Upcycling Polynorbornene Derivatives into Chemically Recyclable Multiblock Linear and Thermoset Plastics

Liu, Kun; Battson, Megan E.; Hu, Zhitao; Zhao, Yucheng; Rettner, Emma M.; Miscall, Joel; Rorrer, Nicholas A.; Miyake, Garret M.

doi:10.1002/anie.202423111

Upcycling Polynorbornene Derivatives into Chemically Recyclable Multiblock Linear and Thermoset Plastics

Journal Article · Fri Jan 17 00:00:00 EST 2025 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202423111· OSTI ID:2526223

Liu, Kun ^[1]; Battson, Megan E. ^[1]; Hu, Zhitao ^[1]; Zhao, Yucheng ^[1]; Rettner, Emma M. ^[1]; Miscall, Joel ^[2]; ^[2]; ^[1]

Colorado State Univ., Fort Collins, CO (United States)
National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Synthetic polymers have found widespread use, but their ineffective end-of-life treatment is causing a significant environmental and human health crisis. Here, we demonstrate the upcycling of polynorbornene derivatives (pNBEs) through their deconstruction into distinct oligomeric buildings blocks that can be repolymerized into chemically recyclable pNBEs-like multiblock polymers via dehydrogenative polymerization. The resulting materials exhibit diverse mechanical properties, while integrating high melting temperatures (T_m as high as 133 °C). Notably, this method could also enable the selective deconstruction of permanently cross-linked polydicyclopentadiene (pDCPD) thermosets into telechelic-OH functionalized oligomers, overcoming the significant challenges posed by their robust network structure in recycling and degradation. The resulting pDCPD oligomers can subsequently be repolymerized with macrodiols to create multiblock thermosets with tunable mechanical properties, including Young's modulus and tensile elongation. After use, upcycled plastics could be effectively deconstructed back to the oligomers for recovery and repolymerization. Overall, this work establishes an approach that can be utilized to upcycle pNBEs into previously inaccessible multiblock thermosets and thermoplastics with full recyclability, and may be generalizable to a range of polymers to shift their end-of-life waste disposal toward sustainable recovery and reuse.

View Accepted Manuscript (DOE)

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

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

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

OSTI ID:: 2526223

Report Number(s):: NREL/JA--2800-93561

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 14 Vol. 64; ISSN 1521-3773; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (67)

Conversion of Waste Plastics into Value‐Added Carbonaceous Fuels under Mild Conditions Jiao, Xingchen; Zheng, Kai; Hu, Zexun Advanced Materials, Vol. 33, Issue 50 https://doi.org/10.1002/adma.202005192	journal	April 2021
Reprocessability in Engineering Thermosets Achieved Through Frontal Ring‐Opening Metathesis Polymerization Cooper, Julian C.; Paul, Justine E.; Ramlawi, Nabil Advanced Materials https://doi.org/10.1002/adma.202402627	journal	May 2024
Monofunctional Metathesis Polymers via Sacrificial Diblock Copolymers Hilf, Stefan; Berger‐Nicoletti, Elena; Grubbs, Robert H. Angewandte Chemie International Edition, Vol. 45, Issue 47 https://doi.org/10.1002/anie.200602323	journal	November 2006
C−H Functionalization of Commodity Polymers Williamson, Jill B.; Lewis, Sally E.; Johnson, Robert R. Angewandte Chemie International Edition, Vol. 58, Issue 26 https://doi.org/10.1002/anie.201810970	journal	June 2019
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
Overcoming the Low Driving Force in Forming Depolymerizable Polymers through Monomer Isomerization Chen, Hanlin; Shi, Zhen; Hsu, Tze‐Gang Angewandte Chemie International Edition, Vol. 60, Issue 48 https://doi.org/10.1002/anie.202111181	journal	October 2021
Catalytic Living Ring‐Opening Metathesis Polymerization Using Vinyl Ethers as Effective Chain‐Transfer Agents Mandal, Ankita; Mandal, Indradip; Kilbinger, Andreas F. M. Angewandte Chemie International Edition, Vol. 62, Issue 4 https://doi.org/10.1002/anie.202211842	journal	December 2022
Living Alternating Ring‐Opening Metathesis Copolymerization of 2,3‐Dihydrofuran to Provide Completely Degradable Polymers An, Taeyang; Ryu, Hanseul; Choi, Tae‐Lim Angewandte Chemie International Edition, Vol. 62, Issue 47 https://doi.org/10.1002/anie.202309632	journal	October 2023
Recent Progress in the Chemical Upcycling of Plastic Wastes Chen, Xi; Wang, Yudi; Zhang, Lei ChemSusChem https://doi.org/10.1002/cssc.202100868	journal	June 2021
Metathetic Selective Degradation of Polyisoprene: Low-Molecular-Weight Telechelic Oligomer Obtained from Both Synthetic and Natural Rubber Solanky, Shailendra Singh; Campistron, Irène; Laguerre, Albert Macromolecular Chemistry and Physics, Vol. 206, Issue 10 https://doi.org/10.1002/macp.200400416	journal	May 2005
Degradable precision polynorbornenes via ring-opening metathesis polymerization Moatsou, Dafni; Nagarkar, Amit; Kilbinger, Andreas F. M. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 54, Issue 9 https://doi.org/10.1002/pola.27964	journal	November 2015
Optimization and analysis of reaction injection molding of polydicyclopentadiene using response surface methodology Kim, Hyeon-Gook; Son, Hye Jeong; Lee, Dong-Koo Korean Journal of Chemical Engineering, Vol. 34, Issue 7 https://doi.org/10.1007/s11814-017-0102-5	journal	May 2017
Catalytic processing of plastic waste on the rise Martín, Antonio J.; Mondelli, Cecilia; Jaydev, Shibashish D. Chem, Vol. 7, Issue 6 https://doi.org/10.1016/j.chempr.2020.12.006	journal	June 2021
Combining Reclaimed PET with Bio-based Monomers Enables Plastics Upcycling Rorrer, Nicholas A.; Nicholson, Scott; Carpenter, Alberta Joule, Vol. 3, Issue 4 https://doi.org/10.1016/j.joule.2019.01.018	journal	April 2019
Synthesis and characterization of hydrogenated poly(norbornene endo-dicarboximide)s prepared by ring opening metathesis polymerization Yoon, Kyung-Hwan; Kim, Kyung Oh; Schaefer, Mark Polymer, Vol. 53, Issue 11 https://doi.org/10.1016/j.polymer.2012.02.047	journal	May 2012
Olefin polymer technologies—History and recent progress at The Dow Chemical Company Chum, P. Steve; Swogger, Kurt W. Progress in Polymer Science, Vol. 33, Issue 8 https://doi.org/10.1016/j.progpolymsci.2008.05.003	journal	August 2008
Degradable polymers via olefin metathesis polymerization Sun, Hao; Liang, Yifei; Thompson, Matthew P. Progress in Polymer Science, Vol. 120 https://doi.org/10.1016/j.progpolymsci.2021.101427	journal	September 2021
Heteroatom-containing degradable polymers by ring-opening metathesis polymerization Xu, Jiaxi; Hadjichristidis, Nikos Progress in Polymer Science, Vol. 139 https://doi.org/10.1016/j.progpolymsci.2023.101656	journal	April 2023
Mechanical and chemical recycling of solid plastic waste Ragaert, Kim; Delva, Laurens; Van Geem, Kevin Waste Management, Vol. 69 https://doi.org/10.1016/j.wasman.2017.07.044	journal	November 2017
Frontal Polymerization of Dihydrofuran Comonomer Facilitates Thermoset Deconstruction Davydovich, Oleg; Paul, Justine E.; Feist, John David Chemistry of Materials, Vol. 34, Issue 19 https://doi.org/10.1021/acs.chemmater.2c02045	journal	September 2022
Deconstruction of Polymers through Olefin Metathesis Sathe, Devavrat; Yoon, Seiyoung; Wang, Zeyu Chemical Reviews, Vol. 124, Issue 11 https://doi.org/10.1021/acs.chemrev.3c00748	journal	May 2024
50th Anniversary Perspective : Polymer Functionalization Blasco, Eva; Sims, Michael B.; Goldmann, Anja S. Macromolecules, Vol. 50, Issue 14 https://doi.org/10.1021/acs.macromol.7b00465	journal	June 2017
Efficient Manufacture, Deconstruction, and Upcycling of High-Performance Thermosets and Composites Lloyd, Evan M.; Cooper, Julian C.; Shieh, Peyton ACS Applied Engineering Materials, Vol. 1, Issue 1 https://doi.org/10.1021/acsaenm.2c00115	journal	November 2022
A Model Ensemble Approach Enables Data-Driven Property Prediction for Chemically Deconstructable Thermosets in the Low-Data Regime AlFaraj, Yasmeen S.; Mohapatra, Somesh; Shieh, Peyton ACS Central Science, Vol. 9, Issue 9 https://doi.org/10.1021/acscentsci.3c00502	journal	September 2023
Degradable Polyphosphoramidate via Ring-Opening Metathesis Polymerization Liang, Yifei; Sun, Hao; Cao, Wei ACS Macro Letters, Vol. 9, Issue 10 https://doi.org/10.1021/acsmacrolett.0c00401	journal	September 2020
Tandem ROMP/Hydrogenation Approach to Hydroxy-Telechelic Linear Polyethylene Sample, Caitlin S.; Kellstedt, Elizabeth A.; Hillmyer, Marc A. ACS Macro Letters, Vol. 11, Issue 5 https://doi.org/10.1021/acsmacrolett.2c00144	journal	April 2022
Catalytic Living ROMP: Synthesis of Degradable Star Polymers Mandal, Ankita; Kilbinger, Andreas F. M. ACS Macro Letters, Vol. 12, Issue 10 https://doi.org/10.1021/acsmacrolett.3c00441	journal	September 2023
Well-Defined and Precision-Grafted Bottlebrush Polypentenamers from Variable Temperature ROMP and ATRP Neary, William J.; Fultz, Brandon A.; Kennemur, Justin G. ACS Macro Letters, Vol. 7, Issue 9 https://doi.org/10.1021/acsmacrolett.8b00576	journal	August 2018
Peptides Displayed as High Density Brush Polymers Resist Proteolysis and Retain Bioactivity Blum, Angela P.; Kammeyer, Jacquelin K.; Yin, Jian Journal of the American Chemical Society, Vol. 136, Issue 43 https://doi.org/10.1021/ja5088216	journal	October 2014
Efficient Synthesis of Narrowly Dispersed Brush Copolymers and Study of Their Assemblies: The Importance of Side Chain Arrangement Xia, Yan; Olsen, Bradley D.; Kornfield, Julia A. Journal of the American Chemical Society, Vol. 131, Issue 51, p. 18525-18532 https://doi.org/10.1021/ja908379q	journal	December 2009
Backbone-Photodegradable Polymers by Incorporating Acylsilane Monomers via Ring-Opening Metathesis Polymerization Huang, Banruo; Wei, Mufeng; Vargo, Emma Journal of the American Chemical Society, Vol. 143, Issue 43 https://doi.org/10.1021/jacs.1c06836	journal	October 2021
The Fluorocarbene Exploit: Enforcing Alternation in Ring-Opening Metathesis Polymerization Tashiro, Kaoru; Akiyama, Midori; Kashiwagi, Kimiaki Journal of the American Chemical Society, Vol. 145, Issue 5 https://doi.org/10.1021/jacs.2c11373	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
Chemically Recyclable Linear and Branched Polyethylenes Synthesized from Stoichiometrically Self-Balanced Telechelic Polyethylenes Jang, Yoon-Jung; Nguyen, Sam; Hillmyer, Marc A. Journal of the American Chemical Society, Vol. 146, Issue 7 https://doi.org/10.1021/jacs.3c12660	journal	February 2024
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
ROMP Reactivity of e ndo - and e xo -Dicyclopentadiene Rule, Joseph D.; Moore, Jeffrey S. Macromolecules, Vol. 35, Issue 21 https://doi.org/10.1021/ma0209489	journal	October 2002
Hydrogenated Ring-Opened Polynorbornene: A Highly Crystalline Atactic Polymer Lee, Li-Bong W.; Register, Richard A. Macromolecules, Vol. 38, Issue 4 https://doi.org/10.1021/ma048013a	journal	February 2005
Thiol-functionalized ROMP polymers via Sacrificial Synthesis Hilf, Stefan; Kilbinger, Andreas F. M. Macromolecules, Vol. 42, Issue 12 https://doi.org/10.1021/ma900036c	journal	May 2009
Solvent-Free Olefin Metathesis Depolymerization of 1,4-Polybutadiene Watson, Mark D.; Wagener, Kenneth B. Macromolecules, Vol. 33, Issue 5 https://doi.org/10.1021/ma991560p	journal	March 2000
Circular olefin copolymers made de novo from ethylene and α-olefins Han, Xing-Wang; Zhang, Xun; Zhou, Youyun Nature Communications, Vol. 15, Issue 1 https://doi.org/10.1038/s41467-024-45219-w	journal	February 2024
Tailored silyl ether monomers enable backbone-degradable polynorbornene-based linear, bottlebrush and star copolymers through ROMP Shieh, Peyton; Nguyen, Hung V. -T.; Johnson, Jeremiah A. Nature Chemistry, Vol. 11, Issue 12 https://doi.org/10.1038/s41557-019-0352-4	journal	October 2019
A versatile approach for the synthesis of degradable polymers via controlled ring-opening metathesis copolymerization Feist, John D.; Lee, Daniel C.; Xia, Yan Nature Chemistry, Vol. 14, Issue 1 https://doi.org/10.1038/s41557-021-00810-2	journal	November 2021
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
Cleavable comonomers enable degradable, recyclable thermoset plastics Shieh, Peyton; Zhang, Wenxu; Husted, Keith E. L. Nature, Vol. 583, Issue 7817 https://doi.org/10.1038/s41586-020-2495-2	journal	July 2020
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
Ethylene glycol as an efficient and reversible liquid-organic hydrogen carrier Zou, You-Quan; von Wolff, Niklas; Anaby, Aviel Nature Catalysis, Vol. 2, Issue 5 https://doi.org/10.1038/s41929-019-0265-z	journal	April 2019
Chemical and biological catalysis for plastics recycling and upcycling Ellis, Lucas D.; Rorrer, Nicholas A.; Sullivan, Kevin P. Nature Catalysis, Vol. 4, Issue 7 https://doi.org/10.1038/s41929-021-00648-4	journal	July 2021
Cyclic–acyclic monomers metathesis polymerization for the synthesis of degradable thermosets, thermoplastics and elastomers Si, Guifu; Chen, Changle Nature Synthesis, Vol. 1, Issue 12 https://doi.org/10.1038/s44160-022-00163-9	journal	September 2022
Synthesis and characterization of anion-exchange membranes based on hydrogenated poly(norbornene) Price, S. C.; Ren, X.; Savage, A. M. Polymer Chemistry, Vol. 8, Issue 37 https://doi.org/10.1039/C7PY01084B	journal	January 2017
Oxadiazabicyclooctenone as a versatile monomer for the construction of pH sensitive functional polymers via ROMP Mallick, Asadulla; Xu, Yuan; Lin, Yichao Polymer Chemistry, Vol. 9, Issue 3 https://doi.org/10.1039/C7PY01413A	journal	January 2018
Ring-opening Metathesis Polymerisation derived poly(dicyclopentadiene) based materials Kovačič, Sebastijan; Slugovc, Christian Materials Chemistry Frontiers, Vol. 4, Issue 8 https://doi.org/10.1039/D0QM00296H	journal	January 2020
Melt polycondensation of carboxytelechelic polyethylene for the design of degradable segmented copolyester polyolefins Arrington, Anastasia S.; Brown, James R.; Win, Max S. Polymer Chemistry, Vol. 13, Issue 21 https://doi.org/10.1039/D2PY00394E	journal	January 2022
Insertion metathesis depolymerization Schulz, Michael D.; Ford, Rachel R.; Wagener, Kenneth B. Polymer Chemistry, Vol. 4, Issue 13 https://doi.org/10.1039/c3py00531c	journal	January 2013
Efficient and selective degradation of polyethylenes into liquid fuels and waxes under mild conditions Jia, Xiangqing; Qin, Chuan; Friedberger, Tobias Science Advances, Vol. 2, Issue 6 https://doi.org/10.1126/sciadv.1501591	journal	June 2016
Production, use, and fate of all plastics ever made Geyer, Roland; Jambeck, Jenna R.; Law, Kara Lavender Science Advances, Vol. 3, Issue 7 https://doi.org/10.1126/sciadv.1700782	journal	July 2017
The Convergence of Synthetic Organic and Polymer Chemistries Hawker, C. J. Science, Vol. 309, Issue 5738 https://doi.org/10.1126/science.1109778	journal	August 2005
Multiblock Polymers: Panacea or Pandora's Box? Bates, F. S.; Hillmyer, M. A.; Lodge, T. P. Science, Vol. 336, Issue 6080 https://doi.org/10.1126/science.1215368	journal	April 2012
The future of plastics recycling Garcia, Jeannette M.; Robertson, Megan L. Science, Vol. 358, Issue 6365 https://doi.org/10.1126/science.aaq0324	journal	November 2017
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
The global threat from plastic pollution MacLeod, Matthew; Arp, Hans Peter H.; Tekman, Mine B. Science, Vol. 373, Issue 6550 https://doi.org/10.1126/science.abg5433	journal	July 2021
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
Chemical upcycling of polyethylene, polypropylene, and mixtures to high-value surfactants Xu, Zhen; Munyaneza, Nuwayo Eric; Zhang, Qikun Science, Vol. 381, Issue 6658 https://doi.org/10.1126/science.adh0993	journal	August 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
Polyurethane elastomers based on Krasol LBH 3000 oligobutadienediol Medvedev, V. P. Polymer Science Series D, Vol. 6, Issue 2 https://doi.org/10.1134/S1995421213020068	journal	April 2013
7-Oxa-2,3-Diazanorbornene: A One-Step Accessible Monomer for Living Ring-Opening Metathesis Polymerization to Produce Backbone-Biodegradable Polymers Wang, Xiaoyang; Wen, Yixing; Wang, Yu CCS Chemistry, Vol. 6, Issue 9 https://doi.org/10.31635/ccschem.024.202303697	journal	September 2024
Cross-metathesis of polynorbornene with polyoctenamer: a kinetic study Denisova, Yulia I.; Gringolts, Maria L.; Peregudov, Alexander S. Beilstein Journal of Organic Chemistry, Vol. 11 https://doi.org/10.3762/bjoc.11.195	journal	October 2015

Similar Records

Chemically recyclable polyolefin-like multiblock polymers

Journal Article · Wed Oct 18 20:00:00 EDT 2023 · Science · OSTI ID:2205316

Cleavable Strand‐Fusing Cross‐Linkers as Additives for Chemically Deconstructable Thermosets with Preserved Thermomechanical Properties

Journal Article · Wed Mar 26 20:00:00 EDT 2025 · Angewandte Chemie · OSTI ID:2543100

Related Subjects

36 MATERIALS SCIENCE
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY,MATERIALS SCIENCE
pDCPD
synthetic polymers
upcycled plastics

Upcycling Polynorbornene Derivatives into Chemically Recyclable Multiblock Linear and Thermoset Plastics

Citation Formats

References (67)

Similar Records

Related Subjects