Title: Alkali cation binding to nonionic polymers
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Permanent Link: http://ufdc.ufl.edu/UF00099144/00001
 Material Information
Title: Alkali cation binding to nonionic polymers
Physical Description: xii, 129 leaves : ill. ; 28 cm.
Language: English
Creator: Cambron, Ronald Edward, 1948- ( Dissertant )
Esch, Thieo E. Hogan ( Thesis advisor )
Bates, Roger G. ( Reviewer )
Butler, George B. ( Reviewer )
Gabbay, Edmond J. ( Reviewer )
Shah, Dinesh O. ( Reviewer )
Publisher: University of Florida
Place of Publication: Gainesville, Fla.
Publication Date: 1976
Copyright Date: 1976
 Subjects
Subjects / Keywords: Polymers and polymerization   ( lcsh )
Cations   ( lcsh )
Chemistry thesis Ph. D
Dissertations, Academic -- Chemistry -- UF
Genre: bibliography   ( marcgt )
non-fiction   ( marcgt )
 Notes
Abstract: The alkali cation binding of nonelectrolyte polyether type polymers in several nonaqueous solvents was measured by viscometric, spec tropho to.me tr i c , potentiometric and conductance techniques. An attempt was made, to correlate these findings to the ability of those polymers to catalyze nucleophilic substitution reactions to acetate salts with n-butyl bromide. UV-visible studies indicated that the complexation of sodium salts to polyethers in chloroform increased with increasing chain length up to tetraglyme, which contains five oxygen atoms. Further increase in chain length had no apparent effect on the complexing power of the polyethers. Viscometric and potent io metric studies indicated that in these systems many cations were bound to a single high molecular weight chain. These studies also showed that cation binding initially led to chain expansion due to chain bound cation-cation repulsion. Addition of more salt, however, gave a reduction in viscosity as more anions within the polymer domain shielded the positive charges. From conductance results it was shown that the number of cations bound per chain increased with increasing molecular weight. Further addition of polymer led to a redistribution of cations from polymer chains containing more than one cation to chains containing no cations. Binding of cations was strongest in THF, followed by acetoni tri 1 e , and acetone. Binding constants were calculated for the complexation of NaBPh to PEO 1000 and PEO 6000 in aceton i tr i 1 e . Distribution equilibria were used to study the interaction between alkali cations and poly (aery 1 oyltyroci di ne ) , a polymer containing a cyclic antibiotic. It was found that the ion selectivity of the polymer was similar to that of tyrocidine itself. The effect of po ly ( ethyl ene oxide) and similar polymers in the pha se- transfer reaction of sodium and potassium acetate with n-butyl bromide in acetonitrile was investigated as well as the corresponding homogeneous reaction in 5% H 2 / 9 5 ?i CH 3 CN (v/v) medium. In both cases a correlation was found between the complexing abilities and catalytic efficiencies of the lower molecular weight polyethers, although the effects were more pronounced showed that cation binding initially led to chain expansion due to chain bound cation-cation repulsion. Addition of more salt, however, gave a reduction in viscosity as more anions within the polymer domain shielded the positive charges. From conductance results it was shown that the number of cations bound per chain increased with increasing molecular weight. Further addition of polymer led to a redistribution of cations from polymer chains containing more than one cation to chains containing no cations. Binding of cations was strongest in THF, followed by acetoni tri 1 e , and acetone. Binding constants were calculated for the complexation of NaBPh to PEO 1000 and PEO 6000 in aceton i tr i 1 e . Distribution equilibria were used to study the interaction between alkali cations and poly (aery 1 oyltyroci di ne ) , a polymer containing a cyclic antibiotic. It was found that the ion selectivity of the polymer was similar to that of tyrocidine itself. The effect of poly ( ethyl ene oxide) and similar polymers in the pha se- transfer reaction of sodium and potassium acetate with n-butyl bromide in acetonitrile was investigated as well as the corresponding homogeneous reaction in 5% H 2 / 9 5 ?i CH 3 CN (v/v) medium. In both cases a correlation was found between the complexing abilities and catalytic efficiencies of the lower molecular weight polyethers, although the effects were more pronounced
Thesis: Thesis--University of Florida.
Bibliography: Bibliography: leaves 124-128.
Statement of Responsibility: Ronald E. Cambron.
General Note: Typescript.
General Note: Vita.
 Record Information
Bibliographic ID: UF00099144
Volume ID: VID00001
Source Institution: University of Florida
Holding Location: University of Florida
Rights Management: All rights reserved by the source institution and holding location.
Resource Identifier: alephbibnum - 000184805
oclc - 03324919
notis - AAV1380

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