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Reactivity and selectivity in the polymerization of multifunctional acrylic monomers by chiral zirconocenium catalysts

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dc.contributor.authorPeña, Fernando Vidal, author
dc.contributor.authorChen, Eugene Y.-X., advisor
dc.contributor.authorFinke, Richard G., committee member
dc.contributor.authorStrauss, Steven, committee member
dc.contributor.authorFisher, Ellen, committee member
dc.contributor.authorWang, David, committee member
dc.date.accessioned2017-09-14T16:05:25Z
dc.date.available2017-09-14T16:05:25Z
dc.date.issued2017
dc.description.abstractDescribed in this dissertation are the results of investigating the reactivity and selectivity in the polymerization of multifunctional acrylic monomers by chiral cationic zirconocenium catalysts. The unprecedented precision polymer synthesis method developed in this work-the polymerization of polar divinyl monomers that is not only living but also simultaneously chemoselective and stereoselective-has enabled the synthesis of well-defined highly stereoregular functionalized polymers bearing reactive C=C bonds on every chiral repeat unit. Thus, under ambient conditions, chiral ansa-ziroconocenium catalysts of the appropriate symmetry (C2- vs CS-ligated) have afforded highly isotactic and highly syndiotactic double-bond-carrying polymers, respectively, with controlled molecular weights and narrow dispersities. The enantiomorphic-site controlled, conjugate-addition coordination polymerization mechanism is responsible for the observed high degree of control over the polymerization characteristics, chemoselectivity and stereochemistry. Soft-material applications of such stereoregular and reactive ene-bearing polymers have also explored, including chemical post-functionalization to functional materials, photocuring to elastic films, and molecular recognition to robust crystalline supramolecular stereocomplexes and helical C60 inclusion complexes. A class of important biorenewable monomers containing one methacrylic C=C and two ester groups, namely itaconic esters and anhydride, have been examined, for the first time, for their polymerizability towards both neutral and cationic bridged ansa-zirconocenes and nonbridged zirconocenes. This investigation has yielded a fundamental understanding of the reactivity of the zirconocene complexes towards such monomers, specifically the fundamental chain initiation and propagation steps, structures of resting metallocyclic chelates, as well as kinetic and thermodynamic intermediates.
dc.format.mediumborn digital
dc.format.mediumdoctoral dissertations
dc.identifierVidalPena_colostate_0053A_14330.pdf
dc.identifier.urihttps://hdl.handle.net/10217/183962
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.subjectchemoselectivity
dc.subjectpolymerization
dc.subjectstereoselectivity
dc.subjectmethacrylate
dc.subjectcatalysts
dc.subjectpost-functionalization
dc.titleReactivity and selectivity in the polymerization of multifunctional acrylic monomers by chiral zirconocenium catalysts
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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