Substituted Thiols in Dynamic Thiol–Thioester Reactions

Abstract

The thiol–thioester reaction has emerged as a promising method for developing covalent adaptable networks (CANs) due to its ability to exchange rapidly under low temperature conditions in a number of solvents, orthogonality among other functional groups, and tunability. Here, the effects of thiol substitution (i.e., primary vs secondary) were assessed with respect to their reactivity in two dynamic thioester reactions: the thiol–thioester exchange and the reversible thiol–anhydride addition. Model NMR experiments were conducted using small-molecule compounds to observe how polymers of similar components would behave in thiol–thioester exchange. It was determined that the Keq was near unity for mixtures of primary thiols and secondary thioesters, and vice versa, in both a polar solvent, DMSO-d6, and at most slightly favors primary thioesters in a relatively nonpolar solvent, CDCl3. Dielectric spectroscopy and stress relaxation experiments were used to determine the relaxation times and activation energies of the two thioester-containing networks: Thiol-ene networks, which undergo thioester exchange, displayed activation energies of 73 and 71 kJ/mol from dielectric measurements and 36 and 53 kJ/mol from stress relaxation for the primary and secondary thiols, respectively. Thiol–anhydride-ene networks, which undergo both thioester exchange and reversible thiol–anhydride addition, displayed activation energies of 94 and 114 kJ/mol from dielectric and 111 and 139 kJ/mol from stress relaxation for primary and secondary thiols, respectively. In both types of networks, the secondary thioester-based networks demonstrated slower dynamics as compared to the same primary network by at least one order of magnitude. In the anhydride network, the secondary thiol also biased the dynamics toward reversible addition.