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Circularly Recyclable Polymers Featuring Topochemically Weakened Carbon–Carbon Bonds

Xuyi Luo, Zitang Wei, Bumjoon Seo, Qixuan Hu, Xiaokang Wang, Joseph A. Romo, Mayank Jain, Mükerrem Çakmak, Bryan W. Boudouris, Kejie Zhao, Jianguo Mei, Brett M. Savoie, Letian Dou

2022Journal of the American Chemical Society57 citationsDOI

Abstract

Closed-loop circular utilization of plastics is of manifold significance, yet energy-intensive and poorly selective scission of the ubiquitous carbon-carbon (C-C) bonds in contemporary commercial polymers pose tremendous challenges to envisioned recycling and upcycling scenarios. Here, we demonstrate a topochemical approach for creating elongated C-C bonds with a bond length of 1.57∼1.63 Å between repeating units in the solid state with decreased bond dissociation energies. Elongated bonds were introduced between the repeating units of 12 distinct polymers from three classes. In all cases, the materials exhibit rapid depolymerization via breakage of the elongated bond within a desirable temperature range (140∼260 °C) while otherwise remaining remarkably stable under harsh conditions. Furthermore, the topochemically prepared polymers are processable and 3D-printable while maintaining a high depolymerization yield and tunable mechanical properties. These results suggest that the crystalline polymers synthesized from simple photochemistry and without expensive catalysts are promising for practical applications with complete materials' circularity.

Topics & Concepts

DepolymerizationPolymerChemistryBond cleavageCarbon fibersDissociation (chemistry)Bond-dissociation energyYield (engineering)BreakageSolid-stateNanotechnologyPolymer scienceCatalysisPolymer chemistryChemical engineeringOrganic chemistryComposite materialMaterials sciencePhysical chemistryComposite numberEngineeringCovalent Organic Framework ApplicationsPolymer composites and self-healingbiodegradable polymer synthesis and properties