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At least 415 records · Page 23

Tougher Addition Polyimides Containing Siloxane

Laminates show increased impact resistances and other desirable mechanical properties. Bismaleamic acid extended by reaction of diaminosiloxane with maleic anhydride in 1:1 molar ratio, followed by reaction with half this molar ratio of aromatic dianhydride. Bismaleamic acid also extended by reaction of diaminosiloxane with maleic anhydride in 1:2 molar ratio, followed by reaction with half this molar ratio of aromatic diamine (Michael-addition reaction). Impact resistances improved over those of unmodified bismaleimide, showing significant increase in toughness. Aromatic addition polyimides developed as both matrix and adhesive resins for applications on future aircraft and spacecraft.

St. Clair, T. L.↗

Structure-to-glass transition temperature relationships in high temperature stable condensation polyimides

The presence of a hexafluoroisopropylidene (6F) connecting group in aryl dianhydrides used to prepare aromatic condensation polyimides provides high glass transition temperature (T sub g) polyimides with excellent thermo-oxidative stability. The purpose of this study was to determine if a trifluorophenyl-ethylidene (3F) connecting group would have a similar effect on the T sub g of aromatic condensation polyimides. A new dianhydride containing the 3F connecting group was synthesized. This dianhydride and an aromatic diamine also containing the 3F connecting group were used together and in various combinations with known diamines or known dianhydrides, respectively, to prepare new 3F containing condensation polyimides. Known polyimides, including some with the 6F connecting linkage, were also prepared for comparison purposes. The new 3F containing polymers and the comparison polymers were prepared by condensation polymerization via the traditional amic-acid polymerization method in N,N-dimethylacetamide solvent. The solutions were characterized by determining their inherent viscosities and then were thermally converted into polyimide films under nitrogen atmosphere at 300 to 500 C, usually 350 C. The T sub g's of the films and resin discs were then determined by thermomechanical analysis and were correlated as a function of the final processing temperatures of the films and resin discs. The results showed that similarities existed in the T sub g's depending on the nature of the connecting linkage in the monomers used to prepare the condensation polyimides.

Alston, W. B.↗

Acetylene-Terminated Polyimide Siloxanes

Siloxane-containing addition polyimides yield toughened high-temperature adhesives and matrix resins. Addition polyimide made by reaction of aromatic tetracarboxylic acid dianhydride with aromatic diamine in presence of ethynyl-substituted aromatic monoamine. Acetylene-terminated siloxane imide cured by heating to yield acetylene-terminated polyimide siloxane.

St. Clair, Terry L.↗

Polyimides Containing Carbonyl and Ether Connecting Groups

Semicrystallinity gives rise to tough, solvent-resistant polymers. New polyimides prepared from reaction of aromatic dianhydrides with new diamines containing carbonyl and ether connecting groups between aromatic rings. Damines prepared from reaction of 4-aminophenol with activated aromatic difluoro compounds in presence of potassium carbonate. These types of polymers have potential applications in molded products, films, adhesives, and composites.

Hergenrother, Paul M.↗

Polyether-polyester graft copolymer

Described is a polyether graft polymer having improved solvent resistance and crystalline thermally reversible crosslinks. The copolymer is prepared by a novel process of anionic copolymerization. These polymers exhibit good solvent resistance and are well suited for aircraft parts. Previous aromatic polyethers, also known as polyphenylene oxides, have certain deficiencies which detract from their usefulness. These commercial polymers are often soluble in common solvents including the halocarbon and aromatic hydrocarbon types of paint thinners and removers. This limitation prevents the use of these polyethers in structural articles requiring frequent painting. In addition, the most popular commercially available polyether is a very high melting plastic. This makes it considerably more difficult to fabricate finished parts from this material. These problems are solved by providing an aromatic polyether graft copolymer with improved solvent resistance and crystalline thermally reversible crosslinks. The graft copolymer is formed by converting the carboxyl groups of a carboxylated polyphenylene oxide polymer to ionic carbonyl groups in a suitable solvent, reacting pivalolactone with the dissolved polymer, and adding acid to the solution to produce the graft copolymer.

Bell, Vernon L.↗

Initial adhesive screening of novel polyamide-imides and their copolymers

Continued interest by the research community in thermally stable, tough, high temperature adhesives has resulted in the investigation by Langley Research Center of two linear aromatic polyamide-imide (PAI) homopolymers and two linear aromatic PAI copolymers. The homopolymers were made with either 3,3'=DABA or 4,4'-DABA and BTDA. The two polymers were prepared with a monomer ratio of 0.75 DABP:0.25 DABA:1.00 BTDA. These aromatic PAIs possess high thermal stability because of intermolecular hydrogen bonding and chain stiffness. Lap shear strength (LSS) was the main criteria used to evaluate the polymers as adhesives. LSS of bonded Ti-6Al-4V was determined at room temperature (RT), 177, 204 and 232 C. The glass transition temperature and the type of bond failure were also determined. The best LSS values of the four adhesive systems investigated were obtained with the PAI copolymer identified in the report as LARC-TPI (25 percent 3,3'-DABA); however, it did not produce LSSs nearly as high as LARC-TPI. The poor flow properties observed appear to be due to a combination of high molecular weight and the increased interchain electronic interactions associated with the amide group.

Donald J Progar↗

Isotopic characterisation of kerogen-like material in the Murchison carbonaceous chondrite

Data on isotopic composition of C, H, and N in insoluble organic fraction from the Murchison CM chondrite were used to discriminate between different theories for the origin of prebiotic organic material in the early solar system. Considerable isotopic variability was found among the samples and attributed to kerogen-like organic fraction. Three to four different isotopic components, two of them of polycyclic aromatic nature, were tentatively identified. Aliphatic moieties in the kerogen-like material, most of the polycyclic aromatic network, and extractable amino acids were found to carry a highly D-enriched component believed to have originated in an interstellar molecular cloud. A least part of the polycyclic aromatic fraction may also represent interstellar material.

Kerridge, John F.↗

Insoluble organic material of the Orgueil carbonaceous chondrite and the unidentified infrared bands

Infrared spectra have been obtained of the acid insoluble residue, residue after heating in vacuum, and condensate of the Orgueil carbonaceous chondrite using an FTIR spectrometer. Bulk acid insoluble residue was pressed into KBr pellets and also heated under high vacuum to sublimate a volatile component onto KBr disks. The remaining nonvolatile organic component of the meteorite from such evaporations pressed into KBr pellets exhibits a spectral signature similar to that observed in emission from the Orion Nebula and found in Raman spectra of interplanetary dust particles. It also has an 11.3 micron band indicating polycyclic aromatic hydrocarbons (PAHs) having single hydrogens per peripheral aromatic ring. It is concluded that the nonvolatile material is similar to interstellar PAHs since the observed 11.3 micron unidentified infrared emission suggests interstellar PAHs have single hydrogens per peripheral aromatic ring.

Wdowiak, Thomas J.↗

Initial evaluation of novel polyamide-imides and their copolymers as adhesives

Continued interest by the research community in thermally stable, tough, high temperature adhesives has resulted in the investigation by Langley Research Center of two linear aromatic polyamide-imide (PAI) homopolymers and two linear aromatic PAI copolymers. The homopolymers were made with either 3,3'=DABA or 4,4'-DABA and BTDA. The two polymers were prepared with a monomer ratio of 0.75 DABP:0.25 DABA:1.00 BTDA. These aromatic PAIs possess high thermal stability because of intermolecular hydrogen bonding and chain stiffness. Lap shear strength (LSS) was the main criteria used to evaluate the polymers as adhesives. LSS of bonded Ti-6Al-4V was determined at room temperature (RT), 177, 204 and 232 C. The glass transition temperature and the type of bond failure were also determined. The best LSS values of the four adhesive systems investigated were obtained with the PAI copolymer identified in the report as LARC-TPI (25 percent 3,3'-DABA); however, it did not produce LSSs nearly as high as LARC-TPI. The poor flow properties observed appear to be due to a combination of high molecular weight and the increased interchain electronic interactions associated with the amide group.

Progar, Donald J.↗

Polyimides Containing Carbonyl And Ether Connecting Groups

Polyimides of new class made from chemical reactions of aromatic dianhydrides with novel aromatic diamines in which carbonyl and ether groups connect aromatic rings. New polyimides melt-processable, strong, resistant to impacts, and resistant to solvents and other chemicals. Useful as adhesives, coatings, films, membranes, and composite matrices.

Hergenrother, Paul M.↗

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.↗

Copolyimide with a combination of flexibilizing groups

Copolyimides are prepared by reacting one or more aromatic dianhydrides with a meta-substituted phenylene diamine and an aromatic bridged diamine. The incorporation of meta-substituted phenylene diamine derived units and bridged aromatice diamine derived units into the linear aromatic polymer backbone results in a copolyimide of improved flexibility, processability, and melt-flow characteristics. The copolyimides are especially useful as thermoplastic hot-melt adhesives.

Stclair, Terry L.↗

Acetylene terminated aspartimides and resins therefrom

Acetylene terminated aspartimides are prepared using two methods. In the first, an amino-substituted aromatic acetylene is reacted with an aromatic bismaleimide in a solvent of glacial acetic acid and/or m-cresol. In the second method, an aromatic diamine is reacted with an ethynyl containing maleimide, such an N-(3-ethynyl phenyl) maleimide, in a solvent of glacial acetic acid and/or m-cresol. In addition, acetylene terminated aspartimides are blended with various acetylene terminated oligomers and polymers to yield composite materials exhibiting improved mechanical properties.

Hergenrother, Paul M.↗

Process for lowering the dielectric constant of polyimides using diamic acid additives

Linear aromatic polyimides with low dielectric constants are produced by adding a diamic acid additive to the polyamic acid resin formed by the condensation of an aromatic dianhydride with an aromatic diamine. The resulting modified polyimide is a better electrical insulator than state-of-the-art commercially available polyimides.

Stoakley, Diane M.↗

The possible presence of interstellar PAHs in meteorites and interplanetary dust particles

The Raman spectra of interplanetary dust particles (IDPs) collected in the stratosphere show two bands at about 1350 and 1600 delta cm(-1) and a broader feature between 2200 and 3300 delta cm(-1) that are characteristic of aromatic molecular units with ordered domains smaller than 25A in diameter. This suggests that the carbonaceous material in IDPs may be similar to the polymeric component seen in meteorites, where this material is thought to consist of aromatic molecular units that are randomly inter-linked by short aliphatic bridges. The features in the Raman spectra of IDPs are similar in position and relative strength to interstellar infrared emission features that have been attributed to vibrational transitions in free molecular polycyclic aromatic hydrocarbons (PAHs). The Raman spectra of some IDPs also showed photoluminescence that is similar to the excess red emission from some astronomical objects and that has also been attributed to PAHs and PAH-related materials. Moreover, a part of the carbonaceous phase in IDPs contains deuterium to hydrogen ratios that are far greater than those found in terrestrial samples. Deuterium enrichment is expected in small free PAHs that are exposed to ultraviolet radiation in the interstellar medium. Taken together, these observations suggest that some fraction of the carbonaceous material in IDPs may have been produced in circumstellar dust shells and only slightly modified in interstellar space. Since many, if not most, IDPs come from comets, this supports the view that cometary material contains primitive components which can provide clues about early solar system (and perhaps even interstellar and circumstellar) processes.

Allamandola, L. J.↗

On the driving force of PAH production

The kinetic factors affecting the production of polycyclic aromatic hydrocarbons (PAH) in high-temperature pyrolysis and combustion environments are analyzed. A lumped kinetic model representing polymerization-type growth by one irreversible step and two reversible steps is considered. It is shown that at high temperatures, PAH growth is controlled by the superequilibrium of hydrogen atoms; at low temperatures and low H2 concentrations, the PAH growth rate is proportional to the rate of the H-abstraction of a hydrogen atom from aromatic molecules; while at low temperatures and high H2 concentrations, it is controlled by the thermodynamics of the H-abstraction and the kinetics of acetylene addition to aromatic radicals. The presence of oxygen mainly affects the small-molecule reactions during the induction period.

Frenklach, Michael↗

N-(3-ethynylphenyl)maleimide

Acetylene terminated aspartimides are prepared using two methods. In the first, an amino-substituted aromatic acetylene is reacted with an aromatic bismaleimide in a solvent of glacial acetic acid and/or m-cresol. In the second method, an aromatic diamine is reacted with an ethynyl containing maleimide, such as N-(3-ethynylphenyl) maleimide, in a solvent of glacial acetic acid and/or m-cresol. In addition, acetylene terminated aspartimides are blended with various acetylene terminated oligomers and polymers to yield composite materials exhibiting improved mechanical properties.

Hergenrother, Paul M.↗

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.↗