Furandicarboxylic Acid Research Articles

Environmental Profile and Technological Validation of New High-Tg Unsaturated Polyesters from Fully Bio-Based Monomers and Reactive Diluents

This study was focused on the synthesis and characterization of a fully bio-based unsaturated polyester resin (UPR) with good thermal properties suitable for the commercial production of composite polymers. UPRs based on different ratios of bio-based furan dicarboxylic acid (FDCA), itaconic acid, and diols were synthesized. The unsaturated polymers prepared were evaluated by differential scanning calorimetry, gel permeation chromatography, FTIR and 1H-NMR spectroscopy. The results showed positive effects of FDCA on the glass transition temperature (Tg) of these fully bio-based polyesters, especially when FDCA was combined with 1,2-propanediol. Optimal values of Tg were obtained in the range of 30–32 °C for UPRs synthesized starting with a higher concentration of FDCA in the monomer feed. The possibility of substituting styrene, which usually acts as a reactive diluent, with a greener and safer alternative during the crosslinking of UPRs, was also explored. Two bio-based reactive diluents were considered: dimethyl itaconate (DMI) and butanediol dimethacrylate. After crosslinking, an average Tg of 75 °C and a good crosslinking efficiency indicated by a gel content of 90% were achieved for the fully bio-based polyester obtained under milder reaction conditions and dilution with DMI. Life cycle assessment was performed on selected UPRs, and comparison with a reference fossil-based resin in terms of the calculated category indicator results confirmed the lower environmental impact of the newly prepared bio-based polyesters.

Towards High Molecular Weight Furan-Based Polyesters: Solid State Polymerization Study of Bio-Based Poly(Propylene Furanoate) and Poly(Butylene Furanoate).

In the era of polymers from renewable resources, polyesters derived from 2,5 furan dicarboxylic acid (FDCA) have received increasing attention due to their outstanding features. To commercialize them, it is necessary to synthesize high molecular weight polymers through efficient and simple methods. In this study, two furan-based polyesters, namely poly (propylene furanoate) (PPF) and poly(butylene furanoate) (PBF), were synthesized with the conventional two-step melt polycondensation, followed by solid-state polycondensation (SSP) conducted at different temperatures and reaction times. Molecular weight, structure and thermal properties were measured for all resultant polyesters. As expected, increasing SSP time and temperature results in polymers with increased intrinsic viscosity (IV), increased molecular weight and reduced carboxyl end-group content. Finally, those results were used to generate a simple mathematical model that prognosticates the time evolution of the materials’ IV and end groups concentration during SSP.

Designing anti-migration furan-based plasticizers and their plasticization properties in poly (vinyl chloride) blends

The use of bio-based plasticizers with low toxicity and good compatibility with polyvinyl chloride (PVC) has attracted more attention in the recent years. With bio-based 2, 5-furandicarboxylic acid (FDCA) and butyl oligo-glycol ethers as raw materials, three liquid furan-based plasticizers of di(butyl glycol) furan-2,5-dicarboxylate, di(butyldiglycol) furan-2,5-dicarboxylate and di(butyltriglycol) furan-2,5-dicarboxylate were synthesized by direct esterification. The chemical structure of three plasticizers was characterized with FTIR, 1H NMR and 13C NMR. From DMA measurement, the glass transition temperature (Tg) of the plasticized PVC was decreased gradually when furan-based plasticizers were added to PVC formulation from 30 up to 50 phr. Due to lots of ether bonds in furan-based plasticizers, they expressed over two-fold lower migration in organic solvent compared with the traditional plasticizer diethylhexyl phthalate (DEHP). Through the characterization of elongation at break, hardness and thermal stability, furan-based plasticizers presented the same plasticization properties as DEHP, and had potential industrial application prospects.

Heterogeneous Catalytic Conversion of Sugars Into 2,5-Furandicarboxylic Acid.

Achieving the goal of living in a sustainable and greener society, will need the chemical industry to move away from petroleum-based refineries to bio-refineries. This aim can be achieved by using biomass as the feedstock to produce platform chemicals. A platform chemical, 2,5-furandicarboxylic acid (FDCA) has gained much attention in recent years because of its chemical attributes as it can be used to produce green polymers such polyethylene 2,5-furandicarboxylate (PEF) that is an alternative to polyethylene terephthalate (PET) produced from fossil fuel. Typically, 5-(hydroxymethyl)furfural (HMF), an intermediate product of the acid dehydration of sugars, can be used as a precursor for the production of FDCA, and this transformation reaction has been extensively studied using both homogeneous and heterogeneous catalysts in different reaction media such as basic, neutral, and acidic media. In addition to the use of catalysts, conversion of HMF to FDCA occurs in the presence of oxidants such as air, O2, H2O2, and t-BuOOH. Among them, O2 has been the preferred oxidant due to its low cost and availability. However, due to the low stability of HMF and high processing cost to convert HMF to FDCA, researchers are studying the direct conversion of carbohydrates and biomass using both a single- and multi-phase approach for FDCA production. As there are issues arising from FDCA purification, much attention is now being paid to produce FDCA derivatives such as 2, 5-furandicarboxylic acid dimethyl ester (FDCDM) to circumvent these problems. Despite these technical barriers, what is pivotal to achieve in a cost-effective manner high yields of FDCA and derivatives, is the design of highly efficient, stable, and selective multi-functional catalysts. In this review, we summarize in detail the advances in the reaction chemistry, catalysts, and operating conditions for FDCA production from sugars and carbohydrates.

Engineered PQQ-Dependent Alcohol Dehydrogenase for the Oxidation of 5-(Hydroxymethyl)furoic Acid

Furan-2,5-dicarboxylic acid (FDCA) is a bio-based platform chemical with the potential to replace terephthalic acid in the production of polymers. A critical step for enzymatic and whole-cell production of FDCA from 5-(hydroxymethyl)furfural (HMF) is the transformation of 5-(hydroxymethyl)furoic acid (HMFA) into 5-formylfuroic acid (FFA). Here, we establish periplasmic pyrroloquinoline quinone (PQQ)-dependent alcohol dehydrogenases (ADHs) as biocatalytic tools for the oxidation of HMFA, HMF, and 5-formylfurfural (FFF). Further, we identify several amino acid residues including the “lid loop” of the substrate channel as promising targets for future engineering steps toward a fully periplasmic oxidation pathway to FDCA.

Combined CO2-Electroreduction Towards Formate Production and HMF Oxidation

Recent advancement on carbon dioxide reduction reaction (CO2RR) has shown promising results on CO2 conversion to value-added carbon products as renewable fuels or valuable chemical feedstocks. Formic acid is one of the products that requires low applied voltage in CO2RR. However, it remains with a low full cell energy efficiency, mainly due to the large full cell applied potential. Traditionally, the anodic reaction is carried out with oxygen evolution reaction (OER), which requires a higher applied potential on the counter electrode. This work reports a viable alternative anodic reaction on electro-oxidative upgrading of biomass-derived 5-hydroxymethylfurfural (HMF) into valorized chemicals such as furandicarboxylic acid (FDCA) using Ni-based catalyst. Experimental results have demonstrated that in the combined electrolyzer, the Faradaic efficiency of formate can increase from 41% to 76%, while keeping the applied potential as low as 2 V for achieving a current density of 10 mA/cm2. In addition, at the anode, the Faradaic efficiency reached 60% towards FDCA using the same combined setup. It is postulated that due to the lower overpotential at anode, the cathodic potential becomes more negative for the same current density, and hence a higher Faradaic efficiency towards formate can be attained. Moreover, compared to conventional systems with OER, the combined system is able to produce a value-added product such as FDCA with a considerable FE, approaching a more economic application.

Synthesis of Poly(Ethylene 2,5-Furanoate): I. Kinetics of 2,5-Dimethyl Ester of Furandicarboxylic Acid Transesterification

The kinetics of the 2,5-dimethyl ester of furandicarboxylic acid transesterification in the presence of various catalysts at different temperatures was investigated. It was shown that the catalytic activity follows the order: Mn (OAc)2 < Co (OAc)2 < Zn (OAc)2 < Ti (OBu)4. The transesterification catalyzed by Ti (OBu)4 leads to the formation of the polymers with the higher molecular weight compared to Me (OAc)2.

Positive Impact of Natural Deep Eutectic Solvents on the Biocatalytic Performance of 5-Hydroxymethyl-Furfural Oxidase

Deep eutectic solvents (DESs) have been applied as cosolvents in various biocatalytic processes during recent years. However, their use in combination with redox enzymes has been limited. In this study, we have explored the beneficial effects of several DES as cosolvents on the performance of 5-hydroxymethylfurfural oxidase (HMFO), a valuable oxidative enzyme for the preparation of furan-2,5-dicarboxylic acid (FDCA), and other compounds, such as carbonyl compounds and carboxylic acids. The use of natural DESs, based on glucose and fructose, was found to have a positive effect. Higher conversions are obtained for the synthesis of several oxidized compounds, including FDCA. Depending on the type of DES, the stability of HMFO could be significantly improved. As the use of DES increases the solubility of many substrates while they only mildly affect dioxygen solubility, this study demonstrates that biocatalysis based on HMFO and other redox biocatalysts can benefit from a carefully selected DES.

Selective oxidation of 5-formyloxymethylfurfural to 2, 5-furandicarboxylic acid with Ru/C in water solution

Selective oxidation of 5-formyloxymethylfurfural to 2, 5-furandicarboxylic acid with Ru/C in water solution

Immobilization of the engineered Raoultella ornithinolytica BF60 for biocatalytic synthesis of 2, 5-furandicarboxylic acid.

As a bio-based platform chemical, 2, 5-furandicarboxylic acid (FDCA) is a promising substitute of terephthalic acid to synthesize poly (ethylene furanoate) used for bio-substitute of polyethylene terephthalate (PET). In previous work, we engineered a Raoultella ornithinolytica BF60 strain and achieved the effective biocatalytic synthesis of FDCA from 5-hydroxymethylfurfural (HMF). Herein, to improve the reusability of the engineered R. ornithinolytica BF60 cells, we used two materials PVA1799-boric acid and sodium alginate-Ca2+ to immobilize the cells. The sodium alginate-Ca2+ was more suitable for FDCA production, and 22 mmol/L FDCA was obtained with Ca(H2PO4)2 as the cross-linker. In addition, the immobilization conditions were optimized and FDCA production was further increased to 74.8 mmol/L. Here the developed immobilization strategy for R. ornithinolytica BF60 cells may be helpful for the economical production of FDCA in the future.

Endocrine activities of phthalate alternatives; assessing the safety profile of furan dicarboxylic acid esters using a panel of human cell based reporter gene assays

Ensuring non-regrettable substitution of fossil derived chemicals by biobased alternatives using human cell based reporter gene assays.

A unique pathway to platform chemicals: aldaric acids as stable intermediates for the synthesis of furandicarboxylic acid esters

A novel method for the efficient production of furandicarboxylic acid from sugar diacids by acid-catalysed dehydration.

Stora Enso, Avantium advance FDCA plants

Stora Enso will invest $10 million in a pilot facility for converting sugars into furandicarboxylic acid (FDCA), an intermediate for the plastic polyethylene furanoate. It will be located at Stora Enso’s paper mill in Langerbrugge, Belgium. Meanwhile, the European Union has given a consortium led by Avantium $28 million of the $170 million it needs to build a 5,000-metric-ton-per-year FDCA plant. BASF pulled out of an FDCA joint venture with Avantium earlier this year.

Sequential oxidation of 5-hydroxymethylfurfural to furan-2,5-dicarboxylic acid by an evolved aryl-alcohol oxidase

Furan-2,5-dicarboxylic acid (FDCA) is a building block of biodegradable plastics that can be used to replace those derived from fossil carbon sources. In recent years, much interest has focused on the synthesis of FDCA from the bio-based 5-hydroxymethylfurfural (HMF) through a cascade of enzyme reactions. Aryl-alcohol oxidase (AAO) and 5-hydroxymethylfurfural oxidase (HMFO) are glucose-methanol-choline flavoenzymes that may be used to produce FDCA from HMF through three sequential oxidations, and without the assistance of auxiliary enzymes. Such a challenging process is dependent on the degree of hydration of the original aldehyde groups and of those formed, the rate-limiting step lying in the final oxidation of the intermediate 5-formyl-furancarboxylic acid (FFCA) to FDCA. While HMFO accepts FFCA as a final substrate in the HMF reaction pathway, AAO is virtually incapable of oxidizing it. Here, we have engineered AAO to perform the stepwise oxidation of HMF to FDCA through its structural alignment with HMFO and directed evolution. With a 3-fold enhanced catalytic efficiency for HMF and a 6-fold improvement in overall conversion, this evolved AAO is a promising point of departure for further engineering aimed at generating an efficient biocatalyst to synthesize FDCA from HMF.

Novamont plans demo plant for FDCA

Novamont plans to spend about $11 million to build a demonstration facility at its site in Terni, Italy, for the sugar-derived monomer furandicarboxylic acid (FDCA). Novamont says it will use FDCA as a raw material for biodegradable polyesters used in its Mater-Bi line of plastics. Separately, Novamont has opened a Mater-Bi plant in Patrica, Italy, that complements a similar facility in Terni.

Complete oxidation of hydroxymethylfurfural to furandicarboxylic acid by aryl-alcohol oxidase

Background5-Hydroxymethylfurfural (HMF) is a highly valuable platform chemical that can be obtained from plant biomass carbohydrates. HMF can be oxidized to 2,5-furandicarboxylic acid (FDCA), which is used as a renewable substitute for the petroleum-based terephthalic acid in polymer production.ResultsAryl-alcohol oxidase (AAO) from the white-rot fungus Pleurotus eryngii is able to oxidize HMF and its derivative 2,5-diformylfuran (DFF) producing formylfurancarboxylic acid (FFCA) thanks to its activity on benzylic alcohols and hydrated aldehydes. Here, we report the ability of AAO to produce FDCA from FFCA, opening up the possibility of full oxidation of HMF by this model enzyme. During HMF reactions, an inhibitory effect of the H2O2 produced in the first two oxidation steps was found to be the cause of the lack of AAO activity on FFCA. In situ monitoring of the whole reaction by 1H-NMR confirmed the absence of any unstable dead-end products, undetected in the HPLC analyses, that could be responsible for the incomplete conversion. The deleterious effect of H2O2 was confirmed by successful HMF conversion into FDCA when the AAO reaction was carried out in the presence of catalase. On the other hand, no H2O2 formation was detected during the slow FFCA conversion by AAO in the absence of catalase, in contrast to typical oxidase reaction with HMF and DFF, suggesting an alternative mechanism as reported in some reactions of related flavo-oxidases. Moreover, several active-site AAO variants that yield nearly complete conversion in shorter reaction times than the wild-type enzyme have been identified.ConclusionsThe use of catalase to remove H2O2 from the reaction mixture leads to 99% conversion of HMF into FDCA by AAO and several improved variants, although the mechanism of peroxide inhibition of the AAO action on the aldehyde group of FFCA is not fully understood.

Electro-Oxidation of Furans to Value-Added Chemicals

Aqueous electrochemistry presents a unique platform for the valorization of biomass-derived oxygenates through rearrangements involving H or O atoms under ambient conditions. In addition, the electrochemical environment can alter product distributions and efficiencies in comparison to analogous thermochemical routes. For example, oxidation product selectivities can vary with potential by changing the surface coverage of hydroxyl groups and/or through the stabilization of products requiring electron transfer as opposed to neutral atom transfer steps. This study focuses on characterizing the partial electro-oxidation of furfural and HMF under acidic conditions on various noble metal catalysts. These biomass-derived model compounds are derived from the acid-catalyzed conversion of lignocellulosic feedstocks and can yield value-added products such as furoic acid,maleic acid, and furan-dicarboxylic acid. A differential “flow-through” electrochemical reactor was paired with membrane-inlet mass spectrometry (MIMS) and LC-MS. We analyze the partial electro-oxidation of furans under a variety of conditions and discuss trends in product distributions as they pertain to possible reaction pathways. Ongoing work involves investigation of the reaction mechanisms through isotopic labeling experiments and electrochemical ATR-FTIR.

Bio-binders for the improvement of the performance of natural fibers as reinforcements in composites to increase the sustainability in the transport sector

In order to reduce the negative impact on the environment of the current composite materials, renewable sources have been used as raw materials. One of the most promising approaches is the substitution of the reinforcement material by natural fibers, which are usually obtained from more sustainable resources (agro-waste). However, these materials have still some limitations and drawbacks for their use in high performance applications, one of the reasons being a poor interaction between fiber and matrix. Recent studies show the possibility of improving their mechanical properties by means of the application of a third material to increase interaction between fiber and matrix. In this paper the use of humins (a by-product of the production of furandicarboxylic acid) has been proved to be an efficient bio-binder for natural fibers and epoxy resin. Bio-composites containing different loadings of humins for large parts for ground transportation applications have been produced by liquid resin infusion, validating the aforementioned approach. The results obtained have demonstrated the feasibility of the strategy of using humins for improving the mechanical properties of bio-composites, accelerating the potential for their market acceptance.

Avantium advances bottle polymer

Four months after breaking with partner BASF, Avantium says it will proceed on its own to commercialize polyethylene furanoate (PEF), a biobased alternative to the beverage-bottle polymer polyethylene terephthalate (PET). At a meeting with investors on June 6, Avantium said it plans to make PEF and its raw material, furandicarboxylic acid (FDCA), at a plant with an annual capacity of 5,000 metric tons (t). The firm said it has engaged the engineering firm Worley to draw up engineering studies for the roughly $170 million facility, which it hopes to start up in 2023 at a still-to-be-determined site in northwestern Europe. Avantium CEO Tom van Aken told investors that his firm continues to believe in the technology and “the unique properties of PEF.” The Dutch firm originally planned a much larger project when it partnered with BASF in 2016. Their joint venture, Synvina, expected to build a 50,000 t FDCA plant

Enzymatic Carboxylation of 2-Furoic Acid to 2,5-Furandicarboxylic Acid

Key words furandicarboxylic acid - furoic acid - carboxylation - HmfF enzyme