The thermolysis under argon of various polysiloxane resins containing D, T, DH, or TH units was investigated using thermogravimetric analysis combined with mass spectroscopy (TG/MS analysis) and solid‐state 29Si‐NMR. Redistribution reactions involving the exchange of SiC/SiO bonds or SiH/SiO bonds were evidenced in addition to the exchange of SiO/SiO bonds reported to date. These reactions significantly modify the initial siloxane units and lead to an escape of volatile silanes or siloxanes. The exchange of SiH/SiO bonds takes place at lower temperatures (300°C) than the exchange of SiC/SiO bonds (500°C).
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