Selective Lanthanide‐Organic Catalyzed Depolymerization of Nylon‐6 to ϵ‐Caprolactam

Wursthorn, Lukas; Beckett, Kristen; Rothbaum, Jacob O.; Cywar, Robin M.; Lincoln, Clarissa; Kratish, Yosi; Marks, Tobin J.

doi:10.1002/ange.202212543

Title: Selective Lanthanide‐Organic Catalyzed Depolymerization of Nylon‐6 to ϵ‐Caprolactam

Journal Article · Fri Dec 16 00:00:00 EST 2022 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.202212543· OSTI ID:1905343

Wursthorn, Lukas ^[1]; Beckett, Kristen ^[1];

^[1]; Cywar, Robin M. ^[2]; Lincoln, Clarissa ^[2];

^[1];

^[1]

Department of Chemistry Northwestern University 2145 Sheridan Road Evanston IL 60208-3113 USA
Renewable Resources and Enabling Sciences Center National Renewable Energy Laboratory Golden CO 80401 USA

Abstract Nylon‐6 is selectively depolymerized to the parent monomer ϵ‐caprolactam by the readily accessible and commercially available lanthanide trisamido catalysts Ln(N(TMS) ₂ ) ₃ (Ln=lanthanide). The depolymerization process is solvent‐free, near quantitative, highly selective, and operates at the lowest Nylon‐6 to ϵ‐caprolactam depolymerization temperature reported to date. The catalytic activity of the different lanthanide trisamides scales with the Ln ³⁺ ionic radius, and this process is effective with post‐consumer Nylon‐6 as well as with Nylon‐6+polyethylene, polypropylene or polyethylene terephthalate mixtures. Experimental kinetic data and theoretical (DFT) mechanistic analyses suggest initial deprotonation of a Nylon terminal amido N−H bond, which covalently binds the catalyst to the polymer, followed by a chain‐end back‐biting process in which ϵ‐caprolactam units are sequentially extruded from the chain end.

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Sponsoring Organization:: USDOE

OSTI ID:: 1905343

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 135 Journal Issue: 4; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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