Chemically Recyclable Ester-Linked Polypropylene
Abstract
Polyolefins represent the largest class of commodity materials due to their excellent material properties; however, they have limited pathways to chemical recycling and are often difficult to mechanically recycle. Here we demonstrate a new catalyst for the isoselective copolymerization of propylene and butadiene capable of favoring 1,4-insertion over 1,2-insertion while maintaining good molecular weights and turnover frequencies. This isotactic propylene copolymer with main-chain unsaturation was depolymerized to a telechelic macromonomer using an olefin metathesis catalyst and 2-hydroxyethyl acrylate. After hydrogenation, the telechelic macromonomer was repolymerized to form an ester-linked polypropylene material. This polymer shows thermal and mechanical properties comparable to linear low-density polyethylene. Finally, the telechelic macromonomer could be regenerated through the depolymerization of the ester-linked polypropylene material, which allows for the chemical recycling to macromonomer. This process provides a route to transform partially unsaturated polyolefins to chemically recyclable materials with similar properties to their parent polymers.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
Cites
Production, use, and fate of all plastics ever made
Geyer, R., Jambeck, J. R., & Law, K. L. (2017) · Science Advances · doi:10.1126/sciadv.1700782 · Cited by 18,606 · see citing works
Efficient and Recyclable Monomeric and Dendritic Ru-Based Metathesis Catalysts
Garber, S. B., Kingsbury, J. S., Gray, B. L., & Hoveyda, A. H. (2000) · Journal of the American Chemical Society · doi:10.1021/ja001179g · Cited by 2,020 · see citing works
Evidence that the Great Pacific Garbage Patch is rapidly accumulating plastic
Lebreton, L., Slat, B., Ferrari, F., Sainte-Rose, B., Aitken, J., Marthouse, R., Hajbane, S., Cunsolo, S., Schwarz, A., Levivier, A., et al. (2018) · Scientific Reports · doi:10.1038/s41598-018-22939-w · Cited by 1,839 · see citing works
Evaluating scenarios toward zero plastic pollution
Lau, W. W. Y., Shiran, Y., Bailey, R. M., Cook, E., Stuchtey, M. R., Koskella, J., Velis, C. A., Godfrey, L., Boucher, J., Murphy, M. B., et al. (2020) · Science · doi:10.1126/science.aba9475 · Cited by 1,766 · see citing works
Mechanical Recycling of Packaging Plastics: A Review
Schyns, Z. O. G., & Shaver, M. P. (2020) · Macromolecular Rapid Communications · doi:10.1002/marc.202000415 · Cited by 1,709 · see citing works
Chemical recycling to monomer for an ideal, circular polymer economy
Coates, G. W., & Getzler, Y. D. Y. L. (2020) · Nature Reviews Materials · doi:10.1038/s41578-020-0190-4 · Cited by 1,644 · see citing works
Self-citationClosed-loop recycling of polyethylene-like materials
Häußler, M., Eck, M., Rothauer, D., & Mecking, S. (2021) · Nature · doi:10.1038/s41586-020-03149-9 · Cited by 753 · see citing works
Cleavable comonomers enable degradable, recyclable thermoset plastics
Shieh, P., Zhang, W., Husted, K. E. L., Kristufek, S. L., Xiong, B., Lundberg, D. J., Lem, J., Veysset, D., Sun, Y., Nelson, K. A., et al. (2020) · Nature · doi:10.1038/s41586-020-2495-2 · Cited by 498 · see citing works
Chemically recyclable thermoplastics from reversible-deactivation polymerization of cyclic acetals
Abel, B. A., Snyder, R. L., & Coates, G. W. (2021) · Science · doi:10.1126/science.abh0626 · Cited by 483 · see citing works
Self-citationCoordinative Chain Transfer Polymerization
Valente, A., Mortreux, A., Visseaux, M., & Zinck, P. (2013) · Chemical Reviews · doi:10.1021/cr300289z · Cited by 411 · see citing works
Stempfle, F., Ortmann, P., & Mecking, S. (2016) · Chemical Reviews · doi:10.1021/acs.chemrev.5b00705 · Cited by 397 · see citing works
Telechelic polymers by living and controlled/living polymerization methods
Taşdelen, M. A., Kahveci, M. U., & Yağcı, Y. (2010) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2010.10.002 · Cited by 395 · see citing works
Thermodynamics and Crystallization of Random Copolymers
Sanchez, I. C., & Eby, R. K. (1975) · Macromolecules · doi:10.1021/ma60047a012 · Cited by 288 · see citing works
How to Polymerize Ethylene in a Highly Controlled Fashion?
Kempe, R. (2007) · Chemistry - A European Journal · doi:10.1002/chem.200601842 · Cited by 281 · see citing works
100th Anniversary of Macromolecular Science Viewpoint: Redefining Sustainable Polymers
Fagnani, D. E., Tami, J. L., Copley, G., Clemons, M. N., Getzler, Y. D. Y. L., & McNeil, A. J. (2020) · ACS Macro Letters · doi:10.1021/acsmacrolett.0c00789 · Cited by 279 · see citing works
Recent Trends in Catalytic Polymerizations
Walsh, D. J., Hyatt, M. G., Miller, S. A., & Guironnet, D. (2019) · ACS Catalysis · doi:10.1021/acscatal.9b03226 · Cited by 258 · see citing works
Organocatalytic depolymerization of poly(ethylene terephthalate)
Fukushima, K., Coulembier, O., Lecuyer, J. M., Al‐Megren, H. A., Alabdulrahman, A. M., Alsewailem, F. D., McNeil, M., Dúbois, P., Waymouth, R. M., Horn, H. W., et al. (2011) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.24551 · Cited by 250 · see citing works
Enzyme-Catalyzed Ring-Opening Polymerization of ω-Pentadecalactone
Bisht, K. S., Henderson, L. A., Gross, R. A., Kaplan, D. L., & Swift, G. (1997) · Macromolecules · doi:10.1021/ma961869y · Cited by 186 · see citing works
Feist, J. D., Lee, D. C., & Xia, Y. P. (2021) · Nature Chemistry · doi:10.1038/s41557-021-00810-2 · Cited by 178 · see citing works
van der Meulen, I., Gubbels, E., Huijser, S., Sablong, R., Koning, C. E., Heise, A., & Duchateau, R. (2011) · Macromolecules · doi:10.1021/ma200685u · Cited by 140 · see citing works
Toward the Copolymerization of Propylene with Polar Comonomers
Luckham, S. L. J., & Nozaki, K. (2020) · Accounts of Chemical Research · doi:10.1021/acs.accounts.0c00628 · Cited by 131 · see citing works
Degradable polymers via olefin metathesis polymerization
Sun, H. R., Liang, Y., Thompson, M. P., & Gianneschi, N. C. (2021) · Progress in Polymer Science · doi:10.1016/j.progpolymsci.2021.101427 · Cited by 116 · see citing works
Hillmyer, M. A., & Grubbs, R. H. (1993) · Macromolecules · doi:10.1021/ma00056a051 · Cited by 113 · see citing works
Long-Spaced Aliphatic Polyesters
Ortmann, P., & Mecking, S. (2013) · Macromolecules · doi:10.1021/ma401305u · Cited by 111 · see citing works
Fraser, C. L., Hillmyer, M. A., Gutierrez, E., & Grubbs, R. H. (1995) · Macromolecules · doi:10.1021/ma00125a031 · Cited by 107 · see citing works
Acyclic diene metathesis (ADMET) polymerization: the synthesis of unsaturated polyesters
Patton, J. T., Boncella, J. M., & Wagener, K. B. (1992) · Macromolecules · doi:10.1021/ma00041a006 · Cited by 97 · see citing works
Aliphatic Long‐Chain C20 Polyesters from Olefin Metathesis
Trzaskowski, J., Quinzler, D., Bährle, C., & Mecking, S. (2011) · Macromolecular Rapid Communications · doi:10.1002/marc.201100319 · Cited by 96 · see citing works
Chemical Upcycling of Polyethylene to Value-Added α,ω-Divinyl-Functionalized Oligomers
Zeng, M., Lee, Y.-H., Strong, G., LaPointe, A. M., Kocen, A. L., Qu, Z., Coates, G. W., Scott, S. L., & Abu-Omar, M. M. (2021) · ACS Sustainable Chemistry & Engineering · doi:10.1021/acssuschemeng.1c05272 · Cited by 94 · see citing works
Self-citationHuang, B., Wei, M., Vargo, E., Qian, Y., Xu, T., & Toste, F. D. (2021) · Journal of the American Chemical Society · doi:10.1021/jacs.1c06836 · Cited by 93 · see citing works
Telechelic Polyethylene from Catalyzed Chain‐Growth Polymerization
German, I. M., Kelhifi, W., Norsic, S., Boisson, C., & D’Agosto, F. (2013) · Angewandte Chemie International Edition · doi:10.1002/anie.201208756 · Cited by 88 · see citing works
Yang, J., Wang, R.-H., Wang, Y.-X., et al. (2016) · Angewandte Chemie International Edition · doi:10.1002/anie.201607893 · Cited by 81 · see citing works
Hodge, P., & Kamau, S. D. (2003) · Angewandte Chemie International Edition · doi:10.1002/anie.200250842 · Cited by 79 · see citing works
Chang, C., & Emrick, T. S. (2014) · Macromolecules · doi:10.1021/ma500121a · Cited by 78 · see citing works
First Synthesis of Poly(ethene-<i>c</i><i>o</i>-1,3-butadiene) with Neodymocene Catalysts
Barbotin, F., Monteil, V., Llauro, M.-F., Boisson, C., & Spitz, R. (2000) · Macromolecules · doi:10.1021/ma0012043 · Cited by 77 · see citing works
Isotactic Poly(propylene oxide): A Photodegradable Polymer with Strain Hardening Properties
Lipinski, B. M., Morris, L. S., Silberstein, M. N., & Coates, G. W. (2020) · Journal of the American Chemical Society · doi:10.1021/jacs.0c01768 · Cited by 73 · see citing works
Self-citationWu, C., Liu, B., Lin, F., Wang, M., & Cui, D. (2017) · Angewandte Chemie International Edition · doi:10.1002/anie.201702128 · Cited by 67 · see citing works
Makio, H., Ochiai, T., Mohri, J.-I., Takeda, K., Shimazaki, T., Usui, Y., Matsuura, S., & Fujita, T. (2013) · Journal of the American Chemical Society · doi:10.1021/ja403626g · Cited by 65 · see citing works
Norsic, S., Thomas, C., D’Agosto, F., & Boisson, C. (2015) · Angewandte Chemie International Edition · doi:10.1002/anie.201411223 · Cited by 64 · see citing works
Chain Multiplication of Fatty Acids to Precise Telechelic Polyethylene
Witt, T., Häußler, M., Kulpa, S., & Mecking, S. (2017) · Angewandte Chemie International Edition · doi:10.1002/anie.201702796 · Cited by 61 · see citing works
Shah, T., Bhatty, J. I., Gamlen, G. A., & Dollimore, D. (1984) · Polymer · doi:10.1016/0032-3861(84)90386-0 · Cited by 60 · see citing works
Sawaguchi, T., Ikemura, T., & Senō, M. (1995) · Macromolecules · doi:10.1021/ma00128a001 · Cited by 60 · see citing works
Stereospecific Octahedral Group 4 Bis(phenolate) Ether Complexes for Olefin Polymerization
Kiesewetter, E. T., Randoll, S., Radlauer, M. R., et al. (2010) · Journal of the American Chemical Society · doi:10.1021/ja100627x · Cited by 58 · see citing works
Capacchione, C., Avagliano, A., & Proto, A. (2008) · Macromolecules · doi:10.1021/ma800864y · Cited by 51 · see citing works
Woodman, T. J., Sarazin, Y., Fink, G., Hauschild, K., & Bochmann, M. (2005) · Macromolecules · doi:10.1021/ma047454r · Cited by 50 · see citing works
Mathers, R. T., & Coates, G. W. (2004) · Chemical Communications · doi:10.1039/b313954a · Cited by 48 · see citing works
Self-citationSynthesis of telechelic polyolefins
Yan, T., & Guironnet, D. (2021) · Polymer Chemistry · doi:10.1039/d1py00819f · Cited by 43 · see citing works
Highly Versatile Strategy for the Production of Telechelic Polyolefins
Burkey, A. A., Fischbach, D. M., Wentz, C. M., Beers, K. L., & Sita, L. R. (2022) · ACS Macro Letters · doi:10.1021/acsmacrolett.2c00108 · Cited by 39 · see citing works
Ishihara, T., & Shiono, T. (2005) · Journal of the American Chemical Society · doi:10.1021/ja050987a · Cited by 37 · see citing works
Lucas, F., Peruch, F., Carlotti, S., Deffieux, A., Leblanc, A., & Boisson, C. (2008) · Polymer · doi:10.1016/j.polymer.2008.09.012 · Cited by 34 · see citing works
Catalytic synthesis of functionalized (polar and non-polar) polyolefin block copolymers
Walsh, D. J., Su, E., & Guironnet, D. (2018) · Chemical Science · doi:10.1039/c8sc00450a · Cited by 33 · see citing works
Synthesis of Poly(propylene-ran-1,3-butadiene) and Its Metathesis Degradation with Ethylene
Ishihara, T., & Shiono, T. (2003) · Macromolecules · doi:10.1021/ma0349480 · Cited by 32 · see citing works
Ungesättigte Polyester und Polyester‐Kautschuk‐Copolymerisate durch Olefin‐Metathese
Ast, W., Rheinwald, G., & Kerber, R. (1976) · Die Makromolekulare Chemie · doi:10.1002/macp.1976.021770509 · Cited by 30 · see citing works
Efficient Synthesis of α,ω‐Divinyl‐Functionalized Polyolefins
Patil, V. B., Saliu, K. O., Jenkins, R. M., Carnahan, E. M., Kramer, E. J., Fredrickson, G. H., & Bazan, G. C. (2014) · Macromolecular Chemistry and Physics · doi:10.1002/macp.201400139 · Cited by 29 · see citing works
Synthesis and applications of triblock and multiblock copolymers using telechelic oligopropylene
Sasaki, D., Suzuki, Y., Hagiwara, T., Yano, S., & Sawaguchi, T. (2008) · Polymer · doi:10.1016/j.polymer.2008.07.045 · Cited by 28 · see citing works
Fu, P., & Tomalia, M. K. (2003) · Macromolecules · doi:10.1021/ma0303061 · Cited by 27 · see citing works
Hagiwara, T., Saitoh, H., Tobe, A., Sasaki, D., Yano, S., & Sawaguchi, T. (2005) · Macromolecules · doi:10.1021/ma051530o · Cited by 27 · see citing works
Shiono, T., Naga, N., & Soga, K. (1993) · Die Makromolekulare Chemie Rapid Communications · doi:10.1002/marc.1993.030140601 · Cited by 26 · see citing works
Catalytic post-modification of alkene polymers
Ray, A., Kissin, Y. V., Zhu, K., et al. (2006) · Journal of Molecular Catalysis A Chemical · doi:10.1016/j.molcata.2006.04.017 · Cited by 25 · see citing works
Advances and Limits in Copolymerization of Olefins with Conjugated Dienes
Boisson, C., Monteil, V., Thuilliez, J., Spitz, R., Monnet, C., Llauro, M., Barbotin, F., & Robert, P. (2005) · Macromolecular Symposia · doi:10.1002/masy.200550802 · Cited by 25 · see citing works
Copolymerization of propylene with 1,3‐butadiene using isospecific zirconocene catalysts
Ishihara, T., Ban, H. T., Hagihara, H., & Shiono, T. (2007) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.22321 · Cited by 21 · see citing works
Hu, N., Mai, C., Fredrickson, G. H., & Bazan, G. C. (2015) · Chemical Communications · doi:10.1039/c5cc09200k · Cited by 21 · see citing works
Yang, Z., & Pelton, R. H. (1998) · Macromolecular Rapid Communications · doi:10.1002/(sici)1521-3927(19980501)19:5 · Cited by 20 · see citing works
Polyethylene Containing Triblock Copolymers Synthesized by Post-polymerization Functionalization
Yan, T., & Guironnet, D. (2020) · Macromolecules · doi:10.1021/acs.macromol.0c00627 · Cited by 20 · see citing works
Jeon, J. Y., Park, S. H., Kim, D. H., Park, S., Park, G., & Lee, B. (2016) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.28212 · Cited by 19 · see citing works
Formation and Activation of Zr/Hf Bis(phenolate‐ether) Precatalysts
Cuthbert, E. N. T., Busico, V., Herbert, D. E., et al. (2019) · European Journal of Inorganic Chemistry · doi:10.1002/ejic.201900716 · Cited by 18 · see citing works
Ethene-1,3-butadiene copolymerizations in the presence of CpTiCl3–MAO: Relevance of the cocatalyst
Pellegrino, M., Costabile, C., Grisi, F., & Pragliola, S. (2008) · European Polymer Journal · doi:10.1016/j.eurpolymj.2008.05.027 · Cited by 15 · see citing works
Pragliola, S., Costabile, C., Bartolomeo, F. D., & Longo, P. (2004) · Macromolecular Rapid Communications · doi:10.1002/marc.200400038 · Cited by 15 · see citing works
Amphiphilic Triblock Copolymers Containing Polypropylene as the Middle Block
Yan, T., & Guironnet, D. (2020) · Angewandte Chemie International Edition · doi:10.1002/anie.202009165 · Cited by 15 · see citing works
Jiang, H., Wang, S., Wang, Y., Yaxian, W., Li, L., Ma, L., Cui, D., & Tang, T. (2021) · Macromolecules · doi:10.1021/acs.macromol.1c00724 · Cited by 14 · see citing works
Hagiwara, T., Matsumaru, S., Okada, Y., Sasaki, D., Yano, S., & Sawaguchi, T. (2006) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.21452 · Cited by 13 · see citing works
Bis(arylimino)pyridyl cobalt catalysts for copolymerization of buta-1,3-diene with ethene
Železník, O., & Merna, J. (2019) · Polymer · doi:10.1016/j.polymer.2019.05.025 · Cited by 13 · see citing works
Ishihara, T., Ban, H. T., Hagihara, H., & Shiono, T. (2010) · Journal of Organometallic Chemistry · doi:10.1016/j.jorganchem.2010.04.003 · Cited by 11 · see citing works
Michiue, K., Mitani, M., & Fujita, T. (2015) · Catalysts · doi:10.3390/catal5042001 · Cited by 11 · see citing works
Metathetical Degradation and Depolymerization of Unsaturated Polymers
Marmo, J. C., & Wagener, K. B. (1997) · Rubber Chemistry and Technology · doi:10.5254/1.3538439 · Cited by 9 · see citing works
Flagged first, then by citations
Cited by
Sorted by citations
Depolymerization within a Circular Plastics System
Clark, R. A., & Shaver, M. P. (2024) · Chemical Reviews · doi:10.1021/acs.chemrev.3c00739 · Cited by 408 · see citing works
Catalytic Chemical Recycling of Post-Consumer Polyethylene
Arroyave, A., Cui, S., Lopez, J. C., Kocen, A. L., LaPointe, A. M., Delferro, M., & Coates, G. W. (2022) · Journal of the American Chemical Society · doi:10.1021/jacs.2c11949 · Cited by 189 · see citing works
Self-citationParke, S. M., Lopez, J. C., Cui, S., LaPointe, A. M., & Coates, G. W. (2023) · Angewandte Chemie International Edition · doi:10.1002/anie.202301927 · Cited by 88 · see citing works
Self-citationCircular olefin copolymers made de novo from ethylene and α-olefins
Han, X.-W., Zhang, X., Zhou, Y., Maimaitiming, A., Sun, X.-L., Gao, Y., Li, P., Zhu, B., Chen, E. Y.-X., Kuang, X., et al. (2024) · Nature Communications · doi:10.1038/s41467-024-45219-w · Cited by 85 · see citing works
Installing a Trigger to Upcycle High-Density Polyethylene
Nan, T., Chen, Q., Zheng, Z., Liang, Y., Qin, Y., Wang, Y., Liu, B., & Cui, D. (2024) · Journal of the American Chemical Society · doi:10.1021/jacs.4c08958 · Cited by 42 · see citing works
A Closed‐Loop Recyclable Low‐Density Polyethylene
Unger, C., Schmalz, H., Lipp, J., Kretschmer, W. P., & Kempe, R. (2024) · Advanced Science · doi:10.1002/advs.202307229 · Cited by 23 · see citing works
- Authors
- Kocen, A. L., Cui, S., Lin, T.-W., LaPointe, A. M., & Coates, G. W.
- Affiliations
- Cornell University (US)
- Corresponding author
- LaPointe, Anne M.
- Coates, Geoffrey W.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2022-07-06
- Volume
- 144
- Issue
- 28
- Pages
- 12613-12618
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W4284666627
- Cited by
- 125
- References
- 75
- Citations by year
- 2026: 19 · 2025: 49 · 2024: 19 · 2023: 32 · 2022: 6
- FWCI
- 8.50
- Type
- journal article
- Language
- en
- Open access
- closed
- Licence
- Locations
- Journal of the American Chemical Society (publishedVersion)
- PubMed (publishedVersion)
- Funders
- Basic Energy Sciences (DE-AC02-07CH11358)
- Topics
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
- Keywords
- chemical recycling, polyolefins, olefin metathesis, 2-hydroxyethyl acrylate, depolymerization, hydrogenation, linear low-density polyethylene
- MeSH terms
- Esters, Molecular Weight, Polymers, Polypropylenes, Polymerization
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review