This thesis describes efforts in theoretical prediction of the macrostructures of poly(norbornadienes) and poly(norbornenes). In contrast to existing synthetic helical polymers such as poly(isocyanides) and poly(methacrylates), the helical parameters of norbornene and norbornadiene polymers may be tunable by judicious choice of substituents. Computer modelling surveys were carried out to qualitatively compare effects from tacticity, steric bulk, pi-stacking and hydrogen-bonding on polymer topology. Models capable of pi-stacking and hydrogen-bonding displayed interactions between substituents on neighbouring repeat units. These modelling studies suggest that helical turns will collapse to form and enforce a tube-like structure. Polymers of functionalized norbornenes and norbornadienes were produced using different achiral and racemic catalysts. Microstructural characterization was conducted by 1H, 1H-1H COSY and 13C{1H} NMR spectroscopy. The tacticities of poly(norbornadienes) agreed well with literature reported values of the catalyst used. However, all three poly(norbornenes) had the same tacticity. Macrostructural characterization was accomplished by GPC, LS, polarimetry and CD spectroscopy. All polymers had a spherical conformation in solution. Polymers made of optically active monomers were optically active whereas polymers made of non-optically active monomers were not.
| Identifer | oai:union.ndltd.org:uottawa.ca/oai:ruor.uottawa.ca:10393/6134 |
| Date | January 2002 |
| Creators | Mainville-Dale, Rachel M. E. |
| Contributors | Fogg, Deryn, |
| Publisher | University of Ottawa (Canada) |
| Source Sets | Université d’Ottawa |
| Detected Language | English |
| Type | Thesis |
| Format | 141 p. |
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