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dc.contributor.authorLee, Minjaeen_US
dc.date.accessioned2017-04-06T15:43:20Z
dc.date.available2017-04-06T15:43:20Z
dc.date.issued2010-08-02en_US
dc.identifier.otheretd-08192010-223814en_US
dc.identifier.urihttp://hdl.handle.net/10919/77166
dc.description.abstractThe convergence of supramolecular and polymer sciences has led to the construction of analogs of traditional covalently-constructed polymeric structures and architectures by supramolecular methods. Host-guest complexations of polymers are also possible through well-defined synthesis of polymeric building blocks, for novel supramolecular polymers. Monotopic polymeric building blocks were synthesized by controlled radical polymerizations with a crown or paraquat initiator. The combinations of terminal and central functionalities of host and guest polymeric building blocks provided chain-extended and tri-armed homopolymers, and diblock and tri-armed copolymers. A supramolecular graft copolymer was formed from a main-chain poly(ester crown ether) and a paraquat terminated polystyrene. This comb-like copolymer was characterized by a large viscosity increase. A four-armed polystyrene-b-poly(n-butyl methacrylate) was synthesized from a pseudorotaxane macroinitiator derived from a complex of a crown-centered polystyrene and a dufunctional paraquat compound. A single peak with higher molecular weight from size exclusion chromatography proved the copolymer formation. Supramolecular interactions enhance the ionic conductivity of semi-crystalline ionic polymers; the ionic conductivity of a C₆-polyviologen and dibenzo-30-crown-10 mixture was 100 times higher than the polyviologen itself. However, ionic conductivities of amorphous polyviologens with polyethers were influenced only by glass transition temperature changes. New imidazolium ionic liquid monomers and imidazolium based polymers were synthesized for potential applications in electroactive devices, such as actuators. Structure-property relationships for pendant imidazolium polyacrylates and main-chain imidazolium polyesters were investigated. Terminal ethyleneoxy moeties enhanced ionic conduction 2~3 times; however, the alkyl chain length effect was negligible. For the imidazoium polyesters, higher ion conductivities result from 1) mono-imidazolium over bis-imidazolium, and 2) bis(trifluoromethanesulfonyl)imide polymers over hexafluorophosphate analogs. A semi-crystalline hexafluorophosphate polyester with C₁₀-sebacate-C₁₀, displayed 400-fold higher ionic conductivity than the amorphous C₆-sebacate-C₆ analogue, suggesting the formation of a biphasic morphology in the former polyester. New dicationic imidazolium salts have interesting features. 1,2-Bis[N-(N'-alkylimidazoilum)]ethane salts stack well in the solid state and possess multiple solid-solid phase transitions. They complex with dibenzo-24-crown-8 and a dibenzo-24-crown-8 based pyridyl cryptand with Ka = ~30 and 360 M¹, respectively. Some of these dicationic imidazolium salts have low entropies of fusion, typical of plastic crystals. These newly discovered imidazolium homopolymers have ionic conductivities up to 10⁴ (S cm⁻¹); however, better properties are still required. Well-designed block copolymers should provide both good electrical and mechanical properties from bicontinuous morphologies, such ion channels.
dc.language.isoen_USen_US
dc.publisherVirginia Techen_US
dc.rightsI hereby certify that, if appropriate, I have obtained and attached hereto a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee. I hereby grant to Virginia Tech or its agents the non-exclusive license to archive and make accessible, under the conditions specified below, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.en_US
dc.subjectHost-Guest Complexationen_US
dc.subjectSelf-Assemblyen_US
dc.subjectPolymeric Building Blocken_US
dc.subjectStructure-Property Relationshipen_US
dc.subjectPseudorotaxaneen_US
dc.subjectDicationic Imidazolium Salten_US
dc.subjectIonic Liquiden_US
dc.subjectPolyviologenen_US
dc.subjectSupramolecular Chemistryen_US
dc.subjectEnd-Functional Polymeren_US
dc.titleDesign, Synthesis and Self-Assembly of Polymeric Building Blocks and Novel Ionic Liquids, Ionic Liquid-Based Polymers and Their Propertiesen_US
dc.typeDissertationen_US
dc.contributor.departmentChemistryen_US
dc.description.degreePh. D.en_US
thesis.degree.namePh. D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen_US
thesis.degree.disciplineChemistryen_US
dc.contributor.committeechairGibson, Harry W.en_US
dc.contributor.committeememberTurner, S. Richarden_US
dc.contributor.committeememberTanko, James M.en_US
dc.contributor.committeememberCarlier, Paul R.en_US
dc.contributor.committeememberEsker, Alan R.en_US
dc.type.dcmitypeTexten_US
dc.identifier.sourceurlhttp://scholar.lib.vt.edu/theses/available/etd-08192010-223814/en_US
dc.date.sdate2010-08-19en_US
dc.date.rdate2016-10-07
dc.date.adate2010-09-09en_US


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