The first part of this study concerns the examination of tetrahydrofuran ring-opening polymerization mediated by the palladium insertion polymerization catalysts, (bipy)Pd(CH3)(L)+ OTf- (L = NCCH3, PhN=C(H)Tol, tBuN=C(H)Tol, CH3 N=C(H)Tol). Mechanistic studies reveal a series of metal-based reactions prior to ring-opening, which can be utilized to control polymer molecular weights and end-groups. / The feasibility of combining this ring-opening reaction to insertion polymerization to generate new block co-polymers is subsequently investigated, and it forms the primary objective of the study. / The dual-functional palladium(II) complex (bipy)Pd(CH3)(NCCH 3)+OTf- is found to mediate a novel, single-step coupling of insertion and ring-opened monomers (CO, norbornene, THF) into new polymers. This coupling process follows an unusual route, involving enol lactone as an intermediate, and facilitated by weak Lewis acid. Similar coupling chemistry has been applied to the synthesis of polyTHF end-capped with a small polynorbornene fragment.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.29908 |
| Date | January 1999 |
| Creators | Lim, Ngiap Kie, 1972- |
| Contributors | Arndtsen, Bruce A. (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 | Master of Science (Department of Chemistry.) |
| Rights | All items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated. |
| Relation | alephsysno: 001737855, proquestno: MQ55076, Theses scanned by UMI/ProQuest. |
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