Sinnathamby, Prash (2000) Synthesis and polymerisation of isotopically labelled methacrylate based monomers. Doctoral thesis, Durham University.
This thesis is concerned with the synthesis and polymerisation of isotopically labelled methacrylate based monomers. Chapter 2 describes the preparation of methyl [2-(^13)C]-and [3-(^13)C]-methacrylate via a Wittig-Homer type reaction and a diethyl malonate route respectively. The results of the free radical polymerisation of these monomers are discussed in Chapter 4. The presence of (^13)C-isotope in the resultant polymer enhanced the low intensity signals from the end groups in the (^13)C-NMR. However, more importantly, this study allowed us to investigate the presence of head to head links by observing for the first order (^13)C-(^13)C coupling from the two quaternary carbons in the polymer of methyl [2-(^13)C]- methacrylate. The findings of this study are reported in Chapter 4, Part 1.Chapter 3 describes the preparation of methyl [a-(^13)C]-(hydroxymethyl)-[3-(^13)C]-acrylate, [(^13)C(_2)]-MHMA and methyl [a-(^2)H(^2)-(hydroxymethyl).[3-(^13)C]-acrylate, [(^2)H(_4)]- MHMA monomers. The copolymeristion with methyl methacrylate and subsequent lactonisation are reported in Chapter 4, Part 2. In the (^13)C-NMR spectrum of lactonised MMA/[(^13)C(_2)]-MHMA copolymer, the signals from any residual (^13)CH(_2)OH groups were absent, indicating that lactonisation was complete under the conditions described. Chapter 5 describes the preparation of fluorinated and non-fluorinated phosphonate based methacrylate monomers to study their potential as ionic materials and extend their application as a fire retarding material. However, attempts to polymerise these monomers by either free radical or anionic methods met with little success. The successful preparation of a polymer from a non-phosphonate based methacrylate monomer indicates that perhaps the phosphonate moiety inhibits the polymerisation by being a radical acceptor.
|Item Type:||Thesis (Doctoral)|
|Award:||Doctor of Philosophy|
|Copyright:||Copyright of this thesis is held by the author|
|Deposited On:||13 Sep 2012 15:46|