The reversible condensation of boronic acids and diols is a popular dynamic covalent reaction for polymer networks due to its selectivity and biocompatibility. Recent studies have demonstrated that the macroscopic properties of covalent adaptable networks are determined by the thermodynamics and the kinetics of the dynamic reaction at the crosslink junction. Boronic acid–diol condensation is sensitive to structural and environmental factors, which can be translated into the resulting network properties. Nevertheless, the effects of these factors on the kinetics of this dynamic reaction have not been studied in a systematic and quantitative way. In this talk, I will discuss how diol structure affects the binding affinity and kinetics of this dynamic covalent reaction, and its translation to network properties. In particular, we discovered previously unrecognized effects of neighboring amide groups and common buffer salts on the rate of both esterification and hydrolysis, which are also observed in boronic ester gels. Our results introduce new design parameters for the control of self-healing and stress relaxation rates in boronic ester networks.

Internal and external catalysis in boronic ester networks

ACS Spring 2022

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