Covalently cross-linked rubbers are indispensable in many important fields due to their unique entropic elasticity. For rubbers cross-linking, the addition of toxic curing agents, release of toxic volatile organic compounds (VOCs), and recycling of waste rubber are three important issues. A combination of green curing chemistry and efficient recycling into commercial polyolefin rubbers is of great importance. Herein, we demonstrate a facile and promising way to incorporate dynamic covalent bonds into ethylene-propylene-diene monomer (EPDM)/carbon black (CB) composites. The epoxy-functionalized EPDM (e-EPDM) was prepared using an in situ epoxidation reaction and then cured with biobased decanedioicacid (DA) through the reactions between the epoxy groups in e-EPDM and the carboxylic groups in DA. Because of the existence of exchangeable β-hydroxyl ester, the covalently cross-linked networks in e-EPDM/CB composites were able to rearrange their topological structure at high temperature, endowing the composites with recycled and reshaped abilities. More importantly, the recycled e-EPDM/CB composites still exhibit outstanding mechanical properties which can meet the needs of practical applications. This strategy may provide an efficient, green, and sustainable way to address the problems brought from rubbers cross-linking.

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The introduction of dynamic covalent bonds into chemically cross-linked networks is an effective strategy to solve intrinsic problems of inability to be reprocessed or recycled for thermosetting polymers. Imine bonds (also known as Schiff bases) are promising candidates for constructing covalent adaptable networks (CANs) because of their easily triggered exchange reactions. However, it remains a challenge for polyimine vitrimers to improve the creep resistance and thermal stability due to their unstable imine-based networks. In this work, we report a green strategy to prepare a series of partially bio-based, malleable, recyclable, and robust poly­(amide–imine) vitrimers by bulk polymerization for the first time. The amide bonds are introduced into polyimine vitrimers for the improvement of mechanical property, thermal stability, and creep resistance. A series of H2N-terminated prepolymers with tunable structures were first synthesized, which combined the amide and imine groups together. Then, a bio-based trimethyl citrate was selected as the curing agent to react with H2N-terminated prepolymers for the construction of CANs with amide bonds as cross-linking points. The imine groups accompanied by a dynamic exchange nature endowed the poly­(amide–imine) vitrimers with reprocessability, self-healing property, and degradability. Meanwhile, the amide groups with inherent intermolecular hydrogen bonding enhanced the mechanical properties, thermal stability, and creep resistance of poly­(amide–imine) thermosets.

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