Model study of the crosslinking of polydimethylsiloxanes by peroxides

The decompositions of di-t-butyl peroxide (TBP) and diaroyl peroxides in permethylated silicone oil (47V20) have been studied by differential scanning calorimetry (DSC). Results show the importance of the solubility of the peroxide in the silicone on their rate of disappearance. For the diaroyl peroxides, according to the nature of the substituents on the phenyl ring and the concentration of the peroxide, the decomposition occurs in solution and/or in the solid phase. Decomposition in solution began at a lower temperature than in the solid phase, which took place immediately after melting and was quite instantaneous. Decomposition of these peroxides was also performed in octamethylcyclotetrasiloxane (D4) and decamethyltetrasiloxane (DMTS). According to DSC results, D4 seems to be a better model of the silicone than the linear one. Analyses of the products of the decomposition of TBP and dibenzoyl peroxide (BP) in this model showed that the dehydrodimer of D4 was produced in low yield relative to peroxide. The main compounds obtained were high molecular weight compounds, which were apparently different for the two peroxides. The free radical origin of these products has been proven in the case of TBP by the addition of TEMPO in the reaction medium.