Search Results (26)

Achieving a circular and climate-neutral bioeconomy by 2050 requires not only high-quality recycling but also the large-scale integration of renewable carbon from biomass and atmospheric CO₂ into material systems. Plastics represent the world’s largest and most rapidly growing carbon sink, positioning them as a critical intervention point for replacing fossil-based feedstocks with renewable alternatives. Because plastic packaging is one of the most visible material streams encountered by consumers in daily life, a transition toward sustainable, recyclable bioplastics has the potential to deliver both meaningful environmental benefits and strong societal impact, accelerating public awareness and acceptance of renewable carbon solutions. Poly(ethylene furanoate) (PEF)—a fully bio-based polyester synthesized from plant-derived 2,5-furandicarboxylic acid (FDCA) and monoethylene glycol (MEG)—offers a promising pathway toward more sustainable packaging due to its superior mechanical strength and gas-barrier performance relative to polyethylene terephthalate (PET). This study presents a cradle to grave life cycle assessment (LCA) of PEF resin production and PEF bottle applications, using industrially relevant, at-scale process data covering biomass feedstock conversion, polymer synthesis, packaging manufacture, use phase, and end of life. Bottle applications were selected as a focal point due to their technical maturity, commercial relevance, and suitability for direct comparison with incumbent PET systems. The results indicate that PEF can reduce greenhouse gas emissions by up to 71% and fossil resource depletion by 26% compared to PET at the resin level when biogenic carbon uptake is included. Moreover, the material’s enhanced functional properties enable lightweight, recyclable bottle designs with carbon footprint reductions of up to 88% for 500 mL formats under a baseline recycling rate scenario of 72%, with the remaining share directed to municipal solid-waste incineration with energy recovery. Sensitivity analyses reveal that virgin PEF maintains environmental advantages over PET even when PET incorporates high levels of recycled content, highlighting the complementary roles of renewable carbon and circular material strategies. Prospective scenario modeling underscores the importance of sustainable feedstock selection and process electrification, with sucrose-based routes offering the largest potential for further decarbonization. Overall, the findings demonstrate that PEF is a scalable biopolymer capable of delivering substantial climate benefits while supporting circularity objectives. By targeting a highly visible consumer application—plastic packaging—this transition amplifies the societal impact of adopting renewable carbon materials. The study provides actionable insights for policymakers, industry stakeholders, and sustainability practitioners working to advance a more resilient, renewable, and consumer-recognizable plastics economy. Full article

Reducing dependence on fossil-based feedstocks for packaging can be achieved through three complementary strategies: minimizing packaging use, increasing closed-loop recycling rates, and expanding the adoption of renewable (e.g., biobased) packaging materials. To ensure these defossilization pathways reinforce rather than hinder one another, it is essential to understand how new biobased materials interact with existing recycling streams. With the market introduction of packaging containing the biobased polyester poly(ethylene 2,5-furandicarboxylate) (PEF) approaching, several studies have investigated blends and copolyesters of poly(ethylene terephthalate) (PET) and PEF. This study expands current knowledge of thermomechanical and crystallization behavior by examining the influence of PEF on the mechanical recycling process of bottle-grade PET. Processing behavior was assessed at various PEF contents at both laboratory and industrial scales, and the resulting recycled resin and bottles were analyzed for color, crystallization behavior, and bottle performance. Although the melting temperature decreased with rising PEF content, no negative impact on the industrial recycling process investigated was observed for PEF levels up to 10 wt%. Two notable trends emerged: increasing PEF content reduced crystallization rate, yielding bottles with higher transparency, while yellowness also increased. Ongoing research aims to understand and mitigate this rise in yellowness. Full article

In a quest to develop more sustainable polymers, decoupling their production from fuel-based resources and searching for alternative greener synthetic pathways are important priorities. Among the numerous polymers that fall into this category are furan-based polyesters. Besides the origin of polymers, their synthesis is another critical topic to consider regarding the overall greenness of the final product. However, despite several studies focusing on bio-based alternatives, such as poly(alkylene 2,5-furandicarboxylate)s, their synthesis still relies on air- and water-sensitive metal-based catalysts and is typically carried out under harsh conditions. This study explores an alternative approach with the application of eutectic solvents (ES) as catalysts for a more sustainable approach for synthesising furan-based polyesters, specifically poly(ethylene 2,5-furandicarboxylate) (PEF), as well as poly(trimethylene furandicarboxylate) (PTF) and poly(butylene furandicarboxylate) (PBF). Two different ES were evaluated as catalysts; the best results were obtained with urea and zinc acetate ES (U:Zn(OAc)₂, 4:1 mol:mol). The resulting polymers were analysed for their structure, molecular weight, and thermal properties. Full article

Two series of environmentally friendly polymer blends of bio-based poly(ethylene 2,5 furanoate) (PEF) and poly(butylene 2,5 furanoate) (PBF) with epoxidized natural rubber (epNR) have been prepared. Both bio-based polyesters were synthesized from dimethyl furan-2,5-dicarboxylate (DMFDC) and 1,2-ethylene glycol (EG) or 1,4-butylene glycol (BG) by a two-stage melt polycondensation process. The miscibility of the components in the blend was assessed using calculations based on Hoy’s method. The chemical interactions, presence of functional groups, miscibility, and possible reactions or cross-linking between polyesters and epNR were analyzed by Fourier Transform Infrared Spectroscopy (FTIR). A significant influence of epNR addition on the melt flow index (MFI), limited viscosity number (LVN), and apparent cross-link density values was also demonstrated. Phase transition temperatures and associated thermal phenomena in polyester/epNR blends were evaluated using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Oxidation onset temperature (OOT) tests were performed to obtain valuable information about the thermal-oxidative stability of the blends. Tensile tests revealed that the addition of epNR to PEF increases flexibility but at the same time reduces stiffness and tensile strength, especially at higher contents of epNR. In the case of PBF, a gradual decrease in tensile strength and elastic modulus is observed with increasing epNR content. Additionally, hardness tests showed that the addition of epNR leads to a decrease in hardness for both PEF- and PBF-based compositions. Full article

Post-processing plays a vital role in the determination of the final structures and properties of oriented materials. As a sustainable candidate of oil-based poly(ethylene terephthalate), biobased poly(ethylene 2,5-furandicarboxylate) (PEF) reflects great promise in green fiber, film, and packaging applications, but it undergoes poor stress-induced crystallization (SIC) under tensile deformation, necessitating a post-processing technique to improve its crystallinity and stability. Here, the structural evolution of pre-stretched PEF under post heating after uniaxial deformation was monitored by online synchrotron X-ray diffraction/scattering, differential scanning calorimetry, and ex situ infrared spectroscopy. The results delineate the significantly enhanced crystallization of pre-deformed PEF that happened far below its cold crystallization temperature. Through the isochronous analyses of the temperature-dependent evolution of mechanical response, the mesophase, crystal structure, orientation factor, chain conformation, and interchain ═C−H···O═C hydrogen bonding, the molecular mechanisms of microstructural transition and oriented crystallization of pre-drawn PEF under post heating were clarified. This research can enhance the understanding of PEF crystallization in an oriented state and provide guidelines on the structural design and technical control for processing high-performance PEF-based materials. Full article

Packaging materials mainly serve the function of protecting products. The most common representative of this group is poly(ethylene terephthalate) (PET), which is not biodegradable and therefore, its waste might be burdensome to the environment. Thus, this work aims to develop outlines for obtaining polyester-based systems, preferably biobased ones, intended for the packaging industry and their detailed characterization. The obtained multilayer systems based on two biobased thermoplastic polyesters, i.e., poly(ethylene 2,5-furandicarboxylate) (PEF) and the “double green” polylactide (PLA), were subjected to various analyses, i.e., UV-Vis spectrophotometry, microscopic evaluation, tensile tests, differential scanning calorimetry (DSC), oxygen transmission rate (OTR), water absorption tests, surface analyses, and biofilm formation. The best possible arrangement was selected in terms of the packaging industry. It was proven that the elastic modulus was significantly higher for multilayer systems, whilst higher-strength parameters were observed for PLA single foils. Regardless of thickness, PLA and PEF foils exhibit similar absorption values in cold water. Moreover, PEF foils demonstrated significantly better barrier properties towards oxygen gas compared to PLA foils of the same thickness. However, a multilayer system composed of two PLA foils with a single inner PEF foil had an OTR value only slightly higher than that of the PEF foil alone. PEF was also found to be a material that exhibited a limited formation of bacterial biofilm, particularly strains of S. aureus and E. coli. All of the above findings clearly confirm the sensibility of the research topic undertaken in this work on the application of biobased thermoplastic polyesters in the packaging industry. Full article

This study presents the synthesis and characterization of a series of multiblock copolymers, poly(ethylene 2,5-furandicarboxylate)-poly(ε-caprolactone) (PEF-PCL), created through a combination of the two-step melt polycondensation method and ring opening polymerization, as sustainable alternatives to fossil-based plastics. The structural confirmation of these block copolymers was achieved through Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR), ensuring the successful integration of PEF and PCL segments. X-ray Photoelectron Spectroscopy (XPS) was employed for chemical bonding and quantitative analysis, providing insights into the distribution and compatibility of the copolymer components. Differential Scanning Calorimetry (DSC) analysis revealed a single glass transition temperature (T_g), indicating the effective plasticizing effect of PCL on PEF, which enhances the flexibility of the copolymers. X-ray Diffraction (XRD) studies highlight the complex relationship between PCL content and crystallization in PEF-PCL block copolymers, emphasizing the need to balance crystallinity and mechanical properties for optimal material performance. Broadband Dielectric Spectroscopy (BDS) confirmed excellent distribution of PEF-PCL without phase separation, which is vital for maintaining consistent material properties. Mechanical properties were evaluated using Nanoindentation testing, demonstrating the potential of these copolymers as flexible packaging materials due to their enhanced mechanical strength and flexibility. The study concludes that PEF-PCL block copolymers are promising candidates for sustainable packaging solutions, combining environmental benefits with desirable material properties. Full article

Crystallization-controlled structure and thermal properties of biobased poly(ethylene 2,5-furandicarboxylate) (PEF) were studied. The cold-crystallization temperature controlled the structure and thermal properties of the biobased PEF. The melting was complex and evidenced the presence of a significant fraction of less-stable crystals with a low melting temperature that linearly increased with T_c, which formed already during the early stages of crystallization, together with those melting at a higher temperature. Low T_c resulted in the α’-phase formation, less crystallinity, and greater content of the rigid amorphous phase. At high T_c, the α-phase formed, higher crystallinity developed, the rigid amorphous phase content was lower, and the melting temperature of the less-stable crystals was higher; however, slight polymer degradation could have occurred. The applied thermal treatment altered the thermal behavior of PEF by shifting the melting of the less stable crystals to a significantly higher temperature. SEM examination revealed a spherulitic morphology. A lamellar order was evidenced with an average long period and small average lamella thickness, the latter about 3–3.5 nm, only slightly increasing with T_c. Full article

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. Full article

Utilizing triethylenediamine (DA), 1,3-propanesultone (PS), whose ring opens during the formation of the dizwiterion-intermediate DA-2PS, and the metal chlorides XCly, where X = Sn(IV), Zn(II),Al(III), Fe(III) and Mn(II), are used for the synthesis of five kinds of acidic metal-based functionalized ionic liquid catalysts ([DA-2PS][XCly]₂). Their chemical structures, thermal stability and dual acidic active site were analyzed. We investigated the performance of [DA-2PS][XCly]₂ in catalyzing the esterification reaction between 2,5-furandicarboxylic acid (FDCA) and ethylene glycol (EG) to synthesize poly (ethylene 2,5-furandicarboxylate)(PEF). Among the catalysts tested, [DA-2PS][SnCl₅]₂ exhibited the best catalytic performance under identical process parameters, and the optimal catalyst dosage was determined to be 0.05 mol% based on FDCA. The optimal conditions for the reaction were predicted using response surface methodology: a feed ratio of EG:FDCA = 1.96:1, an esterification temperature of 219.86 °C, a polycondensation temperature of 240.04 °C and a polycondensation time of 6.3 h, with a intrinsic viscosity of 0.67 dL·g⁻¹. The resulting PEF was experimentally verified to exhibit an intrinsic viscosity of 0.68 dL·g⁻¹ and a number average molecular weight of 28,820 g·mol⁻¹. Finally, the structure and thermal properties of PEF were characterized. The results confirmed that PEF possessed the correct structure, exhibited high thermal stability and demonstrated excellent thermal properties. Full article

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. Full article

We have previously reported that sequence-controlled copolyesters such as poly((ethylene diglycolate) terephthalate) (poly(GEGT)) showed higher melting temperatures than those of the corresponding random copolymers and high biodegradability in seawater. In this study, to elucidate the effect of the diol component on their properties, a series of new sequence-controlled copolyesters composed of glycolic acid, 1,4-butanediol or 1,3-propanediol, and dicarboxylic acid units was studied. 1,4-Butylene diglycolate (GBG) and 1,3-trimethylene diglycolate (GPG) were prepared by the reactions of 1,4-dibromobutane or 1,3-dibromopropane with potassium glycolate, respectively. Polycondensation of GBG or GPG with various dicarboxylic acid chlorides produced a series of copolyesters. Terephthalic acid, 2,5-furandicarboxylic acid, and adipic acid were used as the dicarboxylic acid units. Among the copolyesters bearing terephthalate or 2,5-furandicarboxylate units, the melting temperatures (T_m) of the copolyesters containing 1,4-butanediol or 1,2-ethanediol units were substantially higher than those of the copolyester containing the 1,3-propanediol unit. Poly((1,4-butylene diglycolate) 2,5-furandicarboxylate) (poly(GBGF)) showed a T_m at 90 °C, while the corresponding random copolymer was reported to be amorphous. The glass-transition temperatures of the copolyesters decreased as the carbon number of the diol component increased. Poly(GBGF) was found to show higher biodegradability in seawater than that of poly(butylene 2,5-furandicarboxylate) (PBF). On the other hand, the hydrolysis of poly(GBGF) was suppressed in comparison with that of poly(glycolic acid). Thus, these sequence-controlled copolyesters have both improved biodegradability compared to PBF and lower hydrolyzability than PGA. Full article

The biaxial behavior of PEF has been analyzed for equilibrated and simultaneous biaxial stretching. The ability of PEF to develop an organized microstructure through strain induced crystallization (SIC) has been described. Upon biaxial stretching, SIC can be difficult to perform because the stretching is performed in two perpendicular directions. However, thanks to the time/temperature superposition principle and an accurate heating protocol, relevant stretching settings have been chosen to stretch the material in its rubbery-like state and to reach high levels of deformation. By the protocol applied, the mechanical behavior is easily transposable to the industry. This work has shown that PEF can, as in uniaxial stretching, develop well-organized crystals and a defined microstructure upon biaxial stretching. This microstructure allows the obtention of improved mechanical properties and thermal stability of the biaxially stretched samples. The crystals induced upon biaxial stretching are similar to the one that has been developed and observed after uniaxial stretching and upon static crystallization. Moreover, the furan cycles seem to appear in a state similar to the one of a sample crystallized upon quiescent condition. The rigidity is increased, and the α-relaxation temperature is increased by 15 °C. Full article

Poly(ethylene 2,5-furandicarboxylate) (PEF) nanocomposites reinforced with Graphene nanoplatelets (GNPs) and Carbon nanotubes (CNTs) were in situ synthesized in this work. PEF is a biobased polyester with physical properties and is the sustainable counterpart of Polyethylene Terephthalate (PET). Its low crystallizability affects the processing of the material, limiting its use to packaging, films, and textile applications. The crystallization promotion and the reinforcement of PEF can lead to broadening its potential applications. Therefore, PEF nanocomposites reinforced with various loadings of GNPs, CNTs, and hybrids containing both fillers were prepared, and the effect of each filler on their structural characteristics was investigated by X-ray Diffraction (XRD), Fourier transform infrared spectroscopy—attenuated total reflectance (FTIR–ATR), and X-Ray Photoelectron Spectroscopy (XPS). The morphology and structural properties of a hybrid PEF nanocomposite were evaluated by Transmission Electron Microscopy (TEM). The thermo-oxidative degradation, as well as lifetime predictions of PEF nanocomposites, in an ambient atmosphere, were studied using Thermogravimetric Analysis (TGA). Results showed that the fillers’ incorporation in the PEF matrix induced changes in the lamellar thickness and increased crystallinity up to 27%. TEM analysis indicated the formation of large CNTs aggregates in the case of the hybrid PEF nanocomposite as a result of the ultrasonication process. Finally, the presence of CNTs caused the retardation of PEF’s carbonization process. This led to a slightly longer lifetime under isothermal conditions at higher temperatures, while at ambient temperature the PEF nanocomposites’ lifetime is shorter, compared to neat PEF. Full article

Poly(ethylene 2,5-furandicarboxylate) (PEF) nanocomposites reinforced with various content of graphene nanoplatelets (GNPs) were synthesized in situ in this work. PEF is a widely known biobased polyester with promising physical properties and is considered as the sustainable counterpart of PET. Despite its exceptional gas barrier and mechanical properties, PEF presents with a low crystallization rate. In this context, a small number of GNPs were incorporated into the material to facilitate the nucleation and overall crystallization of the matrix. Kinetic analysis of both the cold and melt crystallization processes of the prepared materials was achieved by means of differential scanning calorimetry (DSC). The prepared materials’ isothermal crystallization from the glass and melt states was studied using the Avrami and Hoffman–Lauritzen theories. The Dobreva method was applied for the non-isothermal DSC measurements to calculate the nucleation efficiency of the GNPs on the PEF matrix. Furthermore, Vyazovkin’s isoconversional method was employed to estimate the effective activation energy values of the amorphous materials’ glass transition. Finally, the nanomechanical properties of the amorphous and semicrystalline PEF materials were evaluated via nanoindentation measurements. It is shown that the GNPs facilitate the crystallization process through heterogeneous nucleation and, at the same time, improve the nanomechanical behavior of PEF, with the semicrystalline samples presenting with the larger enhancements. Full article