Chain Multiplication of Fatty Acids to Precise Telechelic Polyethylene
Abstract
Starting from common monounsaturated fatty acids, a strategy is revealed that provides ultra‐long aliphatic α,ω‐difunctional building blocks by a sequence of two scalable catalytic steps that virtually double the chain length of the starting materials. The central double bond of the α,ω‐dicarboxylic fatty acid self‐metathesis products is shifted selectively to the statistically much‐disfavored α,β‐position in a catalytic dynamic isomerizing crystallization approach. “Chain doubling” by a subsequent catalytic olefin metathesis step, which overcomes the low reactivity of this substrates by using waste internal olefins as recyclable co‐reagents, yields ultra‐long‐chain α,ω‐difunctional building blocks of a precise chain length, as demonstrated up to a C 48 chain. The unique nature of these structures is reflected by unrivaled melting points (Tm=120 °C) of aliphatic polyesters generated from these telechelic monomers, and by their self‐assembly to polyethylene‐like single crystals.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
Claims other papers make about this one
Each is checked against this paper’s own text: does it say what the citing paper says it does?
From 1,48-tetraoctacontane diol, the diethyl carbonate polymerisation method yielded a high molecular weight (Mw ~ 90.000 g mol -1 , Mn ~ 40.000 g mol -1 ) ductile PC-48 with a narrow melt transition at Tm = 113 °C.
“From 1,48-tetraoctacontane diol, generated by catalytic chaindoubling of erucic acid, 24 the diethyl carbonate polymerisation method yielded a high molecular weight (Mw ~ 90.000 g mol -1 , Mn ~ 40.000 g mol -1 ) ductile PC-48 with a narrow melt transition at Tm = 113 °C”
From Closed-loop recycling of polyethylene-like materials (2021) · cites this paper as [24]
Cites
A General Model for Selectivity in Olefin Cross Metathesis
Chatterjee, A., Choi, T., Sanders, D. P., & Grubbs, R. H. (2003) · Journal of the American Chemical Society · doi:10.1021/ja0214882 · Cited by 1,552 · see citing works
Oils and Fats as Renewable Raw Materials in Chemistry
Biermann, U., Bornscheuer, U. T., Meier, M. A. R., Metzger, J. O., & Schäfer, H. J. (2011) · Angewandte Chemie International Edition · doi:10.1002/anie.201002767 · Cited by 1,006 · see citing works
Biopolyester Membranes of Plants: Cutin and Suberin
Kolattukudy, P. E. (1980) · Science · doi:10.1126/science.208.4447.990 · Cited by 815 · see citing works
Lipid bilayer thickness varies linearly with acyl chain length in fluid phosphatidylcholine vesicles
Lewis, B. A., & Engelman, D. M. (1983) · Journal of Molecular Biology · doi:10.1016/s0022-2836(83)80007-2 · Cited by 786 · see citing works
Prevention of Undesirable Isomerization during Olefin Metathesis
Hong, S. H., Sanders, D. P., Lee, C. W., & Grubbs, R. H. (2005) · Journal of the American Chemical Society · doi:10.1021/ja052939w · Cited by 648 · see citing works
The important role of stratum corneum lipids for the cutaneous barrier function
van Smeden, J., Janssens, M., Gooris, G. S., & Bouwstra, J. A. (2014) · Biochimica et Biophysica Acta (BBA) - Molecular and Cell Biology of Lipids · doi:10.1016/j.bbalip.2013.11.006 · Cited by 549 · see citing works
Decomposition of a Key Intermediate in Ruthenium-Catalyzed Olefin Metathesis Reactions
Hong, S. H., Day, M. W., & Grubbs, R. H. (2004) · Journal of the American Chemical Society · doi:10.1021/ja0488380 · Cited by 416 · see citing works
Stempfle, F., Ortmann, P., & Mecking, S. (2016) · Chemical Reviews · doi:10.1021/acs.chemrev.5b00705 · Cited by 397 · see citing works
Self-citationWeerheim, A., & Ponec, M. (2001) · Archives of Dermatological Research · doi:10.1007/s004030100212 · Cited by 302 · see citing works
Refining of Plant Oils to Chemicals by Olefin Metathesis
Chikkali, S. H., & Mecking, S. (2012) · Angewandte Chemie International Edition · doi:10.1002/anie.201107645 · Cited by 217 · see citing works
Self-citationStempfle, F., Quinzler, D., Heckler, I., & Mecking, S. (2011) · Macromolecules · doi:10.1021/ma200627e · Cited by 203 · see citing works
Self-citationBlokker, P., Schouten, S., ENDE, H. V. D., et al. (1998) · Organic Geochemistry · doi:10.1016/s0146-6380(98)00111-9 · Cited by 196 · see citing works
Production, chemistry, and commercial applications of various chemicals from castor oil
Naughton, F. C. (1974) · Journal of the American Oil Chemists Society · doi:10.1007/bf00000015 · Cited by 188 · see citing works
Gelin, F., Boogers, I., Noordeloos, A. A. M., Damsté, J. S. S., Riegman, R., & de Leeuw, J. W. (1997) · Organic Geochemistry · doi:10.1016/s0146-6380(97)00035-1 · Cited by 186 · see citing works
Mechanistic Features of Isomerizing Alkoxycarbonylation of Methyl Oleate
Roesle, P., Dürr, C. J., Möller, H. M., et al. (2012) · Journal of the American Chemical Society · doi:10.1021/ja307411p · Cited by 166 · see citing works
O’Connor, K. S., Watts, A., Vaidya, T., LaPointe, A. M., Hillmyer, M. A., & Coates, G. W. (2016) · Macromolecules · doi:10.1021/acs.macromol.6b01567 · Cited by 155 · see citing works
A Comprehensive Mechanistic Picture of the Isomerizing Alkoxycarbonylation of Plant Oils
Roesle, P., Caporaso, L., Schnitte, M., et al. (2014) · Journal of the American Chemical Society · doi:10.1021/ja508447d · Cited by 151 · see citing works
Olefin isomerization promoted by olefin metathesis catalysts
Lehman, S. E., Schwendeman, J. E., O’Donnell, P. M., & Wagener, K. B. (2003) · Inorganica Chimica Acta · doi:10.1016/s0020-1693(02)01307-5 · Cited by 142 · see citing works
Gelin, F., Boogers, I., Noordeloos, A. A. M., Damsté, J. S. S., Hatcher, P. G., & de Leeuw, J. W. (1996) · Geochimica et Cosmochimica Acta · doi:10.1016/0016-7037(96)00038-5 · Cited by 141 · see citing works
Single Lamella Nanoparticles of Polyethylene
Weber, C. H. M., Chiche, A., Krausch, G., Rosenfeldt, S., Ballauff, M., Harnau, L., Göttker‐Schnetmann, I., Tong, Q., & Mecking, S. (2007) · Nano Letters · doi:10.1021/nl070859f · Cited by 128 · see citing works
Self-citationGas chromatographic—mass spectrometric studies of long chain hydroxy acids—II
Eglinton, G., HUNNEMAN, D. H., & Douraghi-Zadeh, K. (1968) · Tetrahedron · doi:10.1016/s0040-4020(01)90979-2 · Cited by 127 · see citing works
Fette und Öle als nachwachsende Rohstoffe in der Chemie
Biermann, U., Bornscheuer, U. T., Meier, M. A. R., Metzger, J. O., & Schäfer, H. J. (2011) · Angewandte Chemie · doi:10.1002/ange.201002767 · Cited by 118 · see citing works
Metathesis of unsaturated fatty acids: Synthesis of long‐chain unsaturated‐α,ω‐dicarboxylic acids
Ngo, H. L., Jones, K. C., & Foglia, T. A. (2006) · Journal of the American Oil Chemists Society · doi:10.1007/s11746-006-1249-0 · Cited by 110 · see citing works
α,ω‐Functionalized C19 Monomers
Walther, G., Deutsch, J., Martin, A., et al. (2011) · ChemSusChem · doi:10.1002/cssc.201100187 · Cited by 89 · 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
Carboxy-Telechelic Polyolefins by ROMP Using Maleic Acid as a Chain Transfer Agent
Pitet, L. M., & Hillmyer, M. A. (2011) · Macromolecules · doi:10.1021/ma102975r · Cited by 87 · 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-citationSelf-metathesis of fatty acid methyl esters: full conversion by choosing the appropriate plant oil
Mutlu, H., Hofsäß, R., Montenegro, R. E., & Meier, M. A. R. (2013) · RSC Advances · doi:10.1039/c3ra40330k · Cited by 77 · 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
Bertheas, O., Metzger, P., & Largeau, C. (1999) · Phytochemistry · doi:10.1016/s0031-9422(98)00481-6 · Cited by 55 · see citing works
Künkel, A., Becker, J., Börger, L., Hamprecht, J., Koltzenburg, S., Loos, R., Schick, M. B., Schlegel, K., Sinkel, C., Skupin, G., et al. (2016) · Ullmann's Encyclopedia of Industrial Chemistry · doi:10.1002/14356007.n21_n01.pub2 · Cited by 54 · see citing works
Jeremic, D. (2014) · Ullmann's Encyclopedia of Industrial Chemistry · doi:10.1002/14356007.a21_487.pub3 · Cited by 50 · see citing works
Cell wall-specific ω-hydroxy fatty acids in some freshwater green microalgae
Blokker, P., Stefan Schouten, A., ENDE, H. V. D., de Leeuw, J. W., & Damsté, J. S. S. (1998) · Phytochemistry · doi:10.1016/s0031-9422(98)00229-5 · Cited by 47 · see citing works
Espelie, K. E., & Kolattukudy, P. E. (1979) · PLANT PHYSIOLOGY · doi:10.1104/pp.63.3.433 · Cited by 39 · see citing works
Raffination von Pflanzenölen für die Chemie durch Olefinmetathese
Chikkali, S. H., & Mecking, S. (2012) · Angewandte Chemie · doi:10.1002/ange.201107645 · Cited by 38 · see citing works
Self-citationThermoplastic polyester elastomers based on long-chain crystallizable aliphatic hard segments
Stempfle, F., Schemmer, B., Oechsle, A. L., & Mecking, S. (2015) · Polymer Chemistry · doi:10.1039/c5py01209k · Cited by 34 · see citing works
Self-citationDirect 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 · doi:10.1002/ange.201607754 · Cited by 27 · see citing works
Self-citationTelechelic Polyethylene from Catalyzed Chain‐Growth Polymerization
German, I. M., Kelhifi, W., Norsic, S., et al. (2013) · Angewandte Chemie · doi:10.1002/ange.201208756 · Cited by 22 · see citing works
Augustin, K. E., & Schäfer, H. J. (1991) · Liebigs Annalen der Chemie · doi:10.1002/jlac.1991199101178 · Cited by 19 · see citing works
Behr, A. (2010) · Ullmann's Encyclopedia of Industrial Chemistry · doi:10.1002/14356007.o05_o01 · Cited by 10 · see citing works
Ouhadi, T., Abdou‐Sabet, S., Wussow, H., et al. (2014) · Ullmann's Encyclopedia of Industrial Chemistry · doi:10.1002/14356007.a26_633.pub4 · Cited by 7 · see citing works
Flagged first, then by citations
Cited by
Sorted by citations
Bio-based polymers with performance-advantaged properties
Cywar, R. M., Rorrer, N. A., Hoyt, C. B., Beckham, G. T., & Chen, E. Y.-X. (2021) · Nature Reviews Materials · doi:10.1038/s41578-021-00363-3 · Cited by 811 · see citing works
Closed-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
Self-citationCatalytic 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
Chemically Recyclable Ester-Linked Polypropylene
Kocen, A. L., Cui, S., Lin, T.-W., LaPointe, A. M., & Coates, G. W. (2022) · Journal of the American Chemical Society · doi:10.1021/jacs.2c04499 · Cited by 125 · see citing works
Parke, 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
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
Synthesis of telechelic polyolefins
Yan, T., & Guironnet, D. (2021) · Polymer Chemistry · doi:10.1039/d1py00819f · Cited by 43 · see citing works
- Authors
- Witt, T., Häußler, M., Kulpa, S., & Mecking, S.
- Affiliations
- University of Konstanz (DE)
- Corresponding author
- Mecking, Stefan
- Venue
- Angewandte Chemie International Edition
- Publisher
- Wiley
- Published
- 2017-05-23
- Volume
- 56
- Issue
- 26
- Pages
- 7589-7594
- ISSN
- 1433-7851 (ISSN-L)
- 1521-3773
- OpenAlex
- W2611486301
- Cited by
- 61
- References
- 41
- Citations by year
- 2026: 6 · 2025: 8 · 2024: 11 · 2023: 5 · 2022: 5 · 2021: 13 · 2020: 4 · 2019: 4 · 2018: 4 · 2017: 1
- FWCI
- 1.48
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Angewandte Chemie International Edition (publishedVersion)
- PubMed (publishedVersion)
- KOPS (University of Konstanz) (submittedVersion)
- Funders
- Baden-Württemberg Stiftung
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Synthetic Organic Chemistry Methods
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Keywords
- olefin metathesis, self-metathesis, aliphatic polyesters, melting point, self-assembly, single crystals, monounsaturated fatty acids
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
