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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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80 records · Page 5
All sourcesNASA NTRSDOE OSTI
NASA NTRS2003

Bisadducts from the Diels-Alder Trapping of Bis(o-Xylenols) Photochemically Generated from 2,5-Dibenzoyl-p-xylene

Photolysis of 2,5-dibenzoyl-p-xylene produces two discrete o-xylenols which undergo Diels-Alder cycloadditions with standard dienophiles, such as methyl acrylate, to produce 1,5-dihydroxy-1,5-diphenyl-l,2,3,4,5,6,7,8-octahydroanthracenes, 2a, in good yield (greater than 80%). The anti bisadduct crystallizes into hydrogen bonded stacks. Conversion of both syn- and anti-bisadducts to the corresponding anthracenes was achieved through the use of standard dehydration and aromatization chemistry.

Meador, Michael A.↗
NASA NTRS2004

Photo-Curing: UV Radiation curing of polymers

The Polymers Branch of the Materials Division is dedicated to the development of high-performance for a variety of applications. Areas of significant interest include high- temperature polymers, low density, and high strength insulating materials, conductive polymers, and high density polymer electrolytes. This summer our group is working diligently on a photo-curing project. There is interest in the medical community feel the need for a new and improved balloon that will be used for angioplasty (a form of heart surgery). This product should maintain flexibility but add many other properties. Like possibly further processability and resistance to infection. Our group intends on coming up with this product by using photo-enolization (or simply, photo-curing) by Diels-Alder trapping. The main objective was to synthesize a series of new polymers by Diels-Alder cycloaddition of photoenols with more elastomeric properties. Our group was responsible for performing the proper photo-curing techniques of the polymers with diacrylates and bismaleimides, synthesizing novel monomers, and evaluating experimental results. We attempted to use a diacrylate to synthesize the polymer because of previous research done within the Polymers Branch here at NASA. Most acrylates are commercially available, have more elastometric properties than a typical rigid aromatic structure has and they contain ethylene oxides in the middle of their structure that create extensive flexibility. The problem we encountered with the acrylates is that they photo chemically and thermally self polymerize and create diradicals at low temperatures; these constraints caused a lot of unnecessary side reactions. We want to promote solely, diketone polymerization because this type of polymerization has the ability to cause very elastic polymers. We chose to direct our attention towards the usage of maleimides because they are known for eliminating these unnecessary side reactions.

Inman, Christina A.↗
NASA NTRS2004

Diels-Alder Trapping of Photochemically Generated o-Quinodimethane Intermediates: An Alternative Route to Photocured Polymer Film Development

Photolysis of o-methylphenyl ketones generates bis-o-quinodimethane intermediates that can be trapped in situ by dienophiles through Diels-Alder cycloadditions. This well-known photochemical process is applied to a series of six new photoreactive monomers containing bis-(o-methylphenyl ketone) functionalities combined with diacrylate and triacrylate ester monomers for the development of acrylic ester copolymer blends. Irradiation of cyclohexanone solutions of the bis-(o-methylphenyl ketone)s and acrylate esters produce thin polymer films. Solid state 13C NMR data indicated 47- 100% reaction of the bis-(o-methylphenyl ketone)s, depending on experimental conditions, to yield the desired products. DSC and TGA analyses were performed to determine the glass transition temperature, T,, and onset of decomposition, Td, of the resulting polymer films. A statistical Design of Experiments approach was used to obtain a systematic understanding of the effects of experimental variables on the extent of polymerization and the final polymer properties.

Tyson, Daniel S.↗
NASA NTRS2005

Polyimides by Photochemical Cyclopolymerization

The novel polyimides of this invention are derived from Diels-Alder cyclopolymerization of photochemically generated bisdienes with dienophiles, such as bismaleimides, trismaleimides and mixtures thereof with maleimide endcaps. Irradiation of one or more diketones produces two distinct hydroxy o-quinodimethane (photoenol) intermediates. These intermediates are trapped via Diels-Alder cycloaddition with appropriate dienophiles, e.g., bismaleimide and/or trismaleimides to give the corresponding polyimides in quantitative yields. When bismaleimides, trismaleimides or mixtures thereof with maleimide end-caps are used as the dienophile, the resulting polyimides have glass transition temperatures (Tg) as high as 300 C. Polyimide films can be prepared by ultraviolet irradiation of high solids content varnishes of the monomers in a small amount of solvent, e.g., cyclohexanone, dimethyl formamide, N-methylpyrollidone and the like. These novel polyimides are characterized as having high glass transition temperatures, good mechanical properties and improved processing in the manufacture of adhesives, electronic materials and films.

Meador, Michael A.↗
NASA NTRS2005

Polyimides by photochemical cyclopolymerization

The novel polyimides of this invention are derived from Diels-Alder cyclopolymerization of photochemically generated bisdienes with dienophiles, such as bismaleimides, trismaleimides and mixtures thereof with maleimide end-caps. Irradiation of one or more diketones produces two distinct hydroxy o-quinodimethane (photoenol) intermediates. These intermediates are trapped via Diels-Alder cycloaddition with appropriate dienophiles, e.g., bismaleimide and/or trismaleimides to give the corresponding polyimides in quantitative yields. When bismaleimides, trismaleimides or mixtures thereof with maleimide end-caps are used as the dienophile, the resulting polyimides have glass transition temperatures (Tg) as high as 300? C. Polyimide films can be prepared by ultraviolet irradiation of high solids content varnishes of the monomers in a small amount of solvent, e.g., cyclohexanone, dimethyl formamide, N-methylpyrollidone and the like. These novel polyimides are characterized as having high glass transition temperatures, good mechanical properties and improved processing in the manufacture of adhesives, electronic materials and films.

Meador, Michael A.↗
DOE OSTI2022

Phosphorus-containing solid catalysts and reactions catalyzed thereby, including synthesis of p-xylene

Methods and phosphorus-containing solid catalysts for catalyzing dehydration of cyclic ethers (e.g., furans, such as 2,5-dimethylfuran) and alcohols (e.g., ethanol and isopropanol). The alcohols and cyclic ethers may be derived from biomass. One example includes a tandem Diels-Alder cycloaddition and dehydration of biomass-derived 2,5-dimethyl-furan and ethylene to renewable p-xylene. The phosphorus-containing solid catalysts are also active and selective for dehydration of alcohols to alkenes.

Cho, Hong Je↗
DOE OSTI2020

Bis(Nitroxymethylisoxazolyl) Furoxan: A Promising Standalone Melt-Castable Explosive

The synthesis and crystal structure of the heterocyclic explosive bis(nitroxymethylisoxazolyl) furoxan, C 10 H 6 N 6 O 10 , are described. In addition, we report its physical properties and theoretical performance. This material was found to exhibit standalone melt-castable explosive properties, with a melting point of 89.8 °C and an onset decomposition temperature of 193.8 °C. Bis(nitroxymethylisoxazolyl) furoxan features an insensitive behavior to impact, friction, and electrostatic discharge, with a calculated detonation pressure about 25 % higher than the state-of-the-art melt-castable explosive TNT.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Aqueous Diels–Alder reactions for thermochemical storage and heat transfer fluids identified using density functional theory

Thermal storage and transfer fluids have important applications in industrial, transportation, and domestic settings. Current thermal fluids have relatively low specific heats, often significantly below that of water. However, by introducing a thermochemical reaction to a base fluid, it is possible to enhance the fluid's thermal properties. Here, density functional theory (DFT) is used to screen Diels–Alder reactions for use in aqueous thermal fluids. From an initial set of 52 reactions, four are identified with moderate aqueous solubility and predicted turning temperature near the liquid region of water. These reactions are selectively modified through 60 total functional group substitutions to produce novel reactions with improved solubility and thermal properties. Among the reactions generated by functional group substitution, seven have promising predicted thermal properties, significantly improving specific heat (by as much as 30.5%) and energy storage density (by as much as 4.9%) compared to pure water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗