Strong yet Tough Catalyst‐Free Transesterification Vitrimer with Excellent Fire‐Retardancy, Durability, and Closed‐Loop Recyclability

Abstract

Despite great advances in vitrimer, it remains highly challenging to achieve a property portfolio of excellent mechanical properties, desired durability, and high fire safety. Thus, a catalyst-free, closed-loop recyclable transesterification vitrimer (TPN_1.50) with superior mechanical properties, durability, and fire retardancy is developed by introducing a rationally designed tertiary amine/phosphorus-containing reactive oligomer (TPN) into epoxy resin (EP). Because of strong covalent interactions between TPN and EP and its linear oligomer structure, as-prepared TPN_1.50 achieves a tensile strength of 86.2 MPa and a toughness of 6.8 MJ m^-3, superior to previous vitrimer counterparts. TPN_1.50 containing 1.50 wt% phosphorus shows desirable fire retardancy, including a limiting oxygen index of 35.2% and a vertical burning (UL-94) V-0 classification. TPN_1.50 features great durability and can maintain its structure integrity in 1 M HCl or NaOH solution for 100 days. This is because the tertiary amines are anchored within the cross-linked network and blocked by rigid P-containing groups, thus effectively suppressing the transesterification. Owing to its good chemical recovery, TPN_1.50 can be used as a promising resin for creating recyclable carbon fiber-reinforced polymer composites. This work offers a promising integrated method for creating robust durable fire-safe vitrimers which facilitate the sustainable development of high-performance polymer composites.