Monomer synthesis and polymer pyrolysis

dc.contributor.authorGrubbs, Harvey J.en
dc.contributor.committeechairMcGrath, James E.en
dc.contributor.committeememberCastagnoli, Neal Jr.en
dc.contributor.committeememberRiffle, Judy S.en
dc.contributor.committeememberLong, Gary L.en
dc.contributor.committeememberMerola, Joseph S.en
dc.contributor.committeememberMarand, Hervé L.en
dc.contributor.departmentChemistryen
dc.date.accessioned2014-03-14T21:11:35Zen
dc.date.adate2007-05-22en
dc.date.available2014-03-14T21:11:35Zen
dc.date.issued1993-12-05en
dc.date.rdate2007-05-22en
dc.date.sdate2007-05-22en
dc.description.abstractMethods for the large scale preparation and purification of bis( 4-aminopheny 1)-1- phenyl-2,2,2-trifluoroethane (3F-diamine) and bis( 4-hydroxyphenyl)-1-phenyl-2,2,2- trifluoroethane (3F bis-phenol) have been developed. Spectroscopic characterization of by-products was used to develop a mechanistic understanding for synthetic design and to formulate purification techniques needed to produce monomer grade products. Utilizing the preparative methods represented in the present work, it was possible to obtain sufficiently pure 3F-diamine to allow the synthesis of soluble, end-capped, fully cyclized polyimides with glass transition temperatures greater than 430°C. The direct preparation of 3F bis-phenol from phenol and trifluoroacetophenone by trifluoromethanesulfonic acid catalyzed hydroxy alkylation was optimized to produce monomer grade 3F bisphenol. Previously reported methods were less direct and produced lower purity product. Current research efforts are exploring the utility of this monomer system for the preparation of novel poly(arylene ethers), polycarbonates, and polyesters. Bis(4-hydroxy-3- aminophenyI)-1-phenyl-2,2,2-trifluoroethane [3F-bis(aminophenol)] has recently been successfully prepared from 3F-phenol. Soluble, high glass transition temperature, fully-cyclized polybenzoxazoles have been obtained from 3F-bis(aminophenol). The synthesis and characterization of polymer systems containing the phosphine oxide unit as an integral part of the backbone continue to be areas of active research. To date the majority of research activity has centered on the synthesis and features of poly(arylene ether phosphine oxide) (PEPO). All PEPOs gave significant amounts of phosphorus-containing char at temperatures where other engineering polymers are completely volatilized. This behavior was related to the superior self-extinguishing behavior of all the phosphorus containing systems. A detailed pyrolytic degradation study of the phosphorus containing PEPO system was carried out. The study utilized analytical techniques such as pyrolysis-gas chromatography-mass spectroscopy and neutron activation analysis. To continue the exploration of the phosphine oxide systems, the synthesis and characterization of a novel phosphorus containing diamine, bis( 4-amino-phenyl) phenylphosphine oxide, has been completed. Further research is in progress preparing phosphine oxide based polyimides from this diamine. Synthesis of bis(4-hydroxyphenyl)phenylphosphine oxide and additional phosphine oxide intermediates are also reported.en
dc.description.degreePh. D.en
dc.format.extentxx, 269 leavesen
dc.format.mediumBTDen
dc.format.mimetypeapplication/pdfen
dc.identifier.otheretd-05222007-091414en
dc.identifier.sourceurlhttp://scholar.lib.vt.edu/theses/available/etd-05222007-091414/en
dc.identifier.urihttp://hdl.handle.net/10919/37897en
dc.language.isoenen
dc.publisherVirginia Techen
dc.relation.haspartLD5655.V856_1993.G783.pdfen
dc.relation.isformatofOCLC# 30935515en
dc.rightsIn Copyrighten
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subject.lccLD5655.V856 1993.G783en
dc.subject.lcshHeat resistant plastics -- Synthesisen
dc.subject.lcshMonomers -- Synthesisen
dc.subject.lcshPolymers -- Thermal propertiesen
dc.titleMonomer synthesis and polymer pyrolysisen
dc.typeDissertationen
dc.type.dcmitypeTexten
thesis.degree.disciplineChemistryen
thesis.degree.grantorVirginia Polytechnic Institute and State Universityen
thesis.degree.leveldoctoralen
thesis.degree.namePh. D.en

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