Green and Facile Preparation of Readily Dual-Recyclable Thermosetting Polymers with Superior Stability Based on Asymmetric Acetal

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 energy-intensive, 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.