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Poly(1,4-butylene succinate) (PBS) is a promising sustainable and biodegradable synthetic polyester. In this study, we synthesized PBS-based copolyesters by incorporating 5-20 mol% of -O 2 CC 6 H 4 CO 2 - and -OCH 2 CH 2 O- units through the polycondensation of succinic acid (SA) with 1,4-butanediol (BD) and bis(2-hydroxyethyl) terephthalate (BHET). Two different catalysts, H 3 PO 4 and the conventional catalyst (nBuO) 4 Ti, were used comparatively in the synthesis process. The copolyesters produced using the former were treated with M(2-ethylhexanoate) 2 (M = Mg, Zn, Mn) to connect the chains through ionic interactions between M 2+ ions and either -CH 2 OP(O)(OH)O - or (-CH 2 O) 2 P(O)O - groups. By incorporating BHET units (i.e., -O 2 CC 6 H 4 CO 2 - and -OCH 2 CH 2 O-), the resulting copolyesters exhibited improved ductile properties with enhanced elongation at break, albeit with reduced tensile strength. The copolyesters prepared with H 3 PO 4 /M(2-ethylhexanoate) 2 displayed a less random distribution of -O 2 CC 6 H 4 CO 2 - and -OCH 2 CH 2 O- units, leading to a faster crystallization rate, higher T m value, and higher yield strength compared to those prepared with (nBuO) 4 Ti using the same amount of BHET. Furthermore, they displayed substantial shear-thinning behavior in their rheological properties due to the presence of long-chain branches of (-CH 2 O) 3 P=O units. Unfortunately, the copolyesters prepared with H 3 PO 4 /M(2-ethylhexanoate) 2 , and hence containing M 2+ , -CH 2 OP(O)(OH)O - , (-CH 2 O) 2 P(O)O - groups, did not exhibit enhanced biodegradability under ambient soil conditions.

Superparamagnetic iron oxide nanoparticles (SPIONs) have their use approved for the diagnosis/treatment of malignant tumors and can be metabolized by the organism. To prevent embolism caused by these nanoparticles, they need to be coated with biocompatible and non-cytotoxic materials. Here, we synthesized an unsaturated and biocompatible copolyester, poly (globalide- co -ε-caprolactone) (PGlCL), and modified it with the amino acid cysteine (Cys) via a thiol-ene reaction (PGlCLCys). The Cys-modified copolymer presented reduced crystallinity and increased hydrophilicity in comparison to PGlCL, thus being used for the coating of SPIONS (SPION@PGlCLCys). Additionally, cysteine pendant groups at the particle's surface allowed the direct conjugation of (bio)molecules that establish specific interactions with tumor cells (MDA-MB 231). The conjugation of either folic acid (FA) or the anti-cancer drug methotrexate (MTX) was carried out directly on the amine groups of cysteine molecules present in the SPION@PGlCLCys surface (SPION@PGlCLCys_FA and SPION@PGlCLCys_MTX) by carbodiimide-mediated coupling, leading to the formation of amide bonds, with conjugation efficiencies of 62% for FA and 60% for MTX. Then, the release of MTX from the nanoparticle surface was evaluated using a protease at 37 °C in phosphate buffer pH~5.3. It was found that 45% of MTX conjugated to the SPIONs were released after 72 h. Cell viability was measured by MTT assay, and after 72 h, 25% reduction in cell viability of tumor cells was observed. Thus, after a successful conjugation and subsequent triggered release of MTX, we understand that SPION@PGlCLCys has a strong potential to be treated as a model nanoplatform for the development of treatments and diagnosis techniques (or theranostic applications) that can be less aggressive to patients.

This study evaluated the efficacy of different cleaning methods with respect to changes in the color and light transmittance of both rough and smooth thermoformed, copolyester retainer specimens, after staining in different solutions. Four hundred copolyester sheets (Essix ACE) specimens were fabricated over molds with different surface textures, smooth and rough. The specimens were stained in four different solutions ( n = 100 per solution) over 28 days; then, each of the four groups of 100 stained specimens was sub-divided into five groups of 20 specimens and subjected to a different destaining solution. The specimens were sub-divided with half subjected to an additional ultrasonic cleaning procedure. Light transmittance and color changes were analyzed using a spectrometer/integrating sphere assembly and a spectrophotometer. Mean difference comparisons were performed using appropriate statistical tests at p = 0.05. All five destaining solutions proved to be effective at removing coffee and tea stains. The surface roughness of the retainer material plays a significant role in the ability of cleaning solutions to remove stains, demonstrating a greater effect on cleaning rough specimens with respect to improvements in light transmittance and greater changes in color. Additionally, an ultrasonic cleaning unit generally enhanced the ability of all five solutions to clean the tea-stained specimens. However, the enhancements were only significant for light transmittance.

The ever-increasing use of plastics, their fossil origin, and especially their persistence in nature have started a wave of new innovations in materials that are renewable, offer the functionalities of plastics, and are biodegradable. One such class of biopolymers, polyhydroxyalkanoates (PHAs), are biosynthesized by numerous microorganisms through the conversion of carbon-rich renewable resources. PHA homo- and heteropolyesters are intracellular products of secondary microbial metabolism. When isolated from microbial biomass, PHA biopolymers mimic the functionalities of many of the top-selling plastics of petrochemical origin, but biodegrade in soil, freshwater, and marine environments, and are both industrial- and home-compostable. Only a handful of PHA biopolymers have been studied in-depth, and five of these reliably match the desired material properties of established fossil plastics. Realizing the positive attributes of PHA biopolymers, several established chemical companies and numerous start-ups, brand owners, and converters have begun to produce and use PHA in a variety of industrial and consumer applications, in what can be described as the emergence of the "PHA industry". While this positive industrial and commercial relevance of PHA can hardly be described as the first wave in its commercial development, it is nonetheless a very serious one with over 25 companies and start-ups and 30+ brand owners announcing partnerships in PHA production and use. The combined product portfolio of the producing companies is restricted to five types of PHA, namely poly(3-hydroxybutyrate), poly(4-hydroxybutyrate), poly(3-hydroxybutyrate- co -3-hydroxyvalerate), poly(3-hydroxybutyrate- co -4-hydroxybutyrate), and poly(3-hydroxybutyrate- co -3-hydroxyhexanoate), even though PHAs as a class of polymers offer the potential to generate almost limitless combinations of polymers beneficial to humankind. To date, by varying the co-monomer type and content in these PHA biopolymers, their properties emulate those of the seven top-selling fossil plastics, representing 230 million t of annual plastics production. Capacity expansions of 1.5 million t over the next 5 years have been announced. Policymakers worldwide have taken notice and are encouraging industry to adopt biodegradable and compostable material solutions. This wave of commercialization of PHAs in single-use and in durable applications holds the potential to make the decisive quantum leap in reducing plastic pollution, the depletion of fossil resources, and the emission of greenhouse gases and thus fighting climate change. This review presents setbacks and success stories of the past 40 years and the current commercialization wave of PHA biopolymers, their properties, and their fields of application.

This research synthesizes novel copolyester (PCITN) containing biobased isosorbide, 1,4-cyclohexandimethanol, terephthalic acid, and 2,6-naphthalene dicarboxylic acid and characterize its properties. The PCITN copolyester was extruded into film, and its performance properties including: tensile strength, Young's modulus, thermal, dimensional stability, barrier (water barrier), and optical (birefringence and transmittance) were analyzed after uniaxial stretching. The films have higher T g , T m , dimensional stability, and mechanical properties than other polyester-type polymers, and these performance properties are significantly increased with increasing stretching. This is due to the increased orientation of molecular chains inside the films, which was confirmed by differential scanning calorimetry (DSC), X-ray diffraction (XRD), and birefringence results. Good water barrier (0.54%) and lower birefringence (△n: 0.09) of PCITN film compared to poly(ethylene terephthalate) (PET), poly(ethylene 2,6-naphthalate) (PEN), and polyimide (PI) films, used as conventional substrate materials for optical devices, make it an ideal candidate as performance material for next-generation flexible devices., Competing Interests: The authors declare no conflict of interest.

Bio-based unsaturated poly(butylene adipate-co-butylene itaconate) (PBABI) aliphatic copolyesters were synthesized with pentaerythritol (PE) as a modifier, observing the melting point, crystallization, and glass transition temperatures were decreased from 59.5 to 19.5 °C and 28.2 to -9.1 °C as an increase of itaconate concentration, and T g ranged from -54.6 to -48.1 °C. PBABI copolyesters tend to the amorphous state by the existence of the BI unit above 40 mol%. The yield strength, elongation, and Young's modulus at different BA/BI ratios were valued in a range of 13.2-13.8 MPa, 575.2-838.5%, and 65.1-83.8 MPa, respectively. Shear-thinning behavior was obtained in all BA/BI ratios of PBABI copolyesters around an angular frequency range of 20-30 rad s -1 . Furthermore, the thermal and mechanical properties of PBABI copolyesters can be well regulated via controlling the itaconic acid contents and adding the modifier. PBABI copolyesters can be coated on a 3D air mesh polyester fabric to reinforce the mechanical property for replacing traditional plaster applications.

The hydrophilic copolyester polyethylene terephthalate (PET) (ENCDP-X) was successfully synthesized by chemical modification consisting of copolymerization and blending and the comonomers, including sodium isophthalate-5-sulfonate (SIPE), polyethylene glycol (PEG), 2,2-dimethyl-1,3-propanediol (NPG) and matting agent TiO 2 with different content. Moreover, the structural characterization of sequential structure, crystallization and thermal properties were studied. The results showed that the comonomers were successfully embedded in the copolyester, the actual molar ratio in the copolyester was consistent with the relative feed ratio and the degree of randomness was calculated to be 0.99, showing that the random copolymers synthesized during the melt polycondensation process and the chemical structure was roughly consistent with the expected molecular chain sequence structure. The thermal parameters of the modified copolyester, containing the glass transition temperature ( T g ), melting point ( T m ), crystallinity ( X content, it improves the thermal performance of the copolyester and it is beneficial to processing and application. The above conclusion is further verified by non-isothermal kinetic analysis. In addition, the copolyester exhibited the better hydrophilicity than pure PET.c ) and thermal degradation temperature, were decreased, and the cold crystallization temperature ( T c ) was increased. In addition, with the increasing of the TiO 2 content, it improves the thermal performance of the copolyester and it is beneficial to processing and application. The above conclusion is further verified by non-isothermal kinetic analysis. In addition, the copolyester exhibited the better hydrophilicity than pure PET.

Unsaturated poly (butylene adipate-co-butylene itaconate) (PBABI) copolyesters were synthesized through melt polymerization composed of 1,4-butanediol (BDO), adipic acid (AA), itaconic acid (IA) and 1,2,4,5-benzenetetracarboxylic acid (BTCA) as a cross-linking modifier. The melting point, crystallization and glass transition temperature of the PBABI copolyesters were detected around 29.8-49 °C, 7.2-29 °C and -51.1 and -58.1 °C, respectively. Young's modulus can be modified via partial cross-linking by BTCA in the presence of IA, ranging between 32.19-168.45 MPa. Non-isothermal crystallization kinetics were carried out to explore the crystallization behavior, revealing the highest crystallization rate was placed in the BA/BI = 90/10 at a given molecular weight. Furthermore, the thermal, mechanical properties, and crystallization rate of PBABI copolyesters can be tuned through the adjustment of BTCA and IA concentrations.

Aromatic copolyesters, derived from bio-based nipagin and eugenol, were synthesized with renewable 1,6-hexandiol as the spacer. Number-average, weight-average molecular weights ( M n , M w ), and polydispersity ( D ) values were determined by size exclusion chromatography (SEC). Chemical structures were confirmed by 1 H NMR and 13 C NMR spectroscopies. Chemical microstructure analysis suggested that the nipagin and eugenol-derived units were inserted into polymer chains in an arbitrary manner. Due to the short chain of 1,6-hexanediol, the splitting of magnetically different methylene carbons, adjacent to the alcohol-oxygens, proved to be more sensitive towards sequence distributions, at the dyed level, than those from 1,10-decanediol. Thermal gravimetric analysis (TGA) demonstrated that these polyester materials have excellent thermal stability (> 360 °C), regardless of the content of eugenol-derived composition incorporated. Differential scanning calorimetric (DSC) and wide-angle X-ray diffraction (WXRD) experiments revealed the semicrystalline nature for this kind of copolyesters. The crystallinities gradually decreased with the increase of eugenol-derived composition. Thermal and crystalline properties were well discussed from the microscopic perspective. The point of this work lies in establishing guidance for future design and modification of high-performance polymer materials from the microscopic perspective., Competing Interests: The authors declare no conflict of interest.

Recently, we have developed an eco-friendly method for the preparation of a renewable dicarboxylic acid 2,5-furandicarboxylic acid (FDCA) from biomass-based 5-hydroxymethylfrufural (HMF). In the present work, we optimized our reported method, which used phosphate buffer and Fe(OH)₃ as the stabilizer to improve the stability of potassium ferrate, then got a purified FDCA (up to 99%) in high yield (91.7 wt %) under mild conditions (25 °C, 15 min, air atmosphere). Subsequently, the obtained FDCA, along with 1,6-hexanediol (HDO), which was also made from HMF, were used as monomers for the synthesis of poly(hexylene 2,5-furandicarboxylate) (PHF) via direct esterification, and triphenyl phosphite was used as the antioxidant to alleviate the discoloration problem during the esterification. The intrinsic viscosity, mechanical properties, molecular structure, thermal properties, and degradability of the PHFs were measured or characterized by Koehler viscometer, universal tensile tester, Nuclear Magnetic Resonance (NMR), Fourier-transform Infrared (FTIR), X-ray diffraction (XRD), Differential Scanning Calorimeter (DSC), Derivative Thermogravimetry (DTG), Scanning Electron Microscope (SEM), and weight loss method. The experimental evidence clearly showed that the furan-aromatic polyesters prepared from biomass-based HMF are viable alternatives to the petrochemical benzene-aromatic polyesters, they can serve as low-melting heat bondable fiber, high gas-barrier packaging material, as well as specialty material for engineering applications.

Devulcanized rubber (DR) was prepared from waste truck tire rubber via thermo-chemical devulcanization process. Thermoplastic vulcanizates (TPVs) based on blending of DR and copolyester (DR/COPE) were prepared. Effects of carbon black loading on microstructure, mechanical properties and elastomeric behaviors of dynamically cured DR/COPE blends were investigated. It was found that increasing of the carbon black loadings leads to transformation from co-continuous phase structure to dispersion of smaller vulcanized rubber domains in the COPE matrix. Furthermore, the carbon black was well dispersed in the DR/COPE matrix up to 10 wt% and then the aggregates slightly occurred with increasing of carbon black loadings. In addition, dynamic experiments proved that a progressive non-linear behavior was more pronounced with increasing of carbon black loadings. Also, tan δ max of the DR phase decreases with increasing carbon black concentration indicating mainly localization of filler in rubber phase. Moreover, it was found that increases of CB loadings resulted in increase of tensile strength and hardness while the elongation at break was slightly decreased. Additionally, the rate of stress relaxations was found to be increased with increasing CB loadings., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Based on direct sucrose conversion, the bacterium Burkholderia sacchari is an excellent producer of the microbial homopolyester poly(3-hydroxybutyrate) (PHB). Restrictions of the strain's wild type in metabolizing structurally related 3-hydroxyvalerate (3HV) precursors towards 3HV-containing polyhydroxyalkanoate (PHA) copolyester calls for alternatives. We demonstrate the highly productive biosynthesis of PHA copolyesters consisting of 3-hydroxybuytrate (3HB) and 4-hydroxybutyrate (4HB) monomers. Controlled bioreactor cultivations were carried out using saccharose from the Brazilian sugarcane industry as the main carbon source, with and without co-feeding with the 4HB-related precursor γ-butyrolactone (GBL). Without GBL co-feeding, the homopolyester PHB was produced at a volumetric productivity of 1.29 g/(L•h), a mass fraction of 0.52 g PHB per g biomass, and a final PHB concentration of 36.5 g/L; the maximum specific growth rate µmax amounted to 0.15 1/h. Adding GBL, we obtained 3HB and 4HB monomers in the polyester at a volumetric productivity of 1.87 g/(L•h), a mass fraction of 0.72 g PHA per g biomass, a final PHA concentration of 53.7 g/L, and a µmax of 0.18 1/h. Thermoanalysis revealed improved material properties of the second polyester in terms of reduced melting temperature Tm (161 °C vs. 178 °C) and decreased degree of crystallinity Xc (24% vs. 71%), indicating its enhanced suitability for polymer processing.

Copolyesters are a subset of polymers that have the desirable properties of strength and clarity while retaining chemical resistance, and are thus potential candidates for enhancing the impact resistance of soda-lime glass. Adhesion between the polymer and the glass relates to the impact performance of the system, as well as the longevity of the bond between the polymer and the glass under various conditions. Modifying the types of diols and diacids present in the copolyester provides a method for fine-tuning the physical properties of the polymer. In this study, we used molecular dynamics (MD) simulations to examine the influence of the chemical composition of the polymers on adhesion of polymer film laminates to two soda-lime glass surfaces, one tin-rich and one oxygen-rich. By calculating properties such as adhesion energies and contact angles, these results provide insights into how the polymer-glass interaction is impacted by the polymer composition, temperature, and other factors such as the presence of free volume or pi stacking. These results can be used to optimize the adhesion of copolyester films to glass surfaces.

Liquefied wood (LW) prepared in a microwave process was applied as a novel; inexpensive precursor feedstock for incorporation of ( R )-3-hydroxyvalerate (3HV) into polyhydroxyalkanoate (PHA) biopolyesters in order to improve the biopolyester's material quality; Cupriavidus necator was applied as microbial production strain. For proof of concept, pre-experiments were carried out on a shake flask scale using different mixtures of glucose and LW as carbon source. The results indicate that LW definitely acts as a 3HV precursor, but, at the same time, displays toxic effects on C. necator at concentrations exceeding 10 g/L. Based on these findings, PHA biosynthesis under controlled conditions was performed using a fed-batch feeding regime on a bioreactor scale. As major outcome, a poly(3HB- co -0.8%-3HV) copolyester was obtained displaying a desired high molar mass of M w = 5.39 × 10⁵ g/mol at low molar-mass dispersity ( Đ M of 1.53), a degree of crystallinity ( X c ) of 62.1%, and melting temperature T m (176.3 °C) slightly lower than values reported for poly([ R ]-3-hydroxybutyrate) (PHB) homopolyester produced by C. necator ; thus, the produced biopolyester is expected to be more suitable for polymer processing purposes.

Together with other so-called "bio-plastics", Polyhydroxyalkanoates (PHAs) are expected to soon replace established polymers on the plastic market. As a prerequisite, optimized process design is needed to make PHAs attractive in terms of costs and quality. Nowadays, large-scale PHA production relies on discontinuous fed-batch cultivation in huge bioreactors. Such processes presuppose numerous shortcomings such as nonproductive time for reactor revamping, irregular product quality, limited possibility for supply of certain carbon substrates, and, most of all, insufficient productivity. Therefore, single- and multistage continuous PHA biosynthesis is increasingly investigated for production of different types of microbial PHAs; this goes for rather crystalline, thermoplastic PHA homopolyesters as well as for highly flexible PHA copolyesters, and even blocky-structured PHAs consisting of alternating soft and hard segments. Apart from enhanced productivity and constant product quality, chemostat processes can be used to elucidate kinetics of cell growth and PHA formation under constant process conditions. Furthermore, continuous enrichment processes constitute a tool to isolate novel powerful PHA-producing microbial strains adapted to special environmental conditions. The article discusses challenges, potential and case studies for continuous PHA production, and shows up new strategies to further enhance such processes economically by developing unsterile open continuous processes combined with the application of inexpensive carbon feedstocks.

It is completely plausible that unmodified materials of natural origin, such as the native macromolecules cellulose or starch, are biodegradable. If these materials are modified then degradation may, depending on the degree of modification, be more difficult or even impossible. In the same manner synthesized macromolecules, whether from renewable or petrochemical sources, could be inert or completey biodegradable, depending on their chemical structure., (© 1999 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.)