Mzanywa, Neeba Lucky (2003) Ring opening metathesis polymerisation of phenylnorbornene dicarboxyimide derivatives. Masters thesis, Durham University.
The work described in this thesis illustrates that a series of exo-phenyl norbomene dicarboxyimide derivatives are synthesised and characterised using several spectroscopic methods. It also demonstrates that polymeric material can be prepared from phenylnorbomene dicarboxyimide derivatives using ROMP. Three well-defined initiators, ruthenium C1(_2)[(C(_6)H(_11)(_3)P](_2)Ru=CHC(_6)H(_5), t-butoxy molybdenum Mo[CHC(CH(_3))(_3)][C(_10)H(_17)N][OC(CH(_3))(_3)](_2), Mo (1), and hexafluoro-t-butoxy molybdenum Mo[CHC(CH3)(_2)C(_6)H(_5)][c(_10)H(_17)N][OC(CF(_3)(_2)CH(_3)](_2), Mo (2), were used. The polymers prepared were fully characterised using (^1)H NMR, (^13)CNMR, elemental analysis, GPC and DSC. The cis / trans contents of the polymers are readily determined from the 'H NMR spectrum from the integration of the resonance attributable to cis and trans olefinic hydrogen. Generally the trans vinylene content for polymers prepared by ruthenium initiator is about 83%, for the polymers prepared by t-butoxy molybdenum initiator is about 97% and for the polymers prepared by hexafluoro-t-butoxy molybdenum initiator is about 31%. The t-butoxy molybdenum initiator produced polymers with narrow PDI compared to hexafluoro-t-butoxy molybdenum and ruthenium initiators. This is an indication of a well-controlled living polymerisation reaction. The hexafluoro-t-butoxy molybdenum initiator produced polymers with broader PDI. This can be attributed to the secondary metathesis reactions or to the rate of propagation being faster than the rate of initiation. Polymers obtained by ruthenium initiator also gave polymers with broader PDI due to secondary metathesis reaction. The Tg for the polymers prepared by t-butoxy molybdenum initiator were about 15 C higher than the polymers produced using hexafluoro-t-butoxy molybdenum and the ruthenium initiators, suggesting that the higher the trans content of the polymer, the higher the Tg. It was also found that the longer the alkyl chain in the polymer, the lower the glass transition temperatures. The Tg for the polymers prepared from of exo-phenyl norbomene dicarboxyimides are generally higher than the polymers obtained from exoalkyl norbomene dicarboxyimides.
|Item Type:||Thesis (Masters)|
|Award:||Master of Science|
|Copyright:||Copyright of this thesis is held by the author|
|Deposited On:||26 Jun 2012 15:20|