Persistent Link:
http://hdl.handle.net/10150/186235
Title:
Polyarylanthraquinoneimines: A new family of polymers.
Author:
Williams, Paul Allan.
Issue Date:
1993
Publisher:
The University of Arizona.
Rights:
Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
Abstract:
This work describes a novel technique to prepare a family of polymers which contain a polyquinoneimine backbone. The polymerization utilized a condensation reaction which yielded novel substituted polyanilines. The polymer generating reaction, formation of the imine, was optimized to a quantitative yield via a model compound study. The model quinoneimine was prepared from anthraquinone and two equivalents aniline in the presence of excess of titanium tetrachloride and 1,4-diazabicyclo[2.2.2]octane. The X-ray crystal structure of the model compound from anthraquinone had indicated that the ring system is not planar due to steric hindrance between the peri-hydrogen of anthraquinone and the ortho-hydrogen of the N-phenyl ring. The X-ray crystal structure of the model compound prepared from 4,8-dehydrobenzo-[1,2-b:4,5-b']dithiophene-4,8-dione reveals the quinone moiety to be planar. This indicates that the incorporation of a benzoquinone moiety with two fused thiophene rings in the model compound relieved the steric hindrance observed in the anthraquinone model compound. The model compound synthetic strategy was used to prepare polyquinoneimines from either of the above mentioned quinones and aromatic diamines. The polyquinoneimines were prepared in high yields with molecular weights up to 20,000. The polymers are red powders which are soluble in common organic solvents such as tetrahydrofuran, chloroform and chlorobenzene and form red transparent films. In contrast, polyanilines are typically black insoluble and intractible polymers. Characterization of the polymers prepared from either 4,4'-methylenedianiline or 4,4'-thiodianiline and anthraquinone revealed that 5-20% of the product is a novel low molecular weight macrocyclic quinoneimine.
Type:
text; Dissertation-Reproduction (electronic)
Keywords:
Dissertations, Academic.; Polymer solutions.
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Chemistry; Graduate College
Degree Grantor:
University of Arizona
Committee Chair:
Hall, Henry K., Jr.

Full metadata record

DC FieldValue Language
dc.language.isoenen_US
dc.titlePolyarylanthraquinoneimines: A new family of polymers.en_US
dc.creatorWilliams, Paul Allan.en_US
dc.contributor.authorWilliams, Paul Allan.en_US
dc.date.issued1993en_US
dc.publisherThe University of Arizona.en_US
dc.rightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.en_US
dc.description.abstractThis work describes a novel technique to prepare a family of polymers which contain a polyquinoneimine backbone. The polymerization utilized a condensation reaction which yielded novel substituted polyanilines. The polymer generating reaction, formation of the imine, was optimized to a quantitative yield via a model compound study. The model quinoneimine was prepared from anthraquinone and two equivalents aniline in the presence of excess of titanium tetrachloride and 1,4-diazabicyclo[2.2.2]octane. The X-ray crystal structure of the model compound from anthraquinone had indicated that the ring system is not planar due to steric hindrance between the peri-hydrogen of anthraquinone and the ortho-hydrogen of the N-phenyl ring. The X-ray crystal structure of the model compound prepared from 4,8-dehydrobenzo-[1,2-b:4,5-b']dithiophene-4,8-dione reveals the quinone moiety to be planar. This indicates that the incorporation of a benzoquinone moiety with two fused thiophene rings in the model compound relieved the steric hindrance observed in the anthraquinone model compound. The model compound synthetic strategy was used to prepare polyquinoneimines from either of the above mentioned quinones and aromatic diamines. The polyquinoneimines were prepared in high yields with molecular weights up to 20,000. The polymers are red powders which are soluble in common organic solvents such as tetrahydrofuran, chloroform and chlorobenzene and form red transparent films. In contrast, polyanilines are typically black insoluble and intractible polymers. Characterization of the polymers prepared from either 4,4'-methylenedianiline or 4,4'-thiodianiline and anthraquinone revealed that 5-20% of the product is a novel low molecular weight macrocyclic quinoneimine.en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
dc.subjectDissertations, Academic.en_US
dc.subjectPolymer solutions.en_US
thesis.degree.namePh.D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.chairHall, Henry K., Jr.en_US
dc.contributor.committeememberMulvaney, James E.en_US
dc.contributor.committeememberBates, Robert B.en_US
dc.contributor.committeememberKukolich, Stephen G.en_US
dc.contributor.committeememberBuckner, Steven W.en_US
dc.identifier.proquest9322767en_US
dc.identifier.oclc716315308en_US
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