Search Results (23)

PET (polyethylene terephthalate) bottles contain different chemicals that can act as endocrine disruptors. Phthalates and bisphenol A can be found in various foods and beverages packaged in PET packaging or aluminum cans. For some phthalates, the European Union has established specified tolerable daily intakes for humans. This study aimed to establish the changes, types of phthalates (dimethyl phthalate, diethyl phthalate, diisobutyl phthalate, dibutyl phthalate, bis(2-ethylhexyl) phthalate, di-n-octyl phthalate), and bisphenol A concentrations in beer packaged in PET bottles and stored at two temperatures (4 °C and 20 °C) for four months. Beers were obtained from a local brewery after packaging into PET bottles and stored at the designated temperatures. GC-MS analysis was performed to determine phthalates and bisphenol A. Obtained data show that beers packaged in PET bottles can contain significant amounts of bisphenol A, and that their concentration increases with storage time. Phthalates were also identified in the samples, with the highest concentration of bis(2-ethylhexyl) phthalate found in the sample kept at 20 °C after 1 month of storage, sample P5; this concentration was 164.814 µg/L. BPA was recorded with the highest concentration in sample P11, which underwent 4 months of storage at a temperature of 20 °C. Full article

The esterification of terephthalic acid (PTA) with methanol to dimethyl terephthalate (DMT) was investigated using commercially available zeolite catalysts as the eco-friendly solid acids. Six typical zeolites (ZSM-5-25, ZSM-5-50, ZSM-5-100, ZSM-35, MOR, and β) were systematically evaluated. Among them, β zeolite showed excellent catalytic performance, achieving nearly 100% PTA conversion and 76.1% DMT selectivity under the conditions of 200 °C, of 0.5 MPa N₂ pressure, m(PTA):V(methanol) of 1:40 (g/mL), m(PTA):m(catalyst) of 10:1 over 4 h. The characterization results show that the catalytic efficiency was correlated with acid site strength, specific surface area, and mesoporous structure of the zeolite. After optimization, β zeolite achieved 100% PTA conversion and 94.1% DMT selectivity under the conditions of 200 °C, of 1 MPa N₂ pressure, m(PTA)/V(methanol) of 1:30 (g/mL), m(PTA)/m(catalyst) of 8:1 over 8 h. Moreover, β zeolite exhibited superior stability, maintaining over 92% of its initial activity after five cycles, highlighting its potential for sustainable DMT production. Full article

To tackle growing resource and environmental challenges, closed-loop chemical recycling of waste PET is gaining significant attention. Methanolysis demonstrates significant industrial potential due to the ease of separation and purification of its depolymerization product, dimethyl terephthalate (DMT). However, conventional methanolysis processes for PET typically require harsh conditions (>200 °C and 2–4 MPa), highlighting the need for more efficient and milder methods. In this work, leveraging Hansen’s solubility parameter theory, a bio-based solvent gamma-valerolactone (GVL) was introduced to construct a binary mixed solvent system, enabling highly efficient depolymerization of PET. Through systematic optimization of reaction conditions, an in-depth analysis of the effects of various factors on depolymerization efficiency and kinetics was conducted. The incorporation of GVL markedly enhanced the compatibility between the solvent and PET, thereby significantly improving depolymerization efficiency while effectively lowering the reaction temperature and pressure. Complete depolymerization of PET can be achieved within 2 h at 150 °C under a pressure of 0.9 MPa, with a DMT yield of up to 97.8%. This GVL/methanol depolymerization system exhibits higher efficiency, milder reaction conditions, and substantial advantages in terms of environmental impact and energy consumption indicators. By using the renewable bio-based solvent GVL, this technology aligns with the core principles of green chemistry and provides an efficient, feasible, and innovative pathway for sustainable closed-loop PET recycling. Full article

An accurate, rapid, and selective quantitative nuclear magnetic resonance method was developed and validated to assess the purity of IMM-H014, a novel drug for the treatment of metabolic-associated fatty liver disease (MAFLD), and four related substances (impurities I, II, III, and IV). In this study, we obtained spectra of IMM--H014 and related substances in deuterated chloroform using dimethyl terephthalate (DMT) as the internal standard reference. Quantification was performed using the ¹H resonance signals at δ 8.13 ppm for DMT and δ 6.5–7.5 ppm for IMM-H014 and its related substances. Several key experimental parameters were investigated and optimized, such as pulse angle and relaxation delay. Methodology validation was conducted based on the International Council for Harmonization guidelines and verified with satisfactory specificity, precision, linearity, accuracy, robustness, and stability. In addition, the calibration results of the samples were consistent with those obtained from the mass balance method. Thus, this research provides a reliable and practical protocol for purity analysis of IMM-H014 and its critical impurities and contributes to subsequent clinical quality control research. Full article

Polymer composites with various recycled poly(ethylene terephthalate)-based (PET-based) polyester matrices (poly(ethylene terephthalate), copolyesters, and unsaturated polyester resins), similar in properties to the primary ones, can be obtained based on PET glycolysis products after purification. PET glycolysis allows one to obtain bis(2-hydroxyethyl) terephthalate and oligo(ethylene terephthalates) with various molecular weights. A kinetic model of poly(ethylene terephthalate) homogeneous glycolysis under the combined or separate action of oligo(ethylene terephthalates), bis(2-hydroxyethyl) terephthalate, and ethylene glycol is proposed. The model takes into account the interaction of bound, terminal, and free ethylene glycol molecules in the PET feedstock and the glycolysis agent. Experimental data were obtained on the molecular weight distribution of poly(ethylene terephthalate) glycolysis products and the content of bis(2-hydroxyethyl) terephthalate monomer in them to verify the model. Homogeneous glycolysis of PET was carried out at atmospheric pressure in dimethyl sulfoxide (DMSO) and N-methyl-2-pyrrolidone (NMP) solvents with catalyst based on antimony trioxide (Sb₂O₃) under the action of different agents: ethylene glycol at temperatures of 165 and 180 °C; bis(2-hydroxyethyl) terephthalate at 250 °C; and oligoethylene terephthalate with polycondensation degree 3 at 250 °C. Homogeneous step-by-step glycolysis under the successive action of the oligo(ethylene terephthalate) trimer, bis(2-hydroxyethyl) terephthalate, and ethylene glycol at temperatures of 250, 220, and 190 °C, respectively, was also studied. The composition of products was confirmed using FTIR spectroscopy. Molecular weight characteristics were determined using gel permeation chromatography (GPC), the content of bis(2-hydroxyethyl) terephthalate was determined via extraction with water at 60 °C. The developed kinetic model was found to be in agreement with the experimental data and it could be used further to predict the optimal conditions for homogeneous PET glycolysis and to obtain polymer-based composite materials with desired properties. Full article

2,5-furandicarboxylic acid (FDCA) is one of the most studied bio-based monomers, being considered the best substitute for fossil-derived terephthalic acid in plastic production. FDCA is employed in the preparation of polyethylene furanoate (PEF), demonstrating superior mechanical and thermal proprieties compared to the widely used polyethylene terephthalate (PET). Nevertheless, FDCA synthesis mostly relies on the oxidation of the bio-based platform chemical hydroxymethyl furfural (HMF), whose notoriously instable nature renders FDCA yield and industrial scale-up production complicated. On the contrary, FDCA esters are less studied, even though they have greater solubility in organic media, which would favor their isolation and potential application as monomers for PEF. On these premises, we report herein an alternative green synthetic approach to FDCA methyl ester (FDME) using galactaric acid as the substrate, dimethyl carbonate (DMC) as the green media, and Fe₂(SO₄)₃ as the heterogeneous Lewis acid. Optimization of the reaction conditions allowed the selective production of FDME in a 70% isolated yield; product purification was achieved via flash column chromatography over silica. Furthermore, it was possible to employ up to 5.0 g of galactaric acid in a single reaction, leading to a good isolated yield of FDME. Full article

Τhe fabrication of organic light-emitting diodes (OLEDs) from solution involves the major problem of stack integrity, setting the determination of the composition and the characteristics of the resulting interfaces prerequisite for the optimization of the growth processes and the achievement of high devices’ performance. In this work, a poly(9,9-dioctylfluorene) (F8) and poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) blend is used for the emissive layer (EML), poly-3,4-ethylene dioxythiophene; poly-styrene sulfonate (PEDOT:PSS) is used for a hole transport layer (HTL), and Poly(9,9-bis(3′-(N,N-dimethyl)-N-ethylammoinium-propyl-2,7-fluorene)-alt-2,7-(9,9-dioctylfluore-ne))dibromide (PFN-Br) for an electron transport layer (ETL) to produce the OLED device. All the layers are developed using the slot-die process, onto indium tin oxide (ITO)-coated polyethylene terephthalate (PET) flexible substrates, whereas Ag cathode was formed by ink-jet printing under ambient conditions. Spectroscopic ellipsometry measurements were performed upon completion of the successive films’ growth, in sequential steps, for the multilayer OLED development. Ellipsometry analysis using different models demonstrate the degree of intermixing within the layers and provide information about the interfaces. These interfacial properties are correlated with the emission characteristics as well as the final performance of the OLED devices. Full article

Public health concerns associated with the potential leaching of substances from Polyethylene terephthalate (PET) packaging have been raised due to the role of phthalates as endocrine-disrupting chemicals or obesogens. In particular, changes in the environment such as pH, temperature, and irradiation can improve contaminant migration from PET food packaging. In this study, the in vitro effects of p-phthalates terephthalic acid (TPA) and dimethyl terephthalate (DMT) on murine adipocytes (3T3-L1) were evaluated using concentrations that might be obtained in adult humans exposed to contaminated sources. TPA and, in particular, DMT exposure during 3T3-L1 differentiation increased the cellular lipid content and induced adipogenic markers PPAR-γ, C/EBPß, FABP4, and FASN, starting from low nanomolar concentrations. Interestingly, the adipogenic action of TPA- and DMT-induced PPAR-γ was reverted by ICI 182,780, a specific antagonist of the estrogen receptor. Furthermore, TPA and DMT affected adipocytes’ thermogenic program, reducing pAMPK and PGC-1α levels, and induced the NF-κB proinflammatory pathway. Given the observed effects of biologically relevant chronic concentrations of these p-phthalates and taking into account humans’ close and constant contact with plastics, it seems appropriate that ascertaining safe levels of TPA and DMT exposure is considered a high priority. Full article

We report a fiber-structured hybrid nanogenerator wearable device fabricated on a single polyethylene terephthalate (PET) textile cylindrical substrate. The device can be described as a capacitor with inner and outer carbon-black-dispersed poly dimethyl siloxane (PDMS:Carbon black) electrodes, and zinc oxide and polyvinylidene fluoride (PVDF) as the dielectric medium between the electrodes. The compositional analysis in terms of X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy of the synthesized ZnO/PVDF has been measured and analyzed. The combined effect of triboelectricity between PDMS:Carbon black and PVDF, and piezoelectricity in a ZnO/PVDF hybrid, was investigated. Current–voltage characteristics were observed with varying load from 0–20 g, and resistance was observed to be decreased with load. Compared to earlier reports, there was a significant enhancement in voltage (≈5.1 V) and current (≈92.5 nA) at 10 g. Due to the introduction of interfacial polarization between PVDF and ZnO, the piezoelectric properties and pressure sensitivity of the hybrid ZnO/PVDF is enhanced. The hysterical behavior in the device’s response while measuring voltage and current with varying time shows the signature of the triboelectric effect between PVDF and ZnO, as well as PDMS:Carbon black and ZnO/PVDF layers. Reduction of triboelectric behavior was confirmed with increasing relaxation time. Because of the enhancement in piezoelectricity, fiber-structured nanogenerator (FNG) ZnO/PVDF proved to a potential candidate to be used for wearable computing devices, such as smart watches and sports bracelets. Full article

Vanillin, as a promising aromatic aldehyde, possesses worthy structural and bioactive properties useful in the design of novel sustainable polymeric materials. Its versatility and structural similarity to terephthalic acid (TPA) can lead to materials with properties similar to conventional poly(ethylene terephthalate) (PET). In this perspective, a symmetrical dimethylated dialkoxydivanillic diester monomer (DEMV) derived from vanillin was synthesized via a direct-coupling method. Then, a series of poly(ether-ester)s were synthesized via melt-polymerization incorporating mixtures of phenyl/phenyloxy diols (with hydroxyl side-chains in the 1,2-, 1,3- and 1,4-positions) and a cyclic diol, 1,4-cyclohexanedimethanol (CHDM). The polymers obtained had high molecular weights (M_w = 5.3–7.9 × 10⁴ g.mol⁻¹) and polydispersity index (Đ) values of 1.54–2.88. Thermal analysis showed the polymers are semi-crystalline materials with melting temperatures of 204–240 °C, and tunable glass transition temperatures (T_g) of 98–120 °C. Their 5% decomposition temperature (T_d,5%) varied from 430–315 °C, which endows the polymers with a broad processing window, owing to their rigid phenyl rings and trans-CHDM groups. These poly(ether-ester)s displayed remarkable impact strength and satisfactory gas barrier properties, due to the insertion of the cyclic alkyl chain moieties. Ultimately, the synergistic influence of the ester and ether bonds provided better control over the behavior and mechanism of in vitro degradation under passive and enzymatic incubation for 90 days. Regarding the morphology, scanning electron microscopy (SEM) imaging confirmed considerable surface degradation in the polymer matrices of both polymer series, with weight losses reaching up to 35% in enzymatic degradation, which demonstrates the significant influence of ether bonds for biodegradation. Full article

Biodegradable polyesters represent an advanced alternative to polyolefin plastics in various applications. Polybutylene adipate terephthalate (PBAT) can compete with polyolefins in terms of their mechanical characteristics and melt processing conditions. The properties of PBAT depend on the molecular weight, dispersity, and architecture of the copolymer. Long-chain branching (LCB) of the PBAT backbone is an efficient method for the improvement of the copolymer characteristics. In the present work, we studied branching agents (BAs) 1–7 of different structures in the two-stage polycondensation of 1,4-butanediol, dimethyl terephthalate, and adipic acid and investigated the composition and melt rheology of the copolymers. According to the results of the research, 1,1,1-tris(hydroxymethyl)ethane 2 and 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoic acid 5 outperformed glycerol 1 as BAs in terms of shear thinning behavior and viscoelasticity. Full article

Multi-walled carbon nanotubes (MWCNTs) were grown on a stainless-steel foil by thermal chemical vapor deposition (CVD) process. The MWCNTs were functionalized with carboxylic groups (COOH) on their surfaces by using oxidation and acid (3:1 H₂SO₄/HNO₃) treatments for improving the solubility property of them in the solvent. The functionalized MWCNTs (f-MWCNTs) were conducted to prepare the solution by continuous stir in poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), dimethyl sulfoxide (DMSO), ethylene glycol (EG) and Triton X-100. The solution was deposited onto a bendable substrate such as polyethylene terephthalate (PET) with a fabricated silver interdigitated electrode for application in a room-temperature gas sensor. A homemade-doctor blade coater, an UNO R3 Arduino board and a L298N motor driver are presented as a suitable system for screen printing the solution onto the gas-sensing substrates. The different contents of f-MWCNTs embedded in PEDOT:PSS were compared in the gas response to ammonia (NH₃), ethanol (C₂H₅OH), benzene (C₆H₆), and acetone (C₃H₆O) vapors. The results demonstrate that the 3.0% v/v of f-MWCNT solution dissolved in 87.8% v/v of PEDOT:PSS, 5.4% v/v of DMSO, 3.6% v/v of EG and 0.2% v/v of Triton X-100 shows the highest response to 80 ppm NH₃. Finally, the reduction in the NH₃ response under heavy substrate-bending is also discussed. Full article

The thermal degradation kinetics of high-performance polymer composite electrolyte membranes were investigated by thermal gravimetric analysis in this study. The novel porous polymer composite membranes were fabricated by crosslinking poly (ethylene-co-vinyl alcohol) (EVOH) with polybutylene terephthalate (PBT) nano fiber. The PBT nano-scale fiber non-woven cloth was first prepared by the electrospinning method to form a labyrinth-like structure, and the crosslinking was carried out by filtering it through a solution of EVOH and crosslinking agent triallylamine using the Porcelain Buchner funnel vacuum filtration method. The PBT–EVOH composite membranes with various crosslinking agent ratios and ethylene carbonate/dimethyl carbonate (EC/DMC) immersion times were investigated for their thermal stability and ionic conductivity. The results showed that the higher crosslinking agent content would lower the crystallinity and enhance thermal stability. The thermal degradation activation energy was dramatically increased from 125 kJ/mol to 340 kJ/mol for the 1.5% crosslinking agent content sample at 80% conversion. The triallylamine crosslinking agent was indeed effective in improving thermal degradation resistivity. The best ionic conductivity of the polymer composite membranes was exhibited at 5.04 × 10⁻³ S cm⁻¹ using the optimal weight ratio of EVOH/PBT composite controlled at 1/2. On the other hand, the EC/DMC immersion time was more effective in controlling the R_b value, thus the ionic conductivity of the membranes. A higher immersion time, such as 48 h, not only gave higher conductivity data but also provided more stable results. The triallylamine crosslinking agent improved the membrane ionic conductivity by about 22%. Full article

In this work, the feasibility of replacing petroleum-based poly(ethylene terephthalate) (PET) with fully bio-based copolyesters derived from dimethyl 2,5-thiophenedicarboxylate (DMTD), dimethyl 2,5-dimethoxyterephthalate (DMDMT), and polysaccharide-derived 1,6-hexanediol (HDO) was investigated. A systematic study of structure-property relationship revealed that the properties of these poly(thiophene–aromatic) copolyesters (PHS(20–90)) can be tailored by varying the ratio of diester monomers in the reaction, whereby an increase in DMTD content noticeably shortened the reaction time in the transesterification step due to its higher reactivity as compared with DMDMT. The copolyesters had weight-average molar masses (Mw) between 27,500 and 38,800 g/mol, and dispersity Đ of 2.0–2.5. The different polarity and stability of heterocyclic DMTD provided an efficient mean to tailor the crystallization ability of the copolyesters, which in turn affected the thermal and mechanical performance. The glass transition temperature (T_g) could be tuned from 70–100 °C, while the tensile strength was in a range of 23–80 MPa. The obtained results confirmed that the co-monomers were successfully inserted into the copolyester chains. As compared with commercial poly(ethylene terephthalate), the copolyesters displayed not only enhanced susceptibility to hydrolysis, but also appreciable biodegradability by lipases, with weight losses of up to 16% by weight after 28 weeks of incubation. Full article

Over 30 million ton of poly(ethylene terephthalate) (PET) is produced each year and no more than 60% of all PET bottles are reclaimed for recycling due to material property deteriorations during the mechanical recycling process. Herein, a sustainable approach is proposed to produce redox-active nanoparticles via the chemical upcycling of poly(ethylene terephthalate) (PET) waste for application in energy storage. Redox-active nanoparticles of sizes lower than 100 nm were prepared by emulsion polymerization of a methacrylic-terephthalate monomer obtained by a simple methacrylate functionalization of the depolymerization product of PET (i.e., bis-hydroxy(2-ethyl) terephthalate, BHET). The initial cyclic voltammetry results of the depolymerization product of PET used as a model compound show a reversible redox process, when using a 0.1 M tetrabutylammonium hexafluorophosphate/dimethyl sulfoxide electrolyte system, with a standard redox potential of −2.12 V vs. Fc/Fc⁺. Finally, the cycling performance of terephthalate nanoparticles was investigated using a 0.1 M TBAPF₆ solution in acetonitrile as electrolyte in a three-electrode cell. The terephthalate anode electrode displays good cycling stability and performance at high C-rate (i.e., ≥5C), delivering a stable specific discharge capacity of 32.8 mAh.g⁻¹ at a C-rate of 30 C, with a capacity retention of 94% after 100 cycles. However, a large hysteresis between the specific discharge and charge capacities and capacity fading are observed at lower C-rate (i.e., ≤2C), suggesting some irreversibility of redox reactions associated with the terephthalate moiety, in particular related to the oxidation process. Full article