Synthesis and polymerizations of nitrile substituted quinodimethanes

Persistent Link:
http://hdl.handle.net/10150/184341
Title:
Synthesis and polymerizations of nitrile substituted quinodimethanes
Author:
Brandt, Martin William
Issue Date:
1988
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:
The spontaneous polymerization behavior of an acceptor substituted quinodimethane was investigated. High molecular weight homopolymers of 7,8,-di(ethoxycarbonyl)-7,8-dicyanoquinodimethane (DEDCQ) or copolymers of DEDCQ-styrene (St) and DEDCQ-p-methoxystyrene (p-MeOSt) were formed spontaneously in chloroform containing acetic acid. All polymerizations occurred by a radical mechanism. High molecular weight polymers formed at low conversion. Radical homopolymerization of DEDCQ was promoted by ambient light or heat. DEDCQ-p-MeOSt copolymerizations yielded alternating copolymers, which formed rapidly relative to the DEDCQ homopolymers and copolymers (rich in styrene). All of these polymerizations are thought to begin with a bond forming mechanism and propagate by polyaddition. A new acceptor group substituted quinodimethane was synthesized, characterized and copolymerized with electron donating monomers. Oxidation of the dianion of α, α'-dicyano-α, α'-diphenyl-p-xylene yielded 45% 7,8-dicyano-7,8-diphenylquinodimethane. In solution this compound exists in both the trans and cis forms but forms a sharply melting crystalline solid. It was resistant to homopolymerization but did form low molecular weight copolymers with electron rich aromatic monomers.
Type:
text; Dissertation-Reproduction (electronic)
Keywords:
Polymers.; Polymerization.; Alkenes.; Hydrocarbons.
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Chemistry; Graduate College
Degree Grantor:
University of Arizona
Advisor:
Mulvaney, J. E.

Full metadata record

DC FieldValue Language
dc.language.isoenen_US
dc.titleSynthesis and polymerizations of nitrile substituted quinodimethanesen_US
dc.creatorBrandt, Martin Williamen_US
dc.contributor.authorBrandt, Martin Williamen_US
dc.date.issued1988en_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.abstractThe spontaneous polymerization behavior of an acceptor substituted quinodimethane was investigated. High molecular weight homopolymers of 7,8,-di(ethoxycarbonyl)-7,8-dicyanoquinodimethane (DEDCQ) or copolymers of DEDCQ-styrene (St) and DEDCQ-p-methoxystyrene (p-MeOSt) were formed spontaneously in chloroform containing acetic acid. All polymerizations occurred by a radical mechanism. High molecular weight polymers formed at low conversion. Radical homopolymerization of DEDCQ was promoted by ambient light or heat. DEDCQ-p-MeOSt copolymerizations yielded alternating copolymers, which formed rapidly relative to the DEDCQ homopolymers and copolymers (rich in styrene). All of these polymerizations are thought to begin with a bond forming mechanism and propagate by polyaddition. A new acceptor group substituted quinodimethane was synthesized, characterized and copolymerized with electron donating monomers. Oxidation of the dianion of α, α'-dicyano-α, α'-diphenyl-p-xylene yielded 45% 7,8-dicyano-7,8-diphenylquinodimethane. In solution this compound exists in both the trans and cis forms but forms a sharply melting crystalline solid. It was resistant to homopolymerization but did form low molecular weight copolymers with electron rich aromatic monomers.en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
dc.subjectPolymers.en_US
dc.subjectPolymerization.en_US
dc.subjectAlkenes.en_US
dc.subjectHydrocarbons.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.advisorMulvaney, J. E.en_US
dc.contributor.committeememberHall, H. K.en_US
dc.contributor.committeememberGreen, G. D.en_US
dc.identifier.proquest8814212en_US
dc.identifier.oclc701107148en_US
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