This thesis describes a study of the effect of microstructure on the thermal stability of poly(vinyl chloride), PVC, vinyl chloride-ethylene, VC-E, and vinyl chloride-propylene, VC-P, copolymers obtained by chemical modification of PVC. The VC-E copolymers, with an ethylene content between 1.1 and 21 mole %, are random copolymers with approximately the same degree of polymerization as the original PVC. A decrease in the number of defect sites is observed with extent of reaction. Concomitantly, the syndiotacticity increases. The VC-P copolymers, with propylene content of ca. 0.1%, also have less labile chlorines than the homopolymer since these react preferentially. / The thermal stability of solid state samples was studied, at temperatures between 150 and 190$ sp circ$C under a nitrogen atmosphere, using a conductimetric method to measure evolved HCl. The thermal stability of the modified samples is improved relative to that of the initial homopolymers. For the VC-E copolymers, a linear relationship is observed between the rates of degradation and the number of labile chlorines, total double bonds and the degree of syndiotacticity. The role of syndiotacticity on the thermal degradation behavior is confirmed in results obtained with two unmodified PVC samples, with a similar number of defect sites but different syndiotacticity. The more syndiotactic resin shows a higher thermal stability. The average polyene sequence length is independent of the ethylene concentration. Thus, the ethylene units do not interfere in the development of polyene sequences. / The VC-P copolymers also show improved thermal stability as compared to that of PVC. However, the improvement is less than that of the VC-E copolymers, due to a lower extent of substitution of labile sites. / PVC previously saturated with HCl shows a markedly increased rate of degradation reflecting the autocatalytic role of HCl. For the PVC coated samples, a decrease in the degradation rates with decreasing PVC film thickness is observed due to more efficient removal of HCl. The PVC mixtures with Chromosorb W or silica gel exhibit a decrease in the dehydrochlorination rate constants with decreasing PVC content. The inert substrate acts as a diluent and avoids agglomeration of the samples and thus facilitates the removal of HCl.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.74243 |
| Date | January 1989 |
| Creators | Velazquez, Alberto |
| 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: 000967493, proquestno: AAINL57294, Theses scanned by UMI/ProQuest. |
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