Aldehyde End‐Capped Degradable Polyethylenes From Hydrogen‐Controlled Ethylene/CO Copolymerization
Abstract
To access degradable polyolefin plastic, non‐alternating copolymerization of ethylene (E) and carbon monoxide (CO) for producing polyethylene (PE) with in‐chain ketones is particularly appealing; however, it still presents significant challenges such as molecular weight modulation (hydrogen response) and chain endgroup control (functional terminal). In this study, we achieved hydrogen‐controlled E/CO non‐alternating copolymerization using late transition metal catalysts. This process results in linear PEs containing the desired non‐alternating in‐chain keto groups (1.0–9.3 mol %) and with tunable molecular weights ranging from 43 to 195 kDa. In this reaction, H 2 serves as a chain transfer agent, modulating the polymer's molecular weight, forming unique aldehyde endgroups and eliminating usual olefinic endgroups; CO undergoes non‐alternating insertion into the PE chain, resulting in a strictly non‐alternating structure (>99 %) for the keto‐PE. The dispersed incorporation of in‐chain keto groups retains bulk properties of PE and makes PE susceptible to photodegradation, which produces significantly lower molecular weight polymers and oligomers with unambiguous vinyl and acetyl terminals.
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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
Palladium-Catalyzed Alternating Copolymerization of Alkenes and Carbon Monoxide
Drent, E., & Budzelaar, P. H. M. (1996) · Chemical Reviews · doi:10.1021/cr940282j · Cited by 977 · see citing works
From Multisite Polymerization Catalysis to Sustainable Materials and All-Polyolefin Composites
Stürzel, M., Mihan, S., & Mülhaupt, R. (2016) · Chemical Reviews · doi:10.1021/acs.chemrev.5b00310 · Cited by 822 · see citing works
Post‐Metallocenes in the Industrial Production of Polyolefins
Baier, M. C., Zuideveld, M. A., & Mecking, S. (2014) · Angewandte Chemie International Edition · doi:10.1002/anie.201400799 · Cited by 543 · see citing works
New Nickel(II) Diimine Complexes and the Control of Polyethylene Microstructure by Catalyst Design
Meinhard, D., Wegner, M., Kipiani, G., et al. (2007) · Journal of the American Chemical Society · doi:10.1021/ja070224i · Cited by 307 · see citing works
Insertion Polymerization of Acrylate
Guironnet, D., Roesle, P., Rünzi, T., et al. (2008) · Journal of the American Chemical Society · doi:10.1021/ja808017n · Cited by 285 · see citing works
Polyethylene materials with in-chain ketones from nonalternating catalytic copolymerization
Baur, M., Lin, F., Morgen, T. O., Odenwald, L., & Mecking, S. (2021) · Science · doi:10.1126/science.abi8183 · Cited by 284 · see citing works
Kochi, T., Noda, S., Yoshimura, K., et al. (2007) · Journal of the American Chemical Society · doi:10.1021/ja0725504 · Cited by 270 · see citing works
Photochemistry of Ketone Polymers. I. Studies of Ethylene-Carbon Monoxide Copolymers
Hartley, G. H., & Guillet, J. E. (1968) · Macromolecules · doi:10.1021/ma60002a012 · Cited by 228 · see citing works
Synthesis and Deconstruction of Polyethylene-type Materials
Schwab, S. T., Baur, M., Nelson, T. F., & Mecking, S. (2024) · Chemical Reviews · doi:10.1021/acs.chemrev.3c00587 · Cited by 203 · see citing works
Na, Y., Dai, S., & Chen, C. (2018) · Macromolecules · doi:10.1021/acs.macromol.8b00467 · Cited by 173 · see citing works
High Density Polyethylenes Bearing Isolated In‐Chain Carbonyls**
Tang, S., Seidel, F. W., & Nozaki, K. (2021) · Angewandte Chemie International Edition · doi:10.1002/anie.202110957 · Cited by 104 · see citing works
Photodegradable branched polyethylenes from carbon monoxide copolymerization under benign conditions
Morgen, T. O., Baur, M., Göttker‐Schnetmann, I., & Mecking, S. (2020) · Nature Communications · doi:10.1038/s41467-020-17542-5 · Cited by 96 · see citing works
Synthesis of Nonalternating Polyketones Using Cationic Diphosphazane Monoxide-Palladium Complexes
Chen, S.-Y., Pan, R.-C., Chen, M., Liu, Y., Chen, C., & Lu, X.-B. (2021) · Journal of the American Chemical Society · doi:10.1021/jacs.1c04964 · Cited by 95 · see citing works
Drent, E., & Budzelaar, P. H. M. (2000) · Journal of Organometallic Chemistry · doi:10.1016/s0022-328x(99)00554-9 · Cited by 85 · see citing works
Direct Synthesis of Telechelic Polyethylene by Selective Insertion Polymerization
Jian, Z., Falivene, L., Boffa, G., Sánchez, S. O., Caporaso, L., Grassi, A., & Mecking, S. (2016) · Angewandte Chemie International Edition · doi:10.1002/anie.201607754 · Cited by 81 · see citing works
Self-citationPoisoning studies on chromium/silica. 2. Carbon monoxide
McDaniel, M. P., & Martin, S. J. (1991) · The Journal of Physical Chemistry · doi:10.1021/j100161a059 · Cited by 57 · see citing works
Photodegradable polar-functionalized polyethylenes
Wang, C., Xia, J., Zhang, Y., Hu, X., & Jian, Z. (2023) · National Science Review · doi:10.1093/nsr/nwad039 · Cited by 55 · see citing works
Self-citationMechanistic Insights into Ni(II)-Catalyzed Nonalternating Ethylene–Carbon Monoxide Copolymerization
Voccia, M., Odenwald, L., Baur, M., Lin, F., Falivene, L., Mecking, S., & Caporaso, L. (2022) · Journal of the American Chemical Society · doi:10.1021/jacs.2c04563 · Cited by 53 · see citing works
Dodge, H. M., Natinsky, B. S., Jolly, B. J., Zhang, H., Mu, Y., Chapp, S. M., Tran, T. V., Diaconescu, P. L., Do, L. H., Wang, D., et al. (2023) · ACS Catalysis · doi:10.1021/acscatal.3c00769 · Cited by 49 · see citing works
Synthesis of telechelic polyolefins
Yan, T., & Guironnet, D. (2021) · Polymer Chemistry · doi:10.1039/d1py00819f · Cited by 43 · see citing works
Ethylene Polymerizations Catalyzed by Fluorinated “Sandwich” Diimine-Nickel and Palladium Complexes
Medina, J. T., Tran, Q. H., Hughes, R. P., et al. (2024) · Journal of the American Chemical Society · doi:10.1021/jacs.4c01322 · Cited by 40 · see citing works
Controlled Cobalt-Mediated Free-Radical Co- and Terpolymerization of Carbon Monoxide
Fuchs, A. S., & Mecking, S. (2022) · Journal of the American Chemical Society · doi:10.1021/jacs.2c07200 · Cited by 33 · see citing works
Chen, S., Ren, B., Li, S.-H., Song, Y., Jiao, S., Zou, C., Chen, C., Lu, X., & Liu, Y. (2022) · Angewandte Chemie International Edition · doi:10.1002/anie.202204126 · Cited by 32 · see citing works
Chen, S., Song, Y., Jiao, S., Zou, C., Li, S.-H., Chen, C., Lu, X., & Liu, Y. (2022) · Journal of Catalysis · doi:10.1016/j.jcat.2022.12.020 · Cited by 31 · see citing works
Han, X., Daugulis, O., & Brookhart, M. (2020) · Journal of the American Chemical Society · doi:10.1021/jacs.0c06644 · Cited by 25 · see citing works
Zhou, F., Dai, H., Tang, S., et al. (2023) · CCS Chemistry · doi:10.31635/ccschem.023.202303275 · Cited by 24 · see citing works
Baur, M., & Mecking, S. (2022) · ACS Macro Letters · doi:10.1021/acsmacrolett.2c00459 · Cited by 21 · see citing works
Yonezaki, G., Seidel, F. W., Takahashi, K., & Nozaki, K. (2023) · Bulletin of the Chemical Society of Japan · doi:10.1246/bcsj.20230073 · Cited by 21 · see citing works
Marques, M. M., Nunes, C. P., Tait, P. J. T., et al. (1993) · Journal of Polymer Science Part A Polymer Chemistry · doi:10.1002/pola.1993.080310126 · Cited by 16 · see citing works
Baur, M., Habé, R., & Mecking, S. (2024) · ACS Macro Letters · doi:10.1021/acsmacrolett.4c00313 · Cited by 11 · see citing works
Li, S.-H., Pan, R., Ren, B., Jian-Wei, Y., Kang, X., & Liu, Y. (2022) · Chinese Journal of Chemistry · doi:10.1002/cjoc.202200450 · Cited by 10 · see citing works
Controlled Catalyst Dosing: An Elegant Approach in Molecular Weight Regulation for UHMWPE
Padmanabhan, S., Sarma, K. R., Sharma, S., et al. (2009) · Macromolecular Reaction Engineering · doi:10.1002/mren.200900001 · Cited by 8 · see citing works
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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
- Authors
- Song, C., Yang, D., Wang, C., Tang, Z., Long, Y., Zhang, Y., & Jian, Z.
- Affiliations
- Chinese Academy of Sciences (CN)
- University of Science and Technology of China (CN)
- State Key Laboratory of Polymer Physics and Chemistry Changchun Institute of Applied Chemistry Chinese Academy of Sciences Renmin Street 5625 Changchun 130022 China
- Corresponding author
- Jian, Zhongbao
- Venue
- Angewandte Chemie International Edition
- Publisher
- Wiley
- Published
- 2024-09-20
- Volume
- 63
- Issue
- 44
- Pages
- e202410885-e202410885
- ISSN
- 1433-7851 (ISSN-L)
- 1521-3773
- OpenAlex
- W4401217133
- Cited by
- 29
- References
- 33
- Citations by year
- 2026: 12 · 2025: 16 · 2024: 1
- FWCI
- 4.18
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Angewandte Chemie International Edition (publishedVersion)
- PubMed (publishedVersion)
- Funders
- National Natural Science Foundation of China (22122110, U23B6011)
- Department of Science and Technology of Jilin Province (20230101347JC)
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Keywords
- late transition metal catalysts, chain transfer agent, molecular weight control, photodegradation
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