Synthesis and Characterization of Multifunctional Secondary Thiol Hardeners Using 3-Mercaptobutanoic Acid and Their Thiol–Epoxy Curing Behavior

3-Mercaptobutanoic acid (3-MBA) was synthesized by the less odorous Michael addition pathway using an isothiouronium salt intermediate. Using the synthesized 3-MBA, multifunctional secondary thiol (sec-thiol) compounds were obtained and applied to thiol–epoxy curing systems as hardeners. As the functionality of the sec-thiol hardeners increased, the purity of the product obtained after distillation decreased. The equivalent epoxy mixtures with multifunctional sec-thiol hardeners were evaluated based on their impact on the curing behavior in thiol–epoxy click reactions by differential scanning calorimetry. The thermal features of sec-thiol–epoxy click reactions in the presence of a base catalyst were assessed according to the functionality of the sec-thiol hardeners. Our results showed that sec-thiol hardeners with less reactivity to the epoxy group provide long-term storage stability for the formulated epoxy resin, promising for industrial applications.