SYNTHESIS OF ELECTRON-POOR TETRASUBSTITUTED OLEFINS AND THEIR REACTIONS WITH ELECTRON-RICH COMONOMERS.

Persistent Link:
http://hdl.handle.net/10150/187859
Title:
SYNTHESIS OF ELECTRON-POOR TETRASUBSTITUTED OLEFINS AND THEIR REACTIONS WITH ELECTRON-RICH COMONOMERS.
Author:
SENTMAN, ROBERT CRAIG.
Issue Date:
1982
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:
Six electron-poor tetrasubstituted olefins were reacted with electron-rich comonomers. Of these, three {dimethyl dicyanofumarate (DDCF), dimethyl 1,1-dicyanoethylene-2,2-dicarboxylate (DDED), and dicarbomethoxymaleic anhydride (DCMA)} were found to polymerize with styrenes and vinyl ethers to form 1:1 alternating copolymers of low molecular weight. All polymerizations with vinyl ethers and DCMA required initiation, while the copolymerizations of DDED and DDCF with styrenes were spontaneous. Tetramethyl ethylenetetracarboxylate, diisopropylidene ethylenetetracarboxylate, and trimethyl cyanoethylenetricarboxylate failed to copolymerize under any conditions. The spontaneous reactions of these tetrasubstituted olefins can best be explained as proceeding via tetramethylene intermediates, resonance hybrids of biradicals and zwitterions. Spontaneous copolymerizations occur from biradical intermediates; cycloadduct formation occurs from both. Tetramethylene formation is electronically controlled during the reaction of DDED and electron-rich comonomers, as reflected by the structure of the isolated cyclobutanes. The orientation of this monomer is the copolymer with styrene is sterically controlled, as suggested by ('13)C NMR. Methyl 3,3-dicyanoacrylate, a new tetrasubstituted olefin, was found to spontaneously copolymerize with styrenes, and to form cyclobutanes with vinyl ethers. It could be copolymerized with vinyl ethers with radical initiation.
Type:
text; Dissertation-Reproduction (electronic)
Keywords:
Alkenes.; Polymers.; Polymerization.; Electron donor-acceptor complexes.
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Chemistry; Graduate College
Degree Grantor:
University of Arizona

Full metadata record

DC FieldValue Language
dc.language.isoenen_US
dc.titleSYNTHESIS OF ELECTRON-POOR TETRASUBSTITUTED OLEFINS AND THEIR REACTIONS WITH ELECTRON-RICH COMONOMERS.en_US
dc.creatorSENTMAN, ROBERT CRAIG.en_US
dc.contributor.authorSENTMAN, ROBERT CRAIG.en_US
dc.date.issued1982en_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.abstractSix electron-poor tetrasubstituted olefins were reacted with electron-rich comonomers. Of these, three {dimethyl dicyanofumarate (DDCF), dimethyl 1,1-dicyanoethylene-2,2-dicarboxylate (DDED), and dicarbomethoxymaleic anhydride (DCMA)} were found to polymerize with styrenes and vinyl ethers to form 1:1 alternating copolymers of low molecular weight. All polymerizations with vinyl ethers and DCMA required initiation, while the copolymerizations of DDED and DDCF with styrenes were spontaneous. Tetramethyl ethylenetetracarboxylate, diisopropylidene ethylenetetracarboxylate, and trimethyl cyanoethylenetricarboxylate failed to copolymerize under any conditions. The spontaneous reactions of these tetrasubstituted olefins can best be explained as proceeding via tetramethylene intermediates, resonance hybrids of biradicals and zwitterions. Spontaneous copolymerizations occur from biradical intermediates; cycloadduct formation occurs from both. Tetramethylene formation is electronically controlled during the reaction of DDED and electron-rich comonomers, as reflected by the structure of the isolated cyclobutanes. The orientation of this monomer is the copolymer with styrene is sterically controlled, as suggested by ('13)C NMR. Methyl 3,3-dicyanoacrylate, a new tetrasubstituted olefin, was found to spontaneously copolymerize with styrenes, and to form cyclobutanes with vinyl ethers. It could be copolymerized with vinyl ethers with radical initiation.en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
dc.subjectAlkenes.en_US
dc.subjectPolymers.en_US
dc.subjectPolymerization.en_US
dc.subjectElectron donor-acceptor complexes.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.identifier.proquest8217459en_US
dc.identifier.oclc681968449en_US
All Items in UA Campus Repository are protected by copyright, with all rights reserved, unless otherwise indicated.