Thermal degradation of poly(dimethylsilylene) homopolymer (PDMS) and poly(tetramethyldisilylene-co-styrene) copolymer (PTMDSS) was investigated by pyrolysis-gas chromatography and thermogravimetry (TG). PDMS decomposes by depolymerization, producing linear and cyclic oligomeric products, whereas PTMDSS decomposes by random degradation along the chain resulting in each monomeric product and various other combination products. The homopolymer was found to be much less stable than the copolymer. The decomposition mechanisms leading to the formation of various products are shown. The kinetic parameters of thermal degradation were evaluated by different integral methods using TG data. The activation energies of decomposition (E) for the homopolymer and the copolymer are found to be 122 and 181 kJ/mol, respectively, and the corresponding values of order of reaction are 1 and 1.5. The observed difference in the thermal stability and the values of the kinetic parameters for decomposition of these polymers are explained in relation with the mechanism of decomposition. (c) 2005 Wiley Periodicals, Inc.