NMR-ANALYSIS OF MECHANISM INVOLVED IN THE MERCAPTIDE DECOMPOSITION IN POLYMER MEDIUM FOR NANOCOMPOSITE PREPARATION P. Conte, G. Carotenuto, G.

Pepe
Dipartimento di Scienze del Suolo, della Pianta e dellAmbiente, Universit di Napoli Federico II, via Universit 100, 80055, Portici (Na) Italy Institute of Composite and Biomedical Materials, National Research Council, Piazzale Tecchio, 80, 80125, Napoli Italy Dipartimento di Scienze Fisiche, Universit di Napoli Federico II, Piazzale Tecchio, 80 80125 Napoli Italy

Polymer-embedded nano-sized metals are an important class of functional materials. In fact, such systems can be applied in material chemistry for their unique optical, magnetic, photonic, and high chemical stability properties. These materials behave just like polymers and therefore they can be processed in a number of ways. Large-scale production of these nanocomposite materials requires metal precursors that can be mixed with polymer to generate clusters by thermal decomposition during the material hot-processing stage. Some organic precursors have been investigated for this purpose, however a general compound class is not available yet. It has been recently found that homoleptic mercaptides (i.e., Mex(SR)y) can be conveniently used as metal or metalsulfide precursors, in the preparation of polymer-based nanocomposites. Mercaptides of transition metals are covalent organic compounds, characterized by a high compatibility with polymers, because of their hydrophobic nature, in addition to interesting thermolytic characteristics. In particular, mercaptides are quite thermally stable at roomtemperature and therefore they can be handled and stored without special care, but quantitatively decompose at little higher temperatures (180-250C) to produce zerovalence metal or metal sulfides, depending on the mercaptide nature. Here, the mechanism involved in the preparation of silver/polystyrene nanocomposites has been investigated by NMR. In particular, the mechanism for silver cluster formation should involve the homolysis of Ag-S bonds, with formation of zero-valence silver atoms and sulfur radicals, SR. When the polymer phase is saturated by silver atoms, clusters may precipitate. Sulfur radicals removed hydrogen from the polymer matrix producing thiol molecules, which partially evolved during the annealing treatment. Benzyl radicals should be preferentially generated because of their high stabilization by resonance; then, these carbon radicals combined together, cross-linking the polystyrene chains.