Bio-based long-chain aliphatic polyamide with intrinsic flame retardancy and great overall properties

•Novel flame-retardant bio-based long-chain aliphatic polyamide with great overall properties.•The copolymer exhibited high LOI value of 32.6%, and achieved an UL-94 V-0 rating.•Successful inhibition of the release of heat and toxic gasses in cone calorimetry test.•The copolymer showed largely improved tg and maintained thermal and mechanical properties. Bio-based long-chain aliphatic polyamides show remarkable potential in pursuing high-performance, sustainable bio-plastics. However, the aliphatic structure also leads to high flammability that severely restricts their applications. Herein, we demonstrate a novel flame-retardant system to fabricate high-performance, flame-retardant bio-based long-chain aliphatic polyamide. In this system, a novel reactive nitrogen-based flame-retardant monomer, PDB, was designed and synthesized. Subsequently, the corresponding bio-based long-chain polyamide copolymer was prepared through a facile polycondensation process. The nitrogen-based groups exhibited highly efficient free-radical-capturing effect, helping the copolymer achieve a high limiting oxygen index value of 32.6%, the UL-94 V-0 rating, a 33.3% lower peak heat release rate, and inhibited the release of toxic gasses at a PDB content of 6 wt%. Furthermore, the copolymer exhibited largely maintained crystallinity, thermal stability, and mechanical properties, owing to the high reactivity of PBD with polyamide monomers. At the same time, the incorporation of PBD increased the rigidity of the copolymer, resulting in a significant increase of 16.4 °C in the glass transition temperature and lower dielectric properties. This work provides a new perspective on the preparation of bio-based long-chain aliphatic polyamide with enhanced overall properties.