In this study the triglycidyl ether of phloroglucinol (TGPh) was chosen as the first fully bio-aromatic monomer capable of self-crosslinking through controlled homopolymerisation, providing a simplified, hardener-free route. The TGPh homopolymerisation was investigated using tertiary amine catalysts (BDMA, DMP30) and imidazole initiators (1MIM, 2E4M, 1,2DMIM) to tune network formation and performance. These systems were systematically assessed to determine how variations in nucleophilicity and basicity influence the curing reaction, crosslinking efficiency, thermal stability, and mechanical properties. Comparative analysis revealed distinct structure–property relationships, with polymerization agent selection critically governing both reactivity and network architecture. These findings demonstrate that TGPh can be transformed into high-performance epoxy networks with T g = 165–255 °C, E’ ∼3.5–4.3 GPa, E ∼1.75 GPa, T 5% = 305–315°C, WA< 1.1%, BOC ∼95–98%, through tailored polymerization strategies, providing a sustainable pathway for advanced thermosetting resins in industrial applications. This study explores the homopolymerization of fully biobased triglycidyl ether of phloroglucinol (TGPh) using various polymerization agents to tailor high-performance thermosets with excellent thermal, mechanical, and environmental properties for advanced industrial applications. • First fully bio-based aromatic triglycidyl monomer (TGPh) enabling hardener-free self-crosslinking. • Controlled homopolymerization achieved using tertiary amine catalysts and imidazole initiators. • Polymerization agent selection governs reactivity, crosslinking efficiency, and network architecture. • Resulting epoxy networks exhibit high performance (Tg up to 255 °C, E’ ≈ 4.3 GPa, low water uptake <1.1%).
Dinu et al. (Fri,) studied this question.