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At least 55 records · Page 3

New polyarylene ethers

A series of new polyarylene ethers (PAEs) were prepared from the reaction of activated dihalo compounds with various bisphenols. Measured number average molecular weights for the PAEs ranged from 13,500 to 39,400 g/mole, and glass transition temperatures varied from 152 to 280 C. Ethynyl-terminated polyarylene ethers (ETPAEs) were also prepared by endcapping hydroxy-terminated polyarylene ethers with 4-ethynylbenzoyl chloride. Structure/property relationships for the PAEs, and the advantages offered by the ETPAEs, are discussed.

Hergenrother, P. M.↗

Polyarylene Ethers With Improved Properties

Series of new polyarylene ethers (PAE's) prepared from reaction of activated dihalo compounds with various bisphenols. Compounds exhibit excellent processability by compression molding, plus good mechanical properties. All PAE's prepared suitable for use as adhesives, coatings, films, membranes, and composite matrices. Potentially useful for spacecraft and aircraft applications.

Hergenrother, Paul M.↗

Linear and nonlinear mechanical properties of a series of epoxy resins

The linear viscoelastic properties have been measured for a series of bisphenol-A-based epoxy resins cured with the diamine DDS. The linear viscoelastic master curves were constructed via time-temperature superposition of frequency dependent G-prime and G-double-prime isotherms. The G-double-prime master curves exhibited two sub-Tg transitions. Superposition of isotherms in the glass-to-rubber transition (i.e., alpha) and the beta transition at -60 C was achieved by simple horizontal shifts in the log frequency axis; however, in the region between alpha and beta, superposition could not be effected by simple horizontal shifts along the log frequency axis. The different temperature dependency of the alpha and beta relaxation mechanisms causes a complex response of G-double-prime in the so called alpha-prime region. A novel numerical procedure has been developed to extract the complete relaxation spectra and its temperature dependence from the G-prime and G-double-prime isothermal data in the alpha-prime region.

Curliss, D. B.↗

Radiation-resistant, amorphous, all-aromatic poly(arylene ether sulfones) - Synthesis, physical behavior, and degradation characteristics

The effects of Co-60 gamma radiation on a series of poly(arylene ether sulfones) prepared by nucleophilic activated aromatic substitution are investigated experimentally. The preparation of the test compounds is described, and the test results are presented in extensive tables and graphs. Radiation-induced degradation, as measured by SO2 production, was found to be lowest in compounds based on biphenol rather than bisphenol A; these findings were also well correlated with ultimate-tensile-strain measurements.

Lewis, D. A.↗

Polyimidazoles Via Aromatic Nucleophilic Displacement

Experiments show variety of polyimidazoles prepared by aromatic nucleophilic displacement, from reactions of bisphenol imidazoles with activated difluoro compounds. Polyimidazoles have good mechanical properties making them suitable for use as films, moldings, and adhesives.

Connell, John W.↗

Tough poly(arylene ether) thermoplastics as modifiers for bismaleimides

Several aspects of research on thermoplastics as toughness modifiers are discussed, including the contribution of the backbone chemistry and the concentration of the poly(arylene ether) thermoplastic to fracture toughness, influence of the molecular weight of the poly(arylene ether) thermoplastic on neat resin fracture toughness, and the morphology of the thermoplastic modified networks. The results show that fracture toughness of brittle bismaleimide resins can be improved significantly with poly(arylene ether) thermoplastic levels of 20 percent by weight, and that high molecular weight poly(arylene ether) based on bisphenol A provides the highest degree of toughening. Preliminary composite evaluation shows that improvements in neat resin toughness translate into carbon fabric composite.

Stenzenberger, H. D.↗

Low dielectric fluorinated poly(phenylene ether ketone) film and coating

The present invention relates to film and coating materials prepared from novel fluorinated poly(phenylene ether ketones). A fluorinated poly(phenylene ether ketone) is prepared by reacting a bisphenol with 1,1,1,3,3,3 hexafluoro-2,2-bis 4-(4-halobenzoyl) phenyl propane (wherein halo is fluoro or chloro), which is a novel monomer formed as the reaction product of halobenzene (wherein halo is fluoro or chloro) and 1,1,1,3,3,3 hexafluoro-2,2-bis (p-chloro formyl phenyl) propane. Especially beneficial results of this invention are that films and coating materials prepared from the novel fluorinated poly(phenylene ether ketone) are essentially optically transparent/colorless and have a lower dielectric constant than otherwise comparable, commercially available poly(phenylene ether ketones). Moreover, unlike the otherwise comparable commercially available materials, the novel fluorinated poly(phenylene ether ketones) of the present invention can be solution cast or sprayed to produce the films and coatings. Furthermore, the long term thermal stability of the polymers of the present invention is superior to that of the commercially available materials.

Cassidy, Patrick E.↗

Probability of brittle failure

A methodology was developed for collecting statistically representative data for crack initiation and arrest from small number of test specimens. An epoxy (based on bisphenol A diglycidyl ether and polyglycol extended diglycyl ether and cured with diethylene triamine) is selected as a model material. A compact tension specimen with displacement controlled loading is used to observe multiple crack initiation and arrests. The energy release rate at crack initiation is significantly higher than that at a crack arrest, as has been observed elsewhere. The difference between these energy release rates is found to depend on specimen size (scale effect), and is quantitatively related to the fracture surface morphology. The scale effect, similar to that in statistical strength theory, is usually attributed to the statistics of defects which control the fracture process. Triangular shaped ripples (deltoids) are formed on the fracture surface during the slow subcritical crack growth, prior to the smooth mirror-like surface characteristic of fast cracks. The deltoids are complementary on the two crack faces which excludes any inelastic deformation from consideration. Presence of defects is also suggested by the observed scale effect. However, there are no defects at the deltoid apexes detectable down to the 0.1 micron level.

Kim, A.↗

Free-volume characteristics of epoxies

Positron annihilation spectroscopy was used to measure free-volume characteristics of selected epoxies. Fluorene resins, a new family of high-temperature thermosetting resins, were selected as the test medium. Experimental results indicate that the free-volume cell size V sub f varies with the molecular weight between the cross-links M sub c according to an equation of the form V sub f = AM sub c sup B, where A and B are structural constants. In two of the samples, the concentration of bulky fluorene groups was increased in the network backbone by replacement of some of the conventional bisphenol A epoxy resin with fluorene-derived epoxy resin. This resulted in an increase in their glass transition temperature for a given level of cross-linking. It was found that in these samples, the Doppler broadening of the annihilation peak decreases with the increasing fluorene content, presumably due to enhanced damping of the chain motions.

Singh, Jag J.↗

The synthesis of monomers with pendent ethynyl group for modified high performance thermoplastics

The objectives of this project were to develop synthetic schemes for the following classes of modified monomers: (1) difunctional triarylethanes with pendent acetylenic groups; and (2) tertiary aspartimides with terminal acetylene groups at the two ends. Our efforts have resulted in the successful development of high yield schemes for the syntheses of several diamino and bisphenolic analogs of difunctional triarylethanes with pendent ethynyl group. A scheme for one new tertiary aspartimide was also established. Multi-gram samples of all prepared new monomers were provided to our technical contact at NASA-LaRC and preliminary polymerization studies were encouraging. Details of the accomplished work within the last four years are described.

Nwokogu, Godson C.↗

Chemistry and adhesive properties of poly(arylene ether)s containing heterocyclic units

Novel poly(arylene ether)s containing heterocyclic units were prepared, characterized, and evaluated as adhesives and composite matrices. The polymers were prepared by reacting a heterocyclic bisphenol with an activated aromatic dihalide in a polar aprotic solvent, using potassium carbonate. The polymerizations were generally carried out in N,N-dimethylacetamide at 155 C. In some cases, where the polymers were semicrystalline, higher temperatures and thus higher boiling solvents were necessary to keep the polymers in solution. Heterocyclic rings incorporated into the poly(arylene ether) backbone include phenylquinoxaline, phenylimidazole, benzimidazole, benzoxazole, 1,3,4-oxadiazole, and 1,2,4-triazole. The polymers were characterized by differential scanning calorimetry, solution viscosity, X-ray diffraction, thin film, and adhesive and (in some cases) composite properties. The glass transition temperatures, crystalline melt temperature, solubility, and mechanical properties varied depending upon the heterocyclic ring. The chemistry and properties of these materials are discussed.

Connell, John W.↗

Poly(arylene ether)s That Resist Atomic Oxygen

Novel poly(arylene ether)s containing phosphine oxide (PAEPO's) made via aromatic nucleophilic displacement reactions of activated aromatic dihalides (or, in some cases, activated aromatic dinitro compounds) with new bisphenol monomers containing phosphine oxide. Exhibited favorable combination of physical and mechanical properties and resistance to monatomic oxygen in oxygen plasma environment. Useful as adhesives, coatings, films, membranes, moldings, and composite matrices.

Connell, John W.↗

Polybenzoxazole via aromatic nucleophilic displacement

Polybenzoxazoles (PBO) are heterocyclic macromolecules which were first synthesized in a two-step process by the initial formation of aromatic diacid chlorides with bis(o-aminophenol)s through solution condensation of aromatic diacid chlorides with bis(o-aminophenol)s followed by thermal cyclodehydration. Since then several methods were utilized in their synthesis. The most common synthetic method for PBO involves a polycondensation of bis(o-aminophenol)s with aromatic diacid diphenyl esters. Another preparative route involves the solution polycondensation of the hydrochloride salts of bis(o-amino phenol)s with aromatic diacids in polyphosphoric acid. Another synthetic method involves the initial formation of poly(o-hydroxy amide)s from silylated bis(o-aminophenol)s with aromatic diacid chlorides followed by thermal cyclodehydration to PBO. A recent preparative route involves the reaction of aromatic bisphenols with bis(fluorophenyl) benzoxazoles by the displacement reaction to form PBO. The novelty of the present invention is that high molecular weight PBO of new chemical structures are prepared that exhibit a favorable combination of physical and mechanical properties.

Hergenrother, Paul M.↗

Development and Preliminary Evaluation of Aryl Ester Boundary Additives for Perfluoropolyethers

A series of additives were developed for evaluation as boundary lubrication enhancers for perfluoropolyethers. They are composed of a hydrocarbon aryl component (for lubrication improvement) and a fluorinated side chain (for solubility enhancement). The two moieties are joined by an ester linkage. Five boundary additives were evaluated in a perfluoropolyether basestock (Fomblin Z25) using a specially designed four-ball apparatus. Additives were evaluated at a one wt percent concentration. Conditions included: an atmosphere of dry air at atmospheric pressure, a 200N load, a speed of 100 rpm, room temperature, and 440C stainless steel specimens. Two monoesters, 2,4,6-trimethyl E2 and H5PDFO yielded wear rate reductions of approximately 60 and 35 percent, respectively. One diester, H4(E2)(sub 2), had no activity, while two other diesters (a diester of bisphenol A and H4(E4)(sub 2)) were pro-wear.

Williams, John R.↗

Poly(arylene ether)s containing pendent ethynyl groups

Poly(arylene ether)s containing pendent ethynyl and substituted ethynyl groups and poly(arylene ether) copolymers containing pendent ethynyl and substituted ethynyl groups are readily prepared from bisphenols containing ethynyl and substituted ethynyl groups. The resulting polymers are cured up to 350 C to provide crosslinked poly(arylene ether)s with good solvent resistance, high strength and modulus.

Hergenrother, Paul M.↗

Structure-Property Relationships of Bismaleimides

The purpose of this research was to control and systematically vary the network topology of bismaleimides through cure temperature and chemistry (addition of various coreactants) and subsequently attempt to determine structure-mechanical property relationships. Characterization of the bismaleimide structures by dielectric, rheological, and thermal analyses, and density measurements was subsequently correlated with mechanical properties such as modulus, yield strength, fracture energy, and stress relaxation. The model material used in this investigation was 4,4'-BismaleiMidodIphenyl methane (BMI). BMI was coreacted with either 4,4'-Methylene Dianiline (MDA), o,o'-diallyl bisphenol A (DABA) from Ciba Geigy, or Diamino Diphenyl Sulfone (DDS). Three cure paths were employed: a low- temperature cure of 140 C where chain extension should predominate, a high-temperature cure of 220 C where both chain extension and crosslinking should occur simultaneously, and a low-temperature (140 C) cure followed immediately by a high-temperature (220 C) cure where the chain extension reaction or amine addition precedes BMI homopolymerization or crosslinking. Samples of cured and postcured PMR-15 were also tested to determine the effects of postcuring on the mechanical properties. The low-temperature cure condition of BMI/MDA exhibited the highest modulus values for a given mole fraction of BMI with the modulus decreasing with decreasing concentration of BMI. The higher elastic modulus is the result of steric hindrance by unreacted BMI molecules in the glassy state. The moduli values for the high- and low/high-temperature cure conditions of BMI/MDA decreased as the amount of diamine increased. All the moduli values mimic the yield strength and density trends. For the high-temperature cure condition, the room- temperature modulus remained constant with decreasing mole fraction of BMT for the BMI/DABA and BMI/DDS systems. Postcuring PMR-15 increases the modulus over that of the cured material even though density values of cured and postcured PMR were essentially the same. Preliminary results of a continuous and intermittent stress relaxation experiment for BMI:MDA in a 2:1 molar ratio indicate that crosslinking is occurring when the sample is in the undeformed state. Computer simulation of properties such as density, glass transition temperature, and modulus for the low- temperature cure conditions of BMI/MDA and BMI/DABA were completed. The computer modeling was used to help further understand and confirm the structure characterization results. The simulations correctly predicted the trends of these properties versus mole fraction BMI and were extended to other BMI/diamine systems.

Tenteris-Noebe, Anita D.↗

Gas Sensor Evaluations in Polymer Combustion Product Atmospheres

Toxic gases produced by the combustion or thermo-oxidative degradation of materials such as wire insulation, foam, plastics, or electronic circuit boards in space shuttle or space station crew cabins may pose a significant hazard to the flight crew. Toxic gas sensors are routinely evaluated in pure gas standard mixtures, but the possible interferences from polymer combustion products are not routinely evaluated. The NASA White Sands Test Facility (WSTF) has developed a test system that provides atmospheres containing predetermined quantities of target gases combined with the coincidental combustion products of common spacecraft materials. The target gases are quantitated in real time by infrared (IR) spectroscopy and verified by grab samples. The sensor responses are recorded in real time and are compared to the IR and validation analyses. Target gases such as carbon monoxide, hydrogen cyanide, hydrogen chloride, and hydrogen fluoride can be generated by the combustion of poly(vinyl chloride), polyimide-fluoropolymer wire insulation, polyurethane foam, or electronic circuit board materials. The kinetics and product identifications for the combustion of the various materials were determined by thermogravimetric-IR spectroscopic studies. These data were then scaled to provide the required levels of target gases in the sensor evaluation system. Multisensor toxic gas monitors from two manufacturers were evaluated using this system. In general, the sensor responses satisfactorily tracked the real-time concentrations of toxic gases in a dynamic mixture. Interferences from a number of organic combustion products including acetaldehyde and bisphenol-A were minimal. Hydrogen bromide in the products of circuit board combustion registered as hydrogen chloride. The use of actual polymer combustion atmospheres for the evaluation of sensors can provide additional confidence in the reliability of the sensor response.

Delgado, Rafael H.↗

Poly(arylene ether)s containing pendent ethynyl groups

Poly(arylene ether)s containing pendent ethynyl and substituted ethynyl groups and poly(arylene ether) copolymers containing pendent ethynyl and substituted ethynyl groups are readily prepared from bisphenols containing ethynyl and substituted ethynyl groups. The resulting polymers are cured up to 350.degree. C. to provide crosslinked poly(arylene ether)s with good solvent resistance, high strength and modulus.

Hergenrother, Paul M.↗