Increasing the Dissolution Rate of Polystyrene Waste in Solvent-Based Recycling.

Solvent-based recycling of plastic waste is a promising approach for cleaning polymer chains without breaking them. However, the time required to actually dissolve the polymer in a lab environment can take hours. Different factors play a role in polymer dissolution, including temperature, turbulence, and solvent properties. This work provides insights into bottlenecks and opportunities to increase the dissolution rate of polystyrene in solvents. The paper starts with a broad solvent screening in which the dissolution times are compared. Based on the experimental results, a multiple regression model is constructed, which shows that within several solvent properties, the viscosity of the solvent is the major contributor to the dissolution time, followed by the hydrogen, polar, and dispersion bonding (solubility) parameters. These results also indicate that cyclohexene, 2-pentanone, ethylbenzene, and methyl ethyl ketone are solvents that allow fast dissolution. Next, the dissolution kinetics of polystyrene in cyclohexene in a lab-scale reactor and a baffled reactor are investigated. The effects of temperature, particle size, impeller speed, and impeller type were studied. The results show that increased turbulence in a baffled reactor can decrease the dissolution time from 40 to 7 min compared to a lab-scale reactor, indicating the importance of a proper reactor design. The application of a first-order kinetic model confirms that dissolution in a baffled reactor is at least 5-fold faster than that in a lab-scale reactor. Finally, the dissolution kinetics of a real waste sample reveal that, in optimized conditions, full dissolution occurs after 5 min.

Synthesis of Novel Nanocomposite Materials with Enhanced Antimicrobial Activity based on Poly(Ethylene Glycol Methacrylate)s with Ag, TiO2 or ZnO Nanoparticles.

The aim of this investigation was to prepare novel hybrid materials with enhanced antimicrobial properties to be used in food preservation and packaging applications. Therefore, nanocomposite materials were synthesized based on two stimuli-responsive oligo(ethylene glycol methacrylate)s, namely PEGMA and PEGMEMA, the first bearing hydroxyl side groups with three different metal nanoparticles, i.e., Ag, TiO2 and ZnO. The in situ radical polymerization technique was employed to ensure good dispersion of the nanoparticles in the polymer matrix. FTIR spectra identified the successful preparation of the corresponding polymers and XRD scans revealed the presence of the nanoparticles in the polymer matrix. In the polymer bearing hydroxyl groups, the presence of Ag-NPs led to slightly lower thermal stability as measured by TGA, whereas both ZnO and TiO2 led to nanomaterials with better thermal stability. The antimicrobial activity of all materials was determined against the Gram-negative bacteria E. coli and the Gram-positive S. aureus, B. subtilis and B. cereus. PEGMEMA nanocomposites had much better antimicrobial activity compared to PEGMA. Ag NPs exhibited the best inhibition of microbial growth in both polymers with all four bacteria. Nanocomposites with TiO2 showed a very good inhibition percentage when used in PEGMEMA-based materials, while in PEGMA material, high antimicrobial activity was observed only against E. coli and B. subtilis, with moderate activity against B. cereus and almost absent activity against S. aureus. The presence of ZnO showed antimicrobial activity only in the case of PEGMEMA-based materials. Differences observed in the antibacterial activity of the polymers with the different nanoparticles could be attributed to the different structure of the polymers and possibly the more efficient release of the NPs.

Bioactive Edible Gel Films Based on Wheat Flour and Glucose for Food Packaging Applications.

In order to prepare bioactive edible gel films with enhanced properties, the feasibility of using wheat flour as a raw material with glucose added at several concentrations was studied in this investigation. Films were prepared with glucose concentrations of 0.5, 0.7 and 1 g/g of flour and characterized for their physicochemical properties, including water content, solubility, degree of swelling, chemical structure by FT-IR (ATR) spectroscopy, morphology by SEM microscopy, thermal properties by DSC, gas and water vapor permeability and antioxidant activity. Biodegradation studies were also carried out in soil for 27 days and evaluated by weight loss measurements. It was found that the gel film with the higher glucose concentration exhibits a homogeneous and continuous structure with no cracks and no fragility, accompanied by an increased thickness and solubility and a decreased degree of swelling compared to those with lower concentrations. The chemical structure of all films was verified. Moreover, the increase in glucose content leads to better gas barrier properties with lower oxygen, CO2 and water vapor transmission rates and increased water vapor permeability. A slightly elevated melting temperature was observed in the films with higher glucose content. Higher antioxidant activity was also associated with higher percentage of glucose. Finally, the biodegradation of the films ranged from 13 to nearly 70%. Therefore, it can be concluded that the addition of glucose to wheat flour in concentration up to 1 g/g could result in edible gel films with excellent properties to be used in food packaging applications.

An Evaluation of Experimental Calcium Ion-Leachable Nanocomposite Glass Ionomer Cements.

Glass ionomer cements (GICs) are among the main restorative dental materials used broadly in daily clinical practice. The incorporation of clay nanoparticles as reinforcing agents is one potential approach to improving GIC properties. This study aims to investigate whether the incorporation of calcium-modified clay (Ca-clay) nanoparticles in conventional GICs alters their structural characteristics, along with their physicochemical and mechanical properties. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses were performed to assess the surface characterization of GIC nanocomposites, whereas a setting reaction was carried out via an attenuated total reflection Fourier transform infrared spectrometer (ATR-FTIR). A universal testing machine was used for compression tests, while calcium ion release was quantified using inductively coupled plasma optical emission spectrometry (ICP-OES). GIC composite groups reinforced with Ca-clay were found to release a fine amount of calcium ions (5.06-9.91 ppm), with the setting reaction being unaffected for low Ca-clay loadings. The median compressive strength of 3 wt% in the Ca-clay group (68.97 MPa) was nearly doubled compared to that of the control group (33.65 MPa). The incorporation of Ca-clay nanoparticles in GICs offers a promising alternative among dental restorative materials regarding their chemical and mechanical properties.

Synthesis and Characterization of Dental Nanocomposite Resins Reinforced with Dual Organomodified Silica/Clay Nanofiller Systems.

Quaternary ammonium (QA) compounds have been widely studied as potential disinfectants in dental restorative materials. The present work investigates whether the gradual displacement of nanosilica by QA-clay nanoparticles may have an impact on the physicochemical and mechanical properties of dental nanocomposite resins. For this purpose, Bis-GMA/TEGDMA-based composite resins were initially synthesized by incorporating 3-(trimethoxysilyl)propyl methacrylate (γ-MPS)-modified nanosilica/QA-clay nanoparticles at 60/0, 55/5, 50/10, 40/20, and 30/30 wt% filler loadings. Their structural characterization was performed by means of scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD). The degree of double bond conversion (DC) over time and the polymerization shrinkage were determined with Fourier transform infrared spectroscopy (FTIR) and a linear variable displacement transducer (LVDT), respectively. Mechanical properties as well as water sorption and solubility parameters were also evaluated after storage of nanocomposites in water for 7 days at 37 °C. Spectral data revealed intercalated clay configurations along with areas characterized by silica-clay clusters for clay loadings up to 30 wt%. Furthermore, the insertion of 10 wt% QA-clay enhanced the auto-acceleration effect also sustaining the ultimate (DC), reduced the setting contraction and solubility, and, finally, yielded flexural modulus and strength very close to those of the control nanocomposite resin. The acquired results could herald the advanced design of dental restorative materials appropriate for contemporary clinical applications.

Effect of the Filler Modification on the Thermal and Mechanical Properties of Composite Polypropylene/Wollastonite Drawn Fibers.

Polypropylene (PP) is one of the most commercially used thermoplastics, while a significant amount of PP is used in the form of fibers. In this study, the effects of modification of the filler on the thermal and mechanical properties of composite polypropylene/wollastonite drawn fibers were investigated. In this direction, the surface modification of wollastonite with various organic acids, such as myristic, maleic, malonic glutaric, pimelic, and suberic acid, and the use of two solvents were studied. The surface-modified wollastonite particles were used to produce composite polypropylene drawn fibers. The modification efficiency was found to be slightly better when a non-polar solvent (carbon tetrachloride) was used instead of a polar one (ethanol). FTIR experiments showed that myristic, maleic, malonic, and pimelic acid can strongly interact with wollastonite's surface. However, the mechanical strength of the composite fibers was not increased compared to that of the neat PP fibers, suggesting inadequate interactions between PP and wollastonite particles. Furthermore, it was observed that the drawing process increased around 10% the crystallinity of all samples. Wollastonite modified with malonic acid acted as a nucleating agent for ß-crystals. The onset decomposition temperature increased by 5-10 °C for all samples containing 2% wollastonite, either modified or not. The suggested modifications of wollastonite might be more suitable for less hydrophobic polymers.

Removal of Bromine from Polymer Blends with a Composition Simulating That Found in Waste Electric and Electronic Equipment through a Facile and Environmentally Friendly Method.

The increasing volume of plastics from waste electric and electronic equipment (WEEE) nowadays is of major concern since the various toxic compounds that are formed during their handling enhance the difficulties in recycling them. To overcome these problems, this work examines solvent extraction as a pretreatment method, prior to thermochemical recycling by pyrolysis. The aim is to remove bromine from some polymeric blends, with a composition that simulates WEEE, in the presence of tetrabromobisphenol A (TBBPA). Various solvents-isopropanol, ethanol and butanol-as well as several extraction times, were investigated in order to find the optimal choice. Before and after the pretreatment, blends were analysed by X-ray fluorescence (XRF) to estimate the total bromine content. Blends were pyrolyzed before and after the soxhlet extraction in order to evaluate the derived products. FTIR measurements of the polymeric blends before and after the soxhlet extraction showed that their structure was maintained. From the results obtained, it was indicated that the reduction of bromine was achieved in all cases tested and it was ~34% for blend I and ~46% and 42% for blend II when applying a 6 h soxhlet with isopropanol and ethanol, respectively. When using butanol bromine was completely eliminated, since the reduction reached almost 100%. The latter finding is of great importance, since the complete removal of bromine enables the recycling of pure plastics. Therefore, the main contribution of this work to the advancement of knowledge lies in the use of a solvent (i.e., butanol) which is environmentally friendly and with a high dissolving capacity in brominated compounds, which can be used in a pretreatment stage of plastic wastes before it is recycled by pyrolysis.

Toward More Universal Prediction of Polymer Solution Viscosity for Solvent-Based Recycling.

The viscosity of polymer solutions is important for both polymer synthesis and recycling. Polymerization reactions can become hampered by diffusional limitations once a viscosity threshold is reached, and viscous solutions complicate the cleaning steps during the dissolution-precipitation technique. Available experimental data is limited, which is more severe for green solvents, justifying dedicated viscosity data recording and interpretation. In this work, a systematic study is therefore performed on the viscosity of polystyrene solutions, considering different concentrations, temperatures, and conventional and green solvents. The results show that for the shear rate range of 1-1000 s-1, the solutions with concentrations between 5 and 39 wt % display mainly Newtonian behavior, which is further confirmed by the applicability of the segment-based Eyring-NRTL and Eyring-mNRF models. Moreover, multivariate data analysis successfully predicts the viscosity of polystyrene solutions under different conditions. This approach will facilitate future data recording for other polymer-solvent combinations while minimizing experimental effort.

Development of Bio-Composites with Enhanced Antioxidant Activity Based on Poly(lactic acid) with Thymol, Carvacrol, Limonene, or Cinnamaldehyde for Active Food Packaging.

The new trend in food packaging films is to use biodegradable or bio-based polymers, such as poly(lactic acid), PLA with additives such as thymol, carvacrol, limonene or cinnamaldehyde coming from natural resources (i.e., thyme, oregano, citrus fruits and cinnamon) in order to extent foodstuff shelf-life and improve consumers' safety. Single, triple and quadruple blends of these active compounds in PLA were prepared and studied using the solvent-casting technique. The successful incorporation of the active ingredients into the polymer matrix was verified by FTIR spectroscopy. XRD and DSC data revealed that the crystallinity of PLA was not significantly affected. However, the Tg of the polymer decreased, verifying the plasticization effect of all additives. Multicomponent mixtures resulted in more intense plasticization. Cinnamaldehyde was found to play a catalytic role in the thermal degradation of PLA shifting curves to slightly lower temperatures. Release of thymol or carvacrol from the composites takes place at low rates at temperatures below 100 °C. A combined diffusion-model was found to simulate the experimental release profiles very well. Higher antioxidant activity was noticed when carvacrol was added, followed by thymol and then cinnamaldehyde and limonene. From the triple-component composites, higher antioxidant activity measured in the materials with thymol, carvacrol and cinnamaldehyde.

State-Of-The-Art Quantification of Polymer Solution Viscosity for Plastic Waste Recycling.

Solvent-based recycling is a promising approach for closed-loop recovery of plastic-containing waste. It avoids the energy cost to depolymerize the plastic but still allows to clean the polymer of contaminants and additives. However, viscosity plays an important role in handling the polymer solutions at high concentrations and in the cleaning steps. This Review addresses the viscosity behavior of polymer solutions, available data, and (mostly algebraic) models developed. The non-Newtonian viscosity models, such as the Carreau and Yasuda-Cohen-Armstrong models, pragmatically describe the viscosity of polymer solutions at different concentrations and shear rate ranges. This Review also describes how viscosity influences filtration and centrifugation processes, which are crucial steps in the cleaning of the polymer and includes a polystyrene/styrene case study.

Synthesis of Novel Dental Nanocomposite Resins by Incorporating Polymerizable, Quaternary Ammonium Silane-Modified Silica Nanoparticles.

Diverse approaches dealing with the reinforcement of dental composite resins with quaternary ammonium compounds (QAC) have been previously reported. This work aims to investigate the physicochemical and mechanical performance of dental resins containing silica nanofillers with novel QAC. Different types of quaternary ammonium silane compounds (QASiC) were initially synthesized and characterized with proton nuclear magnetic resonance (1H-NMR) and Fourier transform infrared (FTIR) spectroscopy. Silica nanoparticles were surface modified with the above QASiC and the structure of silanized products (S.QASiC) was confirmed by means of FTIR and thermogravimetric analysis. The obtained S.QASiC were then incorporated into methacrylate based dental resins. Scanning electron microscopy images revealed a satisfactory dispersion of silica nanoclusters for most of the synthesized nanocomposites. Curing kinetics disclosed a rise in both the autoacceleration effect and degree of conversion mainly induced by shorter QASiC molecules. Polymerization shrinkage was found to be influenced by the particular type of S.QASiC. The flexural modulus and strength of composites were increased by 74% and 19%, while their compressive strength enhancement reached up to 19% by adding 22 wt% S.QASiC nanoparticles. These findings might contribute to the proper design of multifunctional dental materials able to meet the contemporary challenges in clinical practice.

A New Era in Engineering Plastics: Compatibility and Perspectives of Sustainable Alipharomatic Poly(ethylene terephthalate)/Poly(ethylene 2,5-furandicarboxylate) Blends.

The industrialisation of poly(ethylene 2,5-furandicarboxylate) for total replacement of poly(ethylene terephthalate) in the polyester market is under question. Preparation of high-performing polymer blends is a well-established strategy for tuning the properties of certain homopolymers and create tailor-made materials to meet the demands for a number of applications. In this work, the structure, thermal properties and the miscibility of a series of poly(ethylene terephthalate)/poly(ethylene 2,5-furandicarboxylate) (PET/PEF) blends have been studied. A number of thermal treatments were followed in order to examine the thermal transitions, their dynamic state and the miscibility characteristics for each blend composition. Based on their glass transition temperatures and melting behaviour the PET/PEF blends are miscible at high and low poly(ethylene terephthalate) (PET) contents, while partial miscibility was observed at intermediate compositions. The multiple melting was studied and their melting point depression was analysed with the Flory-Huggins theory. In an attempt to further improve miscibility, reactive blending was also investigated.

Effect of Na- and Organo-Modified Montmorillonite/Essential Oil Nanohybrids on the Kinetics of the In Situ Radical Polymerization of Styrene.

The great concern about the use of hazardous additives in food packaging materials has shown the way to new bio-based materials, such as nanoclays incorporating bioactive essential oils (EO). One of the still unresolved issues is the proper incorporation of these materials into a polymeric matrix. The in situ polymerization seems to be a promising technique, not requiring high temperatures or toxic solvents. Therefore, in this study, the bulk radical polymerization of styrene was investigated in the presence of sodium montmorillonite (NaMMT) and organo-modified montmorillonite (orgMMT) including thyme (TO), oregano (OO), and basil (BO) essential oil. It was found that the hydroxyl groups present in the main ingredients of TO and OO may participate in side retardation reactions leading to lower polymerization rates (measured gravimetrically by the variation of monomer conversion with time) accompanied by higher polymer average molecular weight (measured via GPC). The use of BO did not seem to affect significantly the polymerization kinetics and polymer MWD. These results were verified from independent experiments using model compounds, thymol, carvacrol and estragol instead of the clays. Partially intercalated structures were revealed from XRD scans. The glass transition temperature (from DSC) and the thermal stability (from TGA) of the nanocomposites formed were slightly increased from 95 to 98 °C and from 435 to 445 °C, respectively. Finally, better dispersion was observed when orgMMT was added instead of NaMMT.

Synthesis of D-Limonene Loaded Polymeric Nanoparticles with Enhanced Antimicrobial Properties for Potential Application in Food Packaging.

Mini-emulsion polymerization was applied for the synthesis of cross-linked polymeric nanoparticles comprised of methyl methacrylate (MMA) and Triethylene Glycol Dimethacrylate (TEGDMA) copolymers, used as matrix-carriers for hosting D-limonene. D-limonene was selected as a model essential oil, well known for its pleasant odor and its enhanced antimicrobial properties. The synthesized particles were assessed for their morphology and geometric characteristics by Dynamic Light Scattering (DLS) and Scanning Electron Microscopy (SEM), which revealed the formation of particles with mean diameters at the nanoscale (D[3,2] = 0.135 µm), with a spherical shape, while the dried particles formed larger clusters of several microns (D[3,2] = 80.69 µm). The percentage of the loaded D-limonene was quantified by Thermogravimetric Analysis (TGA), complemented by Gas Chromatography-Mass Spectrometry analysis coupled with a pyrolysis unit (Py/GC-MS). The results showed that the volatiles emitted by the nanoparticles were composed mainly of D-limonene (10% w/w of dry particles). Particles subjected to higher temperatures tended to decompose. The mechanism that governs the release of D-limonene from the as-synthesized particles was studied by fitting mathematical models to the release data obtained by isothermal TGA analysis of the dry particles subjected to accelerated conditions. The analysis revealed a two-stage release of the volatiles, one governed by D-limonene release and the other governed by TEGDMA release. Finally, the antimicrobial potency of the D-limonene-loaded particles was demonstrated, indicating the successful synthesis of polymeric nanoparticles loaded with D-limonene, owing to enhanced antimicrobial properties. The overall performance of these nanoparticles renders them a promising candidate material for the formation of self-sterilized surfaces with enhanced antimicrobial activity and potential application in food packaging.

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.

Sustainable Plastics from Biomass: Blends of Polyesters Based on 2,5-Furandicarboxylic Acid.

Intending to expand the thermo-physical properties of bio-based polymers, furan-based thermoplastic polyesters were synthesized following the melt polycondensation method. The resulting polymers, namely, poly(ethylene 2,5-furandicarboxylate) (PEF), poly(propylene 2,5-furandicarboxylate) (PPF), poly(butylene 2,5-furandicarboxylate) (PBF) and poly(1,4-cyclohexanedimethylene 2,5-furandicarboxylate) (PCHDMF) are used in blends together with various polymers of industrial importance, including poly(ethylene terephthalate) (PET), poly(ethylene 2,6-naphthalate) (PEN), poly(L-lactic acid) (PLA) and polycarbonate (PC). The blends are studied concerning their miscibility, crystallization and solid-state characteristics by using wide-angle X-ray diffractometry (WAXD), differential scanning calorimetry (DSC) and polarized light microscopy (PLM). PEF blends show in general dual glass transitions in the DSC heating traces for the melt quenched samples. Only PPF-PEF blends show a single glass transition and a single melt phase in PLM. PPF forms immiscible blends except with PEF and PBF. PBF forms miscible blends with PCHDMF and PPF, whereas all other blends show dual glass transitions in DSC and phase separation in PLM. PCHDMF-PEF and PEN-PEF blends show two glass transition temperatures, but they shift to intermediate temperature values depending on the composition, indicating some partial miscibility of the polymer pairs.

Effect of Graphene oxide or Functionalized Graphene Oxide on the Copolymerization Kinetics of Styrene/n-butyl Methacrylate.

Nanocomposite materials based on copolymers of styrene and n-butyl methacrylate with either graphene oxide (GO) or functionalized graphene oxide (F-GO) were synthesized using the in-situ bulk radical copolymerization technique. Reaction kinetics was studied both experimentally and theoretically using a detailed kinetic model also taking into account the effect of diffusion-controlled phenomena on the reaction kinetic rate constants. It was found that the presence of GO results in lower polymerization rates accompanied by the synthesis of copolymers having higher average molecular weights. In contrast, the presence of F-GO did not seem to significantly alter the conversion vs time curves, whereas it results in slightly lower average molecular weights. The first observation was attributed to side reactions of the initiator primary radicals with the hydroxyl groups on the surface of GO, resulting in lower initiator efficiency, whereas the second to grafted structures formed from copolymer macromolecules on the F-GO surface. The copolymerization model predictions including MWD data were found to be in satisfactory agreement with the experimental data. At least four adjustable parameters were employed and their best-fit values were provided.

Biobased Engineering Thermoplastics: Poly(butylene 2,5-furandicarboxylate) Blends.

Poly(butylene 2,5-furandicarboxylate) (PBF) constitutes a new engineering polyester produced from renewable resources, as it is synthesized from 2,5-furandicarboxylic acid (2,5-FDCA) and 1,4-butanediol (1,4-BD), both formed from sugars coming from biomass. In this research, initially high-molecular-weight PBF was synthesized by applying the melt polycondensation method and using the dimethylester of FDCA as the monomer. Furthermore, five different series of PBF blends were prepared, namely poly(l-lactic acid)-poly(butylene 2,5-furandicarboxylate) (PLA-PBF), poly(ethylene terephthalate)-poly(butylene 2,5-furandicarboxylate) (PET-PBF), poly(propylene terephthalate)-poly(butylene 2,5-furandicarboxylate) (PPT-PBF), poly(butylene 2,6-naphthalenedicarboxylate)-poly(butylene 2,5-furandicarboxylate) (PBN-PBF), and polycarbonate-poly(butylene 2,5-furandicarboxylate) (PC-PBF), by dissolving the polyesters in a trifluoroacetic acid/chloroform mixture (1/4 v/v) followed by coprecipitation as a result of adding the solutions into excess of cold methanol. The wide-angle X-ray diffraction (WAXD) patterns of the as-prepared blends showed that mixtures of crystals of the blend components were formed, except for PC which did not crystallize. In general, a lower degree of crystallinity was observed at intermediate compositions. The differential scanning calorimetry (DSC) heating scans for the melt-quenched samples proved homogeneity in the case of PET-PBF blends. In the remaining cases, the blend components showed distinct Tgs. In PPT-PBF blends, there was a shift of the Tgs to intermediate values, showing some partial miscibility. Reactive blending proved to improve compatibility of the PBN-PBF blends.

Solid-State Polymerization of Poly(Ethylene Furanoate) Biobased Polyester, III: Extended Study on Effect of Catalyst Type on Molecular Weight Increase.

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.

Exploring Next-Generation Engineering Bioplastics: Poly(alkylene furanoate)/Poly(alkylene terephthalate) (PAF/PAT) Blends.

Polymers from renewable resources and especially strong engineering partially aromatic biobased polyesters are of special importance for the evolution of bioeconomy. The fabrication of polymer blends is a creative method for the production of tailor-made materials for advanced applications that are able to combine functionalities from both components. In this study, poly(alkylene furanoate)/poly(alkylene terephthalate) blends with different compositions were prepared by solution blending in a mixture of trifluoroacetic acid and chloroform. Three different types of blends were initially prepared, namely, poly(ethylene furanoate)/poly(ethylene terephthalate) (PEF/PET), poly(propylene furanoate)/poly(propylene terephthalate) (PPF/PPT), and poly(1,4-cyclohenedimethylene furanoate)/poly(1,4-cycloxehane terephthalate) (PCHDMF/PCHDMT). These blends' miscibility characteristics were evaluated by examining the glass transition temperature of each blend. Moreover, reactive blending was utilized for the enhancement of miscibility and dynamic homogeneity and the formation of copolymers through transesterification reactions at high temperatures. PEF⁻PET and PPF⁻PPT blends formed a copolymer at relatively low reactive blending times. Finally, poly(ethylene terephthalate-co-ethylene furanoate) (PETF) random copolymers were successfully introduced as compatibilizers for the PEF/PET immiscible blends, which resulted in enhanced miscibility.