Reversible Redox Crosslinking of Thiopropylsilicones

Most silicone elastomers are thermosets. As a response to the new paradigm of polymer recyclability, the development of silicone elastomers that can be reversibly and repeatedly cured and uncrosslinked using redox conditions is reported. Thiopropyl‐modified silicones are oxidized to elastomers with disulfide crosslinks using the organosoluble oxidant PhI(OAc)2. As with any elastomer, mechanical properties can be tuned by varying crosslink density. Thermal stabilities in air show that the products are comparable to traditional silicone thermosets, with degradation only starting over 300 °C. Uncrosslinking back to the same thiopropyl‐modified silicones involves reductive S–S bridge cleavage using a Piers–Rubinsztajn reaction with hydrosilanes catalyzed by B(C6F5)3; HSiMe2OSiMe3 is identified as a convenient reducing agent. The initially formed silicone‐(CH2)3S‐SiMe2OSiMe3 products need deprotection with water in isopropanol/water to completely regenerate the thiopropylsilicones. This oxidation/reduction crosslinking/uncrosslinking cycle is practiced thrice, with a yield of 89% per cycle, with essentially no change in the Young's moduli of the elastomers, or 1H NMR spectra of the uncrosslinked fluids after reduction. Further oxidation of disulfide groups on the elastomer surface permanently and significantly improved water wettability.

The Young's moduli of rubber samples were determined using an MACH-1 micromechanical system (Biomomentum Instruments) with a 0.5 mm hemispherical indenter radius and Poisson ratio of 0.5.