SEARCH · Search NASA

Results for “biobased polymer”

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.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

50 records · Page 3

All sources NASA NTRS DOE OSTI

DOE OSTI2022

From Petroleum to Biobased Crude: A Thermoplastic Polyurethane from Lignin-Oil Without Isocyanates

The movement to transfer from petroleum-based products and materials to renewables does not necessarily have to bypass the use of oil. A new type of "black-gold" is readily abundant from the earth's most abundant source of aromatic carbon: lignin. While fractionation of petroleum yields fuels and chemicals for a diverse set of industries, lignin fractionation using targeted catalysts has demonstrated the ability to generate monomers and oligomers rich in functional groups for polymer synthesis. This study explores the use of lignin-oil, generated from reductive catalytic fractionation of popular wood, to a hydroxyl-rich mixture of aromatics that is used to synthesize a thermoplastic non-isocyanate polyurethane. The lignin-oil is first converted to a cyclocarbonated derivative using a benign synthetic sequence and further polymerized with a diamine to yield the non-isocyanate TPU. While more work is underway to optimize the reaction conditions and meet typical mechanical properties of commercial materials, initial analysis shows thermoplastic behavior and flexible properties consistent with traditional thermoplastic polyurethanes.

BIOMASS FUELS↗

DOE OSTI2025

Recent Advances in the Use of Ionic Liquids and Deep Eutectic Solvents for Lignocellulosic Biorefineries and Biobased Chemical and Material Production

Biorefineries, which process biomass feedstocks into valuable (bio)products, aim to replace fossil fuel-based refineries to produce energy and chemicals, reducing environmental and health hazards, including climate change, and supporting a sustainable economy. In particular, lignocellulose-based biorefineries, utilizing the most abundant renewable feedstock on Earth, have significant potential to supply sustainable energy, chemicals and materials. Ionic liquids (ILs, organic salts with low melting temperatures) and deep eutectic solvents (DESs, mixtures with eutectic points lower than the ideal mixture) are capable of dissolving some of the key lignocellulose polymers, and even the whole biomass. Furthermore, they have intrinsic advantages over molecular solvents, including safer usage profiles and high tunability, which allow tailored physicochemical properties. Such properties provide unique opportunities for the development of new processes that could unlock the full potential of future biorefineries. Here, we review the current state of lignocellulosic biomass processing with ILs and DESs, with a specific focus on the pretreatment chemistry, process flow and products from each component; followed by discussions on sustainability assessments and technological challenges. We aim to inform the research community about the opportunities, challenges and perspectives in developing truly sustainable lignocellulose-based biorefineries.

09 BIOMASS FUELS↗

DOE OSTI2020

Materials for the biorefinery: high bio-content, shape memory Kraft lignin-derived non-isocyanate polyurethane foams using a non-toxic protocol

Polyurethanes are among the top six polymers produced in the world and are widely used in the automotive, furniture, construction and appliance industry for their light weight, impact resistance, and insulating properties. However, the use of hazardous diisocyanates used in polyurethane formulations has led many to search for more sustainable alternatives. The lignin component of biomass has been targeted to replace the often toxic and petroleum-derived precursors to polymer synthesis in support of the biorefinery concept where natural materials are used as the feedstock for commodity plastics. The use of lignin is often hampered due to its low reactivity, heterogeneity and the necessity of employing extensive purification and/or functionalization measures to ensure materials are of comparable quality. In this report, a unique method is presented for the synthesis and processing of a non-toxic, non-isocyanate polyurethane foam utilizing unmodified Kraft lignin and a biobased curing agent. Here, raw Kraft lignin is functionalized with green organic carbonates and a non-toxic approach is taken to solubilize the precursors with a curing agent from renewable fatty acids enabling rapid gel-times. For the first time, a NIPU foam from lignin is synthesized while the structure–property relationship of different reaction mixtures is studied demonstrating shape memory capacity and 100% biobased carbon content.

36 MATERIALS SCIENCE↗

DOE OSTI2021

Application of Machine Learning to Improve Biobased Glucaric Acid Production (CRADA 504)

The Agile Biofoundry (ABF) is a multi-national lab consortium funded by the DOE Bioenergy Technologies Office that has developed a biofoundry that enables the rapid deployment of bioproducts into the market. Working with four ABF laboratory members (National Renewable Energy Laboratory (NREL), Pacific Northwest National Laboratory (PNNL), Lawrence Berkeley National Laboratory (LBNL), and Argonne National Laboratory (ANL)), Kalion will use advanced high throughput techniques, advanced analytics, and machine learning to optimize the production environment for glucaric acid. Low-cost, high-purity glucaric acid enables products in a wide range of fields to improve the chemical properties of products and applications ranging from water treatment, polymers & textiles, coatings, detergents, and pharmaceuticals. With its broad range of applications, glucaric acid has the potential to demonstrate how such bio-based materials offer great benefit to the US economy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Effect of Fatty Acid Polyunsaturation on Synthesis and Properties of Emulsion Polymers Based on Plant Oil-Based Acrylic Monomers

This study demonstrated that polymerization behavior of plant oil-based acrylic monomers (POBMs) synthesized in one-step transesterification reaction from naturally rich in oleic acid olive, canola, and high-oleic soybean oils is associated with a varying mass fraction of polyunsaturated fatty acid fragments (linoleic (C18:2) and linolenic (C18:3) acid esters) in plant oil. Using miniemulsion polymerization, a range of stable copolymer latexes was synthesized from 60 wt.% of each POBM and styrene to determine the impact of POBM chemical composition (polyunsaturation) on thermal and mechanical properties of the resulted polymeric materials. The unique composition of each plant oil serves as an experimental tool to determine the effect of polyunsaturated fatty acid fragments on POBM polymerization behavior and thermomechanical properties of crosslinked films made from POBM-based latexes. The obtained results show that increasing polyunsaturation in the copolymers results in an enhanced crosslink density of the latex polymer network which essentially impacts the mechanical properties of the films (both Young’s modulus and toughness). Maximum toughness was observed for crosslinked latex films made from 50 wt.% of each POBM in the monomer feed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Application of Machine Learning to Improve Biobased Glucaric Acid Production: Cooperative Research and Development Final Report, CRADA Number CRD-20-17260

The Agile Biofoundry (ABF) is a multi-national lab consortium funded by the DOE Bioenergy Technologies Office that has developed a biofoundry that enables the rapid deployment of bioproducts into the market. Working with four ABF laboratory members (National Laboratory of the Rockies (NLR), Pacific Northwest National Laboratory (PNNL), Lawrence Berkeley National Laboratory (LBNL), and Argonne National Laboratory (ANL)), Kalion will use advanced high throughput techniques, advanced analytics, and machine learning to optimize the production environment for glucaric acid. Low-cost, high-purity glucaric acid enables products in a wide range of fields to improve the chemical properties of products and applications ranging from water treatment, polymers & textiles, coatings, detergents, and pharmaceuticals. With its broad range of applications, glucaric acid has the potential to demonstrate how such bio-based materials offer great benefit to the US economy.

09 BIOMASS FUELS↗

DOE OSTI2024

Scale-Up of a Two-Stage Cu-Catalyzed Alkaline-Oxidative Pretreatment of Hybrid Poplar

A two-stage alkaline-oxidative pretreatment of hybrid poplar was investigated at scale (20 L reactor volume) with the goals of understanding how reaction conditions as well as interstage mechanical refining impact downstream process responses. The pretreatment comprises a first stage of alkaline delignification (alkaline pre-extraction) followed by a second delignification stage employing Cu-catalyzed alkaline hydrogen peroxide with supplemental O 2 (O 2 -enhanced Cu-AHP). Increasing pre-extraction severity (i.e., temperature and alkali loading) and pre-treatment oxidation (increasing H 2 O 2 loading) were found to increase mass and lignin solubilization in each stage. Lignin recovered from the first stage was subjected to oxidative depolymerization and led to aromatic monomer yields as high as 23.0% by mass. As a result, lignins recovered from the second stage Cu-AHP pretreatment liquors were shown to exhibit aliphatic hydroxyl contents more than six-fold higher than for a typical hardwood kraft lignin, indicating these lignins could serve as a biobased polyol for a range of polyurethane applications.

09 BIOMASS FUELS↗

DOE OSTI2022

Development of high‐performance partially biobased thermoset polyester using renewable building blocks from isosorbide, 1,3‐propanediol, and fumaric acid

Abstract Research on biobased thermoset resins has been overlooked when compared with the rapid progress on biobased thermoplastics. The objective of this work was to develop unsaturated polyester prepolymers based on building blocks derived from renewable raw materials, namely, biobased isosorbide, 1,3‐propanediol, and fumaric acid, with petroleum‐derived phthalic anhydride. The prepolymers developed herein behaved as low‐molecular weight macromolecules (oligoesters), with M n varying between 1.2 and 1.5 kDa, but achieved a high bio‐content of up to 87.1 wt%. The prepolymers were incorporated into reactive diluents comprising a blend of 2‐hydroxyethyl methacrylate and styrene, formulated to be eco‐friendlier and less toxic than typical styrene‐only incorporation approach, thus resulting in resins with viscosities between 750 and 950 cP. These resins are suitable for use in various fiber‐reinforced polymer production techniques, such as manual lamination, vacuum infusion, and pultrusion, having the benefit of presenting over 50 wt% of bio‐content in some formulations. Moreover, the crosslinked polyester resins (thermosets) exhibit comparable mechanical and thermomechanical behavior to their petrochemical‐based counterparts, with modulus of elasticity and tensile strength of up to 3.9 GPa and 62.1 MPa, respectively, and glass transition temperatures of up to 106°C, making them greener alternatives for high‐performance structural applications.

Hofmann, Mateus↗

DOE OSTI2022

Preparation and characterization of aminated co-solvent enhanced lignocellulosic fractionation lignin as a renewable building block for the synthesis of non-isocyanate polyurethanes

Lignin is a major bioresource from 2nd generation biorefinery process streams and from pulp and paper production that is still severely underutilized nowadays. Its natural polymeric and aromatic structures make it suitable as a potential building block for biopolymer production. Due to the growing environmental and health concerns over conventional polyurethane (PU) manufacturing processes that utilize toxic isocyanates, there is a great interest to develop a non-isocyanate PU (NIPU) route. Herein, we demonstrate a novel strategy that uses highly pure lignin isolated from co-solvent enhanced lignocellulosic fractionation (CELF) pretreatment of poplar wood to produce biobased NIPUs. In this strategy, hardwood poplar is firstly fractionated via a CELF pretreatment to produce a clean lignin stream that is rich in phenolics. The CELF lignin was then aminated by a Mannich reaction, and the aminated CELF lignin was finally reacted with bicyclic carbonates to yield an advanced NIPU. In this work, the structure, mechanical, and thermal properties of these novel NIPUs were elucidated by FTIR, NMR, tensile test, dynamic mechanical analysis (DMA), and thermogravimetric analysis (TGA). The mechanical properties of these lignin based NIPUs could be tuned from highly rigid to elastic polymers by simply modifying the lignin constituents of the polymer. The thermal stabilities of NIPUs were improved because of the addition of aminated lignin, and NIPU containing 55 and 23 wt% lignin showed the highest tensile strength (~1.2 MPa) and elongation at break (~140%), respectively. The results obtained in this study demonstrate that the reaction of cyclic carbonate with aminated lignin represents an interesting pathway for the synthesizing of lignin based NIPU with a relative high lignin content.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2023

Dihydroxyterephthalate—A Trojan Horse PET Counit for Facile Chemical Recycling

Abstract Here, low‐energy poly(ethylene terephthalate) (PET) chemical recycling in water: PET copolymers with diethyl 2,5‐dihydroxyterephthalate (DHTE) undergo selective hydrolysis at DHTE sites, autocatalyzed by neighboring group participation, is demonstrated. Liberated oligomeric subchains further hydrolyze until only small molecules remain. Poly(ethylene terephthalate‐ stat ‐2,5‐dihydroxyterephthalate) copolymers were synthesized via melt polycondensation and then hydrolyzed in 150–200 °C water with 0–1 wt% ZnCl 2 , or alternatively in simulated sea water. Degradation progress follows pseudo‐first order kinetics. With increasing DHTE loading, the rate constant increases monotonically while the thermal activation barrier decreases. The depolymerization products are ethylene glycol, terephthalic acid, 2,5‐dihydroxyterephthalic acid, and bis(2‐hydroxyethyl) terephthalate dimer, which could be used to regenerate virgin polymer. Composition‐optimized copolymers show a decrease of nearly 50% in the Arrhenius activation energy, suggesting a 6‐order reduction in depolymerization time under ambient conditions compared to that of PET homopolymer. This study provides new insight to the design of polymers for end‐of‐life while maintaining key properties like service temperature and mechanical properties. Moreover, this chemical recycling procedure is more environmentally friendly compared to traditional approaches since water is the only needed material, which is green, sustainable, and cheap.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Greenhouse Gas Emissions Associated with Pretreatment Techniques Utilized for Biosugar Production

Less carbon-intensive production of biosugars from lignocellulosic materials can lead to improved manufacturing of biofuels and bioproducts. In this study, the production of biosugars is analyzed to understand the potential of producing bioproducts from biosugars with a low carbon intensity. Life-cycle assessment is conducted on five lignocellulosic feedstocks along with seven pretreatment techniques to produce biosugars as an important platform intermediate for producing bioproducts. The production of electricity using lignin with and without heat integration was also incorporated. In addition, seven bioproducts are analyzed for the estimation of the GHG emissions budget, which represents the emissions available to convert, separate, and upgrade biosugars into bioproducts within the 70% emissions reduction target. Corn stover-deacetylation and dilute acid pretreatment (CS-DDA) provide the lowest GHG emissions for biosugar (0.03 kg CO 2 eq/kg biosugar) and thereby the highest GHG emissions budget for the case of lactic acid production (3.76 kg CO 2 eq/kg lactic acid). Natural gas and chemicals are the major contributors to all of the pretreatment techniques under study. The outcomes from this study can benefit the advancement of upcoming biobased processes that meet decarbonization targets.

Biopolymers↗

DOE OSTI2025

Synthesis and Characterization of Soy Hull Biochar-Based Flexible Polyurethane Foam Composites

Flexible polyurethane foams are a diverse class of materials encompassing furniture, packaging, automotive, and many other industrial and domestic applications. Polyurethane foams are synthesized by the addition of polyols and isocyanates; however, the petroleum origin and toxic nature of isocyanates have driven many to look for more sustainable routes to production. Renewable fillers have emerged as a biobased resource to decrease the carbon footprint of this widely used polymeric material. In this study, soy hulls, as mass-produced, industrial by-products of soybean production, were used to create a biochar beneficial in the synthesis of flexible polyurethane foam composites. The addition of soy hull biochar was found to maintain the compression properties of foams at a decreasing isocyanate index, reducing the amount of isocyanates needed for production. In addition, the addition of biochar decreased the flammability of foams, important for many applications where consumer safety is important. The results point to the ability to create safer, more sustainable, and even more cost-effective polyurethane foams through the reduction in isocyanate use while maintaining the properties of this important class of polymers.

Chemistry↗

DOE OSTI2024

Catalytic production of δ-valerolactone (DVL) from biobased 2-hydroxytetrahydropyran (HTHP) – Combined experimental and modeling study

δ-Valerolactone (DVL) is a five-carbon (C5) cyclic ester that can undergo ring-opening polymerization to yield high-performance, biocompatible polyesters. But current market prices of C5 chemicals like DVL are very high due to poor availability of C5 feedstock in petroleum. Herein, we demonstrate a novel route to DVL synthesis via dehydrogenation of biomass-derived 2-hydroxytetrahydropyran (HTHP) over Cu/SiO 2 without the use of toxic reagents. Since HTHP exists in thermal equilibrium with 3,4-dihydropyran (DHP) via dehydration, and with 2,2’-oxybis(tetrahydropyran) and 5-(tetrahydropyran-2-yloxy)pentanal via acetalization, we have also determined the thermochemistry (ΔH rxn and ΔG rxn ) of each competing reaction using density functional theory (DFT) calculations at the M06-2X/cc-pVTZ level. Finally, by developing a kinetic model of all 8 reactions involved, we have achieved 84% selectivity to DVL at 150°C in a packed bed reactor for over 72 hours of time on stream.

42 ENGINEERING↗

DOE OSTI2024

Final Technical Report

The Department of Energy is interested in technologies that support the sustainable production of fuels, chemicals, and other bioproducts from plant biomass, to offset the nation’s reliance on fossil resources. The plant cell wall of energy crops provides the largest reservoir of raw materials for bioproducts. However, the widespread use of plant cell walls is hampered by their complexity and resistance to breakdown. To improve the productivity and cost-effectiveness of using energy crops to generate bioproducts, the fundamental problem of deconstructing plant cell walls must be addressed. This project developed and evaluated an innovative genetic modification technology to produce strategically designed enzymes that specifically accumulate in the plant cell wall. The resulting enzyme-engineered energy crops are expected to grow normally under natural conditions but break down more quickly and easily under high temperature during the production of biobased products. As such, this plant cell wall targeting enzyme engineering effort will reduce the cost of plant cell wall deconstruction and ultimately improve the economics of bioproducts. The overall objective of this project is to develop and evaluate the in-planta enzyme engineering technology to reduce lignocellulose deconstruction cost. The concept was first validated using tobacco plant, a model plant system that is typically used in lab testing for initial concept validation. Then the enzyme optimization was validated using switchgrass, the energy crop to be used to produce bioproducts. There are three specific objectives in this Phase I project: (1) validate the enzyme optimization concept using tobacco plant, a model plant system. (2) validate the enzyme optimization concept using switchgrass. (3) techno-economic analysis (TEA) for further scale-up application. By the end of this project, in-planta enzyme engineering was validated in both tobacco and switchgrass plants, with improved enzyme activity and saccharification efficiency. The in-planta enzyme engineering in Tabacco didn’t have a significant impact on plant growth and development. Transgenic tobacco plants with in-planta cellulose degrading enzymes showed higher biomass digestibility than wild type. Gene construction and transformation in switchgrass was much longer than expected, which delayed the research progress. Besides, in-planta engineering of lignin degrading enzyme is more challenging than cellulose degrading enzyme, in terms of expression detection. Expression of lignin degrading enzyme and cellulose degrading enzyme improved biomass yield and saccharification efficiency of switchgrass, respectively. It is promising to express both genes in switchgrass for optimized overall performance. According to the results of TEA, switchgrass biomass production cost is mainly attributed to by fertility and harvesting. Biomass production profit can increase up to 10-fold depending on biomass price. The PHA production profit is also sensitive to the biomass price. The proposed technology could potentially reduce the biomass deconstruction cost from 33% to 9% of PHA revenue, making the biomass-based PHA competitive to petroleum-based polymers even in case of relatively high biomass price of biomass. Therefore, cultivation of the genetically engineered self-deconstruction switchgrass for Polyhydroxyalkanoate (PHA) production could benefit switchgrass grower and PHA producer with attractive profits for both sectors. This new enzyme optimization approach will be beneficial for bioindustries that use energy crops as feedstocks. It will improve the economic viability of converting energy crops to renewable products that support a sustainable society and helps address the Nation’s long-term strategic needs for renewable products and reduction of reliance on fossil resources.

42 ENGINEERING↗