Allyl methacrylate, AMA was polymerized by chemical initiator and by & / #947 / -radiation under different conditions. The polymer obtained is mostly gel type with some soluble fractions at lower conversions. Arrhenius activation energy is 82.3 kJ/mol for chemical initiated polymerization. The polymer was characterized by FT-IR, NMR, DSC, TGA, XPS, XRD, DLS, and MS methods. It was found that about 98-99% of allyl side groups retained as pendant even after completion of the polymerization, while 1-2% may give crosslinking and/or cyclization that yields lactones and anhydrides. The spectroscopic and thermal results of the work showed that the reaction is not cyclopolymerization, but may have end group cyclization. Molecular weight of 1.1x106 was measured by DLS. Therefore, insolubility is due to the high molecular weight of polymer, even in the early stage of polymerization rather than crosslinking. The Tg of PAMA was observed as 94º / C before curing, upon curing at 150-200º / C, Tg increased to 211º / C as measured by DSC. The thermal treatment of polymer at about 350º / C gave anhydride by linkage type degradation, following side group cyclization. The XPS analysis showed the presence of radical fragments of AIBN and CCl4 associated with oligomers. The MS and TGA thermograms showed two or three stage degradations depending on solubility. The first stage was mostly linkage type degradation for the fragmentation of pendant allyl groups at 225-350º / C. In the second stage, at 395-515º / C, the degradation is random scission and depolymerization.
| Identifer | oai:union.ndltd.org:METU/oai:etd.lib.metu.edu.tr:http://etd.lib.metu.edu.tr/upload/12607469/index.pdf |
| Date | 01 September 2006 |
| Creators | Vardareli, Tugba |
| Contributors | Usanmaz, Ali |
| Publisher | METU |
| Source Sets | Middle East Technical Univ. |
| Language | English |
| Detected Language | English |
| Type | M.S. Thesis |
| Format | text/pdf |
| Rights | To liberate the content for public access |
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