Modification of tetrahydrothiophenium arene oxide systems.
Item
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Title
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Modification of tetrahydrothiophenium arene oxide systems.
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Identifier
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AAI9029922
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identifier
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9029922
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Creator
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Cangiano, Dominick Louis.
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Contributor
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Adviser: George Odian
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Date
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1990
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Language
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English
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Publisher
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City University of New York.
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Subject
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Chemistry, Polymer
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Abstract
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A new isolable zwitterion, 4-(- (1,4-ethylenepiperidinium) -butanethio)-1-naphthol inner salt (NEP zwitterion), was prepared by the ring opening reaction between tetrahydro-1-(4-hydroxy-1-naphthyl)-thiophenium hydrochloride salt, (NZ-HCl salt) and 1,4-ethylene piperidine. The isolated hydrochloride salt was treated with anion exchange resin to give the NEP zwitterion. The NEP zwitterion was isolated as a hydrate, containing 1.8 moles of water, as determined by TGA. The NEP zwitterion was characterized by both 1-D and 2-D NMR and IR techniques.;Polymerization of the NEP zwitterion was investigated over the temperature range of 175-225{dollar}\sp\circ{dollar}C under both sealed tube and continuous vacuum conditions. Polymerization of the NEP zwitterion occurred by a ring opening mechanism whereby the phenoxide end of one molecule attacks the ring methylene carbon {dollar}\alpha{dollar} to the ammonium atom. The structure of the NEP polymer was confirmed by elemental analysis, 1-D and 2-D NMR, Spectral Editing Techniques (DEPT), and IR spectroscopy. The piperidine ring in the polymer backbone was shown to be rigid by the results from the 2-D experiments. The polymer end groups were determined to be olefinic and naphtholic. The highest obtained molecular weight of the NEP polymer was 1.3 {dollar}\times{dollar} 10{dollar}\sp4{dollar} as determined by {dollar}\sp1{dollar}H NMR.;A new random copolymer was prepared by reacting {dollar}\beta{dollar}-butyrolactone, ({dollar}\beta{dollar}-BL), with tetrahydro-1-(4-hydroxy-1-naphthyl)-thiophenium hydroxide inner salt (NZ). The copolymerization was conducted in solution, (DMF), over a temperature range varying from 35 to 100{dollar}\sp\circ{dollar}C. The copolymer structure was characterized by the use of 1-D NMR, Spectral Editing Technique (DEPT), IR spectroscopy, and the preparation and characterization of the respective monomers and homopolymers. The copolymer ratio, NZ/{dollar}\beta{dollar}-BL, was determined to vary between 1.4-1.6:1.0, respectively. The molecular weight of the NZ/{dollar}\beta{dollar}-BL copolymer, as determined by GPC, was low, never exceeding 4000.;Polymerization occurred by a ring opening mechanism whereby the phenoxide end of the NZ zwitterion attacks either the {dollar}\alpha{dollar} carbon on the thiophenium ring to form NZ-NZ homopolymer linkage or the {dollar}\beta{dollar} carbon of the {dollar}\beta{dollar}-BL monomer to form a NZ-{dollar}\beta{dollar}-BL copolymer linkage. The copolymer end groups were found to be olefinic and naphtholic. The assignment of the end groups were verified by preparation of a model compound.
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Type
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dissertation
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Source
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PQT Legacy CUNY.xlsx
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degree
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Ph.D.
