Vanillin-derived co-curing agent for enhanced flame retardancy and mechanical properties in epoxy resin

Herein, we present the synthesis and characterization of a novel phosphorus-containing epoxy co-curing agent, ANVD, fabricated via a one-pot method utilizing vanillin, 1,5-diaminonaphthalene, and DOPO as raw materials. Structural analysis conducted through FTIR and NMR spectroscopy confirmed the composition of ANVD. Differential scanning calorimetry (DSC) results indicated ANVD has significant contribution to the curing crosslinking of DGEBA, resulting in a slightly decreased Tg value for EP/ANVD compared to EP/DOPO, albeit still notably higher. Thermogravimetric analysis (TGA) revealed a reduction in the T5% and Tmax values of EP/ANVD, yet ANVD's superior char-forming ability increased char residue mass at elevated temperatures. Combustion tests showcased the outstanding flame retardancy of EP/ANVD, with EP/ANVD-5 exhibiting a limiting oxygen index (LOI) value of 33.2 % and achieving a V-0 rating in the UL-94 test. Furthermore, EP/ANVD-5 displayed a notable decrease of 38.6 % and 32.1 % in pHRR and av-HRR, respectively, compared to pure EP, surpassing EP/DOPO with equivalent phosphorus content. Analysis of decomposition products in both condensed and gas phases revealed ANVD's role in forming dense and continuous expanded char layers during combustion, releasing phosphorus radicals and non-combustible gases, thus exhibiting dual-phase flame retardant effects. Additionally, EP/ANVD-3 exhibited enhanced mechanical properties, with tensile strength and modulus increasing from 68.5 MPa and 0.75 GPa to 76.5 MPa and 0.86 GPa, respectively, compared to pure EP. Overall, the introduction of the bio-based flame retardant ANVD presents promising opportunities for the utilization of bio-based materials in flame retardancy applications.