Furandicarboxylic Acid Research Articles

Effective Strategy for High-Yield Furan Dicarboxylate Production for Biobased Polyester Applications

A unique strategy for the formation of furan-2,5-dicarboxylic acid (FDCA)-derived esters with methanol and ethylene glycol in concentrated solutions was reported using a six-membered ring acetal of...

Selective aerobic oxidation of the 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid over gold nanoparticles supported on graphitized carbon: Study on reaction pathways

The design of a stable and efficient catalyst is crucial to the creation of high-valued bio-based products, and the catalytic selective oxidation of 5-hydroxymethylfurfural (5-HMF) to 2, 5-furandicarboxylic acid (FDCA) has received increasing attention. Different loadings of Au supported on the graphitized carbon (GC) catalysts (xwt%Au/GC (x = 0.7, 1.0, 1.3, 2.0 and 2.7)) were prepared and characterized via ICP-OES, N2 adsorption-desorption, XRD, FT-IR, TG, XPS and TEM. Results show that 2.0 wt%Au/GC displays 97% selectivity of FDCA and a near 100% conversion of 5-HMF in water under 7 bar O2 pressure for 6 h at 110 °C in the presence of NaOH, which also exhibits good cycling stability. The surface species of Au0 are in favor of the formation of FDCA. In this work, different reaction parameters were explored to optimize the reaction condition. The intermediates and the reaction pathways were also proposed on the basis of the formation and degradation of esters via various characterizations.

Lubricating properties of ester oil prepared from bio-based 2,5-furandicarboxylic acid

The depletion of petroleum resources and the intensification of environmental problems have necessitated the development of renewable products from bio-based chemicals instead of petroleum resources. Herein, a new kind of ester lubricating oil, isooctyl furan dicarboxylate (isooctyl-FD), was prepared from bio-based 2, 5-furandicarboxylic acid. The structure of isooctyl-FD was evaluated using nuclear magnetic resonance imaging and high-resolution mass spectroscopy. Its physicochemical and tribological properties including thermal and oxidation stabilities, flash point and pour point, viscosity and viscosity index, and friction-reducing and anti-wear properties were systematically evaluated. The results show that isooctyl-FD has comparable thermal and oxidation stability to the synthetic ester lubricating oil, isooctyl sebacate (isooctyl-S). Its friction-reducing and anti-wear properties are superior to isooctyl-S; however, its viscosity-temperature and low-temperature properties are inferior to isooctyl-S.

One-Pot FDCA Diester Synthesis from Mucic Acid and Their Solvent-Free Regioselective Polytransesterification for Production of Glycerol-Based Furanic Polyesters.

A one pot-two step procedure for the synthesis of diethyl furan-2,5-dicarboxylate (DEFDC) starting from mucic acid without isolation of the intermediate furan dicarboxylic acid (FDCA) was studied. Then, the production of three different kinds of furan-based polyesters— polyethylene-2,5-furan dicarboxylate (PEF), polyhydropropyl-2,5-furan dicarboxylate(PHPF) and polydiglycerol-2,5-furandicarboxylate (PDGF)—was realized through a Co(Ac)2·4H2O catalyzed polytransesterification performed at 160 °C between DEFDC and a defined diol furan-based prepolymer or pure diglycerol. In parallel to polymerization process, an unattended regioselective 1-OH acylation of glycerol by direct microwave-heated FDCA diester transesterification led to the formation of a symmetric prepolymer ready for further polymerization and clearly identified by 2D NMR sequences. Furthermore, the synthesis of a more soluble and hydrophilic diglycerol-based furanic polyester was also achieved. The resulting biobased polymers were characterized by NMR, FT-IR spectroscopy, DSC, TGA and XRD. The morphologies of the resulted polymers were observed by FE-SEM and the purity of the material by EDX.

Avantium takes over at Synvina

Avantium says it has retaken full ownership of the Synvina furandicarboxylic acid (FDCA) joint venture with BASF. FDCA is used to make polyethylene furanoate, a biobased alternative to the soft-drink-bottle polymer polyethylene terephthalate. BASF decided to withdraw from the joint venture over the timing of an investment decision on an FDCA facility planned for BASF’s Antwerp, Belgium, site. Altogether, Avantium says it has paid BASF $20 million for its former partner’s equity and asset investments.

Catalytic Conversion of Biorenewable Sugar Feedstocks into Market Chemicals

The transformation of low cost sugar feedstocks into market chemicals and monomers for existing or novel high performance polymers by chemical catalysis is reviewed. Emphasis is given to industrially relevant, continuous flow, trickle bed processes. Since long-term catalyst stability under hydrothermal conditions is an important issue to be addressed in liquid phase catalysis using carbohydrate feedstocks, we will primarily discuss the results of catalytic performance for prolonged times on stream. In particular, the selective aerobic oxidation of glucose to glucaric acid and the subsequent selective hydrogenation to adipic acid is reviewed. Hydroxymethylfurfural (HMF), which is readily available from fructose, can be upgraded by oxidation to furan dicarboxylic acid (FDCA) or by consecutive reduction and hydrogenolysis to hexanetriol (HTO) followed by hydrogenolysis to biobased hexanediol (HDO). Direct amination of HDO yields biobased hexamethylene diamine (HMDA). Aerobic oxidation of HDO represents an alternative route to biobased adipic acid. HMDA and adipic acid are the monomers required for the production of nylon- 6,6, a major polymer for engineering and fibre applications.

BASF to exit Synvina venture with Avantium

BASF has told renewable chemicals developer Avantium that it will pull out of their Synvina furandicarboxylic acid (FDCA) join venture effective Jan. 15. BASF had threatened to pull out of the venture in October over a disagreement on the timing of an investment decision for a $600 million FDCA plant. FDCA is used to make polyethylene furanoate, an alternative to the bottle polymer polyethylene terephthalate. Avantium says it will now pursue alternative routes to commercialize FDCA.

A facile method to synthesize bio-based and biodegradable copolymers from furandicarboxylic acid and isosorbide with high molecular weights and excellent thermal and mechanical properties

Biobased, biodegradable copolymers containing isosorbide and 2,5-furandicarboxylic acid with high performance are successfully synthesized through a non-solvent and economical pathway.

Two- and three-dimensional coordination polymers based on zinc(II) and furan-2,5-dicarboxylic acid: structure variation due to metal-to-linker ratio.

Two ZnII-based coordination polymers (CPs) were synthesized by the hydrothermal method, using Zn(NO3)2·6H2O and furan-2,5-dicarboxylic acid (FDCA) in dimethylformamide (DMF) solvent, at 95 °C. Poly[tetrakis(dimethylazanium) [tetrakis(μ2-furan-2,5-dicarboxylato-κ2O2:O5)dizinc(II)]], {(C2H8N)4[Zn2(C6H2O5)4]}n or {[DMA]4[ZnII2(FDC)4]}n (DMA = dimethylazanium and FDC= furan-2,5-dicarboxylate), (1), was obtained with a 1:1 molar ratio of ZnII and FDCA. It crystallized in the monoclinic space group C2/c. Coordinated by ZnII ions, FDC2- ligands form 21 double-stranded helices propagating along the b axis. The helices are interconnected and extend laterally in the a direction, forming a two-dimensional (2D) sheet-like network. The 2D sheets are stacked along the c direction without interconnections. DMA cations are cocrystallized in (1) and are hydrogen bonded with carboxylate O atoms of the FDC2- ligands. The hydrogen-bonding pattern consists of R22(4) and R22(10) motifs alternating in a chain. Poly[bis(dimethylazanium) [bis(μ4-furan-2,5-dicarboxylato-κO2:κO2':κO5:κO5)bis(μ3-furan-2,5-dicarboxylato-κO2:κO2':κO5)dizinc(II)] dimethylformamide 3.08-solvate], {(C2H8N)2[Zn2(C6H2O5)4]·3.08C3H7NO}n or {[DMA]2[ZnII3(FDC)4]·3.08DMF}n, (2), was obtained with a 1:2 molar ratio of ZnII and FDCA. It crystallized in the monoclinic space group P21/c, forming a three-dimensional network. The pores are filled with DMA cations and DMF solvent molecules.

Highly crystalline polyesters synthesized from furandicarboxylic acid (FDCA): Potential bio-based engineering plastic

The bio-based polyester demonstrating great potential to be used as engineering plastic, poly(1,4-cyclohexanedimethylene furandicarboxylate) (PCF) was synthesized from furandicarboxylic acid (FDCA) and 1,4-cyclohexanedimethanol (CHDM) with different steric conformation. After the chemical structures were identified by nuclear magnetic resonance (1H NMR and 13C NMR) and molecular weight was determined by gel permeation chromatography (GPC), their crystallization behaviors, thermal and dynamic mechanical properties were investigated by differential scanning calorimeter (DSC), thermogravimetric analyzer (TGA) and dynamic mechanical analysis (DMA). Results showed that PCFs demonstrated very good crystalline properties and the steric configuration of CHDM, i.e. the ratio of cis- to trans-CHDM in PCFs, had significant influences on their properties. The melting temperature of PCF could be as high as 294 °C and its crystallization half-time could be only several seconds. In addition, its mechanical properties and thermal stability were comparable to or better than those of poly(ethylene terephthalate) (PET) or poly(butylene terephthalate) (PBT). Considering the overall performance of PCF, it has great potential to be used as the bio-based polyester engineering plastics.

Oligomers in polyethylene furanoate - identification and quantification approach via LC-UV LC-MS response ratio

ABSTRACTPolyethylene furanoate polymer is intended to be used as a food contact material. A PEF polymer sample was investigated for its oligomer composition by solvent extraction and using HRLC-MS. The 20 oligomers found were divided into four groups: group I contains cyclic oligomers consisting of furandicarboxylic acid and monoethylene glycol units, group II comprises cyclic oligomers consisting of furandicarboxylic acid, monoethylene glycol units and one diethylene glycol unit, group III are cyclic oligomers were two monoethylene glycol units are substituted by diethylene glycol units and group IV are linear oligomers consisting of furandicarboxylic acid and monoethylene glycol units. Oligomers of group I account for around 87% of the total oligomer content, group II oligomers 12% and group III oligomers 1%. The contribution of group IV oligomers is very small: less than 0.05%. MS-MS experiments showed similar fragmentation patterns for all oligomers. The results of this study demonstrate that oligomers are abundant in the PEF material and are potential migrants to foods that are in contact with the polymer. Oligomers of group I and group II have the same absorption maxima in UV detection which was used to develop a quantification approach for these oligomers using dimethyl 2,5-furandicarboxylate as external standard.

Catalytic Performances of Au–Pt Nanoparticles on Phosphorous Functionalized Carbon Nanofibers towards HMF Oxidation

Herein, we reported the utilization of pre-formed Au–Pt nanoparticles deposited on phosphorus functionalized carbons as effective catalysts for the oxidation of 5-hydroxymethylfurfural (HMF) to furandicarboxylic acid (FDCA). Au–Pt nanoparticles have been prepared by a two-step methodology using polyvinyl alcohol (PVA) as protective agent and a combination of NaBH4 and H2 as reducing agents. Three carbon nanofibers (CNFs) with different graphitization degrees have been functionalized through treatment with an H3PO4–HNO3 mixture at 150 °C, in order to incorporate P groups on carbon surface. Surface and structural properties of the synthesized functionalized materials have been investigated by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. The structural and surface properties of carbon nanofibers determine the amount of P-functionalities, which is a key parameter affecting the catalytic performances of Au–Pt. Indeed, the highest activity and stability has been achieved for Au–Pt deposited on the sample, which showed the largest amount of P-groups on the surface.

Aerobic Oxidation and Oxidative Esterification of 5-Hydroxymethylfurfural by Gold Nanoparticles Supported on Nanoporous Polymer Host Matrix.

The aerobic oxidation and oxidative esterification of 5-hydroxymethylfurfural (HMF) catalyzed by gold nanoparticles (AuNPs) supported on a semicrystalline nanoporous multiblock copolymer matrix consisting of syndiotactic poly(styrene)-cis-1,4-poly(butadiene) (sPSB) have been investigated. Depending on the reaction parameters (support nanoporosity, presence of water, solvent, temperature, cocatalyst, oxygen pressure), the conversion of HMF can be finely addressed to the formation of the desired oxidation product, such as 2,5-diformylfuran (DFF), 5-formylfuran-2-carboxylic acid (FFCA), methyl 5-(hydroxymethyl)furan-2-carboxylate (MHMFC), dimethyl furan-2,5-dicarboxylate (DMFC), and furan-2,5-dicarboxylic acid (FDCA), under optimized reaction conditions. The AuNP-sPSB catalyst is highly effective and selective because the polymer support acts as a conveyor and concentrator of the reactants toward the catalytic sites.

Inexpensive but Highly Efficient Co–Mn Mixed‐Oxide Catalysts for Selective Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Furandicarboxylic Acid

A highly active and inexpensive Co-Mn mixed-oxide catalyst was prepared and used for selective oxidation of 5-hydroxymethylfurfural (HMF) into 2, 5-furandicarboxylic acid (FDCA). Co-Mn mixed-oxide catalysts with different Co/Mn molar ratios were prepared through a simple solid-state grinding method-a low-cost and green catalyst preparation method. The activity of these catalysts was evaluated for selective aerobic oxidation of HMF into FDCA in water. Excellent HMF conversion (99 %) and FDCA yield (95 % ) were obtained under the best reaction conditions (i.e., 120 °C, 5 h, Co-Mn mixed-oxide catalyst with a Co/Mn molar ratio of 0.25 calcined at 300 °C (Co-Mn-0.25) and 1 MPa O2 ). The catalyst could be reused five times without a significant decrease in activity. The results demonstrated that the catalytic activity and selectivity of the Co-Mn mixed-oxide catalysts prepared through solid-state grinding were superior to the same Co-Mn catalyst prepared through a conventional coprecipitation method. The high catalytic activity of the Co-Mn-0.25 catalyst was attributed to its high lattice oxygen mobility and the presence of different valence states of manganese. The high activity and low cost of the Co-Mn mixed-oxide catalysts prepared by solid-state grinding make it promising for industrial application for the manufacturing of polyethylene furanoate, a bioreplacement for polyethylene terephthalate, from sustainable bioresources.

Two furan-2,5-dicarboxylic acid solvates crystallized from dimethylformamide and dimethyl sulfoxide.

Furan-2,5-dicarboxylic acid (FDCA) has been ranked among the top 12 bio-based building-block chemicals by the Department of Energy in the US. The molecule was first synthesized in 1876, but large-scale production has only become possible since the development of modern bio- and chemical catalysis techniques. The structures of two FDCA solvates, namely, FDCA dimethylformamide (DMF) disolvate, C6H4O5·2C3H7NO, (I), and FDCA dimethyl sulfoxide (DMSO) monosolvate, C6H4O5·C2H6OS, (II), are reported. Solvate (I) crystallizes in the orthorhombic Pbcn space group and solvate (II) crystallizes in the monoclinic P-1 space group. In (I), hydrogen bonds form between the carbonyl O atom in DMF and a hydroxy H atom in FDCA. Whilst in (II), the O atom in one DMSO molecule hydrogen bonds with hydroxy H atoms in two FDCA molecules. Combined with intermolecular S...O interactions, FDCA molecules form a two-dimensional network coordinated by DMSO.

Synthesis of furan dimer‐based polyamides with a high melting point

ABSTRACTPolyamide composed of furan dimer, which is prepared from biomass‐derived organic molecule 2‐furfural, is synthesized. The reaction of 2,2′‐furan dimer 5,5′‐dicarbonyl chloride with several 1,ω‐diamines was carried out with a solution or interfacial polycondensation leading to the corresponding polyamide. Measurement of the melting point was performed resulting to exhibit a higher temperature compared with the related polyamide bearing a single furan ring composed of furan‐2,5‐dicarboxylic acid (FDCA). Thermal analyses (TG–DTA) also indicated higher temperatures of decomposition than those of FDCA‐derived polyamide. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1516–1519

Synvina’s FDCA plant delayed by two years

Synvina, a joint venture between BASF and the Dutch firm Avantium, says it is delaying the start-up of its first commercial plant for the biobased chemical furandicarboxylic acid (FDCA) by two or three years to 2023 or 2024. Set to be built in Antwerp, Belgium, the plant will make the key raw material for a new biopolymer, polyethylene furanoate. Synvia says the delay is because it needs to iron out processing inefficiencies identified in the pilot production of FDCA.

Industrial production, application, microbial biosynthesis and degradation of furanic compound, hydroxymethylfurfural (HMF).

Biorefinery is increasingly embraced as an environmentally friendly approach that has the potential to shift current petroleum-based chemical and material manufacture to renewable sources. Furanic compounds, particularly hydroxymethylfurfurals (HMFs) are platform chemicals, from which a variety of value-added chemicals can be derived. Their biomanufacture and biodegradation therefore will have a large impact. Here, we first review the potential industrial production of 4-HMF and 5-HMF, then we summarize the known microbial biosynthesis and biodegradation pathways of furanic compounds with emphasis on the enzymes in each pathway. We especially focus on the structure, function and catalytic mechanism of MfnB (4-(hydroxymethyl)-2-furancarboxyaldehyde-phosphate synthase) and hmfH (HMF oxidase), which catalyze the formation of phosphorylated 4-HMF and the oxidation of 5-HMF to furandicarboxylic acid (2,5-FDCA), respectively. Understanding the structure-function relationship of these enzymes will provide important insights in enzyme engineering, which eventually will find industry applications in mass-production of biobased polymers and other bulk chemicals in future.

Selective synthesis of 2, 5-furandicarboxylic acid by oxidation of 5-hydroxymethylfurfural over MnFe2O4 catalyst

Development of green catalytic processes using biobased feedstock for valuable chemicals such as 5-hydroxymethylfurfural (HMF) is hotly pursued. 2, 5-Furandicarboxylic acid (FDCA), a bio-based alternative to terephthalic acid was efficiently synthesized by oxidation of HMF using MnFe2O4 spinel structured magnetic nanoparticles (MNPs) and tert-butyl hydroperoxide as an oxidant. MnFe2O4 catalyst showed the highest activity and selectivity and gave 85% yield of FDCA at 100°C in 5h. The higher activity of MnFe2O4 catalyst is due to the variable oxidation state of manganese. The combination of MnFe2O4 catalyst and TBHP oxidant requires less time and energy compared to other reported processes of FDCA synthesis. Also, many reported methods have used a homogeneous base for FDCA synthesis which is totally avoided in the current process. The concentration profiles of reactants and products were established and kinetics determined. The effects of various reaction parameters were studied to validate kinetic model. The catalyst was easily recycled due to its magnetic property and showed good catalytic activity up to four cycles. All metal ferrites were characterized by different analytical techniques. The catalyst maintained its fidelity.

New bottle plastic is okay in Europe

A European polyethylene terephthalate (PET) bottle industry group has given interim approval to bottles made out of polyethylene furanoate (PEF), a polymer being developed by Synvina, a joint venture of BASF and Avantium. Whereas PET is made with purified terephthalic acid, a petrochemical, PEF is made with furandicarboxylic acid, which is derived from renewable resources. The industry group concluded that PEF bottles can be recycled alongside PET bottles.