of chiral and sustainable polymers

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dc.contributor.authorMiyake, Garret M., author
dc.contributor.authorChen, Eugene, advisor
dc.contributor.authorBailey, Travis, committee member
dc.contributor.authorPrieto, Amy, committee member
dc.contributor.authorStrauss, Steven, committee member
dc.contributor.authorWang, David, committee member
dc.date.accessioned2007-01-03T08:15:14Z
dc.date.available2007-01-03T08:15:14Z
dc.date.issued2011
dc.description.abstractPolymerization catalysis for the precision synthesis of chiral and sustainable polymers is described in this dissertation. The central theme of chiral polymers has revolved around the employment of newly synthesized enantiomeric zirconocenium ester enolate catalysts. These catalysts have been utilized in the asymmetric coordination polymerization of prochiral functionalized vinyl monomers towards optically-active, solution stable, one-handed helical polymers. These enantiomeric catalysts have also been used in the successful kinetic resolution polymerization of a racemic methacrylamide monomer. The stereospecific polymerization of chiral oxazolidinone functionalized alkenes has been performed, producing highly isotactic polymers that assume helical or random-coil secondary conformations, dictated by the proximity of the chiral oxazolidinone to the main-chain of the polymer. Investigating applications of helical polymers, two pseudo-enantiomeric helical poly(phenyl acetylene)s bearing chiral organocatalyst side-groups have been synthesized and the effects of the helix-sense and helicity on the enantioselectivity of these catalysts was subsequently examined. Towards sustainable polymers, renewable butyrolactone-based vinylidene monomers are of particular interest in exploring the prospects of substituting the petroleum-based methacrylate monomers for specialty chemicals production. The polymerization of such monomers by group III and IV transition metal catalysts has been investigated resulting in the synthesis of sustainable polymers with controlled molecular weights. These butyrolactone-based monomers have also been successfully polymerized in a rapid and living fashion, using ambiphilic silicon propagating species.
dc.format.mediumborn digital
dc.format.mediumdoctoral dissertations
dc.identifierMiyake_colostate_0053A_10268.pdf
dc.identifierETDF2011100024CHEM
dc.identifier.urihttp://hdl.handle.net/10217/69330
dc.languageEnglish
dc.language.isoeng
dc.publisherColorado State University. Libraries
dc.relation.ispartof2000-2019
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.titlePolymerization catalysis for the precision synthesis of chiral and sustainable polymers
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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