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dc.contributor.advisorHadjichristidis, Nikos
dc.contributor.authorAlghamdi, Reem D.
dc.date.accessioned2015-05-24T09:51:31Z
dc.date.available2015-05-24T09:51:31Z
dc.date.issued2015-05
dc.identifier.doi10.25781/KAUST-CXS2Y
dc.identifier.urihttp://hdl.handle.net/10754/555581
dc.description.abstractPoly (vinyl ether)-based graft polymers have been synthesized by the combination of living cationic polymerization of vinyl ethers with other living or controlled/ living polymerization techniques (anionic and ATRP). The process involves the synthesis of well-defined homopolymers (PnBVE) and co/terpolymers [PnBVE-b-PCEVE-b-PSiDEGVE (ABC type) and PSiDEGVE-b-PnBVE-b-PSiDEGVE (CAC type)] by sequential living cationic polymerization of n-butyl vinyl ether (nBVE), 2-chloroethyl vinyl ether (CEVE) and tert-butyldimethylsilyl ethylene glycol vinyl ether (SiDEGVE), using mono-functional {[n-butoxyethyl acetate (nBEA)], [1-(2-chloroethoxy) ethyl acetate (CEEA)], [1-(2-(2-(t-butyldimethylsilyloxy)ethoxy) ethoxy) ethyl acetate (SiDEGEA)]} or di-functional [1,4-cyclohexanedimethanol di(1-ethyl acetate) (cHMDEA), (VEMOA)] initiators. The living cationic polymerizations of those monomers were conducted in hexane at -20 0C using Et3Al2Cl3 (catalyst) in the presence of 1 M AcOEt base.[1] The PCEVE segments of the synthesized block terpolymers were then used to react with living macroanions (PS-DPE-Li; poly styrene diphenyl ethylene lithium) to afford graft polymers. The quantitative desilylation of PSiDEGVE segments by n-Bu4N+F- in THF at 0 °C led to graft co- and terpolymers in which the polyalcohol is the outer block. These co-/terpolymers were subsequently subjected to “grafting-from” reactions by atom transfer radical polymerization (ATRP) of styrene to afford more complex macromolecular architectures. The base assisted living cationic polymerization of vinyl ethers were also used to synthesize well-defined α-hydroxyl polyvinylether (PnBVE-OH). The resulting polymers were then modified into an ATRP macro-initiator for the synthesis of well-defined block copolymers (PnBVE-b-PS). Bifunctional PnBVE with terminal malonate groups was also synthesized and used as a precursor for more complex architectures such as H-shaped block copolymer by “grafting-from” or “grafting-onto” methodologies, which yielding in well-defined PVEs segments with control Mn(GPC) = [VE]/[initiator] and narrow MWDs.
dc.language.isoen
dc.subjectbase-assisted
dc.subjectliving cationic
dc.subjectCross-Linked
dc.subjectn-butyl vinyl ether
dc.subjectdesilylation
dc.subjectpunctionalization
dc.titleComplex Macromolecular Architectures by Living Cationic Polymerization
dc.typeThesis
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
thesis.degree.grantorKing Abdullah University of Science and Technology
dc.contributor.committeememberNunes, Suzana Pereira
dc.contributor.committeememberCavallo, Luigi
thesis.degree.disciplineChemical Science
thesis.degree.nameMaster of Science
refterms.dateFOA2018-06-14T07:53:53Z


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