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At least 145 records · Page 8

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NASA NTRS1972

Polyimidazopyrrolone model compounds.

The model reactions between phthalic anhydride and o-phenylenediamine were studied under conditions analogous to the polymerization and post-cyclization of dianhydrides with bis(o-diamines) to form polyimidazopyrrolones (Pyrrones). The route from the initial amide-acid-amine to the tetracyclic Pyrrone model when the reactions are conducted in aprotic solvents is highly competitive between isolatable benzimidazole-acid and imide-amine intermediates. Solid-state thermal conversion of the amide-acid-amine affords a unique dimeric species containing amide, imide, and benzimidazole functions. It was confirmed that melt techniques lead to disproportionation products. The application of these findings to related polymer synthesis is discussed.

Young, P. R.↗

NASA NTRS1974

Organic synthesis in a simulated Jovian atmosphere. III - Synthesis of aminonitriles

The products from spark and semicorona discharges through mixtures simulating the Jovian atmosphere were analyzed by gas chromatography combined with mass spectrometry. When the reaction was performed at -80 C, 3-ethylaminopropionitrile and a number of higher homologs were formed. On the other hand, at +20 C, higher molecular-weight material appeared which yielded aminonitrile-derived fragments on mass spectrometry. Although the spectra were not identical, there were notable similarities between these and the mass spectra of some compounds present in the Murray and Orgeuil meteorites. Aminonitriles may occur as minor constituents of the Jovian atmosphere and perhaps by cyclization may produce pyrimidines.

Molton, P. M.↗

NASA NTRS1973

Heat-resistant polymers containing bipyridyl units. II Polyamide-imides

Polyamide-amic acids containing bipyridyl units were prepared by polymerization of various bipyridyl diamines with trimellitic anhydride acid chloride. These polymers were converted to polyamide-imides by thermal cyclization. The resulting polyamide-imides exhibited very good solubility in organic solvents.

Kurita, K.↗

NASA NTRS1978

Mechanistic possibilities in prebiotic thiophosphate chemistry

The two types of thiophosphate reactivities were studied in a system that involves reactions of 5'-substituted adenosine derivatives. In this system, both nucleophilic displacement on carbon and P-S cleavage are possible. The products and possible mechanisms of cyclization experiments involving different leaving groups are reported. The data indicate superior reactivity of the 3'-OH of the ribonucleoside, although in most other systems the 2'-OH is found to show superior reactivity. It is suggested that thiophosphates might play a role in prebiotic activation and phosphorylation reactions.

Kapovits, I.↗

NASA NTRS1978

Thermal rearrangements in 1,2-poly/1,4-hexadiene/s

The work described was carried out to study the thermal rearrangements of two unsaturated diene polymers - 1,2-poly(cis-1,4-hexadiene) (CHD) and 1,2-poly(trans-1.4-hexadiene) (THD). It is shown that both CHD and THD have a predominatly 1,8 diene structure and seem to cyclize mainly by the (2 + 2) thermal cycloaddition of double bonds, and to a small extent also by sigmatropic rearrangement with hydrogen shift.

Golub, M. A.↗

NASA NTRS1979

Crystalline polyimides

Aromatic crystalline polyimides are disclosed that are synthesized from polyamide-acid and when heated to 200 C to 300 C become cyclized to afford an opaque polymer. X-ray diffraction of the unoriented film exhibited 47 percent crystallinity. Differential scanning calorimetry reveals a melt at 425 C with no glass transition in these crystalline polyimides.

St.clair, T. L.↗

NASA NTRS1982

Preparation of Perfluorinated Imidoylamidoxime Polymers

Perfluorinated imidoylamidoxime polymers with excellent resistance to heat, chemicals and solvents are prepared by condensing a perfluorinated nitrile with a perfluorinated amidoxime in vacuum or inert atmosphere from 20 degrees to 70 degrees C. When both reactants are difunctional, oligomeric or polymeric products are obtained. After cyclization of imidoylamidoxime groups to 1,2,4-oxadiazole linkages, process yields highly resistant elastomers. Competing side reactions are inhibited by low processing temperature.

Rosser, R. W.↗

NASA NTRS1980

Perfluoroalkyl polytriazines containing pendent iododifluoromethyl groups

New perfluoroalkyl polytriazines containing pendent iododifluoromethyl groups are prepared by the reaction of perfluoroalkyl dinitriles with ammonia to form poly(imidoylamidines), followed by the cyclization of the imidoylamidine groups with, e.g., various mixtures of a perfluoroacyl fluoride with an omega iodoperfluoroacyl fluoride. The polytriazines obtained can be cured by heat which causes crosslinking at the iododifluoromethyl groups by elimination of iodine and formation of carbon-to-carbon bonds.

Rosser, R. W.↗

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.↗