Preferential Control of Forward Reaction Kinetics in Hydrogels Crosslinked with Reversible Conjugate Additions

10 February 2020, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Molecular substitutions were used to demonstrate preferential control over the kinetic rate constants in a poly(ethylene glycol)-based hydrogel with two different reversible thia-conjugate addition reactions. A strong electron withdrawing nitrile group on the conjugate acceptor showed a 20-fold increase in the forward rate constant over a neutral withdrawing group, while the reverse rate constant only increased 6-fold. Rheometry experiments demonstrated that the hydrogel plateau modulus was primarily dictated by reaction equilibrium, while the stress relaxation characteristics of the hydrogel were dominated by the reverse rate constant. Furthermore, the dynamic crosslinking allowed the hydrogel to rapidly and spontaneously self-heal. These results indicate that decoupling the kinetic rate constants of bond exchange allow systematic control over dynamic covalent hydrogel bulk properties, such as their adaptability, stress relaxation ability, and self-healing properties.


Dynamic covalent chemistry
self-healing polymer network

Supplementary materials

Supporting Information final


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