Closed‐Loop Recycling of Mixed Plastics of Polyester and CO 2 ‐Based Polycarbonate to a Single Monomer

Shi, Changxia; Diment, Wilfred T.; Chen, Eugene Y. ‐X.

doi:10.1002/anie.202405083

Title: Closed‐Loop Recycling of Mixed Plastics of Polyester and CO ₂ ‐Based Polycarbonate to a Single Monomer

Journal Article · 23 July 2024 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.202405083 · OSTI ID:2429112

Shi, Changxia ^[1]; Diment, Wilfred T. ^[1];

^[1]

Department of Chemistry Colorado State University Fort Collins Colorado 80523-1872 United States

Abstract Physical blending is an effective strategy for tailoring polymeric materials to specific application requirements. However, physically blended mixed plastics waste adds additional barriers in mechanical or chemical recycling. This difficulty arises from the intricate requirement for meticulous sorting and separation of the various polymers in the inherent incompatibility of mixed polymers during recycling. To overcome this impediment, this work furthers the emerging single‐monomer – multiple‐materials approach through the design of a bifunctional monomer that can not only orthogonally polymerize into two different types of polymers – specifically lactone‐based polyester and CO ₂ ‐based polycarbonate – but the resultant polymers and their mixture can also be depolymerized back to the single, original monomer when facilitated by catalysis. Specifically, the lactone/epoxide hybrid bifunctional monomer (BiL ^O ) undergoes ring‐opening polymerization through the lactone manifold to produce polyester, PE(BiL ^O ), and is also applied to ring‐opening copolymerization with CO ₂ , via the epoxide manifold, to yield polycarbonate, PC(BiL ^O ). Remarkably, a one‐pot recycling process of a BiL ^O ‐derived PE/PC blend back to the constituent monomer BiL ^O in >99 % selectivity was achieved with a superbase catalyst at 150 °C, thereby effectively obviating the requirement for sorting and separation typically required for recycling of mixed polymers.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: AC36-08GO28308

OSTI ID:: 2429112

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 34 Vol. 63; ISSN 1433-7851

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

Country of Publication:: Germany

Language:: English

References (70)

Thermodynamics and Kinetics of Ring-Opening Polymerization Duda, Andrzej; Kowalski, Adam Handbook of Ring‐Opening Polymerization https://doi.org/10.1002/9783527628407.ch1	book	January 2009
The Use of Carbon Dioxide (CO ₂ ) as a Building Block in Organic Synthesis from an Industrial Perspective Dabral, Saumya; Schaub, Thomas Advanced Synthesis & Catalysis, Vol. 361, Issue 2 https://doi.org/10.1002/adsc.201801215	journal	November 2018
Completely Recyclable Monomers and Polycarbonate: Approach to Sustainable Polymers Liu, Ye; Zhou, Hui; Guo, Jia-Zhi Angewandte Chemie International Edition, Vol. 56, Issue 17 https://doi.org/10.1002/anie.201701438	journal	March 2017
Beyond Mechanical Recycling: Giving New Life to Plastic Waste Vollmer, Ina; Jenks, Michael J. F.; Roelands, Mark C. P. Angewandte Chemie International Edition, Vol. 59, Issue 36 https://doi.org/10.1002/anie.201915651	journal	June 2020
Chemical Recycling of Poly(Cyclohexene Carbonate) Using a Di‐Mg^II Catalyst Singer, Frances N.; Deacy, Arron C.; McGuire, Thomas M. Angewandte Chemie International Edition, Vol. 61, Issue 26 https://doi.org/10.1002/anie.202201785	journal	May 2022
Efficient and Selective Chemical Recycling of CO ₂ ‐Based Alicyclic Polycarbonates via Catalytic Pyrolysis Yu, Yan; Gao, Bang; Liu, Ye Angewandte Chemie International Edition, Vol. 61, Issue 34 https://doi.org/10.1002/anie.202204492	journal	July 2022
Highly Selective Preparation and Depolymerization of Chemically Recyclable Poly(cyclopentene carbonate) Enabled by Organoboron Catalysts Yang, Guan‐Wen; Wang, Yuhui; Qi, Huan Angewandte Chemie International Edition, Vol. 61, Issue 46 https://doi.org/10.1002/anie.202210243	journal	October 2022
Mechanochemical Degradation and Recycling of Synthetic Polymers Zhou, Junfeng; Hsu, Tze‐Gang; Wang, Junpeng Angewandte Chemie International Edition, Vol. 62, Issue 27 https://doi.org/10.1002/anie.202300768	journal	April 2023
Hybrid Monomer Design Synergizing Property Trade‐offs in Developing Polymers for Circularity and Performance Shi, Changxia; Reilly, Liam T.; Chen, Eugene Y. ‐X. Angewandte Chemie International Edition, Vol. 62, Issue 31 https://doi.org/10.1002/anie.202301850	journal	May 2023
Learning Nature: Recyclable Monomers and Polymers Lu, Xiao-Bing; Liu, Ye; Zhou, Hui Chemistry - A European Journal, Vol. 24, Issue 44 https://doi.org/10.1002/chem.201704461	journal	June 2018
Emerging Trends in Closed‐Loop Recycling Polymers: Monomer Design and Catalytic Bulk Depolymerization Liu, Ye; Lu, Xiao‐Bing Chemistry – A European Journal, Vol. 29, Issue 23 https://doi.org/10.1002/chem.202203635	journal	February 2023
Update and Challenges in Carbon Dioxide‐Based Polycarbonate Synthesis Huang, Jin; Worch, Joshua C.; Dove, Andrew P. ChemSusChem, Vol. 13, Issue 3 https://doi.org/10.1002/cssc.201902719	journal	January 2020
Endowing Polythioester Vitrimer with Intrinsic Crystallinity and Chemical Recyclability Shi, Changxia; Zhang, Zhen; Scoti, Miriam ChemSusChem, Vol. 16, Issue 8 https://doi.org/10.1002/cssc.202300008	journal	March 2023
Mechanical Recycling of Packaging Plastics: A Review Schyns, Zoé O. G.; Shaver, Michael P. Macromolecular Rapid Communications, Vol. 42, Issue 3 https://doi.org/10.1002/marc.202000415	journal	September 2020
Toward Infinitely Recyclable Plastics Derived from Renewable Cyclic Esters Tang, Xiaoyan; Chen, Eugene Y. -X. Chem, Vol. 5, Issue 2 https://doi.org/10.1016/j.chempr.2018.10.011	journal	February 2019
Hybrid monomer design for unifying conflicting polymerizability, recyclability, and performance properties Shi, Changxia; Li, Zi-Chen; Caporaso, Lucia Chem, Vol. 7, Issue 3 https://doi.org/10.1016/j.chempr.2021.02.003	journal	March 2021
Design principles for intrinsically circular polymers with tunable properties Shi, Changxia; Reilly, Liam T.; Phani Kumar, V. Sai Chem, Vol. 7, Issue 11 https://doi.org/10.1016/j.chempr.2021.10.004	journal	November 2021
Catalytic strategies for upvaluing plastic wastes Zhang, Mei-Qi; Wang, Meng; Sun, Bo Chem, Vol. 8, Issue 11 https://doi.org/10.1016/j.chempr.2022.08.004	journal	November 2022
Mono-material product design with bio-based, circular, and biodegradable polymers Quinn, Ethan C.; Knauer, Katrina M.; Beckham, Gregg T. One Earth, Vol. 6, Issue 6 https://doi.org/10.1016/j.oneear.2023.05.019	journal	June 2023
Mechanical recycling: Compatibilization of mixed thermoplastic wastes Maris, Joachim; Bourdon, Sylvie; Brossard, Jean-Michel Polymer Degradation and Stability, Vol. 147 https://doi.org/10.1016/j.polymdegradstab.2017.11.001	journal	January 2018
Comments on the depolymerization of polycarbonates derived from epoxides and carbon dioxide: A mini review Darensbourg, Donald J. Polymer Degradation and Stability, Vol. 149 https://doi.org/10.1016/j.polymdegradstab.2018.01.019	journal	March 2018
Future Directions for Sustainable Polymers Hong, Miao; Chen, Eugene Y. -X. Trends in Chemistry, Vol. 1, Issue 2 https://doi.org/10.1016/j.trechm.2019.03.004	journal	May 2019
Advances in the Synthesis of Copolymers from Carbon Dioxide, Dienes, and Olefins Tang, Shan; Nozaki, Kyoko Accounts of Chemical Research, Vol. 55, Issue 11 https://doi.org/10.1021/acs.accounts.2c00162	journal	May 2022
Defining the Macromolecules of Tomorrow through Synergistic Sustainable Polymer Research Haque, Farihah M.; Ishibashi, Jacob S. A.; Lidston, Claire A. L. Chemical Reviews, Vol. 122, Issue 6 https://doi.org/10.1021/acs.chemrev.1c00173	journal	February 2022
Sustainable Conversion of Carbon Dioxide: An Integrated Review of Catalysis and Life Cycle Assessment Artz, Jens; Müller, Thomas E.; Thenert, Katharina Chemical Reviews, Vol. 118, Issue 2 https://doi.org/10.1021/acs.chemrev.7b00435	journal	December 2017
Tough and Thermally Recyclable Semiaromatic Polyesters by Ring-Opening Polymerization of Benzo-thia-caprolactones Li, Ling-Gao; Wang, Qi-Yuan; Zheng, Qiu-Yang Macromolecules, Vol. 54, Issue 14 https://doi.org/10.1021/acs.macromol.1c00497	journal	July 2021
Current Challenges and Perspectives in CO₂-Based Polymers Liu, Ye; Lu, Xiao-Bing Macromolecules, Vol. 56, Issue 5 https://doi.org/10.1021/acs.macromol.2c02483	journal	February 2023
Why is Recycling of Postconsumer Plastics so Challenging? Vogt, Bryan D.; Stokes, Kristoffer K.; Kumar, Sanat K. ACS Applied Polymer Materials, Vol. 3, Issue 9 https://doi.org/10.1021/acsapm.1c00648	journal	August 2021
Chemical Synthesis of CO₂-Based Polymers with Enhanced Thermal Stability and Unexpected Recyclability from Biosourced Monomers Yu, Yan; Fang, Li-Ming; Liu, Ye ACS Catalysis, Vol. 11, Issue 13 https://doi.org/10.1021/acscatal.1c01376	journal	June 2021
Unique Base-Initiated Depolymerization of Limonene-Derived Polycarbonates Li, Chunliang; Sablong, Rafaël J.; van Benthem, Rolf A. T. M. ACS Macro Letters, Vol. 6, Issue 7 https://doi.org/10.1021/acsmacrolett.7b00310	journal	June 2017
CO ₂ Copolymers from Epoxides: Catalyst Activity, Product Selectivity, and Stereochemistry Control Lu, Xiao-Bing; Ren, Wei-Min; Wu, Guang-Peng Accounts of Chemical Research, Vol. 45, Issue 10 https://doi.org/10.1021/ar300035z	journal	August 2012
Making Plastics from Carbon Dioxide: Salen Metal Complexes as Catalysts for the Production of Polycarbonates from Epoxides and CO ₂ Darensbourg, Donald J. Chemical Reviews, Vol. 107, Issue 6 https://doi.org/10.1021/cr068363q	journal	June 2007
Catalysis for the Valorization of Exhaust Carbon: from CO ₂ to Chemicals, Materials, and Fuels. Technological Use of CO ₂ Aresta, Michele; Dibenedetto, Angela; Angelini, Antonella Chemical Reviews, Vol. 114, Issue 3 https://doi.org/10.1021/cr4002758	journal	November 2013
Stereoselective Epoxide Polymerization and Copolymerization Childers, M. Ian; Longo, Julie M.; Van Zee, Nathan J. Chemical Reviews, Vol. 114, Issue 16 https://doi.org/10.1021/cr400725x	journal	July 2014
The Reaction Mechanism for the Organocatalytic Ring-Opening Polymerization of l -Lactide Using a Guanidine-Based Catalyst: Hydrogen-Bonded or Covalently Bound? Chuma, Anthony; Horn, Hans W.; Swope, William C. Journal of the American Chemical Society, Vol. 130, Issue 21 https://doi.org/10.1021/ja0764411	journal	May 2008
Closing the “One Monomer–Two Polymers–One Monomer” Loop via Orthogonal (De)polymerization of a Lactone/Olefin Hybrid Shi, Changxia; Clarke, Ryan W.; McGraw, Michael L. Journal of the American Chemical Society, Vol. 144, Issue 5 https://doi.org/10.1021/jacs.1c12278	journal	January 2022
Redesigned Hybrid Nylons with Optical Clarity and Chemical Recyclability Cywar, Robin M.; Rorrer, Nicholas A.; Mayes, Heather B. Journal of the American Chemical Society, Vol. 144, Issue 12 https://doi.org/10.1021/jacs.1c12611	journal	March 2022
Solid-State Chemical Recycling of Polycarbonates to Epoxides and Carbon Dioxide Using a Heterodinuclear Mg(II)Co(II) Catalyst McGuire, Thomas M.; Deacy, Arron C.; Buchard, Antoine Journal of the American Chemical Society, Vol. 144, Issue 40 https://doi.org/10.1021/jacs.2c06937	journal	September 2022
Tough while Recyclable Plastics Enabled by Monothiodilactone Monomers Wang, Yanchao; Zhu, Yinuo; Lv, Wenxiu Journal of the American Chemical Society, Vol. 145, Issue 3 https://doi.org/10.1021/jacs.2c11502	journal	January 2023
Catalytic Chemical Recycling of Post-Consumer Polyethylene Arroyave, Alejandra; Cui, Shilin; Lopez, Jaqueline C. Journal of the American Chemical Society, Vol. 144, Issue 51 https://doi.org/10.1021/jacs.2c11949	journal	December 2022
Reversed Controlled Polymerization (RCP): Depolymerization from Well-Defined Polymers to Monomers Jones, Glen R.; Wang, Hyun Suk; Parkatzidis, Kostas Journal of the American Chemical Society, Vol. 145, Issue 18 https://doi.org/10.1021/jacs.3c00589	journal	May 2023
The Quest for Converting Biorenewable Bifunctional α-Methylene-γ-butyrolactone into Degradable and Recyclable Polyester: Controlling Vinyl-Addition/Ring-Opening/Cross-Linking Pathways Tang, Xiaoyan; Hong, Miao; Falivene, Laura Journal of the American Chemical Society, Vol. 138, Issue 43 https://doi.org/10.1021/jacs.6b07974	journal	October 2016
4-Hydroxyproline-Derived Sustainable Polythioesters: Controlled Ring-Opening Polymerization, Complete Recyclability, and Facile Functionalization Yuan, Jingsong; Xiong, Wei; Zhou, Xuhao Journal of the American Chemical Society, Vol. 141, Issue 12 https://doi.org/10.1021/jacs.9b00031	journal	March 2019
Enol Ethers Are Effective Monomers for Ring-Opening Metathesis Polymerization: Synthesis of Degradable and Depolymerizable Poly(2,3-dihydrofuran) Feist, John D.; Xia, Yan Journal of the American Chemical Society, Vol. 142, Issue 3 https://doi.org/10.1021/jacs.9b11834	journal	December 2019
A total synthesis of N-acetylactinobolamine Askin, David; Angst, Christof; Danishefsky, Samuel The Journal of Organic Chemistry, Vol. 50, Issue 24 https://doi.org/10.1021/jo00224a082	journal	November 1985
Depolymerization of Polycarbonates Derived from Carbon Dioxide and Epoxides to Provide Cyclic Carbonates. A Kinetic Study Darensbourg, Donald J.; Wei, Sheng-Hsuan Macromolecules, Vol. 45, Issue 15 https://doi.org/10.1021/ma301110c	journal	July 2012
An Efficient Method of Depolymerization of Poly(cyclopentene carbonate) to Its Comonomers: Cyclopentene Oxide and Carbon Dioxide Darensbourg, Donald J.; Wei, Sheng-Hsuan; Yeung, Andrew D. Macromolecules, Vol. 46, Issue 15 https://doi.org/10.1021/ma401286x	journal	July 2013
Completely recyclable biopolymers with linear and cyclic topologies via ring-opening polymerization of γ-butyrolactone Hong, Miao; Chen, Eugene Y. -X. Nature Chemistry, Vol. 8, Issue 1 https://doi.org/10.1038/nchem.2391	journal	November 2015
Olefin metathesis-based chemically recyclable polymers enabled by fused-ring monomers Sathe, Devavrat; Zhou, Junfeng; Chen, Hanlin Nature Chemistry, Vol. 13, Issue 8 https://doi.org/10.1038/s41557-021-00748-5	journal	July 2021
Chemical recycling of waste plastics for new materials production Rahimi, AliReza; García, Jeannette M. Nature Reviews Chemistry, Vol. 1, Issue 6 https://doi.org/10.1038/s41570-017-0046	journal	June 2017
Chemical recycling to monomer for an ideal, circular polymer economy Coates, Geoffrey W.; Getzler, Yutan D. Y. L. Nature Reviews Materials, Vol. 5, Issue 7 https://doi.org/10.1038/s41578-020-0190-4	journal	April 2020
Closed-loop recycling of polyethylene-like materials Häußler, Manuel; Eck, Marcel; Rothauer, Dario Nature, Vol. 590, Issue 7846 https://doi.org/10.1038/s41586-020-03149-9	journal	February 2021
Critical advances and future opportunities in upcycling commodity polymers Jehanno, Coralie; Alty, Jill W.; Roosen, Martijn Nature, Vol. 603, Issue 7903 https://doi.org/10.1038/s41586-021-04350-0	journal	March 2022
Dynamic crosslinking compatibilizes immiscible mixed plastics Clarke, Ryan W.; Sandmeier, Tobias; Franklin, Kevin A. Nature, Vol. 616, Issue 7958 https://doi.org/10.1038/s41586-023-05858-3	journal	April 2023
Chemically recyclable polymers: a circular economy approach to sustainability Hong, Miao; Chen, Eugene Y. -X. Green Chemistry, Vol. 19, Issue 16 https://doi.org/10.1039/C7GC01496A	journal	January 2017
Chemically recyclable polymer materials: polymerization and depolymerization cycles Xu, Guangqiang; Wang, Qinggang Green Chemistry, Vol. 24, Issue 6 https://doi.org/10.1039/D1GC03901F	journal	January 2022
A sustainable approach for the synthesis of recyclable cyclic CO₂-based polycarbonates Liao, Xi; Cui, Feng-Chao; He, Jiang-Hua Chemical Science, Vol. 13, Issue 21 https://doi.org/10.1039/D2SC01387H	journal	January 2022
Chain end-group selectivity using an organometallic Al(iii)/K(i) ring-opening copolymerization catalyst delivers high molar mass, monodisperse polyesters Diment, Wilfred T.; Williams, Charlotte K. Chemical Science, Vol. 13, Issue 29 https://doi.org/10.1039/D2SC02752F	journal	January 2022
Base initiated depolymerization of polycarbonates to epoxide and carbon dioxide co-monomers: a computational study Darensbourg, Donald J.; Yeung, Andrew D.; Wei, Sheng-Hsuan Green Chemistry, Vol. 15, Issue 6 https://doi.org/10.1039/c3gc40475g	journal	January 2013
Alternating copolymerization of dihydrocoumarin and epoxides catalyzed by chromium salen complexes: a new route to functional polyesters Van Zee, Nathan J.; Coates, Geoffrey W. Chemical Communications, Vol. 50, Issue 48 https://doi.org/10.1039/c4cc01566e	journal	January 2014
High-performance pan-tactic polythioesters with intrinsic crystallinity and chemical recyclability Shi, Changxia; McGraw, Michael L.; Li, Zi-Chen Science Advances, Vol. 6, Issue 34 https://doi.org/10.1126/sciadv.abc0495	journal	August 2020
Combining polyethylene and polypropylene: Enhanced performance with PE/ i PP multiblock polymers Eagan, James M.; Xu, Jun; Di Girolamo, Rocco Science, Vol. 355, Issue 6327 https://doi.org/10.1126/science.aah5744	journal	February 2017
A synthetic polymer system with repeatable chemical recyclability Zhu, Jian-Bo; Watson, Eli M.; Tang, Jing Science, Vol. 360, Issue 6387 https://doi.org/10.1126/science.aar5498	journal	April 2018
Polyethylene upcycling to long-chain alkylaromatics by tandem hydrogenolysis/aromatization Zhang, Fan; Zeng, Manhao; Yappert, Ryan D. Science, Vol. 370, Issue 6515 https://doi.org/10.1126/science.abc5441	journal	October 2020
Toward polymer upcycling—adding value and tackling circularity Korley, LaShanda T. J.; Epps, Thomas H.; Helms, Brett A. Science, Vol. 373, Issue 6550 https://doi.org/10.1126/science.abg4503	journal	July 2021
Chemically recyclable thermoplastics from reversible-deactivation polymerization of cyclic acetals Abel, Brooks A.; Snyder, Rachel L.; Coates, Geoffrey W. Science, Vol. 373, Issue 6556 https://doi.org/10.1126/science.abh0626	journal	August 2021
Mixed plastics waste valorization through tandem chemical oxidation and biological funneling Sullivan, Kevin P.; Werner, Allison Z.; Ramirez, Kelsey J. Science, Vol. 378, Issue 6616 https://doi.org/10.1126/science.abo4626	journal	October 2022
Catalytic deconstruction of waste polyethylene with ethylene to form propylene Conk, Richard J.; Hanna, Steven; Shi, Jake X. Science, Vol. 377, Issue 6614 https://doi.org/10.1126/science.add1088	journal	September 2022
Chemically circular, mechanically tough, and melt-processable polyhydroxyalkanoates Zhou, Li; Zhang, Zhen; Shi, Changxia Science, Vol. 380, Issue 6640 https://doi.org/10.1126/science.adg4520	journal	April 2023
Chemically recyclable polyolefin-like multiblock polymers Zhao, Yucheng; Rettner, Emma M.; Harry, Katherine L. Science, Vol. 382, Issue 6668 https://doi.org/10.1126/science.adh3353	journal	October 2023

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