Polydiketoenamines for a Circular Plastics Economy

The mismanagement and leakage of plastic waste into the environment are failures of modern society. Once in the environment, plastic waste degrades into microplastics on a time scale dependent on the resin chemistry and the associated biotic or abiotic process. The high surface area of microplastics results in the contamination of ecosystems through the leaching of toxic chemicals compounded with plastics during manufacturing. In addition, the small size of microplastics increases the likelihood that they will be inhaled or ingested, which has led to the bioaccumulation of microplastics with documented harm. Furthermore, microplastics are more readily aerosolized and distributed by weather systems to areas remote from locations where plastic waste has been mismanaged. Consequently, the carbon cycle must now account for plastic waste discharge, degradation, and dispersal in the environment after the end of useful life on a global scale.Circularity in plastics recycling endeavors to solve the waste problem while promoting greater sustainability. Circularity can be conducted at different stages in the plastics life cycle. Post-industrial recycling enabling scrap recovery in manufacturing is desirable for industrial material efficiency. However, the degradation of polymer chains currently limits the extent to which scrap recovery may be practiced repeatedly on the same material, particularly when the conversion of secondary resin to various plastic products is intolerant to deviations in polymer properties. Post-consumer recycling, on the other hand, is desirable for erasing the manufacturing history and use history of plastic-containing products. Post-consumer recycling involves cleaning and sorting plastic waste into bales, followed by mechanical recycling to produce dense feedstocks for downstream chemical processes required for deconstruction, monomer refinement, and secondary resin production. The efficiency and intensity of chemical processes used to recover reusable monomers or polymers remain low for most plastics. Consequently, there is an urgent need for novel polymers with useful or advantageous properties designed for recycling by addressing the challenges of resource recovery for reuse.In this Account, I discuss the design, discovery, and development of circular plastics based on the chemistry of polydiketoenamines. The diketoenamine bond provides a vantage point for the creation of thermoplastics, elastomers, and thermosets from polytopic triketone and amine monomers. The dynamic covalent character of the diketoenamine bond can be exploited during scrap recovery to provide resilience during mechanical recycling, maintaining baseline properties of the primary resin through multiple cycles of reuse. Furthermore, the hydrolyzability of the diketoenamine bond in strong acid can be exploited for efficient monomer recovery during chemical recycling. A systems-level analysis of polydiketoenamine circularity reveals substantive benefits in low-carbon manufacturing as well as a context to quantify the market potential, identifying use cases where circularity might be most effective. Leveraging these insights, it is possible to guide the process chemistry development necessary to scale monomer and resin production to meet imminent needs for more circular plastics in the market. These insights also provide a glimpse into the underlying molecular mechanisms critical to circularity in a new plastics economy while firmly establishing a role for creativity in polymer chemistry to provide innovative solutions.