Dual Polymerization Pathway for Polyolefin–polar Block Copolymer Synthesis

dc.contributor.advisorHarth, Eva M.
dc.contributor.committeeMemberDaugulis, Olafs
dc.contributor.committeeMemberLee, T. Randall
dc.contributor.committeeMemberRobertson, Megan L.
dc.contributor.committeeMemberGuloy, Arnold M.
dc.creatorDau, Quynh Huong
dc.creator.orcid0000-0001-6451-5255
dc.date.accessioned2023-05-26T15:49:17Z
dc.date.createdMay 2022
dc.date.issued2022-04-29
dc.date.updated2023-05-26T15:49:19Z
dc.description.abstractThe incorporation of functional groups into polyolefins is known to overcome its poor surface properties and improve the compatibility, adhesion, and printability of the materials. In addition, copolymers with a blocky architecture comprise segregated polyolefins and polar polymer segments that are covalently bonded can efficiently promote phase boundary expansion and as a result, compatibility. However, the tremendous difference in chemical reactivity between ethylene/ olefins and activated vinyl monomers has caused technical difficulties in their copolymerization. This dissertation focuses on the mechanistic investigation and development of synthetic routes to polyolefinpolar block materials. Chapter 3 directs toward uncovering the mechanism responsible for the activity alteration from coordination-insertion polymerization to free radical polymerization of cationic diimine palladium complex to produce polyolefinpolyacrylic block copolymers. The mechanistic findings suggest that the bridging component was a Pd-macrochelate formed via a single insertion of an acrylate monomer into the growing Pd-polyolefin intermediate. The mechanistic insights also facilitate the preparation of various di- and triblock copolymers using different Pd diimine systems and monomer classes. The obtained materials were rigorously characterized via multiple analytical techniques such as thermal analysis, small-angle X-Ray scattering, dynamic light scattering, and transmission electron microscopy to reveal the segregation that occurred in bulk or selective solvents caused by the exotic nature of the block copolymers. Chapter 4 describes a technique to install an active ester unit onto polyolefin chain ends via the use of a pre-functionalized palladium chelate. The active ester terminated polyolefins can go under functional group exchange to produce polyolefin macroinitiator or macromediator for controlled polymerization methods. Diverging from the approach described in Chapter 4, this technique provides tandem living/controlled polymerizations that allow the preparation of well-defined block copolymers with expanded monomer scopes. Reversible addition-fragmentation chain transfer polymerization-induced self-assembly (RAFT-PISA) of acrylamide monomers from polyethylene was also accomplished to directly produce amphiphilic block copolymer vesicles.
dc.description.departmentChemistry, Department of
dc.format.digitalOriginborn digital
dc.format.mimetypeapplication/pdf
dc.identifier.citationPortions of this document appear in: Dau, Huong, Anthony Keyes, Hatice E. Basbug Alhan, Estela Ordonez, Enkhjargal Tsogtgerel, Anthony P. Gies, Evelyn Auyeung et al. "Dual polymerization pathway for Polyolefin-Polar block copolymer synthesis via MILRad: mechanism and scope." Journal of the American Chemical Society 142, no. 51 (2020): 21469-21483.
dc.identifier.urihttps://hdl.handle.net/10657/14273
dc.language.isoeng
dc.rightsThe author of this work is the copyright owner. UH Libraries and the Texas Digital Library have their permission to store and provide access to this work. UH Libraries has secured permission to reproduce any and all previously published materials contained in the work. Further transmission, reproduction, or presentation of this work is prohibited except with permission of the author(s).
dc.subjectBlock copolymers
dc.subjectOlefin
dc.subjectInsertion
dc.subjectRadical polymerization
dc.titleDual Polymerization Pathway for Polyolefin–polar Block Copolymer Synthesis
dc.type.dcmiText
dc.type.genreThesis
dcterms.accessRightsThe full text of this item is not available at this time because the student has placed this item under an embargo for a period of time. The Libraries are not authorized to provide a copy of this work during the embargo period.
local.embargo.lift2024-05-01
local.embargo.terms2024-05-01
thesis.degree.collegeCollege of Natural Sciences and Mathematics
thesis.degree.departmentChemistry, Department of
thesis.degree.disciplineChemistry
thesis.degree.grantorUniversity of Houston
thesis.degree.levelDoctoral
thesis.degree.nameDoctor of Philosophy

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