Highly efficient oxyfunctionalization of unsaturated fatty acid esters: an attractive route for the synthesis of polyamides from renewable resources

Winkler, Mathias; Meier, Michael A. R.

doi:10.1039/c3gc41921e

Cited by 36 publications

(39 citation statements)

References 28 publications

(34 reference statements)

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“…6 Simultaneously, such huge consumptions bring inevitable environmental pollutions. polyolefins, 30 polyesters, 31 polyethers, 32 polyamides, 33 epoxy 34 and polyurethane resins, 35 and others 36 ). 7 In brief, urgent actions are necessitated to make plastics renewable via using naturally-occurring raw materials and to take advantage of the synthetic potential of nature.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and properties of polyesters derived from renewable eugenol and α,ω-diols via a continuous overheating method

Zhao

et al. 2015

Polym. Chem.

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Two eugenol-based aromatic dimethyl terephthalate (DMT)-like monomers were prepared via thiol-ene click reaction and subsequent nucleophilic substitution reactions with methyl chloroacetate or 1,4-dibromobutane. Two series of thermoplastic polyesters derived from renewable eugenol and linear aliphatic α,ω-diols HO-(CH2)n-OH (n = 2, 3, 4, 6, 10, 12) were successfully synthesized. These prepared polyesters have weight-average molecular weights in the range of 18500-90500 g mol -1 , and polydispersities (PDI) between 1.8 and 2.2. Their chemical structures were all accurately characterized by 1 H NMR, 13 C NMR and FTIR. The random microstructures of synthetic polyesters were also explored by 13 C NMR. The obtained polyesters all exhibit thermal stability above 330°C. More importantly, the thermal stability, the maximum degradation rate and residue weight are intimately associated with the length of the linear aliphatic α,ω-diol. Their thermo-mechanical properties were studied by the differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). The length of linear aliphatic α,ω-diol shows crucial influence on the glass transition temperature (Tg). With the gradually increase of the α,ω-diol length, the Tg of the synthesized polyester uniformly exhibits a tendency of decreasing. The polyesters are all amorphous materials at room temperature, whose Tg values range from -28.4 to 7.6°C. The incorporation of aromatic eugenol into the polyester chains reduces the crystallinity obviously, as well as the mechanical properties compared with conventional PET or PBT. The Young's modulus and ultimate strength are just in the range of 1.2-6.9 MPa and 0.96-3.37 MPa, respectively. On the contrary, the elongation at break reaches up to 840-1000%, indicating the excellent viscosity properties for such unmanageable viscous materials.

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Section: Introductionmentioning

confidence: 99%

Synthesis and properties of polyesters derived from renewable eugenol and α,ω-diols via a continuous overheating method

Zhao

et al. 2015

Polym. Chem.

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“…Interestingly, the employed dimethylacetamide acts as active solvent, allowing a recycling of the catalyst–solvent system as well as the product isolation by simple extraction. Inspired by the aforementioned catalytic oxidation procedure, our group successfully synthesized ketone FAMEs from renewable methyl oleate and methyl erucate, which were subsequently modified into amino‐esters for the synthesis of polyamides . With such an efficient oxidation tool in hands, we have started our investigations by the synthesis of the ketone derived from methyl 10‐undecenoate, which acts as platform chemical for the synthesis of renewable monomers and thereof derived polymers.…”

Section: Introductionmentioning

confidence: 99%

“…Inspired by the aforementioned catalytic oxidation procedure, our group successfully synthesized ketone FAMEs from renewable methyl oleate and methyl erucate, which were subsequently modified into amino-esters for the synthesis of polyamides. [29] With such an efficient oxidation tool in hands, we have started our investigations by the synthesis of the ketone derived from methyl 10-undecenoate, which acts as platform chemical for the synthesis of renewable monomers and thereof derived polymers. For this purpose, the ketone FAME was modified via Baeyer-Villiger oxidation/transesterification, reduction, and reductive amination to yield AB step-growth monomers (hydroxy-esters, amino-ester) readily employed for homopolymerizations.…”

Section: Introductionmentioning

confidence: 99%

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

Czapiewski

Meier

2017

Macromol. Chem. Phys.

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An efficient synthesis strategy for the preparation of two renewable polyesters and one renewable polyamide via catalytic oxyfunctionalization of methyl 10‐undecenoate, a castor oil derived platform chemical, is described. The keto‐fatty acid methyl ester (keto‐FAME) is synthesized applying a cocatalyst‐free Wacker oxidation process using a high‐pressure reactor system. For this purpose, catalytic amounts of palladium chloride are used in the presence of a dimethylacetamide/water mixture and molecular oxygen as sole reoxidant. The thus derived AB monomers (hydroxy‐esters, amine‐ester) are synthesized from the obtained keto‐FAME through Baeyer–Villiger oxidation and subsequent transesterification, reduction, or reductive amination, respectively. The resulting AB step‐growth monomers are then studied in homopolymerizations using 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene, DBU, and titanium(IV) isopropoxide as transesterification catalyst, yielding polymers with molecular weights (Mn) up to 15 kDa. The polyesters and the polyamide are carefully characterized by FTIR, SEC, 1H‐NMR spectroscopy, and differential scanning calorimetry analysis.

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“…For this purpose, the obtained keto-FAMEs (2a-c) were employed in a reductive amination process in order to synthesize the corresponding amino-FAMEs (3a-c). [19] The reactions were carried out in ethanol at room temperature using an activated Raney-Nickel catalyst in the presence of ammonium acetate/ammonium chloride as ammonia source and 30 bar hydrogen pressure. Thus, after 24 h full conversion was achieved for all three ketoFAMEs.…”

Section: Entrymentioning

confidence: 99%

“…[18] The aforementioned protocol was employed by our group for the synthesis of ketone fatty acid methyl ester (keto-FAMEs), which enabled the formation of aminoesters and the thereof derived polyamides. [19] Following this work, we investigated the reductive amination of the keto-FAME (C18) derived from methyl oleate with various commercially available diamines in order to synthesize partially renewable DFAs. Furthermore, the catalytic oxidation process and further reductive amination were applied to methyl 10-undecenoate (C11), methyl oleate (C18), and methyl erucate (C22) in order to build a library of keto-and amino-FAMEs bearing different chain lengths.…”

Section: Introductionmentioning

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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Highly efficient oxyfunctionalization of unsaturated fatty acid esters: an attractive route for the synthesis of polyamides from renewable resources

Cited by 36 publications

References 28 publications

Synthesis and properties of polyesters derived from renewable eugenol and α,ω-diols via a continuous overheating method

Synthesis and properties of polyesters derived from renewable eugenol and α,ω-diols via a continuous overheating method

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

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

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