Catalytic closed-loop recycling of polyethylene-like materials produced by acceptorless dehydrogenative polymerization of bio-derived diols

Liu, Xin; Hu, Zhitao; Rettner, Emma M.; Harry, Katherine L.; Miscall, Joel; Rorrer, Nicholas A.; Miyake, Garret M.

doi:10.1038/s41557-025-01753-8

Catalytic closed-loop recycling of polyethylene-like materials produced by acceptorless dehydrogenative polymerization of bio-derived diols

Journal Article · Thu Feb 20 23:00:00 EST 2025 · Nature Chemistry

DOI:https://doi.org/10.1038/s41557-025-01753-8· OSTI ID:2544979

Liu, Xin ^[1]; Hu, Zhitao ^[1]; ^[1]; Harry, Katherine L. ^[1]; ^[2]; ^[2]; ^[1]

Colorado State University, Fort Collins, CO (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States); BOTTLE Consortium, Golden, CO (United States)

Petroleum-derived polyolefins exhibit diverse properties and are the most important and largest volume class of plastics. However, polyolefins are difficult to efficiently recycle or break down and are now a persistent global contaminant. Broadly replacing polyolefins with bio-derived and degradable polyethylene-like materials is an important yet challenging endeavour towards sustainable plastics. Here, in this study, we report a solution for circular bio-based polyethylene-like materials synthesized by acceptorless dehydrogenative polymerization from linear and branched diols and their catalytic closed-loop recycling. The polymerization and depolymerization processes utilize earth-abundant manganese complexes as catalysts. These materials exhibit a wide range of mechanical properties, encompassing thermoplastics to plastomers to elastomers. The branched diols, produced through a thiol-ene click reaction, can be polymerized to plastics with significantly enhanced tensile properties, toughness and adhesive properties. These materials could be depolymerized back to monomers through hydrogenation and were separatable with a monomer recovery of up to 99%, unaffected by the presence of dyes and additives. Overall, this system establishes a route to more sustainable plastics.

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Bioenergy Technologies Office (BETO); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Energy Efficiency Office. Advanced Materials & Manufacturing Technologies Office (AMMTO); National Institutes of Health (NIH)

Grant/Contract Number:: AC36-08GO28308; SC0022290

OSTI ID:: 2544979

Report Number(s):: NREL/JA--2800-90548; MainId:92326; UUID:ef40d62b-6813-4092-9c1f-509855564ee4; MainAdminId:75701

Journal Information:: Nature Chemistry, Journal Name: Nature Chemistry Journal Issue: 4 Vol. 17; ISSN 1755-4330

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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Catalytic closed-loop recycling of polyethylene-like materials produced by acceptorless dehydrogenative polymerization of bio-derived diols

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