Internal and External Catalysis in Boronic Ester Networks.

In dynamic materials, the reversible condensation between boronic acids and diols provides adaptability, self-healing ability, and responsiveness to small molecules and pH. The thermodynamics and kinetics of bond exchange determine the mechanical properties of dynamic polymer networks. Here, we investigate the effects of diol structure and salt additives on the rate of boronic acid-diol bond exchange, binding affinity, and the mechanical properties of the corresponding polymer networks. We find that proximal amides used to conjugate diols to polymers and buffering anions induce significant rate acceleration, consistent with an internal and external catalysis, respectively. This rate acceleration is reflected in the stress relaxation of the gels. These findings contribute to the fundamental understanding of the boronic ester dynamic bond and offer molecular strategies to tune the macromolecular properties of dynamic materials.