Ethylene Furanoate Research Articles

Task-Specific Deep Eutectic Solvent for Efficient Dissolution and Further Accelerating Alkaline Hydrolysis of Polyesters Into Their Monomers.

Polyester plastics have brought great convenience to modern society. However, the continuous accumulation of their production increasingly threatens human health. Polyethylene terephthalate (PET) is one of the largest type of polyester plastics and its recycling is a major challenge. In this work, deep eutectic solvent (DES) composed of thenyl alcohol and choline chloride (ChCl) was designed for efficient dissolution of PET at 165 °C for 20 min, and further accelerating complete alkaline hydrolysis of PET into its monomer terephthalic acid (TPA) and ethylene glycol (EG) with a high TPA monomer yield (98.2 %) in 25 min at 100 °C. Moreover, the designed DES is also efficient for dissolution and alkaline hydrolysis of other polyester plastics, including poly(trimethylene terephthalate) (PTT) and poly(ethylene furanoate) (PEF) into their monomers. This work provides a feasible and sustainable solution for the recycling of polyester wastes.

Scale-Up Preparation of Biobased Poly(ethylene furanoate) Biaxial Orientation Films with Enhanced Mechanical and Barrier Properties for Packaging

Scale-Up Preparation of Biobased Poly(ethylene furanoate) Biaxial Orientation Films with Enhanced Mechanical and Barrier Properties for Packaging

Furandicarboxylic Acid (FDCA): Electrosynthesis and Its Facile Recovery From Polyethylene Furanoate (PEF) via Depolymerization.

Replacing fossil fuels with renewable, bio-based alternatives is inevitable for the modern chemical industry, in line with the 12 principles of green chemistry. 2,5-Furandicarboxylic acid (FDCA) is a promising platform molecule that can be derived from 5-hydroxymethyl furfural (HMF) via sustainable electrochemical oxidation. Herein, we demonstrate TEMPO-mediated electrooxidation of HMF to FDCA in ElectraSyn 2.0 using inexpensive commercially available electrodes: graphite anode and stainless-steel cathode, thereby avoiding the often cumbersome electrode preparation. Key parameters such as concentration of HMF, KOH, and catalyst loading were optimized by experimental design. Under the optimized conditions, using only a low amount of TEMPO (5 mol%), high yield and Faradaic efficiency of 96% were achieved within 2.5 hours. Moreover, since FDCA is a monomer of the bio-based poly(ethylene furanoate), PEF, we aimed to investigate its recovery by depolymerization, which could be of paramount importance in the circular economy of the FDCA. For this, a new polar aprotic solvent, methyl sesamol (MeSesamol), was used, allowing the facile depolymerization of PEF at room temperature with high monomer yields (up to 85%), while the cosolvent MeSesamol was recycled with high efficiency (95-100%) over five reaction cycles.

DFT study on the depolymerization of PET by Ca-catalyzed glycolysis reaction model

Poly(ethylene terephthalate) (PET) is the most common plastics produced for applications in food and drinking containers. It is degraded to valuable product by several methods. Glycolysis of PET gains bis(2-hydroxyethylene) terephthalate (BHET) as the main product utilized as plasticizer. Calcium catalysts, Ca2+ and Ca(OH)2∙2H2O were explored to study the mechanism of PET cleavage by DFT calculations at B3LYP/6-311++G** level. Two possible pathways, coordination, and non-coordination of ethylene glycol on the calcium in glycolysis reaction, have been investigated. In addition, poly(ethylene furanoate) (PEF), considered as a sustainable polymer with the similar functional properties, was chose for the comparison of conformational structures with PET. The understanding of the relationship between PET (and PEF) structures and calcium catalysts is useful for the future development of linear sustainable polyesters.

Tracking the Conjugated Yellowing Derivatives during the Production of Poly(ethylene furanoate) Using High-Definition Mass Spectrometry

Tracking the Conjugated Yellowing Derivatives during the Production of Poly(ethylene furanoate) Using High-Definition Mass Spectrometry

Fabrication of Poly(ethylene furanoate)/Silver and Titanium Dioxide Nanocomposites with Improved Thermal and Antimicrobial Properties.

Poly(ethylene furanoate) (PEF)-based nanocomposites were fabricated with silver (Ag) and titanium dioxide (TiO2) nanoparticles by the in-situ polymerization method. The importance of this research work is to extend the usage of PEF-based nanocomposites with improved material properties. The PEF-Ag and PEF-TiO2 nanocomposites showed a significant improvement in color concentration, as determined by the color colorimeter. Scanning electron microscopy (SEM) photographs revealed the appearance of small aggregates on the surface of nanocomposites. According to crystallinity investigations, neat PEF and nanocomposites exhibit crystalline fraction between 0-6%, whereas annealed samples showed a degree of crystallinity value above 25%. Combining the structural and molecular dynamics observations from broadband dielectric spectroscopy (BDS) measurements found strong interactions between polymer chains and nanoparticles. Contact angle results exhibited a decrease in the wetting angle of nanocomposites compared to neat PEF. Finally, antimicrobial studies have been conducted, reporting a significant rise in inhibition of over 15% for both nanocomposite films against gram-positive and gram-negative bacteria. From the overall results, the synthesized PEF-based nanocomposites with enhanced thermal and antimicrobial properties may be optimized and utilized for the secondary packaging (unintended food-contact) materials.

A Review of End-of-Life Pathways for Poly(Ethylene Furanoate) and its Derivatives

A Review of End-of-Life Pathways for Poly(Ethylene Furanoate) and its Derivatives

Towards consolidated bioprocessing of biomass and plastic substrates for semi-synthetic production of bio-poly(ethylene furanoate) (PEF) polymer using omics-guided construction of artificial microbial consortia

Poly(ethylene furanoate) (PEF) plastic is a 100% renewable polyester that is currently being pursued for commercialization as the next-generation bio-based plastic. This is in line with growing demand for circular bioeconomy and new plastics economy that is aimed at minimizing plastic waste mismanagement and lowering carbon footprint of plastics. However, the current catalytic route for the synthesis of PEF is impeded with technical challenges including high cost of pretreatment and catalyst refurbishment. On the other hand, the semi-biosynthetic route of PEF plastic production is of increased biotechnological interest. In particular, the PEF monomers (Furan dicarboxylic acid and ethylene glycol) can be synthesized via microbial-based biorefinery and purified for subsequent catalyst-mediated polycondensation into PEF. Several bioengineering and bioprocessing issues such as efficient substrate utilization and pathway optimization need to be addressed prior to establishing industrial-scale production of the monomers. This review highlights current advances in semi-biosynthetic production of PEF monomers using consolidated waste biorefinery strategies, with an emphasis on the employment of omics-driven systems biology approaches in enzyme discovery and pathway construction. The roles of microbial protein transporters will be discussed, especially in terms of improving substrate uptake and utilization from lignocellulosic biomass, as well as from depolymerized plastic waste as potential bio-feedstock. The employment of artificial bioengineered microbial consortia will also be highlighted to provide streamlined systems and synthetic biology strategies for bio-based PEF monomer production using both plant biomass and plastic-derived substrates, which are important for circular and new plastics economy advances.

Synthesis of Poly(ethylene furanoate) Based Nanocomposites by In Situ Polymerization with Enhanced Antibacterial Properties for Food Packaging Applications.

Poly(ethylene 2,5-furandicarboxylate) (PEF)-based nanocomposites containing Ce-bioglass, ZnO, and ZrO2 nanoparticles were synthesized via in situ polymerization, targeting food packaging applications. The nanocomposites were thoroughly characterized, combining a range of techniques. The successful polymerization was confirmed using attenuated total reflectance Fourier-transform infrared (ATR-FTIR) spectroscopy, and the molecular weight values were determined indirectly by applying intrinsic viscosity measurements. The nanocomposites' structure was investigated by depth profiling using time-of-flight secondary ion mass spectrometry (ToF-SIMS), while color measurements showed a low-to-moderate increase in the color concentration of all the nanocomposites compared to neat PEF. The thermal properties and crystallinity behavior of the synthesized materials were also examined. The neat PEF and PEF-based nanocomposites show a crystalline fraction of 0-5%, and annealed samples of both PEF and PEF-based nanocomposites exhibit a crystallinity above 20%. Furthermore, scanning electron microscopy (SEM) micrographs revealed that active agent nanoparticles are well dispersed in the PEF matrix. Contact angle measurements showed that incorporating nanoparticles into the PEF matrix significantly reduces the wetting angle due to increased roughness and introduction of the polar -OH groups. Antimicrobial studies indicated a significant increase in inhibition of bacterial strains of about 9-22% for Gram-positive bacterial strains and 5-16% for Gram-negative bacterial strains in PEF nanocomposite films, respectively. Finally, nanoindentation tests showed that the ZnO-based nanocomposite exhibits improved hardness and elastic modulus values compared to neat PEF.

3D-printing of biomass furan-based polyesters with robust mechanical performance and shape memory property

3D-printing provides a feasible technique for realizing new materials into structural and intelligent parts. In this work, biomass furan-based polyesters poly (ethylene furanoate) (PEF), poly (trimethylene furanoate) (PTF), and poly (butylene furanoate) (PBF) were successfully synthesized in a 5 L reactor through the melt polycondensation process and fabricated into 3D-printing feedstocks. It was demonstrated that the three furan-based polyesters were additively-manufactured into complicated structures. Besides, the mechanical and thermal properties of furan-based polyesters could be tailored by the chain length of diol monomer. The mechanical performance of 3D-printed PEF, PTF and PBF were characterized and compared with commercial filaments. The tensile strength of PEF and PTF could reach 74.6 and 63.8 MPa respectively, which exhibited superior tensile property to poly(ether-ether-ketone) (PEEK), polyamide (PA) and polylactic acid (PLA). Meanwhile, the compression results demonstrated that the PEF and PTF possessed comparable energy absorption capacity with PEEK and PLA respectively, which indicated excellent mechanical properties of furan-based polyesters. It was interesting to find that the 3D-printed structures including solid cube, bionic flower and lattice structures were employed to prove that the PTF possessed excellent shape memory properties. Therefore, the proposed biomass furan-based polymers would offer more freedom in the field of 3D-printing.

Engineering a Carboxyl Methyltransferase for the Formation of a Furan-Based Bioplastic Precursor.

FtpM from Aspergillus fumigatus was the first carboxyl methyltransferase reported to catalyse the dimethylation of dicarboxylic acids. Here the creation of mutant R166M that can catalyse the quantitative conversion of bio-derived 2,5-furandicarboxylic acid (FDCA) to its dimethyl ester (FDME), a bioplastics precursor, was reported. Wild type FtpM gave low conversion due to its reduced catalytic efficiency for the second methylation step. An AlphaFold 2 model revealed a highly electropositive active site, due to the presence of 4 arginine residues, postulated to favour the binding of the dicarboxylic acid over the intermediate monoester. The R166M mutation improved both binding and turnover of the monoester to permit near quantitative conversion to the target dimethyl ester product. The mutant also had improved activity for other diacids and a range of monoacids. R166M was incorporated into 2 multienzyme cascades for the synthesis of the bioplastics precursor FDME from bioderived 5-hydroxymethylfurfural (HMF) as well as from poly(ethylene furanoate) (PEF) plastic, demonstrating the potential to recycle waste plastic.

Effect of Monomer Type on the Synthesis and Properties of Poly(Ethylene Furanoate).

This work aimed to produce bio-based poly(ethylene furanoate) (PEF) with a high molecular weight using 2,5-furan dicarboxylic acid (FDCA) or its derivative dimethyl 2,5-furan dicarboxylate (DMFD), targeting food packaging applications. The effect of monomer type, molar ratios, catalyst, polycondensation time, and temperature on synthesized samples' intrinsic viscosities and color intensity was evaluated. It was found that FDCA is more effective than DMFD in producing PEF with higher molecular weight. A sum of complementary techniques was employed to study the structure-properties relationships of the prepared PEF samples, both in amorphous and semicrystalline states. The amorphous samples exhibited an increase in glass transition temperature of 82-87 °C, and annealed samples displayed a decrease in crystallinity with increasing intrinsic viscosity, as analyzed by differential scanning calorimetry and X-ray diffraction. Dielectric spectroscopy showed moderate local and segmental dynamics and high ionic conductivity for the 2,5-FDCA-based samples. The spherulite size and nuclei density of samples improved with increased melt crystallization and viscosity, respectively. The hydrophilicity and oxygen permeability of the samples were reduced with increased rigidity and molecular weight. The nanoindentation test showed that the hardness and elastic modulus of amorphous and annealed samples is higher at low viscosities due to high intermolecular interactions and degree of crystallinity.

Accelerated weathering of furanoate polyesters: Effect of molecular weight, crystallinity, and time

AbstractFilms of poly(ethylene furanoate) (PEF) and poly(neopentyl furanoate) (PNF) of different molecular weights were artificially weathered in a Q‐SUN test chamber for up to 500 h. The chemical and physical changes of the films have been evaluated with a wide range of techniques. All films, independent of molecular weight or crystallinity, show evidence of partial cross‐linking and the formation of new carbonyl species. Furthermore, all irradiated films show changes in thermal properties and crystallization behavior. The extent of degradation was higher for the amorphous films as compared to their semi‐crystalline counterparts, suggesting that UV degradation predominantly occurs in the amorphous phase. The apparent higher UV‐sensitivity of PNF, as compared to PEF, suggests that the nature of the diol, and the resulting polymer properties, affects the UV‐stability of the polymer. Nevertheless, comparison with poly(ethylene terephthalate) (PET) shows that the different electronic structure and properties of the furan ring are the most likely cause of the observed UV‐instability.

High-Antimicrobial Gallium-Doped Zinc Oxide Thin Films on Bio-Based Poly(Ethylene Furanoate) Substrates for Food Packaging Application

Thin films of gallium-doped zinc oxide (GZO), with a thickness of around fifty nanometers were deposited on bio-based poly(ethylene furanoate) (PEF) substrates by radio-frequency sputtering. By optimizing the Ga concentration in the target, the optics, water vapor barrier and antibacterial properties of PEF/GZO composite films can be adjusted. The highest visible light transmittance of the samples was around 85.1%. Furthermore, by introducing some GZO films with typical concentrations, the water vapor barrier and antibacterial properties of PEF films were improved. The optimized water vapor permeability of PEF/GZO composite film was 5.3 × 10-12 g·m/m2·s·Pa, and the highest antibacterial rate can reach 99.85% after 4 h. By XPS analysis, the antibacterial mechanism in the samples is envisaged to be mainly due cytotoxicity of Ga ions. The above results indicate that PEF/GZO films have great potential in the field of antibacterial food packaging.

Enzyme catalyzes ester bond synthesis and hydrolysis: The key step for sustainable usage of plastics.

Petro-plastic wastes cause serious environmental contamination that require effective solutions. Developing alternatives to petro-plastics and exploring feasible degrading methods are two solving routes. Bio-plastics like polyhydroxyalkanoates (PHAs), polylactic acid (PLA), polycaprolactone (PCL), poly (butylene succinate) (PBS), poly (ethylene furanoate) s (PEFs) and poly (ethylene succinate) (PES) have emerged as promising alternatives. Meanwhile, biodegradation plays important roles in recycling plastics (e.g., bio-plastics PHAs, PLA, PCL, PBS, PEFs and PES) and petro-plastics poly (ethylene terephthalate) (PET) and plasticizers in plastics (e.g., phthalate esters, PAEs). All these bio- and petro-materials show structure similarity by connecting monomers through ester bond. Thus, this review focused on bio-plastics and summarized the sequences and structures of the microbial enzymes catalyzing ester-bond synthesis. Most of these synthetic enzymes belonged to α/β-hydrolases with conserved serine catalytic active site and catalyzed the polymerization of monomers by forming ester bond. For enzymatic plastic degradation, enzymes about PHAs, PBS, PCL, PEFs, PES and PET were discussed, and most of the enzymes also belonged to the α/β hydrolases with a catalytic active residue serine, and nucleophilically attacked the ester bond of substrate to generate the cleavage of plastic backbone. Enzymes hydrolysis of the representative plasticizer PAEs were divided into three types (I, II, and III). Type I enzymes hydrolyzed only one ester-bond of PAEs, type II enzymes catalyzed the ester-bond of mono-ester phthalates, and type III enzymes hydrolyzed di-ester bonds of PAEs. Divergences of catalytic mechanisms among these enzymes were still unclear. This review provided references for producing bio-plastics, and degrading or recycling of bio- and petro-plastics from an enzymatic point of view.

Bio-based poly(ethylene furanoate)/ZnO transparent thin films with improved water vapor barrier and antibacterial properties for food packaging application

Poly(ethylene furanoate) (PEF) biocomposite films incorporating zinc oxide nanoparticle (ZnO NPs) were prepared using a solvent casting method. The ZnO NPs were homogeneously dispersed within the PEF films with the aid of γ−aminopropyltriethoxylsilane (APTES). The water vapor barrier, optical transmittance and antimicrobial properties of the PEF/ZnO films were tested. Water vapor permeability (WVP) and transmittance in the visible (400–800 nm) region of control PEF film were 6.92 × 10–12 g·m m−2 · s·Pa and 87.3%, respectively. WVP value of PEF films decreased 43.2% through ZnO NPs compounding. On the contrary, transmittance of PEF films decreased 6.8% due to the absorption and scattering of ZnO NPs. In addition, the PEF film with modified ZnO NPs exhibited a bacteriostatic rate up to 97.0% after 3 h. Thus, the PEF/ZnO films show great potential in the field of food packaging.

Compatibilization of Polylactide/Poly(ethylene 2,5-furanoate) (PLA/PEF) Blends for Sustainable and Bioderived Packaging.

Despite the advantages of polylactide (PLA), its inadequate UV-shielding and gas-barrier properties undermine its wide application as a flexible packaging film for perishable items. These issues are addressed in this work by investigating the properties of melt-mixed, fully bioderived blends of polylactide (PLA) and poly(ethylene furanoate) (PEF), as a function of the PEF weight fraction (1–30 wt %) and the amount of the commercial compatibilizer/chain extender Joncryl ADR 4468 (J, 0.25–1 phr). J mitigates the immiscibility of the two polymer phases by decreasing and homogenizing the PEF domain size; for the blend containing 10 wt % of PEF, the PEF domain size drops from 0.67 ± 0.46 µm of the uncompatibilized blend to 0.26 ± 0.14 with 1 phr of J. Moreover, the increase in the complex viscosity of PLA and PLA/PEF blends with the J content evidences the effectiveness of J as a chain extender. This dual positive contribution of J is reflected in the mechanical properties of PLA/PEF blends. Whereas the uncompatibilized blend with 10 wt % of PEF shows lower mechanical performance than neat PLA, all the compatibilized blends show higher tensile strength and strain at break, while retaining their high elastic moduli. The effects of PEF on the UV- and oxygen-barrier properties of PLA are also remarkable. Adding only 1 wt % of PEF makes the blend an excellent barrier for UV rays, with the transmittance at 320 nm dropping from 52.8% of neat PLA to 0.4% of the sample with 1 wt % PEF, while keeping good transparency in the visible region. PEF is also responsible for a sensible decrease in the oxygen transmission rate, which decreases from 189 cc/m2·day for neat PLA to 144 cc/m2·day with only 1 wt % of PEF. This work emphasizes the synergistic effects of PEF and J in enhancing the thermal, mechanical, UV-shielding, and gas-barrier properties of PLA, which results in bioderived blends that are very promising for packaging applications.

Harnessing Biobased Materials in Photosynaptic Transistors with Multibit Data Storage and Panchromatic Photoresponses Extended to Near‐Infrared Band

AbstractOwing to ever‐increasing environmental impact, nature‐inspired biomimetic electronics are key to unlock the potential of developing environmentally friendly brain‐like computing and biomimetic artificial‐intelligence systems. Thus far, the development of photosynaptic devices via green processing using biobased materials has become a major challenge, owing to restrictions in complex architecture, material design, and stimulation wavelength. This article reports on the first bioinspired phototransistor using biocomposites comprising semiconducting block copolymers, poly(3‐hexylthiophene)‐block‐maltoheptaose, and bacteriochlorophyll (BCHL), which extend the photoresponse from visible to UV to near‐infrared light, to exhibit fundamental sensing, computing, and memory functions. The superior ultrafast (50 ms) and multilevel (>9 bits) photoresponses of a single cell of the synaptic devices are attributed to hydrogen‐bonding interaction (i) between the block copolymers to facilitate the self‐assembled microstructure, and (ii) within the block copolymer and BCHL to homogeneously disperse the natural chromophore. Notably, a two‐terminal flexible synaptic device comprising biocomposites and a biobased poly(ethylene furanoate) substrate with high mechanical endurance is demonstrated to exhibit synaptic functionality and environmentally benign properties without using a gate impetus and hazardous ingredients. Collectively, the photosynaptic transistor comprising a biocomposite successfully provides an effective guide for applications in artificial visual perception, sensing, and memory in neuromorphic computing and intelligent systems.

Poly(ethylene furanoate-co-ethylene vanillate) biobased copolymers: Impact of the incorporation of vanillic acid units in poly(ethylene furanoate)

Biobased materials have acquired a high interest as a response to the environmental concerns of consumers as well as a solution to the pressing issue of dwindling fossil resources our society is facing. In the present study, five biobased copolymers of poly(ethylene vanillate) (PEV) and poly(ethylene furanοate) (PEF) have been synthesized by bulk polymerization for the first time. The aim was to explore whether PEF properties could be improved by copolymerization with PEV, a more recent but equally promising biobased polyester. The obtained copolymers were thoroughly characterized to assess the impact of the presence of PEV. More specifically, the molecular structure of the synthesized copolymers was characterized by nuclear magnetic spectroscopy and infrared spectroscopy, while their thermal behavior was examined by differential scanning calorimetry and thermogravimetric analysis. In complement, the mechanism of thermal degradation was studied by pyrolysis coupled with gas chromatography/mass spectrometry. Finally, their mechanical properties were investigated by nanoindentation.

Improving the Wet-Spinning and Drawing Processes of Poly(lactide)/Poly(ethylene furanoate) and Polylactide/Poly(dodecamethylene furanoate) Fiber Blends.

This work aims to produce poly(lactic acid) (PLA)/poly(alkylene furanoate)s (PAF)s fiber blends for textile applications and evaluates their microstructural, chemical, thermal, and mechanical properties. The work focuses on two PAFs with very different alkyl chain lengths, i.e., poly(ethylene 2,5−furandicarboxylate) (PEF) and poly(dodecamethylene 2,5−furandicarboxylate) (PDoF), which were blended in solution at various concentrations (in the range 2.5–10 wt %) with PLA, wet spun, and subsequently drawn. Light optical micrographs highlight that PLA/PEF blends present large and concentrate PEF domains, whereas PLA/PDoF blends show small and homogeneously distributed PDoF domains. The blends appear to be immiscible, which is confirmed also by scanning electron microscopy (SEM), Fourier−Transform Infrared (FT−IR) spectroscopy, and differential scanning calorimetry (DSC). Thermogravimetric analysis (TGA) highlights that the addition of the PAFs improves the thermal stability of the fibers. The drawing process, which was carried out at 80 °C with a heat setting step at 95 °C and at three draw ratios, improves the mechanical properties of the fibers upon the addition of the PAFs. The results obtained in this study are promising and may serve as a basis for future investigations on these novel bio−based fiber blends, which can contribute to increase the environmental sustainability of industrial textiles.