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Synthesis and Modification of Bio-Based Reactive Flame Retardants (Guaiacol and Furfural) for Flame Retardancy of Epoxy Resin

Huajun Duan,Ruian Li,Yuan Gao,Jiangtao Geng,Yuan Chen,Ya Li,Weipeng Liu,Huiru Ma

Epoxy resin (EP) is a thermosetting resin of significant commercial value. However, it is afflicted by inherent defects, including flammability and non-self-extinguishing properties. Consequently, it is imperative to modify EP with flame retardant additives. Currently, the majority of flame retardants are characterized by complexity and a cumbersome preparation process, which is not conducive to environmental sustainability. Consequently, there is a growing demand for eco-friendly bio-based flame retardants. In this paper, bio-based reactive flame retardants (HGD) with hydroxymethyl and phenolic hydroxyl groups were prepared in a one-step method by bulk reaction using the bio-based materials 5-hydroxymethylfurfural, guaiacol, and DOPO as raw materials, and were added into EP as co-curing agents to prepare flame retardant epoxy resins (FREPs). Comprehensive evaluation revealed fire safety improvements in HGD-modified EP systems. Specifically, the optimized EP/HGD-7.5 formulation demonstrated reductions in key combustion parameters compared to unmodified EP: 35.7% decrease in peak heat release rate (pHRR), 34.0% reduction in total heat release (THR), 24.3% lower average effective heat of combustion (Av-EHC), and 16.8% suppression of total smoke production (TSP). Meanwhile, the modified composites exhibited concurrent mechanical enhancement. At 7.5% HGD loading, flexural strength and modulus increased by 21.1% and 20.0%, respectively, while tensile performance optimization occurred at 5.0% loading with 20.6% strength improvement and 24.5% modulus elevation. Notably, HGD-modified EP systems maintained superior thermal stability. The glass transition temperature ( T g ) of EP/HGD-7.5 is 154.2°C, exceeding that of EP. This investigation successfully demonstrates a sustainable approach for developing multifunctional epoxy composites with enhanced fire resistance and mechanical performance through bio-based modification.