Thermal Aspects of Kumada Rearrangement in Symmetrical and Asymmetrical Polysilanes-Interdependence of Molecular Structure, Thermal Degradation, and Stability

Thermal degradation behavior, exothermic patterns, and kinetic parameters of symmetrically/asymmetrically substituted polysilanes during the kumada thermal rearrangement in temperature range 100–450 °C, were investigated applying thermogravimetric (TGA) differential scanning calorimetric (DSC) techniques. Three kinds polysilanes, viz., Polydimethylsilane (PDMS), Polydiphenylsilane (PDPS) Polymethylphenylsilane (PMPS) synthesized through Wurtz/Wurtz-Fittig polycondensation. As-synthesized then characterized by FT-IR, CHNO, TGA–DSC FT-IR spectra confirmed presence methyl, phenyl, a combination methyl-phenyl functional groups PDMS, PDPS, PMPS, respectively. From CHNO analysis, chemical/empirical formula PMPS was found to be SiC2.01H6.25, SiC12.50H10.26, SiC6.45H7.76, TGA results that PDPS more thermally stable as compared PDMS PMPS. The determined using isoconversional methods such Ozawa modified Kissinger–Akahira–Sunose (KAS) methods. average value activation energy for obtained from KAS 1078.49 1068.32 kJ/mole, respectively, which is very much higher