Synthesis, Characterization, and Adhesion on Galvanized Steel of Original Thermoset Adhesive Films Based on Aza-Michael Addition Reaction.

Abstract

This study focuses first on the synthesis through an aza-Michael addition reaction of original linear diamine prepolymers and original amine/acrylate thermoset adhesives, and second on their thermal, mechanical and adhesion characterization. The major advantage of the aza-Michael addition reaction is that it takes place at room temperature, without a solvent and without a catalyst. Using the aza-Michael addition reaction, linear secondary diamine prepolymers were first synthesized with a control of the molecular weight, ranging from 867 to 1882 g mol^-1. Then, aza-Michael reactions of diamine prepolymers with three different acrylates allowed the synthesis of new amine/acrylate thermoset adhesives. All the thermoset adhesives were characterized by rheology and thermal analysis, leading, once the crosslinking aza-Michael reaction had occurred, to soft thermoset networks with glass transition temperatures ranging from -23 to -8 °C, gel point times ranging from 40 min to 4 h, and a polar component of the surface energy ranging from 3 to 17 mJ m^-2. Functionality of the acrylates directly influences the crosslinking rate, and a decreasing master curve is obtained when reporting crosslinking rate versus gel point time. Crosslinking density is controlled by the diamine prepolymer chain length. In a second step, thermoset adhesives were applied as thin films between two galvanized steel plates, and adhesion properties were evaluated through a lap-shear test. Results showed that the adhesive strength increases as the dynamic viscosity and molecular weight of the diamines prepolymer increases. Increasing the diamines prepolymer chain length results in an increase in strain at break, a decrease in the shear modulus, and a decrease in the maximum lap-shear strength. It is also observed that the adhesive strength decreases when the adhesive film thickness increases. Moreover, thermoset adhesives with high polarity and a surface energy similar to the surface energy of the substrate will favor high adhesion and a better adhesive strength of the assembly. Lastly, the nature of the acrylates and diamines prepolymer chain length allow tuning a wide range of adhesive strength and toughness of these original soft thermoset adhesives.