Title:
Hybrid Macrocycles for Supramolecular Assemblies

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dc.contributor.advisor Beckham, Haskell W.
dc.contributor.author Watson, Walter Philip en_US
dc.contributor.committeeMember Collard, David
dc.contributor.committeeMember Griffin, Anselm
dc.contributor.committeeMember Leisen, Johannes
dc.contributor.committeeMember Schork, Joseph
dc.contributor.department Textile and Fiber Engineering en_US
dc.date.accessioned 2005-07-28T18:05:40Z
dc.date.available 2005-07-28T18:05:40Z
dc.date.issued 2005-04-27 en_US
dc.description.abstract Hybrid macrocycles, which chimerically integrate multiple chemical compositions and architectures, provide an effective way to impart new properties to polymers that are not found in their linear or homocyclic analogues. This dissertation addresses the incorporation of hydrophilic blocks into hydrophobic polymer, as either a poly(dimethyl siloxane)-block-poly(oxyethylene) (PDMS-POE) tadpole with a hydrophobic head and a hydrophilic tail or as a diblock poly(styrene)-block-diethylene glycol (PS-DEG) hydrophobic-hydrophilic macrocycle. The supramolecular association properties of both kinds of cycles were studied: the PDMS-POE tadpoles in forming micelles, and the PS-DEG macrocycles in threading with linear polymer to form polyrotaxanes. For the PDMS-POE macrocycle, linear alpha,omega-dihydroxy PDMS was cyclized under dilute conditions with dichloromethylhydrosilane as a linking group to produce hydrosilane-functionalized cyclic PDMS. This was joined to alpha-methoxy,omega-allyl POE via a free radical hydrosilylation reaction to produce the hybrid tadpole macrocycle, which was analyzed by GPC, DSC, and 1H, 13C, and 29Si NMR spectroscopy. Supramolecular aggregation consisting of the formation of micelles under both polar and nonpolar conditions was studied by surface tensiometry and quasielastic light scattering. For the PS-DEG macrocycle, linear alpha,omega-dihydroxy PS was prepared by ATRP polymerization of styrene, followed by reaction with KOH to give hydroxyl endgroups. The linear PS was then cyclized under dilute conditions with diethylene glycol ditosylate, and the product was analyzed by GPC, MALDI-TOF MS, DSC, and 1H, 13C and DOSY NMR spectroscopy. The macrocycle was then statistically threaded with linear PS to give the supramolecular structure poly(styrene)-rotaxa-cyclo[poly(styrene)-block-diethylene glycol]. Characterization was performed with DOSY NMR to verify that the product was threaded, and 1H NMR was collected to determine that the product was 13% macrocycle by weight. DSC showed only one Tg, indicating that the linear and cyclic species were present in the same phase. en_US
dc.description.degree Ph.D. en_US
dc.format.extent 1959730 bytes
dc.format.mimetype application/pdf
dc.identifier.uri http://hdl.handle.net/1853/6958
dc.language.iso en_US
dc.publisher Georgia Institute of Technology en_US
dc.subject PDMS en_US
dc.subject Polydimethyl siloxane
dc.subject Hybrids
dc.subject Rotaxanes
dc.subject Polyethylene oxide
dc.subject Macrocycle
dc.subject Polystyrene
dc.subject Polyoxyethylene
dc.subject Polyethylene glycol
dc.subject.lcsh Polymerization en_US
dc.subject.lcsh Macrocyclic compounds en_US
dc.title Hybrid Macrocycles for Supramolecular Assemblies en_US
dc.type Text
dc.type.genre Dissertation
dspace.entity.type Publication
local.contributor.corporatename School of Materials Science and Engineering
local.contributor.corporatename College of Engineering
relation.isOrgUnitOfPublication 21b5a45b-0b8a-4b69-a36b-6556f8426a35
relation.isOrgUnitOfPublication 7c022d60-21d5-497c-b552-95e489a06569
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