Polymerization of tetrahydro-1-(4-hydroxy-3-(2-hydroxyethoxy)) phenyl thiophenium hydroxide inner salt.
Item
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Title
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Polymerization of tetrahydro-1-(4-hydroxy-3-(2-hydroxyethoxy)) phenyl thiophenium hydroxide inner salt.
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Identifier
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AAI9009765
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identifier
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9009765
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Creator
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O'Callaghan, Michael P.
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Contributor
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Adviser: George Odian
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Date
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1989
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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 | Chemistry, Physical | Chemistry, Analytical
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Abstract
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The polymerization of tetrahydro-1-(4-hydroxy-3-(2-hydroxyethoxy)) phenyl thiophenium hydroxide inner salt (hydroxyethoxy zwitterion) has been investigated in bulk and solution (DMSO-d6) at 50-140{dollar}\sp\circ{dollar}C. The hydroxyethoxy zwitterion has been shown to polymerize without added initiator by a zwitterion mechanism as well as through a cationic mechanism in the presence of trifluroacetic acid. Analysis of reaction by-products and end group analysis of polymer, utilizing {dollar}\sp1{dollar}H and {dollar}\sp{13}{dollar}C NMR spectroscopy with reference to low molecular weight model compounds, showed evidence of termination due to cyclization, and destruction of the tetrahydrothiophenium ring forming polymer molecules terminated by phenolic groups on one end and either vinyl or alcoholic groups at the other end. Polymerization in the presence of added nucleophiles and electrophiles in solution affected the mechanism of the polymerization as evidenced by a change in product distribution observed by {dollar}\sp1{dollar}H NMR spectroscopy. The kinetics of the initiated and thermal polymerization of the hydroxyethoxy zwitterion in solution are consistent with initiation being rate determining for the thermal polymerization and faster initiation with the trifluroacetate salt of the hydroxyethoxy zwitterion formed when trifluroacetic acid is added as a cationic catalyst. The kinetics observed are consistent with a chain mechanism, monomer apparently much less prone to react with itself than with an intermediate formed either by slow self reaction of monomer in the case of the zwitterion polymerization, or reaction of monomer with initiator. Analysis of relative molecular weight versus extent of reaction for bulk polymerized samples was also consistent with a chain type of mechanism as high molecular weight material formed early in the course of the reaction. Number average molecular weights, relative to poly (styrene) of up to 94,100 (M{dollar}\sb{lcub}\rm w{rcub}{dollar} = 290,500) were achieved.
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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.
