Recently, the use of block copolymers in preparation of nanocomposites has received great attention as they form well-defined micelles. In this work, the synthesis of different metal functional copolymers, nano structural metal composites and investigation of their reaction mechanism and thermal characteristics by pyrolysis mass spectroscopy have been aimed. Namely, polyisoprene-block-poly2vinylpyridine, (PI-b-P2VP) and poly2vinylpyridine-block-polymetylmethacrylate, (PMMA-b-P2VP) were used as block copolymers and the thermal reaction of these copolymers with two different transition metal complexes Cr(CO)6 and HAuCl4.3H2O were investigated which mostly lead to the coordination of metal through nitrogen atom of the pyridine ring which then degrates to form nano particles. The samples were further characterized by TEM, ATR-FT-IR, UV-Vis and Direct-Pyrolysis Mass Spectroscopy techniques.
TEM images proved the formation of nanoparticles and the results showed that synthesized Au nanoparticles have 2 to 3 fold larger size than Cr nanoparticles. ATR-FT-IR spectrum of metal functional copolymers showed that the disappearance of characteristic peaks of pyridine stretching and bending mode when metal coordinates to the pyridine nitrogen. Furthermore, the spectrum indicated the appearance of a new absorption peak at around 740 cm-1 which may be a clue for the coordination of gold(III) ion to the pyridine nitrogen. Different from chromium case, in the spectrum of Au3+-(PMMA-b-P2VP), CO stretching frequency of PMMA which may appear at around 1720&ndash / 1718 cm-1 decreased in intensity while a new absorption peak appeared at around 1600 cm-1. This results reveals that electron deficient gold (III) ion prefers the coordination from both donor atoms namely carbonyl oxygen PMMA and pyridine nitrogen of P2VP in order to compensate its electron deficiency. In the UV-Vis spectrum of copolymers, Cr-functional copolymers showed a sharp absorption peak appeared at around 290 nm is attributed to a MLCT transition from chromium atom to * orbital of pyridine group. Furthermore, Au-functional copolymers showed a completely new absorption band at around 320 nm which can be associated again with a LMCT transition since gold is electron deficient and more willing to accept electrons from the ligand. Pyrolysis mass spectrometry analysis showed that poly2vinylpyridine blocks for each copolymers were affected similarly but polyisoprene block was not affected much from the coordination of metal compared to poly(methyl methacrylate) block in copolymers. For (PI-b-P2VP), Au3+ coordination to copolymer resulted in the higher thermal stability compared to Cr coordination. For (PMMA-b-P2VP), different from Cr, Au3+ coordination to P2VP nitrogen atom was extensive and
PMMA based products changed drastically due to the coordination of electron deficient Au3+ to PMMA carbonyl group.
| Identifer | oai:union.ndltd.org:METU/oai:etd.lib.metu.edu.tr:http://etd.lib.metu.edu.tr/upload/12610799/index.pdf |
| Date | 01 August 2008 |
| Creators | Orhan, Tugba |
| Contributors | Kayran, Ceyhan |
| 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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