Thiolate Salt Mediated Dynamic Silyl Ether Exchanges for Polymer Network Design and Deconstruction.

Silyl ether exchanges represent an appealing motif for the synthesis of dynamic polymers. In this work, the utility and scope of thiolate salts as a catalytic mediator for silyl ether metathesis are explored. On a small scale, thiolate salts can act as robust medium for this exchange reaction. The reaction is sensitive to thiolate salt type, loading, solvent polarity, and steric bulk surrounding the silicon atom. These fundamental principles were translated to a macromolecular scale where sodium thiolate salts were able to catalyze the formation of polymer networks via condensation reactions of trifunctional silyl ethers and diols. The resulting networks are reprocessable, and their polymerization kinetics and stress relaxation behavior correlate with the steric bulk of the silicon substituents. Furthermore, this thiolate-mediated exchange provides a platform for tunable thermoset deconstruction. In summary, this work highlights thiolate salts as an impactful tool in synthesizing dynamic silicon-containing polymer materials.