Peroxide-Grafted PDMS: Hydrosilylation Reaction and Thiol-Ene Chemistry as an Alternative Pathway

Peroxide-containing PDMS was synthesized according to a new pathway. Although hydrosilylation is one of the main reactions carried out in silicone chemistry, the catalysts used are very sensitive to the chemical nature of the reactants and remained inefficient to graft allylic peroxide. Radical catalyzed thiol-ene chemistry was involved for the first time to yield an initiator group containing polymer. The peroxide-grafted polysiloxane structure and decomposition were characterized using H-1, C-13 and Si-29 NMR, FT-IR and Raman spectroscopies, SEC and DSC. These macroinitiators can be used to obtain polysiloxane able to undergo crosslinking.