Multicatalytic Access to Renewable Poly(Silyl Ether)s with Tunable Properties

Abstract The global reliance on petroleum‐based polymers presents urgent sustainability challenges. Addressing this issue, we present a novel one‐pot multicatalytic strategy for synthesizing partially bio‐based poly(silyl ether)s with tunable properties. This method combines magnesium‐catalyzed esterification of bio‐based diacids and alcohols with borane‐catalyzed hydrosilylation under mild conditions. This approach enables direct incorporation of ester functionalities into the polymer backbone, affording high‐molecular‐weight poly(silyl ether)s with tunable architectures and thermal profiles. The method demonstrates excellent catalyst compatibility and scalability, significantly reducing purification steps while broadening monomer scope. Beyond thermal robustness, the resulting materials exhibit remarkable mechanical performance. Preliminary tensile tests revealed distinctive deformation behavior, with certain polymers achieving extraordinary extensibility (elongation at break > 3800%) and high energy absorption, attributed to the synergistic interplay between flexible siloxane segments and dynamic silyl ether linkages. Degradation studies confirm efficient chemical recycling, underscoring the potential of this one‐pot process to deliver sustainable, high‐performance polymers with customizable properties for advanced applications.