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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 19 records

Toughened polyester composites containing polyester matrix and droplets of high boiling liquid therein

A toughened polyester composite comprising: (i) a polyester matrix and (ii) droplets of a high boiling point liquid having a boiling point of at least 140° C. dispersed in said polyester matrix, wherein the high boiling point liquid is present in an amount of 0.1-10 wt % by weight of the toughened polyester composite, and wherein the composite may further include: (iii) a modifier selected from polycarboxylic, polyol, and polyamine compounds, wherein the modifier is present in an amount of 0.1-10 wt % by weight of the toughened polyester composite. Methods for producing the polyester composite are also described.

Ozcan, Soydan↗

Probing the molecular design of hyper-branched aryl polyesters towards lubricant applications

We report novel polymeric materials that may be used as viscosity index improvers (VII) for lubricant applications. Our efforts included probing the comb-burst hyper-branched aryl polyester architecture for beneficial viscosity and friction behavior when utilized as an additive in a group I oil. The monomer was designed as to undergo polymerization via polycondensation within the architectural construct (AB2), typical of hyperbranched polymers. The monomer design was comprised of aliphatic arms (12 or 16 methylenes) to provide the necessary lipophilicity to achieve solubility in a non-polar medium. Once polymerized, via catalyst and heat, the surface alcohols were functionalized with fatty acids (lauric and palmitic). Controlling the aliphatic nature of the internal arms and peripheral end-groups provided four unique flexible polymer designs. Changing the reaction time and concentration provided opportunities to investigate the influence of molecular weight and branching density on oil-solubility, viscosity, and friction. Oil-solubility was found to decrease with fewer internal carbons, but the number of internal carbons appears to have little influence on the bulk solution viscosity. At concentrations of 2 wt % in a group I base oil, these polymer additives demonstrated an improved viscosity index and reduced friction coefficient, validating the basic approach.

Robinson, Joshua W.↗

All-Polyester Multilayer Plastics (‘All-Polyester MLPs’): A Redesign for Inherently Recyclable Plastics

Multilayer plastics (MLPs) are widely used in modern packaging because they combine multiple functions such as oxygen and moisture barriers, mechanical strength, puncture resistance, and heat sealability into lightweight and cost-effective packaging solutions. These attributes are essential for food, beverage, pharmaceutical, and consumer goods packaging. However, conventional commercial MLPs typically consist of five to twelve layers made from chemically incompatible materials, including polyolefins, polyethylene terephthalate, nylon, ethylene-vinyl alcohol (EVOH), adhesives, and tie layers. This complexity makes MLPs extremely difficult to recycle. As a result, the vast majority of multilayer plastics (MLPs) are disposed of through landfilling or incineration. This disposal pathway perpetuates demand for virgin material production, thereby driving high industrial energy consumption, increasing greenhouse gas (GHG) emissions, and contributing to the long-term accumulation of plastic waste. The scope of work included: (1) Design and fabrication of all-polyester multilayer structures using commercially relevant processing methods; (2) Experimental validation of barrier, mechanical, and sealing performance; (3) Demonstration of both mechanical and chemical recycling pathways; and (4) Comprehensive techno-economic analysis (TEA) and life-cycle assessment (LCA) to quantify cost, energy, and environmental impacts.

36 MATERIALS SCIENCE↗

Plasticized terephthalate-based polyester blends containing fatty acids or esters thereof

A plasticized terephthalate-based polyester blend comprising a terephthalate-based polyester (e.g., polyethylene terephthalate, i.e., PET) homogeneously blended with a fatty acid or ester thereof, wherein said fatty acid or ester thereof is present in said polyester blend in an amount of 1-50 wt %. Also described herein is a method for producing a plasticized terephthalate-based polyester blend, the method comprising melt mixing a terephthalate-based polyester with a fatty acid or ester thereof at a temperature in a range of 230-250° C. to produce said polyester blend, wherein said fatty acid or ester thereof is present in said polyester blend in an amount of 1-50 wt % and is homogeneously blended with said terephthalate-based polyester.

Naskar, Amit K.↗

Techno-Economic Analysis and Life Cycle Assessment of the Production of Biodegradable Polyaliphatic–Polyaromatic Polyesters

Poly(butylene-adipate terephthalate) (PBAT) is a polyaliphatic–polyaromatic polyester that is biodegradable and has found application in several markets, making it a widely produced biodegradable polymer worldwide. However, the production of PBAT is carbon-intensive, as it relies on the use of petroleum-based monomers. There is, thus, significant interest in identifying polyesters that are biodegradable and less carbon-intensive (e.g., use of biomass- derived monomers). In this work, we develop a detailed process model (and an associated database) for the production of polyaliphatic–polyaromatic polyesters including petroleum-based PBAT and biomass-derived alternatives including poly(pentylene- adipate terephthalate) and poly(pentylene-adipate furandicarboxy- late). Techno-economic analysis (TEA) reveals that the production costs of these polyesters strongly depend on monomer costs (accounting for over 90% of the total production cost) and identifies market conditions under which biomass-based polyesters can be cost-competitive to petroleum-based PBAT. Life cycle assessment (LCA) shows that biomass-derived polyesters can reduce the global warming impact of PBAT by half. Altogether, the proposed TEA/LCA model aims to provide guidance into polyesters that are most promising and help assess their overall economic and environmental performance.

42 ENGINEERING↗

Polyester functional graphenic materials as a mechanically enhanced scaffold for tissue regeneration

Traditional metal implants such as titanium, cobalt, and chromium have found wide utility in medicine; however, these come with a risk of toxicity. To overcome metal-related toxicity and enable degradability, polyesters including polycaprolactone (PCL), polylactic acid (PLA), and polyglycolic acid (PGA) show promise for the replacement of various biomedical applications of metals due to their accepted biocompatibility and FDA approval. However, polyesters are less stiff than their metallic counterparts, limiting their application to non-load bearing injury sites, such as fixation hardware for fingers. To improve mechanical properties, graphene oxide (GO)-polyester composites are a promising class of biodegradable scaffolds. Initial reports of these composites are encouraging, but mechanical properties still fall short. Traditional composites rely on non-covalent association between GO and the polyesters, which often leads to failure at the interface and weakens the overall strength of the material. Herein, we present a strategy for attachment of these FDA-approved polyesters onto a derivative of GO using a robust covalent bond. By covalently functionalizing the graphenic backbone with polyesters and without metal catalysts, we create functional graphenic materials (FGMs) to not only simultaneously retain biodegradability and compatibility, but also mechanically strengthen PCL, PLA, and PGA; we observed an average increase in the Young's modulus of over 140% compared to the graphenic backbone. These polyester-functionalized FGMs are a promising platform technology for tissue implants.

60 APPLIED LIFE SCIENCES↗

Silane-modified polyester blends and methods of preparation

A silane-modified polyester blend comprising a polyester polymer homogeneously blended with silane molecules containing two or three alkoxy groups bound to the silicon atom, wherein said silane molecules are present in said polyester blend in an amount of 0.05-20 wt % (or, e.g., 0.05-10 wt %, 0.05-5 wt %, or 0.05-2 wt %). The polyester polymer may, in particular embodiments, be a polyhydroxyalkanoate, terephthalate-based polyester, adipate-based, or succinate-based polyester. The silane molecule may be according to the formula (R2O)2SiR3R4, wherein R2 groups are independently selected from alkyl groups containing 1-4 carbon atoms; and R3 and R4 are independently selected from OR2 groups and alkyl groups containing 1-12 carbon atoms, provided that at least one of R3 and R4 is an alkyl group, wherein the alkyl group optionally includes one or more heteroatoms selected from oxygen, nitrogen, halogen, sulfur, phosphorus, and silicon. Methods for producing the silane-modified polyester blend are also described.

Meng, Xiangtao↗

Thermally stable and self-healable lignin-based polyester

The increased use of plastics and the associated environmental impact has catalyzed research on the development of bio-derived polymers. Bio-based polyesters have gained increased attention due to the abundance of their starting materials and ease of processing. Lignin is naturally occurring in biomass with rich carbon content, whose functionality and rigidity make it an ideal bio-derived candidate for bio-based polyesters. Herein, a lignin-based polyester with good thermal stability and self-repairability was synthesized from carboxylated lignin and epoxidized soybean oil. The synthesized lignin/epoxidized soybean oil (ESO) vitrimer was brittle such that its mechanical performance could not be recorded. However, when polyethylene glycol (PEG) was incorporated as a plasticizer, polymer samples exhibited acceptable ductility. From thermomechanical analysis of the synthesized polyesters, the plasticizer did not impair thermal stability of polymers, but greatly enhanced mechanical properties. Notably, all samples exhibited stability at high temperatures, and good glass transition temperatures (51.0 ± 0.9–78.0 ± 1.2 °C). The highest tensile strength (3.983 ± 0.1 MPa) and storage modulus (1463.67 ± 12.6 MPa) were recorded for the polyester containing 6 % w/w PEG. Moreover, the polymer samples exhibited self-healing capability at 180 °C. This work expands on valorization of lignin through the synthesis of bio-derived materials.

36 MATERIALS SCIENCE↗

On the Mechanism of the Steady-State Gamma Radiolysis-Induced Scissions of the Phenyl-Vinyl Polyester-Based Resins

The major societal problem of polymeric waste necessitates new approaches to break down especially challenging discarded waste streams. Gamma radiation was utilized in conjunction with varying solvent environments in an attempt to discern the efficacy of radiolysis as a tool for the deliberate degradation of model network polyesters. Our EPR results demonstrated that gamma radiolysis of neat resin and in the presence of four widely used solvents induces glycosidic scissions on the backbone of the polyester chains. EPR results clearly show the formation of alkoxy radicals and C-centered radicals as primary intermediate radiolytic products. Despite the protective role of the phenyl groups on the backbone of the radiation-induced polyester chains, the radiolytic-glycosidic scissions predominate. Among the following three solvents used in this study (water, isopropyl alcohol, and dichloromethane), the highest radiolytic yield of glycosidic scission was achieved using water. The •OH radicals produced in the radiolysis of phenyl unsaturated polyester aqueous suspensions very rapidly abstract H atoms from the methylene group, which is followed by a very rapid glycosidic scission. The lowest glycosidic yield was found in the dichloromethane solutions of these polyester resins due to scavenging by the fast electron capture reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation of enzymatic depolymerization of PET, PTT, and PBT polyesters

Millions of tons of waste polyester plastics, including polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), and polybutylene terephthalate (PBT), end up in the environment as soil and water contaminants. Recent advances in enzymatic polyester degradation have motivated researchers toward biorecycling of plastic wastes. Leaf-branch compost cutinase (LCC) enzymes have been proven to be effective in the biodegradation of PET. This study focuses on enzymatic depolymerization of waste PET, PTT, and PBT materials by using an ICCG variant of LCC (LCC ICCG ) produced from Escherichia coli BL21(DE3). The degradation efficiency of the polyesters was determined by the monomer terephthalic acid (TPA) released from the depolymerization reaction. It was found that the most efficient depolymerization was achieved for PET, followed by PTT and PBT. A kinetic model based on Langmuir adsorption and the Michaelis-Menten equation was developed to describe the enzymatic depolymerization of PET, PTT, and PBT with various enzyme and substrate loadings. The model simulation results revealed that the LCCICCG enzyme loading should be linearly increased as the work capacity of the polyester substrate increases. A specific enzyme loading of 0.91 mg/g PET is suggested to achieve 90% depolymerization of PET within three days. Furthermore, the experimental data and model simulation results can be used to help further engineer the enzyme and process to achieve a complete biodegradation of polyester wastes at large scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Screening and Characterization of Novel Polyesterases from Environmental Metagenomes with High Hydrolytic Activity against Synthetic Polyesters

The continuous growth of global plastics production, including polyesters, has resulted in increasing plastic pollution and subsequent negative environmental impacts. Therefore, enzyme-catalyzed depolymerization of synthetic polyesters as a plastics recycling approach has become a focus of research. In this study, we screened over 200 purified uncharacterized hydrolases from environmental metagenomes and sequenced microbial genomes and identified at least 10 proteins with high hydrolytic activity against synthetic polyesters. These include the metagenomic esterases MGS0156 and GEN0105, which hydrolyzed polylactic acid (PLA), polycaprolactone, as well as bis-(benzoyloxyethyl)-terephthalate. With solid PLA as a substrate, both enzymes produced a mixture of lactic acid monomers, dimers, and higher oligomers as products. The crystal structure of MGS0156 was determined at 1.95 angstrom resolution and revealed a modified alpha/beta hydrolase fold, with a lid domain and highly hydrophobic active site. Mutational studies of MGS0156 identified the residues critical for hydrolytic activity against both polyester and monoester substrates, with two-times higher polyesterase activity in the MGS0156 L169A mutant protein. Thus, our work identified novel, highly active polyesterases in environmental metagenomes and provided molecular insights into their activity, thereby augmenting our understanding of enzymatic polyester hydrolysis.

Hajighasemi, Mahbod↗

One-Pot Depolymerization and Polycondensation of PET Based Random Oligo- and Polyesters

The glycolysis of PET is a promising well-developed technique that could be utilized in a wide range of processes. Due to its equilibrial nature, the high ratio of reagents and the purification steps it is an expensive process. In this study our goal was to modify the standard glycolysis to an easily modulateable method (acido-alcoholysis) suited for one-pot oligoester, polyester synthesis. Adipic acid was added to the depolymerization reaction to connect low molecular weighed components into oligoesters. PET depolymerization reaction series were carried out with ethylene–glycol/adipic acid and butane-1,4-diol/adipic acid to demonstrate the tuneability of these systems. The reaction products were thoroughly characterized with NMR, FTIR, TGA, DSC and functional group analysis. One-pot depolymerization-polycondensation reactions were engineered to produce unsaturated and saturated polyesters. The unsaturated polyesters were dissolved in styrene, cross-linked and moulded to be characterized with DMA. A decreasing tendency of the glass transition temperature and cross-link density were found in the function of the ratio of adipic acid used during the depolymerization step. Acido-alcoholysis proved to be a versatile technique that could be used to engineer oligoesters and polyesters. The reagent use can be minimalized, and the raw reaction products can be directly applied as mid-products.

36 MATERIALS SCIENCE↗

Chemically and mechanically recyclable polyester-based multilayer plastics

Approximately 100 million tons of multilayered plastics (MLPs) are produced each year worldwide but are not recycled due to their complex structure. Here, this work aims to design polyester-based multilayer plastics (80–100 % polyester) that provide barrier performance comparable to typical 9–12-layer commercial MLPs, while also enabling both chemical recycling (back to parent monomer) and mechanical recycling (grind-and-melt reprocessing). Such dual recyclability is not achievable with non-polyester multilayers, such as all-polyolefin systems. Furthermore, we emphasize how the multilayer architecture was tailored to balance barrier properties, mechanical integrity, and end-of-life recyclability for both flexible and rigid packaging applications. Two main categories of polyester-based MLPs are reported; in the first type, poly(butylene adipate-co-terephthalate) (PBAT)-70 % polyglycolic acid (PGA) is used as middle barrier layer, while in second type, middle barrier layer is Ethylene-vinyl alcohol (EVOH) copolymers. Polyethylene terephthalate (PET) was used as a structural layer, while either PBAT or poly(butylene succinate) (PBS) was used to enable thermal sealing and serve as the product contact layer. These MLPs are recycled by both chemical and mechanical recycling processes. Techno-economic analysis (TEA) shows that MLPs incorporating EVOH as barrier layer have similar or lower selling costs (0.32 $\$$/m 2 ) than commercial MLPs. Life cycle assessment (LCA) indicates EVOH-based MLPs have a lower carbon footprint and lower energy consumption relative to commercial MLP benchmarks. This work offers simplified MLPs that are easy to manufacture and ready to recycle, which will significantly reduce environmental impact of MLP packaging while also providing a cost-effective and practical solution for industry.

Barrier properties↗

Mixed polyester recycling can enable a circular plastic economy with environmental benefits

The mixed and varied nature of fossil-based and bio-based plastic waste requires complex and costly separations to enable compatibility with recycling technologies. A circular plastic economy based on mixed polyesters through cleaving ester bonds to produce monomers, while re-utilizing bio-based monomers to produce high-quality sustainable plastics, charts an exciting solution. However, the feasibility of such a circular economy solution remains underexplored. Here, in this study, we conducted a techno-economic analysis and life-cycle assessment of three polyester depolymerization recycling processes-methanolysis, glycolysis, and acid hydrolysis-for a mixed feedstock (polyethylene terephthalate [PET], polylactic acid [PLA], and polybutylene adipate terephthalate [PBAT]). Methanolysis outperforms glycolysis and hydrolysis economically and environmentally due to more efficient downstream separations, generating products with a 31% decrease in selling price and 21%-46% reduction in acidification, carcinogenic toxicity, fossil-fuel depletion, global warming potential, particulate formation, and smog formation compared to conventional polyester manufacturing. This study highlights the viability of a circular plastic economy for mixed polyesters via a single chemical recycling process.

09 BIOMASS FUELS↗

Direct Synthesis of Polyester from Biomass Derived 1,6-hexanediol using a Copper-Ceria Catalyst

Biomass derived polyesters are gaining attention due to their increased mechanical and thermal properties, and also because of their biodegradability. These polyesters are typically synthesized from polycondensation reactions between diols with dicarboxylic acids using catalysts. Other methods such as alcoholysis and acidolysis of low molecular weight esters and alcoholysis of acyl chlorides are also well known. Direct conversion of diol to ester without using dicarboxylic acid is not well known, and to our knowledge has not been reported over a solid catalyst. In this study, we report a direct synthesis of polyester from 1,6-hexanediol using a copper-ceria catalyst without using a dicarboxylic acid monomer. The copper-ceria catalysts were synthesized by incipient wetness impregnation method and characterized using X-ray photoelectron spectroscopy (XPS), X-ray diffraction analysis (XRD), Brunauer-Emmett-Teller (BET), and infrared spectroscopy (IR). Our initial studies show that 1,6-hexanediol can be converted to corresponding polyester at higher temperatures under atmospheric pressures of CO2 or N2. The reaction products were analyzed using nuclear magnetic resonance spectroscopy (NMR), gel permeation chromatography (GPC), high performance liquid chromatography (HPLC), and IR spectroscopy.

Biomass derived diols↗

Degradation Study of Biobased Polyester–Polyurethane and its Nanocomposite Under Natural Soil Burial, UV Radiation and Hydrolytic-Salt Water Circumstances

The current study focuses on the development of a formulation of polyester polyurethane (PEPU) samples using castor oil (CO) modified polyester polyol and partially biobased aliphatic isocyanate. The CO modified polyester polyol was synthesized employing transesterification reaction between CO and diethylene glycol in the presence litharge (PbO) catalyst. Subsequently, the modification of CO was confirmed using proton nuclear magnetic resonance ({sup 1}HNMR) spectra analysis. In the next stage, the biobased polyester polyurethane nanocomposites (PEPUNC) were prepared by incorporating 3 wt% OMMT nanoclay within PEPU through in situ polymerization technique. The produced PEPU was confirmed by Fourier transform infrared spectroscopy (FTIR) and {sup 1}HNMR spectra analysis. Further, the degradation properties of developed PEPU subjected to soil-burial, UV exposure and hydrolytic-salt water medium were noted by FTIR spectroscopy. Corresponding weight loss, mechanical measurements and morphological studies through scanning electron microscopy (SEM) analysis were studied. The results showed that the addition of OMMT nanoclay within the PEPU matrix produces significant improvement in the degradation rate which indicated the susceptibility of OMMT nanoclay to humidity upon exposure to soil burial. The produced microorganisms from the soil resulted in significant chemical and morphological changes in the entire structure of the PEPU. Additionally, the highest degradation and percentage of weight loss was observed under soil burial as compared to UV exposure and hydrolytic-salt water medium.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Candida antarctica Lipase B as Catalyst for Cyclic Esters Synthesis, Their Polymerization and Degradation of Aliphatic Polyesters

Candida antarctica: lipase B (CALB) is the most widely studied enzyme, due to its high selectivity and catalytic activity in organic and polymer synthesis. To avoid organometallic catalysts in the synthesis of biodegradable polyesters, the enzymatic ring-opening polymerization of cyclic esters can be carried out with CALB as a biocatalyst. This paper reviews selected examples of the application of lipases in polymer chemistry covering the synthesis of cyclic ester monomers, linear and star oligomers, as well as well-defined high molar mass polymers with improved mechanical properties. It is shown that by the selection of appropriate conditions of temperature and solvent assortment, CALB effectively catalyzes the polymerization of large size lactones obtaining polyesters with M{sub n} up to 80 kg mol{sup −1}. The chemical structure and main applications of described materials are also discussed. As the polymer recycling is an important topic from environmental point of view, we also described the potential applications of CALB in degradation process of aliphatic polyesters.

36 MATERIALS SCIENCE↗