Reversible Redox Crosslinking of Thiopropylsilicones. Issue 5 (13th August 2020)

• Record Type: Journal Article
• Authors: Zheng, Sijia; Brook, Michael A.
• Other Names: Brook Michael A. guestEditor.; Skov Anne L. guestEditor.
• Is Part Of: Macromolecular rapid communications. Volume 42:Issue 5(2021)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2020-08-13
• Subjects: disulfide crosslinking -- Piers–Rubinsztajn reaction -- redox silicones -- reversible crosslinking; Macromolecules -- Periodicals; Polymers -- Periodicals; Chemistry -- Periodicals; 547.705
• DOI: 10.1002/marc.202000375
• Languages: English
• ISSNs: 1022-1336

Abstract

Abstract: 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(C6 F5 )3 ; HSiMe2 OSiMe3 is identified as a convenient reducing agent. The initially formed silicone‐(CH2 )3 S‐SiMe2 OSiMe3 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 1 H NMR spectra of the uncrosslinked fluids after reduction. Further oxidation of disulfide groups on the elastomer surface permanently and significantly improved water wettability. Abstract : Silicone elastomers may be repeatedly, iteratively, formed by oxidation of thiopropylsilicone oils and then reduced using hydrosilanes under Piers Rubinsztajn conditions. Overoxidation of the elastomer surfaces using bleach permits more wettable surfaces to be formed that are less susceptible to hydrophobic recovery.