Unexpected Susceptibility of Poly(ethylene furanoate) to UV Irradiation: A Warning Light for Furandicarboxylic Acid?
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ABSTRACT:
SUBMITTER: Maaskant E
PROVIDER: S-EPMC8697558 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:We report on the pilot scale synthesis and melt spinning of poly(ethylene furanoate) (PEF), a promising bio-based fiber polymer that can heave mechanical properties in the range of commercial poly(ethylene terephthalate) (PET) fibers. Catalyst optimization and solid state polycondensation (SSP) allowed for intrinsic viscosities of PEF of up to 0.85 dL·g-1. Melt-spun multifilament yarns reached a tensile strength of up to 65 cN·tex-1 with an elongation of 6% and a modulus of 1370 cN·tex-1. The crystallization behavior of PEF was investigated by differential scanning calorimetry (DSC) and XRD after each process step, i.e., after polymerization, SSP, melt spinning, drawing, and recycling. After SSP, the previously amorphous polymer showed a crystallinity of 47%, which was in accordance with literature. The corresponding XRD diffractograms showed signals attributable to α-PEF. Additional, clearly assignable signals at 2θ > 30° are discussed. A completely amorphous structure was observed by XRD for as-spun yarns, while a crystalline phase was detected on drawn yarns; however, it was less pronounced than for the granules and independent of the winding speed.
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Project description:In this work, we report the synthesis of poly(ethylene furanoate) (PEF), catalyzed by three different catalysts, namely, titanium (IV) isopropoxide (TIS), tetrabutyltitanate (TBT), and dibutyltin (IV) oxide (DBTO), via the two-stage melt polycondensation method. Solid-state polymerization (SSP) was conducted at different reaction times (1, 2, 3.5, and 5 h) and temperatures 190, 200, and 205 °C, under vacuum. The resultant polymers were analyzed according to their intrinsic viscosity (IV), end groups (⁻COOH), and thermal properties, via differential scanning calorimetry. DSC results showed that the post polymerization process was favorable to enhance the melting point of the prepared PEF samples. As was expected, the intrinsic viscosity and the average molecular weight of PEF increased with the SSP time and temperature, whereas the number of carboxyl end-groups was decreased. A simple kinetic model was also developed and used to predict the time evolution of polymers IV, as well as the carboxyl and hydroxyl content of PEF during the SSP. From both the experimental measurements and the theoretical simulation results it was proved that the presence of the TIS catalyst resulted in higher transesterification kinetic rate constants and higher reaction rates. The activation energies were not much affected by the presence of different catalysts. Finally, using DBTO as a catalyst, the polyesters produced have higher crystallinity, and as a consequence, higher number of inactive carboxyl and hydroxyl groups.
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Project description:In the present study, three new biobased furanoate polyesters with potential use in food packaging applications, named poly(isosorbide furanoate) (PIsF), poly(methyl-propylene furanoate) (PMePF) and poly(1,4-cyclohexane-dimethylene 2,5-furanoate) (PCHDMF) were synthesized. As monomers for the preparation of the polyesters, 2,5-furandicarboxylic acid (FDCA) and diols with irregular or complicated structure were used, including isosorbide (IS), 2-methyl-1,3-propanediol (MPD) and 1,4-cyclohexane-dimethanol (CHDM). The polymerization process was carried out via melt polycondensation method. The structural characteristics and thermal behavior of the polymers were studied. The kinetic fragility of the amorphous phase of the polymers was evaluated. The thermal degradation was studied by means of thermogravimetry and a pyrolysis Py-GC/MS (Pyrolysis-Gas Chromatography/Mass Spectroscopy) system to estimate the degradation mechanism.
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Project description:In this study, the synthesis of poly(ethylene furanoate) (PEF), catalyzed by five different catalysts-antimony acetate (III) (Sb Ac), zirconium (IV) isopropoxide isopropanal (Zr Is Ip), antimony (III) oxide (Sb Ox), zirconium (IV) 2,4-pentanedionate (Zr Pe) and germanium (IV) oxide (Ge Ox)-via an industrially common combination of melt polymerization and subsequent solid-state polymerization (SSP) is presented. In all reactions, proper amounts of 2,5-dimethylfuran-dicarboxylate (DMFD) and ethylene glycol (EG) in a molar ratio of DMFD/EG= 1/2 and 400 ppm of catalyst were used. Polyester samples were subjected to SSP procedure, under vacuum application, at different reaction times (1, 2, 3.5, and 5 h) and temperatures of 190, 200, and 205 °C. Carboxyl end-groups concentration (?COOH), intrinsic viscosity (IV), and thermal properties, via differential scanning calorimetry (DSC), were measured for all resultant polymers to study the effect of the used catalysts on the molecular weight increase of PEF during SSP process. As was expected, it was found that with increasing the SSP time and temperature, the intrinsic viscosity and the average molecular weight of PEF steadily increased. In contrast, the number of carboxyl end-groups content showed the opposite trend as intrinsic viscosity, that is, gradually decreasing during SSP time and temperature increase. It is worthy to note that thanks to the SSP process an obvious and continuous enhancement in the thermal properties of the prepared PEF samples was attained, in which their melting temperatures (Tm) and degree of crystallinity (Xc) increase progressively with increasing of reaction time and temperature. To predict the time evolution of polymers IV, as well as the hydroxyl and carboxyl content of PEF polyesters during the SSP, a simple kinetic model was developed. From both the theoretical simulation results and the experimental measurements, it was demonstrated that surely the Zr Is Ip catalyst shows the best catalytic characteristics compared to all other used catalysts herein, that is, leading in reducing-in a spectacular way-the activation energy of the involved both transesterification and esterification reactions during SSP.
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Project description:The photodegradation of benzothiazole (BTH) in wastewater with the coexistence of iron oxides and oxalic acid under UV light irradiation was investigated. Results revealed that an effective heterogeneous photo-Fenton-like system could be set up for BTH abatement in wastewater under UV irradiation without additional H2O2, and 88.1% BTH was removed with the addition of 2.0?mmol?l-1 oxalic acid and 0.2?g?l-1 ?-Fe2O3 using a 500?W high-pressure mercury lamp (365?nm). The degradation of BTH in the photo-Fenton-like system followed the first-order kinetic model. The photoproduction of hydroxyl radicals (·OH) in different systems was determined by high-performance liquid chromatography. Identification of transformation products by using liquid chromatography coupled with high resolution tandem mass spectrometry provided information about six transformation products formed during the photodegradation of BTH. Further insight was obtained by monitoring concentrations of the sulfate ion (SO42-) and nitrate ion (NO3-) , which demonstrated that the intermediate products of BTH could be decomposed ultimately. Based on the results, the potential photodegradation pathway of BTH was also proposed.
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