Bio‐sourced epoxy resins from resorcinol diglycidyl ether (RDGE) have been obtained by using cationic photopolymerization under UV‐light exposure. The photoinduced bulk resin samples were characterized by three‐point bending tests, dynamic mechanical analysis, as well as differential scanning calorimetry analysis, and thermogravimetric analysis. The influence of processing parameters, that is, reactant contents, UV irradiation time, and postcuring conditions on the thermomechanical behavior has been pointed out. For instance, the flexural modulus of the most performing materials reaches 4.1 GPa with the flexural strength and the glass‐transition temperature of around 105 MPa and 99°C, respectively. Interestingly, our optimized protocol has led to the synthesis of new bio‐based materials with more valuable thermal and mechanical properties than those of thermocured materials obtained from petroleum‐based commercial epoxy resins. Focus has been given on processing parameters to optimize the final properties of the material and to open an interesting alternative for sustainable building materials.
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