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The reaction of thiols and anhydrides to form ring opened thioester/acids is shown to be highly reversible, and it is accordingly employed in the fabrication of covalent adaptable networks (CANs) that possess tunable dynamic covalent chemistry. Maleic, succinic and phthalic anhydride derivatives were used as bifunctional reactants in systems with varied stoichiometries, catalyst, and loadings. Dynamic characteristics such as temperature-dependent stress relaxation, direct reprocessing and recycling abilities of a range of thiol-anhydride elastomers, glasses