The Thermal Degradation Behaviour of a Series of Siloxane Copolymers - a Study by Thermal Volatilisation Analysis

The thermal degradation behaviour of novel high number average molecular mass polysilalkylenesiloxanes is reported. These have been synthesised using anionic ring-opening polymerisation of 1,1,3,3,14,14,16,16-octamethyl-2,15-dioxa-1,3,14,16-tetrasilacyclohexacosane and octamethylcyclotetrasiloxane (D4) mixtures. The thermal degradation behaviour of these materials was evaluated by a combination of thermogravimetric analysis (TGA) and thermal volatilisation analysis (TVA) and compared with a commercial sample of PDMS. The results demonstrated that the thermal degradation of the polysilalkylenesiloxanes is more complex than the PDMS, with the polysilalkylenesiloxanes exhibiting a lower degradation peak maximum temperature. The major volatile degradation products evolved from the PDMS were identified as D3 to D6 cyclic siloxane oligomers, in addition to higher molecular mass cyclic siloxane oligomers. The polysilalkylenesiloxanes, on the other hand, evolved short chain aliphatic hydrocarbons, cyclic and linear siloxane oligomers and silanes. The TVA results indicate that the polysilalkylenesiloxanes degrade mostly by random chain scission of the polymer backbone, whereas the commercial PDMS degrades by the accepted depolymerisation reaction which involves "back-biting" reactions.