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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
NASA NTRS1979

Process for the manufacture of carbon or graphite fibers

Carbon or graphite fibers are manufactured by heating polyacrylonitrile fiber materials in various solutions and gases. They are characterized in that the materials are heated to temperatures from 150 to 300 C in a solution containing one or more acids from the group of carbonic acids, sulfonic acids, and/or phenols. The original molecular orientation of the fibers is preserved by the cyclization that occurs before interlacing, which gives very strong and stiff carbon or graphite fibers without additional high temperature stretching treatments.

Overhoff, D.↗
NASA NTRS1981

Monomers for thermosetting and toughening epoxy resins

Eight glycidyl amines were prepared by alkylating the parent amine with epichlorohydrin to form chlorohydrin, followed by cyclization with aqueous NaOH. Three of these compounds contained propargyl groups with postcuring studies. A procedure for quantitatively estimating the epoxy content of these glycidyl amines was employed for purity determination. Two diamond carbonates and several model propargly compounds were prepared. The synthesis of three new diamines, two which contain propargyloxy groups, and another with a sec-butyl group is in progress. These materials are at the dinitro stage ready for the final hydrogenation step. Four aromatic diamines were synthesized for mutagenic testing purposes. One of these compounds rapidly decomposes on exposure to air.

Pratt, J. R.↗
NASA NTRS1982

Preparation of perfluorinated 1,2,4-oxadiazoles

Fluorinated alkyl or alkylether 1,2,4 oxadiazole compounds are prepared by cyclizing the corresponding alkyl or alkylether imidoyl amidoximes in vacuo or in an inert atmosphere at a temperature within the range of 40 C to 100 C. for a period of 8 to 144 hours in the presence of an acid compound which can accept ammonia to form a salt. The imidoyl amidoximes usable in this process are either polymeric or nonpolymeric. The products, when polymeric, have excellent heat, chemical and solvent resistance.

Kratzer, R. H.↗
NASA NTRS1982

Recent advances in the chemical modification of unsaturated polymers

The present discussion has the objective to update the most comprehensive reviews on the considered subject and to fill in the gaps of less complete, but more modern treatments. Only simple chemical functionalization or structural modification of unsaturated polymers are covered, and the literature of diene polymer modification since 1974 is emphasized. Attention is given to hydrogenation, halogenation and hydrohalogenation, cyclization, cis-trans isomerization, epoxidation, ene and other cycloaddition reactions, sulfonation, carboxylation, phosphonylation, sulfenyl chloride addition, carbene addition, metalation, and silylation. It is pointed out that modern synthetic reagents and catalysts have been advantageously employed to improve process and/or product quality. Synthetic techniques have been refined to allow the selective modification of specific polymer microstructures or blocks.

Schulz, D. N.↗
NASA NTRS1982

Synthesis of perfluorinated polyethers

A series of highly fluorinated acetylenes was prepared and their cyclization reactions were studied. A series of perfluoropolytriazines with -CF2I pendent groups were prepared. These materials can be cured thermally or photochemically to an elastomeric gum. Perfluoropolytriazines with -CN pendent groups were prepared. These materials can be crosslinked by reaction with terephthalonitrile oxide.

Depasquale, R. J.↗
NASA NTRS1985

Characterization of a thermoplastic polyimidesulfone

The detailed characterization of an experimental thermoplastic polyimidesulfone adhesive based on 3,3 prime-diaminodiphenylsulfone and 3,3 prime,4,4 prime-benzophenone tetracarboxylic dianhydride was studied. Model compounds were also examined. Thermal cyclization of the amide-acid to the imide was studied by a variety of techniques including DSC, TGA, MS, in situ diffuse reflectance-FTIR, and flow mearsurement. Characterizations were continued during the processing of adhesive tapes and the fabrication, bonding, and testing of lap shear specimens. Results provide fundamental insights into the role of cure chemistry, and the effects of residual solvent and volatile produces on processing and performance. These insights and the resulting chemical models should lead to more efficient processing cycles for these and other related thermoplastic adhesive systems.

Dezern, J. F.↗
NASA NTRS1985

Process optimization of a thermoplastic polyimidesulphone

The detailed characterization of an experimental thermoplastic polyimidesulfane adhesive based on 3,3 prime-diaminodiphenylsulfone and 3,3 prime,4,4 prime-benzophenone tetracarboxylic dianhydride was studied. Model compounds were also examined. Thermal cyclization of the amide-acid to the imide was studied by a variety of techniques including DSC, TGA, MS, in situ diffuse reflectance-FTIR, and flow measurement. Characterizations were continued during the processing of adhesive tapes and the fabrication, bonding, and testing of lap shear specimens. Results provide fundamental insights into the role of cure chemistry, and the effects of residual solvent and volatile produces on processing and performance. These insights and the resulting chemical models should lead to more efficient processing cycles for these and other related thermoplastic adhesive systems.

Dezern, J. F.↗
NASA NTRS1986

Shock-tube pyrolysis of acetylene - Sensitivity analysis of the reaction mechanism for soot formation

The impact of thermodynamic parameters on the sensitivity of model predictions of soot formation by shock-tube pyrolysis of acetylene were assessed analytically. The pyrolysis process was treated as having three components: initiation, the initial pyrolysis stages; cyclization, formation of larger molecules and radicals and small aromatic molecules; and polymerization, further growth of aromatic rings. Rate equations are reviewed for each component. Thermodynamic effects were assessed by varying the C2H-H and C2H3-H bond energies and the Ct-(Ct) group additivity value. Any change in the C2H-H bond energy had a significant impact on the temperature and the maximum amount of the soot yield. The findings underscore the necessity of using accurate thermodynamic data for modeling high-temperature chemical kinetics.

Frenklach, M.↗
NASA NTRS1989

Formation of polycyclic aromatic hydrocarbons in circumstellar envelopes

Production of polycyclic aromatic hydrocarbons in carbon-rich circumstellar envelopes was investigated using a kinetic approach. A detailed chemical reaction mechanism of gas-phase PAH formation and growth, containing approximately 100 reactions of 40 species, was numerically solved under the physical conditions expected in cool stellar winds. The chemistry is based on studies of soot production in hydrocarbon pyrolysis and combustion. Several first-ring and second-ring cyclization processes were considered. A linear lumping algorithm was used to describe PAH growth beyond the second aromatic ring. PAH production using this mechanism was examined with respect to a grid of idealized constant velocity stellar winds as well as several published astrophysical models. The basic result is that the onset of PAH production in the interstellar envelopes is predicted to occur within the temperature interval of 1100 to 900 K. The absolute amounts of the PAHs formed, however, are very sensitive to a number of parameters, both chemical and astrophysical, whose values are not accurately known. Astrophysically meaningful quantities of PAHs require particularly dense and slow stellar winds and high initial acetylene abundance. It is suggested that most of the PAHs may be produced in a relatively small fraction of carbon-rich red giants.

Frenklach, Michael↗
NASA NTRS1989

Wet spinning of solid polyamic acid fibers

The invention is a process for the production of solid aromatic polyamic acid and polyimide fibers from a wet gel or coagulation bath wet gel using N,N-dimethylacetamide (DMAc) solution of the polyamic acid derived from aromatic dianhydrides such as 3,3',4,4'-benzo phenone tetracarboxylic dianhydride (BTDA) and aromatic diamines such as 4,4'oxydianiline (4,4'-ODA). By utilizing the interrelationship between coagulation medium and concentration, resin inherent viscosity, resin percent solids, filament diameter, and fiber void content, it is possible to make improved polyamic acid fibers. Solid polyimide fibers, obtained by the thermal cyclization of the polyamic acid precursor, have increased tensile properties compared to fibers containing macropores from the same resin system.

Dorogy, William E., Jr.↗
NASA NTRS1990

Template-directed oligomerization of 5-prime-deoxy 5-nucleosideacetic acid derivatives

5-prime-deoxy 5-nucleosideacetic acids H-II are isostructural analogs of nucleotides with a carboxylate group in the place of the 5-prime-phosphate group. In this work, their oligomerization in aqueous solution was studied using a water-soluble carbodiimide as the condensing agent in the presence or absence of an appropriate polynucleotide template. Condensation of adenylic acid analogs IIa, IIIa, and Va in the presence of polyuridylic acid were found to be the most efficient reactions. Cyclization of the activated monomers to lactones and the insolubility of the oligomers in aqueous solution were found to be obstacles to the efficient formation of long oligomers.

Harada, Kazuo↗
NASA NTRS1991

Wet spinning of solid polyamic acid fibers

The invention is a process for the production of solid aromatic polyamic acid and polyimide fibers from a wet gel or coagulation bath wet gel using N,N-dimethylacetamide (DMAc) solutions of the polyamic acid derived from aromatic dianhydrides such as 3,3',4,4' benzophenonetetra carboxylic dianhydride (BTDA) and aromatic diamines such as 4,4'-oxydianiline (4,4'-ODA). By utilizing the relationship among coagulation medium and concentration, resin inherent viscosity, resin percent solids, filament diameter, and fiber void content, it is possible to make improved polyamic acid fibers. Solid polyimide fibers, obtained by the thermal cyclization of the polyamic acid precursor, have increased tensile properties compared to fibers containing macropores from the same resin system.

Dorogy, William E., Jr.↗
NASA NTRS1990

Synthesis of 5'-deoxy-5'-nucleosideacetic acid derivatives

Several new 5'-deoxy-5'-nucleosideacetic acid derivatives have been synthesized by the reactions of alkoxycarbonylmethylene triphenylphosphoranes with nucleoside 5'-aldehydes. The oligomerization of adenine derivatives IIa, IIIa, IV, V and guanine derivatives IIc and IIIc in aqueous solution was studied using a water-soluble carbodiimide as a condensing agent. It is found that the saturated acid (IV) tends to cyclize to the lactone, while IIa and unsaturated acids (IIIa and V) oligomerized efficiently, especially in the presence of poly (U) as a template.

Harada, Kazuo↗
NASA NTRS1991

Disulfide-linked oligonucleotide phosphorothioates - Novel analogues of nucleic acids

The synthesis of phosphorothioate analogs of oligonucleotides by the oxidation of deoxyadenosine 3',5'-bisphosphorothioate (3) was attempted. Cyclization of 3 is much more efficient than oligomerization under all the conditions investigated. However, a preformed oligonucleotide carrying a 5'-terminal phosphorotioate group undergoes efficient chain-extension when oxidized in the presence of 3.

Wu, Taifeng↗
NASA NTRS1993

Polyimides prepared from 3,5-diamino benzo trifluoride

High performance, thermooxidatively stable polyimides are prepared by reacting aromatic diamines with pendant trifluoromethyl groups and dianhydrides in an amide solvent to form a poly(amic acid), followed by cyclizing the poly(amic acid) to form the corresponding polyimide.

Gerber, Margaret K.↗
NASA NTRS1993

Diphenylmethane-containing dianhydride and polyimides prepared therefrom

A high temperature stable, highly optically transparent-to-colorless, low dielectic linear aromatic polyimide is prepared by reacting an aromatic diamine with 3,3'bis (3,4-dicarboxyphenoxy) diphenylmethane dianhydride in an amide solvent to form a linear aromatic polyamic acid. This polyamic acid is then cyclized to form the corresponding polyimide.

St.clair, Anne K.↗
NASA NTRS1995

Proton affinity determinations and proton-bound dimer structure indications in C2 to C15, (alpha),(omega)-alkyldiamines

The 'kinetic method' was used to determine the proton affinity (PA) of a,coalkyldiamines from collision induced dissociation (CID) studies of protonated heterodimers. These PA values were consistently lower than those reported in the proton affinity scale. The apparent discrepancy was rationalized in terms of differences in the conformation of the protonated diamine monomers. The minimum energy species, formed by equilibrium proton transfer processes, have a cyclic conformation and the ion charge is shared by both amino-groups which are bridged by the proton. On the other hand, the species formed through dissociation of protonated dimers have a linear structure and the charge is localized on one of the amino-groups. Thus, the difference in the PA values obtained by both methods is a measure of the additional stability acquired by the protonated diamines through cyclization and charge delocalization. The major collision dissociation pathway of the protonated diamine monomers involved elimination of an ammonia moiety. Other reactions observed included loss of the second amino-group and several other bond cleavages. CID of the protonated dimers involved primarily formation of a protonated monomer through cleavage of the weaker hydrogen bond and subsequently loss of ammonia at higher collision energies. As observed from the CID studies, doubly charged ions were also formed from the diamines under conditions of the electrospray ionization.

Karpas, Z.↗
NASA NTRS1992

The Prebiotic Synthesis of Ethylenediamine Monoacetic Acid, The Repeating Unit of Peptide Nucleic Acids

The polymerization of ribonucleic acids or their precursors constitutes an important event in prebiotic chemistry. The various problems using ribonucleotides to make RNA suggest that there may have been a precursor. An attractive possibility are the peptide nucleic acids (PNA). PNAs are nucleotide analogs that make use of a polymer of ethylenediamine monoacetic acid (EDMA or 2-amninoethyl glycine) with the bases attached by an acetic acid. EDMA is an especially attractive alternative to the ribose phosphate or deoxyribose phosphate backbone because it contains no chiral centers and is potentially prebiotic, but there is no reported prebiotic synthesis. We have synthesized both EDMA and ethylenediamine diacetic acid (EDDA) from the prebiotic compounds ethylenediamine, formaldehyde, and hydrogen cyanide. The yields of EDMA range from 11 to 79% along with some sEDDA and uEDDA. These reactions work with concentrations of 10(exp -1)M and as low as 10(exp -4)M, and the reaction is likely to be effective at even lower concentrations. Ethylenediamine is a likely prebiotic compound, but it has not yet been demonstrated, although compounds such as ethanolamine and cysteamine have been proven to be prebiotic. Under neutral pH and heating at l00 C, EDMA is converted to the lactam, monoketopiperazine (MKP). The cyclization occurs and has an approximate ratio of MKP/EDMA = 3 at equilibrium. We have measured the solubilities of EDMA center dot H20 as 6.4 m, EDMA center dot HCl center dot H20 as 13.7 m, and EDMA center dot 2HCl center dot H20 as 3.4 m. These syntheses together with the high solubility of EDMA suggest that EDMA would concentrate in drying lagoons and might efficiently form polymers. Given the instability of ribose and the poor polymerizability of nucleotides, the prebiotic presence of EDMA and the possibility of its polymerization raises the possibility that PNAs are the progenitors of present day nucleic acids. A pre-RNA world may have existed in which PNAs or polymers with related peptide backbones were the dominant information macromolecules.

Nelson, Kevin E.↗