Closed‐loop recycling of polymers represents the key technology to convert plastic waste in a sustainable fashion. Efficient chemical recycling and upcycling strategies are thus highly sought‐after to establish a circular plastic economy. Here, we present the selective chemical depolymerization of polycarbonate by employing a vanillin derivative as bio‐based feedstock. The resulting di‐vanillin carbonate monomer was used in combination with various amines to construct a library of reprocessable poly(imine‐carbonate)s, which show tailor‐made thermal and mechanical properties. These novel poly(imine‐carbonate)s exhibit excellent recyclability under acidic and energy‐efficient conditions. This allows the recovery of monomers in high yields and purity for immediate reuse, even when mixed with various commodity plastics. This work provides exciting new insights in the design of bio‐based circular polymers produced by upcycling of plastic waste with minimal environmental impact.

Epoxy resins constitute a very significant portion of all highperformance plastics due to their excellent thermal and mechanical properties that appear in a wide range of applications. Nevertheless, traditional epoxy networks show limitations regarding chemical recycling due to their covalently crosslinked structures. The current methods to recycle epoxy resins are not indeed through sustainable ways, but this issue could be solved by developing smart monomers with functional groups, which can be switched between polymerized and depolymerized states. Herein, we developed two bio-based liquid monomers based on vanillin structures containing aldehyde, acetal, and oxirane-ring functionalities. These monomers were polymerized in solventfree conditions using commercially available diamines, resulting in doubledynamic imine-acetal-containing thermosets. These networks combine the excellent properties of the traditional epoxy systems and dynamic polymers. Most importantly, such thermosets were fully depolymerized into vanillin, which can be reused for the preparation of original epoxy monomers, and a mixture of well-defined polyols, which was upcycled into high-performance polyurethane.

Epoxy thermosets constitute a significant portion of high-performance plastics, as they possess excellent thermal and mechanical properties that are applicable in a wide range of industries. Nevertheless, traditional epoxy networks show strict limitations regarding chemical recycling due to their covalently crosslinked structures. Although existing methods provide partial solutions for the recycling of epoxy networks, it is urgent to develop more effective, sustainable, and permanent strategies that will solve the problem at hand. For this purpose, developing smart monomers with functional groups that enable the synthesis and development of fully recyclable polymers is of great importance. This review highlights recent advancements in chemically recyclable epoxy systems and their potential to support a circular plastic economy. Moreover, we evaluate the practicality of polymer syntheses and recycling techniques, and assess the applicability of these networks in industry.

Chemical recycling offers a promising solution for the end‐of‐life treatment of synthetic polymers. However, the efficient recovery of well‐defined recycled building blocks continues to be a major challenge, especially for crosslinked thermosets. Here, we developed vanillin‐based polymer networks functionalized with dual‐cleavable imine and acetal bonds that facilitate chemical recycling to primary building blocks and their convenient separation at the molecular level. A library of crosslinked poly(imine‐acetal)s was synthesized by combining the in‐bulk synthesized liquid di‐vanillin acetal monomer (DVA) with commercially available liquid di‐ and triamines under solvent‐free conditions. These thermosets showed tailor‐made thermal and mechanical properties along with outstanding chemical recyclability. Under aqueous acidic conditions, poly(imine‐acetal)s selectively and completely disintegrate into small molecules. During the polymer design stage, these compounds were carefully selected to enable facile separation without tedious techniques. As a result, the primary building blocks were isolated in high yields and purity and immediately reused to produce fresh polymers with identical thermomechanical properties. Since our “design for recycling” concept aims at obtaining the primary building blocks rather than monomers after depolymerization, a plethora of possibilities are unlocked to utilize these chemical resources, including closed‐loop recycling as portrayed.

Closed‐loop recycling of polymers represents the key technology to convert plastic waste in a sustainable fashion. Efficient chemical recycling and upcycling strategies are thus highly sought‐after to establish a circular plastic economy. Here, we present the selective chemical depolymerization of polycarbonate by employing a vanillin derivative as bio‐based feedstock. The resulting di‐vanillin carbonate monomer was used in combination with various amines to construct a library of reprocessable poly(imine‐carbonate)s, which show tailor‐made thermal and mechanical properties. These novel poly(imine‐carbonate)s exhibit excellent recyclability under acidic and energy‐efficient conditions. This allows the recovery of monomers in high yields and purity for immediate reuse, even when mixed with various commodity plastics. This work provides exciting new insights in the design of bio‐based circular polymers produced by upcycling of plastic waste with minimal environmental impact.