The kinetics of the functionalization of linear and cross-linked poly(methyl acrylate) (PMA) and its low-molecular-weight analogs by reactions with various amines in a series of binary solvents or in the solid state have been studied in situ by $ sp{13}$C NMR. Fitting the kinetic data of reactions of PMA with ethanolamine and n-hexylamine (HAN) in DMSO-rich solvent by use of the neighboring-group model shows an auto-acceleration effect due to hydrogen-bonding and/or polar interactions, and hydrophobic interactions; however, PMA and cyclohexane-methylamine shows an auto-retardation effect due to strong steric hindrance. At low extent of reaction the steric effect dominates the kinetics of the reaction of PMA with benzylamine, but hydrophobic interactions become predominant at high extent of reaction. Monomer sequence distributions of the partially functionalized PMA for some of these reactions are not in accord with the predictions of the neighboring-group model, probably due to the long-range neighboring-group effects and/or side reactions. / Despite a pseudo-first order behavior with respect to the concentration of ester groups found for the reaction of cross-linked PMA with HAN, a mono-amine, deviations from first order behavior were also observed for reactions with multi-functional amines. This is due to the formation of extra cross-links, which restrict the diffusion of amines within the polymeric beads, and is confirmed by NMR studies of the chain mobility using the dipolar dephasing technique by the measurement of the decay time constants. / Studies of the binding of bile acid anions by metal-containing polymeric resins, obtained from amine-functionalized PMA and poly(glycidyl methacrylate), show that the type of metal ion and the complexes formed between metal ions and functional groups play a more important role in the binding than factors such as the hydrophobicity of polymer backbones, the structures of functional groups, and the introduction of a spacer between the functional group and the backbone. It is proposed, in addition to the conventional ion exchange process, ligand exchange is involved in the binding mechanism. This is confirmed by results of $ sp{15}$N NMR and proton spin-lattice relaxation time experiments.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.41796 |
| Date | January 1993 |
| Creators | Yu, Youlu |
| Contributors | Brown, G. R. (advisor) |
| Publisher | McGill University |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Format | application/pdf |
| Coverage | Doctor of Philosophy (Department of Chemistry.) |
| Rights | All items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated. |
| Relation | alephsysno: 001393469, proquestno: NN94727, Theses scanned by UMI/ProQuest. |
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