Synthesis and Non-Covalent Interactions of Novel Phosphonium-Containing Polymers

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dc.contributor.authorAnderson, Emily Bairden
dc.contributor.committeechairLong, Timothy E.en
dc.contributor.committeememberRiffle, Judy S.en
dc.contributor.committeememberTurner, S. Richarden
dc.contributor.committeememberDavis, Richey M.en
dc.contributor.committeememberWard, Thomas C.en
dc.contributor.departmentChemistryen
dc.date.accessioned2014-03-14T20:15:52Zen
dc.date.adate2010-09-28en
dc.date.available2014-03-14T20:15:52Zen
dc.date.issued2010-08-18en
dc.date.rdate2010-12-21en
dc.date.sdate2010-09-01en
dc.description.abstractPhosphonium ions readily compare to ammonium ions in regards to their aggregate characteristics, thermal stability, and antibacterial activity. Ionic aggregation in phosphonium-based polymers provides thermoreversible crosslinks, ideal for reversible self-assembly, self-healing, and smart response. In polymers, these ionic functionalities aggregate, providing improved moduli, and altering the size and structure of ionic aggregates regulates polymer melt processability. This dissertation highlights phosphonium-based chemistry for the synthesis of novel step-growth ionomers and structure-property relationships in ionic polymers. The synthesis of phosphonium endcapping reagents for melt polyester reactions afforded a thermally stable ionic functionality that controlled molecular weight. Weak association was present with phosphonium ions at low ion concentrations below 7.7 mole %. The use of novel ionic bisacetoacetate monomers in the formation of networks from Michael addition reactions led to the synthesis of ionic networks with increased and broadened glass transitions and improved tensile stresses at break and strains at break compared to those in the non-ionic networks. The first electrospun fibers from Michael addition crosslinking reactions are reported, and equilibrium ionic liquid uptake experimental results indicated that ionic functional networks absorb close to three times the amount of ionic liquid as non-ionic, poly(ethylene glycol)-based films. Chain-extending polyurethanes with a phosphonium diol and subsequently varying the hard segment content led to changes in ionic aggregation, crystallinity, and thermal transitions in the polymers. Additionally, novel phosphonium-based methacrylate monomers incorporated into diblock copolymers with styrene exhibited microphase separation. Overall, the inclusion of phosphonium ions pendant to or in the main chain of various types of polymers led to changes in morphology, improved tensile properties, enhanced moduli, broadened transitions, changes in crystalline melting points, changes in solubility, and appearance of ionic aggregation.en
dc.description.degreePh. D.en
dc.identifier.otheretd-09012010-115556en
dc.identifier.sourceurlhttp://scholar.lib.vt.edu/theses/available/etd-09012010-115556/en
dc.identifier.urihttp://hdl.handle.net/10919/28849en
dc.publisherVirginia Techen
dc.relation.haspartAnderson_EB_D_2010.pdfen
dc.rightsIn Copyrighten
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subjectionomersen
dc.subjectnon-covalent interactionsen
dc.subjectpolyurethanesen
dc.subjectpolyestersen
dc.subjectmulti-walled carbon nanotubesen
dc.subjectMichael additionen
dc.subjectionic liquidsen
dc.subjectmethacrylatesen
dc.subjectstep-growth polymerizationen
dc.subjectimdiazoliumen
dc.subjectphosphoniumen
dc.titleSynthesis and Non-Covalent Interactions of Novel Phosphonium-Containing Polymersen
dc.typeDissertationen
thesis.degree.disciplineChemistryen
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen
thesis.degree.leveldoctoralen
thesis.degree.namePh. D.en

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