Catalytic Oxyfunctionalization of Methyl 10-undecenoate for the Synthesis of Step-Growth Polymers

Czapiewski, Marc von; Meier, Michael A. R.

doi:10.1002/macp.201700153

Cited by 10 publications

(14 citation statements)

References 33 publications

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“… [128f] Following the oxidation and amination route, methyl 10‐aminoundecanoate and methyl 10‐hydroxyundecanoate can be obtained from 17 b , resulting in a methyl‐branched polyamide or polyester, respectively. [146] In both cases, steric hindrance resulted in more difficult polymerization and poorer thermal properties. A very different route to polyesters with various degrees of branching was described using ADMET polymerization of linear and branched α,ω‐diene monomers (Scheme 23 ).…”

Section: Polymersmentioning

confidence: 99%

Fatty Acids and their Derivatives as Renewable Platform Molecules for the Chemical Industry

et al. 2021

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Oils and fats of vegetable and animal origin remain an important renewable feedstock for the chemical industry. Their industrial use has increased during the last 10 years from 31 to 51 million tonnes annually. Remarkable achievements made in the field of oleochemistry in this timeframe are summarized herein, including the reduction of fatty esters to ethers, the selective oxidation and oxidative cleavage of C–C double bonds, the synthesis of alkyl‐branched fatty compounds, the isomerizing hydroformylation and alkoxycarbonylation, and olefin metathesis. The use of oleochemicals for the synthesis of a great variety of polymeric materials has increased tremendously, too. In addition to lipases and phospholipases, other enzymes have found their way into biocatalytic oleochemistry. Important achievements have also generated new oil qualities in existing crop plants or by using microorganisms optimized by metabolic engineering.

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Section: Polymersmentioning

confidence: 99%

Fatty Acids and their Derivatives as Renewable Platform Molecules for the Chemical Industry

et al. 2021

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“…However, NMR analysis of the crude reaction mixture revealed that methyl‐ketone 2c was formed in 85% and additionally 15% of regioisomers were present due to double bond isomerization. The purification by subsequent column chromatography led to the pure desired product 2c as colorless liquid in 74% yield (Table , entry 3) …”

Section: Resultsmentioning

confidence: 99%

“…The purification by subsequent column chromatography led to the pure desired product 2c as colorless liquid in 74% yield (Table 1, entry 3). [20] The goal of further investigations was the synthesis of partially renewable DFAs using keto-FAME 2a and various commercially available diamines (Scheme 2). For this purpose, four aliphatic diamines with chain lengths between 3 and 12 carbon atoms (4a-d) were employed in a reductive amination process using sodium triacetoxyborohydride as selective and mild reducing agent.…”

Section: Monomer Synthesismentioning

confidence: 99%

Synthesis of Dimer Fatty Acid Methyl Esters by Catalytic Oxidation and Reductive Amination: An Efficient Route to Branched Polyamides

Czapiewski

Meier

2017

Euro J Lipid Sci & Tech

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A novel and versatile route toward dimer fatty acid methyl esters (dimer FAMEs) via catalytic oxidation and reductive amination is described. The oxyfunctionalization of mono-unsaturated FAMEs bearing different chain lengths (C11, C18, C22) is accomplished by a co-catalyst-free Wacker Oxidation process in a high pressure reactor. The applied catalytic system of palladium(II) chloride in a dimethylacetamide/water mixture enabled the formation of ketoFAMEs in the presence of molecular oxygen as sole re-oxidant. In a first attempt, partially renewable dimer FAMEs are synthesized by reductive amination of keto-FAME (C18) in the presence of various aliphatic and aromatic diamines and sodium triacetoxyborohydride as selective reducing agent. In another approach, the keto-FAMEs directly underwent reductive amination using Raney-Nickel in order to obtain the corresponding aminoFAMEs. Subsequently, the keto-and amino-FAMEs are used for the synthesis of fully renewable dimer FAMEs via reductive amination with sodium triacetoxyborohydride as reducing agent. In order to demonstrate a possible application for these new dimer FAMEs, three out of the thirteen synthesized dimer FAMEs are selected and studied in a polycondensation with renewable 1,10-diaminodecane using TBD as catalyst. The polyamides are obtained in molecular weights (M n ) of up to 33 kDa and are carefully characterized by 1 H-NMR spectroscopy, FTIR, SEC, and DSC analysis. Practical Applications: The described catalytic route to defined dimer fatty acids has potential applications in lubricants, detergents, polymeric materials, and others. Compared to commercially available dimer fatty acids, a molecularly highly defined mixture of regioisomers is obtained, without contamination of monofunctional or trifunctional fatty acid derivatives, which is advantegous for most of the mentioned applications. Especially for polycondensations, the known stoichiometry of exactly two is a considerable benefit.

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“…[128f] Basierend auf der Oxidations-und Aminierungsroute kçnnen aus 17 b auch 10-Aminoundecansäuremethylester und 10-Hydroxyundecansäuremethylester erhalten werden, die sich gleichfalls zu einem methylverzweigten Polyamid oder Polyester polymerisieren lassen. [146] Allerdings führt sterische Hinderung in beiden Fällen zu Schwierigkeiten in der Polymerisation und schlechteren thermischen Eigenschaften. Eine andere Route zu Polyestern mit unterschiedlichem Grad an Verzweigung ist hingegen über ADMET-Polymerisation von linearen und verzweigten a,w-Dienmonomeren mçglich (Schema 23).…”

Section: Angewandte Chemieunclassified

Fettsäuren und Fettsäurederivate als nachwachsende Plattformmoleküle für die chemische Industrie

et al. 2021

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Catalytic Oxyfunctionalization of Methyl 10-undecenoate for the Synthesis of Step-Growth Polymers

Cited by 10 publications

References 33 publications

Fatty Acids and their Derivatives as Renewable Platform Molecules for the Chemical Industry

Fatty Acids and their Derivatives as Renewable Platform Molecules for the Chemical Industry

Synthesis of Dimer Fatty Acid Methyl Esters by Catalytic Oxidation and Reductive Amination: An Efficient Route to Branched Polyamides

Fettsäuren und Fettsäurederivate als nachwachsende Plattformmoleküle für die chemische Industrie

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