A high-performance epoxy vitrimer was facilely prepared from a renewable lignin derivative vanillin, and its carbon-fiber composites were nondestructively recycled.

Conventional thermosets are built by nonrenewable fossil resources and are arduous to be reprocessed, recycled, and reshaped due to their permanent covalent cross-linking, and their flammability makes them unsafe during use. Here, for the first time, we synthesized a novel Schiff base precursor from abundant and renewable lignin derivative vanillin and produced malleable thermosets (Schiff base covalent adaptable networks (CANs)) combining high performance, super-rapid reprocessability, excellent monomer recovery, and arbitrary permanent shape changeability as well as outstanding fire resistance. The Schiff base CANs exhibited high glass transition temperatures of ∼178 °C, tensile strength of ∼69 MPa, tensile modulus of ∼1925 MPa, excellent flame retardancy with UL-94 V0 rating and V1 rating, and high LOI of ∼30%. Meanwhile, three Schiff base CANs showed high malleability with the activation energy of the bond exchange of 49–81 kJ mol–1 and could be reprocessed in 2–10 min at 180 °C. These Schiff base CANs provide a prime example to foster the development of advanced thermosetting materials from renewable bioresources.

Epoxy thermosets containing a two-benzene-ring-conjugated Schiff base structure combined excellent controlled degradability, stability, antibacterial properties, and thermal and mechanical properties.

Vitrimers undergoing dynamic bond exchange enable reprocessing and recycle of thermosets. However, vitrimers are susceptible to creep, leading to their poor dimensional stability, which limits their applications. Here, a facile method via integration of metal complexes was utilized to address this issue, and cross-linked polyimine was selected as an example of vitrimer. Three different metal complexes were introduced into a polyimine vitrimer via a one-pot preparation involving the formation of metal complexes and cross-linking of polyimine. The addition of 0.5 mol % Cu2+ relative to imine bond reduced creep degree from 30% to 20% at 60 °C, and the creep resistance was enhanced with increasing Cu2+ content. Loading 5 mol % Cu2+ increased the initial creep temperature from 60 to about 100 °C and raised the Arrhenius activation energy (E a) for stress relaxation from 52.3 to 67.7 kJ mol–1. The ability of different metal complexes to suppress creep followed the order of Fe3+ > Cu2+ > Mg2+, and the initial creep temperature reached around 120 °C for vitrimer with 5 mol % of Fe3+. Meanwhile, the polyimine–metal complex vitrimers still exhibited excellent reprocessing recyclability. Moreover, the introduction of coordination structures enhanced the thermal and mechanical properties, solvent, and acid resistance. Thus, metal coordination is an efficient approach to achieve high-temperature creep resistance, excellent thermal and mechanical properties, and chemical stability for vitrimers based on the Schiff base.

CFRPs based on degradable thermosets have benefits of low energy consumption and reduced damage to carbon fibers during the recycling process.

This work highlights the exploitation of an acetal motif to build dynamic covalent networks.

Recycling thermosets have become extremely important due to their ecological and economic benefits. The development of thermosets that undergo reversible polymerization provides a solution to the end-life disposal issue of thermosetting materials. However, the synthesis and recycling of the current chemically recyclable thermosets are harsh, complex, and energyintensive, and their stability is often low. Here, we designed asymmetric acetal-containing thermosets (PRCs) from general phenolic resin and 1,4-cyclohexanedimethanol divinyl ether through one-step "click" cross-linking without using catalysts and solvents and without releasing small-molecule byproducts. PRCs exhibited conspicuous stress relaxation via a dissociative mechanism, corresponding to the superior malleability and reprocess recyclability. Importantly, PRCs presented excellent creep resistance even at 100 °C. In addition, PRCs could be readily and highly efficiently recovered to original phenolic resin via hydrolysis under specific mild acidic conditions but possessed high chemical stability under neutral conditions and even weak acidic conditions or acidic conditions in the absence of organic solvents with outstanding wettability and swellability toward the samples. Thermosets with different properties could be easily achieved via regulating raw materials. This work provides a promising dynamic covalent motif and a practical method to produce readily dual-recyclable (reprocess recyclable and chemically recyclable) thermosets with superior performance and stability.

Covalent adaptable networks (CANs) represent a transition material combining favorable features of thermosets and thermoplastics. However, it is still a huge challenge to simultaneously achieve fast reprocessability and high performance for CANs. Here, we designed catechol-based acetal CANs to achieve continuous reprocessing without sacrificing thermal and mechanical properties. A small-molecule model study demonstrated the significantly accelerated acetal exchange by neighboring group participation (NGP) of phenolic hydroxyl. Using this internally catalyzed acetal chemistry, a series of CANs with a broad range of properties were simply prepared from bio-based epigallocatechin gallate (EGCG) and tri­(ethylene glycol) divinyl ether (TEGVE) via one-step “click” cross-linking without using catalysts or releasing small-molecule byproducts. The dynamic nature of the CANs was confirmed via stress relaxation and multiple recycling methods including extrusion. While the dense cross-link density and high rigidity of the network provided high solvent resistance and mechanical properties. This work provides a promising and practical method to produce fast-reprocessing dynamic covalent polymer networks with dense cross-link density and superior performance.