A robust and efficiently reprocessable poly(dimethylsiloxane) elastomers enhanced by self‐catalysis Zn(II)‐ligand bonds and silyl ethers

Abstract In recent years, as an emerging dynamic bonding, silyl ether linkages have been concerned and applied. However, the reprocessability of vitrimers based on it is far from satisfactory because of the inactive dynamic exchange reaction. At the same time, the mechanical properties of polysiloxane elastomers are poor because of the high flexibility of polysiloxane molecular chains and weak intermolecular forces. Herein, we have successfully synthesized a PDMS elastomer incorporating Zn(II)‐amine coordination bonds as sacrificial units, which are crosslinked through dynamic silyl ether linkages. Importantly, the presence of Zn ions promotes the exchange between the silyl ether linkages and hydroxyl groups. The elastomers exhibited excellent mechanical properties (35 times improvement in toughness) and outstanding reprocessability. The mechanical property recovery of the PDMS elastomers reached approximately 90% after four reprocessing cycles. Meanwhile, small‐molecule simulation experiments were conducted to verify the significant catalytic effect of Zn (II) ions as Lewis acid catalysts on the exchange reaction of silyl ether linkages and hydroxyl groups. In a word, this work provides a facile strategy to simultaneously enhance the mechanical properties and reprocessing performance of silyl ether‐linked polysiloxane elastomers.