Syntheses and supramolecular associations of block and grafted phosphonated- and sulfoned-silicone copolymers†

This paper presents some studies exploiting the ate-type addition of electron-withdrawing monomers to hydrogenosiloxane groups so as to generate original silicone materials. Two types of monomers were oligomerized onto silicone backbones, namely unsaturated phosphonate and sulfone monomers. Phosphonated silicones are thermally more resistant than conventional silicones and can be transformed into amphiphilic polymers after selective ester hydrolysis. Sulfoned silicones generate solid supramolecular elastomers thanks to the strong pseudo-ionic interactions between multiple sulfone groups. Rheology and modulated DSC show a transition around 175 °C, corresponding to the disruption of strongly interacting stacked oligomers. Block copolymers can be reprocessed using a chaotropic salt, whereas grafted copolymers are not reprocessable after solvent removal. These results open new avenues in the generation of silicone block- and grafted-copolymers with unique functionality and properties.