Long-Chain Linear C 19 and C 23 Monomers and Polycondensates from Unsaturated Fatty Acid Esters
Abstract
Isomerizing alkoxycarbonylation of methyl oleate and ethyl erucate, respectively, yielded dimethyl 1,19-nonadecanedioate and diethyl 1,23-tricosanedioate in >99% purity. With [κ 2 -(P̂ P)Pd(OTf)][OTf] as a defined catalyst precursor (P̂P = 1,2-bis[(di- tert -butylphosphino)methyl]benzene) the reaction can be carried out without the need for additional added diphosphine. Saponification of the diesters yielded 1,19-nonadecanedicarboxylic acid and 1,23-tricosanedicarboxylic acid in >99% purity. By ruthenium-catalyzed reduction of the diesters with H 2, 1,19-nonadecanediole and 1,23-tricosanediole were formed in high yield and purity (>99%). From the latter, 1,19-nonadecanediamine and 1,23-tricosanediamine were generated. Polyesters with commercially available shorter-chain petrochemical or renewable diols exhibit high melting points due to the crystallizable long-chain methylene segments from the dicarboxylic acid component, e.g., poly[1,6-hexadiyl-1,23-tricosanedioate] T m 92, T c 75 °C. Thermal properties of novel long-chain polyamides are reported.
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Isomerizing alkoxycarbonylation of methyl oleate catalyzed by a palladium catalyst bearing phosphorus ligands can convert the internal double bond deep in the hydrocarbon chain to a terminal ester group with high yield and selectivity.
“In one example, they showed that isomerizing alkoxycarbonylation of methyl oleate catalyzed by a palladium catalyst bearing phosphorus ligands can convert the internal double bond deep in the hydrocarbon chain to a terminal ester group with high yield and selectivity.100”
From Catalysis as an Enabling Science for Sustainable Polymers (2018) · cites this paper as [100]
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Self-citation
- Authors
- Stempfle, F., Quinzler, D., Heckler, I., & Mecking, S.
- Affiliations
- University of Konstanz (DE)
- Corresponding author
- Mecking, Stefan
- ORCID
- Mecking, Stefan
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 2011-05-09
- Volume
- 44
- Issue
- 11
- Pages
- 4159-4166
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2028984848
- Cited by
- 203
- References
- 25
- Citations by year
- 2026: 6 · 2025: 9 · 2024: 19 · 2023: 10 · 2022: 6 · 2021: 15 · 2020: 5 · 2019: 11 · 2018: 10 · 2017: 28 · 2016: 10 · 2015: 20 · 2014: 19 · 2013: 16 · 2012: 17
- FWCI
- 7.07
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- KOPS (University of Konstanz) (submittedVersion)
- Topics
- Physical Sciences › Materials Science › Biomaterials › biodegradable polymer synthesis and properties
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Keywords
- long-chain dicarboxylic acids, unsaturated fatty acid esters, methyl oleate, alkoxycarbonylation, palladium catalysts, saponification, hydrogenation, polyesters, polyamide, thermal properties, crystallization
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