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At least 55 records · Page 3

Low dielectric polyimide fibers

A high temperature resistant polyimide fiber that has a dielectric constant of less than 3 is presented. The fiber was prepared by first reacting 2,2-bis (4-(4aminophenoxy)phenyl) hexafluoropropane with 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride in an aprotic solvent to form a polyamic acid resin solution. The polyamic acid resin solution is then extruded into a coagulation medium to form polyamic acid fibers. The fibers are thermally cured to their polyimide form. Alternatively, 2,2-bis(4-(4-aminophenoxy)phenyl) hexafluoropropane is reacted with 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride to form a polyamic acid, and the polyamic acid is chemically converted to its polyimide form. The polyimide is then dissolved in a solvent to form a polyimide resin solution, and the polyimide resin is extruded into a coagulation medium to form a polyimide wet gel filament. In order to obtain polyimide fibers of increased tensile properties, the polyimide wet gel filaments are stretched at elevated temperatures. The tensile properties of the fibers were measured and found to be in the range of standard textile fibers. Polyimide fibers obtained by either method will have a dielectric constant similar to that of the corresponding polymer, viz., less than 3 at 10 GHz.

Dorogy, William E., Jr.↗

Preparation and characterization of poly (arylene ether isoxazole)s by fluoride ion-mediated aromatic nucleophilic displacement reactions

As part of a continuing effort to prepare novel thermally stable high-performance polymers, poly(arylene ether isoxazole)s have been prepared by fluoride ion-catalyzed aromatic nucleophilic substitution reactions with bis(trimethylsiloxyphenyl) isoxazoles and activated bisarylhalides in diphenyl sulfone. Initial investigation involving the preparation of these materials with isoxazole bisphenols and activated bisarylhalides in the presence of potassium carbonate indicated that, under reaction conditions necessary to prepare high-molecular-weight materials, the isoxazole monomer was converted to an enamino ketone. This side reaction was avoided by using fluoride as a base. However, trimethylsilyl ether derivatives of the isoxazole bisphenols were required in these polymerizations for the preparation of high-molecular-weight materials. Moderate to high inherent viscosity eta(sub inh): 0.43-0.87 dl/g) materials with good thermal stability (air: 409-477 C, helium: 435-512 C) can be prepared by the silyl ether method. Glass transition temperatures ranged from 182 to 225 C for polymers with phenyl pendants and from 170 to 214 C for those without. Molecular weight control by 2% endcapping and the incorporation of a phenyl pendant at the 4 position of the isoxazole is necessary to yield polymers soluble in polar aprotic solvents at room temperature. There is evidence, however, indicating the existence of crosslinks between the polymer chains when the silyl ether approach is utilized.

Herbert, C. G.↗

New RTM/RI Resins for the HSCT

In the first portion of this work, 1,2,3,3,4,4-hexafluoro-1,2-bis[4-(dimethylhydroxysilyl)phenoxy]cyclobutane and 1,2,3,3,4,4-hexafluoro-1,2-bis[3-(dimethylhydroxysilyl)phenoxy]cyclobutane were prepared and homopolymerized to afford polymers with excellent thermal stability and Tgs of 27 C and -12 C, respectively. Despite the moderately high wt% of fluorin in the polymer structure (23.8%), these polymers had poor fuel resistance. In fact, swelling measurements indicate that these polymers had apparent solubility parameters of about 18.2 J (exp 1/2) m (exp -3/2) (toluene). Copolymerization of the disilanol monomers with fluorosilicone monomers afforded copolymers containing 20-30 wt% of the perfluorocyclobutane-containing structure displayed adequate fuel resistance, enhanced thermal stability, and a Tg low enough to meet the requirements of a High Speed Civil Transport (HSCT) fuel tank sealant. In the second part of this work, trifluorovinylether-terminated oligomers were prepared and polymerized via cyclodimerization. Initially, an alpha, omega-silanol-terminated fluorosilicone was endcapped with trifluorovinylether end groups via a two-step synthetic sequence. The oligomer was thermally cyclodimerized to a polymer that displayed thermal stability similar to that of a fluorosilicone homopolymer. Second, 1,3-bis[4-trifluorovinyl(oxy)phenyl]-1,3-(3,3,3-trifluoropropyl)dimethyldisiloxane and 1,3-bis{3-trifluorovinyl(oxy)phenyl]-1,3-(3,3,3-trifluoropropyl)dimethyldisiloxane were prepared and cyclodimerized to afford polymers that contained pendant trifluoropropyl groups. The pendant trifluoropropyl groups did enhance solvent resistance in aliphatic hydrocarbon solvents, however, no improvement was observed in aromatic hydrocarbon solvents. These polymers also displayed excellent thermal stability. In the last part of this work, a series of monomers was prepared by the DCC-promoted esterification of 4-[trifluorovinyl(oxy)benzoic acid with alpha, omega-functionalized hydrogenated and partially fluorinated alcohols. The monomers were cyclodimerized to the corresponding polymers. The polymers that did not contain beta hydrogens displayed significantly higher thermal stability than the fully hydrogenated polymers. A commercially-available alpha,omega-hydroxy-terminated perfluoropolyether was then functionalized with 4-[trifluorovinyl(oxy)benzoylchloride. An attempt was made to polymerize the resulting oligomer via the cyclodimerization of the terminal trifluorovinylether moieties. Although the viscosity of the oligomer increased significantly during polymerization, Gel Permeation Chromatography (GPC) analysis revealed that the Tetrahydrofuran (THF) soluble portion of the polymer did not have high molecular weight.

Harris, Frank W.↗

Synthesis and Properties of Phenylethynyl-Terminated, Star-Branched, Phenylquinoxaline Oligomers

The primary objective of this work was to prepare readily melt and solution processable phenylquinoxaline (PQ) oligomers that could be thermally crosslinked to solvent-resistant resins. Thus, a mixture of 2-(4-hydroxyphenyl)-3-phenyl-6-fluoroquinoxaline and 3-(4-hydroxyphenyl)-2-phenyl-6-fluoroquinoxaline (HPFQ) was used to prepare star-branched PQ oligomers end-capped with 4-fluoro-4-phenylethynylbenzophenone (FPEB). 1,1,1-Tris(4-hydroxyphenyl)ethane (THPE) was used as the branching unit. The oligomer number-average molecular weights (M (bar) (sub n) S) as determined by size exclusion chromatography (SEC) were close to the calculated values of 2922, 4698, 6474, and 13,578 g/mol, and their intrinsic viscosities ranged from 0.16 to 0.57 dl/g (m-cresol at 30 C). The oligomers, which were quite soluble in common organic solvents, had glass transition temperatures (T (sub g) S) that ranged from 181 to 233 C (DSC, DELTA T = 20 C/min). They also underwent an exothermic cure with maxima from 377 to 443 C. The T (sub g) S of the cured oligomers ranged from 259 to 284 C depending on the oligomer M (bar) (sub n) and the curing conditions. The oligomers had low melt viscosities, e.g. an oligomer (SPQ-46) with an M (bar) (sub n) of 4816 g/mol (SEC) had a melt viscosity of 150 Pa s at 348 C. A cured thin film of SPQ-46, which was insoluble in common organic solvents, had a room temperature (RT) tensile strength of 100 MPa, a RT modulus of 2358 MPa, and a RT elongation of 5.9%. A cured sample of SPQ-46 displayed a RT titanium-titanium lap shear tensile strength of 35.2 MPa. SPQ-46/carbon fiber(IM-7) composites, were prepared that displayed a RT flexural strength of 1902 MPa, a RT modulus of 1.38 GPa and a RT open hole compressive strength of 433 MPa.

Ooi, I. H.↗

Polyimides prepared from perfluoroisopropylidene diamine

This invention relates to a novel aromatic diamine and more particularly to the use of said diamine for the preparation of thermally stable high-molecular weight polymers including, for example, polyamides, polyamideimides, polyimides, and the like. This diamine is obtained by reacting a stoichometric amount of a disodium salt of 2,2-bis(4-hydroxyphenyl) hexafluoropropane with 4-chloronitrobenzene to obtain an intermediate, 2,2-bis[4-(4-nitrophenoxy)phenyl] hexafluoropropane, which is reduced to the corresponding 2,2-bis[4-(4-aminophenoxy)phenyl] hexafluoropropane.

Jones, Robert J.↗

Fluorinated aromatic diamine

This invention relates to a novel aromatic diamine and more particularly to the use of said diamine for the preparation of thermally stable high-molecular weight polymers including, for example, polyamides, polyamideimides, polyimides, and the like. This diamine is obtained by reacting a stoichometric amount of a disodium salt of 2,2-bis(4-hydroxyphenyl) hexafluoropropane with 4-chloronitrobenzene to obtain an intermediate, 2,2-bis[4-(4-nitrophenoxy)phenyl] hexafluoropropane, which is reduced to the corresponding 2,2-bis[4-(4-aminophenoxy)phenyl] hexafluoropropane.

Jones, Robert J.↗

Multilayer screen gives cathode ray tube high contrast

Fabrication method for cathode ray tubes uses low-cost siloxane resin formulations. The resins contain sufficient methyl or phenyl groups for solubility in organic solvents. After vaporization and baking, the polymerized material is stable under vacuum and under temperatures required for tube fabrication.

Bullinger, H.↗

Development and characterization of lubricants for use near nuclear reactors in space vehicles

The synthesis and evaluation program was conducted to develop wide-temperature range lubricants suitable for use in space vehicles particularly in the vicinity of nuclear reactors. Synthetic approaches resulted in nonpolymeric, large molecular weight materials, all based on some combination of siloxane and aromatic groups. Evaluation of these materials indicated that certain tetramethyl and hexamethyl disiloxanes containing phenyl thiophenyl substituents are extremely promising with respect to radiation stability, wide temperature range, good lubricity, oxidation resistance and additive acceptance. The synthesis of fluids is discussed, and the equipment and methods used in evaluation are described, some of which were designed to evaluate micro-quantities of the synthesized lubricants.

Robinson, G. L.↗

Flame retardant polyphosphazenes

Six polyphosphazene compositions were prepared by reaction of three bis-tertiary phosphines with two phenyl-s-triazine derived diazides. All six polyphosphazenes produced were completely characterized, four of them were furthermore subjected to isothermal gravimetric analysis, smoke density measurements, flammability and oxidative thermal degradation testing. The results of the characterization studies indicate that only low molecular weight oligomers, possibly of a cyclic structure, were obtained in the polymerization reactions. Despite this, however, two of the materials showed no weight loss after 96 hr at 200 C, one did not autoignite at 500 C in air, and all four self extinguished when exposed to a flame as soon as contact between flame and resin was lost. The only toxic decomposition products to be concerned about were found to be hydrogen cyanide and benzene. Under the conditions employed it was proven, however, that the quantities of toxic products are greatly reduced if no ignition takes place, e.g., if thermal decomposition proceeds at a sufficiently low rate.

Paciorek, K. L.↗

Solubilization and spore recovery from silicone polymers

A non-sporicidal technique for solvent degradation of cured silicone polymers was developed which involves chemical degradation of cured silicone polymers by amine solvents at room temperature. Substantial improvements were obtained in the recovery of seeded spores from room temperature cured polymers as compared to the standard recovery procedures, which indicates that the curing process is not sufficiently exothermic to reduce spore viability. The dissolution reaction of cured silicone polymers whith amine solvents is proposed to occur by bimolecular nucleophilic displacement. The chemical structure of silicone polymers was determined by spectroscopic methods. The phenyl to methyl ratio, R/Si ratio, molecular weight, and hydroxyl content of the silicone resins were determined.

Hsiao, Y. C.↗

Quinoxaline polymers and copolymers derived from 1, 4-BIS(1'-napthalenyloxayl) benzene

A route for the synthesis of a new monomer, 1,4-bis(1'-naphthalenyl)-oxayl benzene, was devised, and six polymers and copolymers were prepared from this monomer, 1,4-bis(phenyloaxaly)benzene, 3,3'-diaminobenzidine and 3,3',4,4'-tetraaminobenzophenone. Thermogravimetric analysis showed that decomposition of these quinoxaline polymers and copolymers sets in at about 500 C but does not become significant in an inert atmosphere below 600 C. Oxidation becomes significant at about 550 C and the phenylquinoxaline homopolymer is somewhat more oxidation resistant than is the 1-naphthalenylquinoxaline homopolymer. Stress-relaxation measurements showed that, with two exceptions, the homopolymers and copolymers exhibited two second-order transition temperatures, one at about 204.4 C (400 F) and the other at about 315.6 C (600 F). No gross differences in the high temperature plasticity was observed between the naphthalenyl- and the phenyl-quinoaxaline homopolymers. Work was begun on a method for cross-linking polyquinoxalines. A new monomer, p-(methyloxaly)benzil, was synthesized, and model reaction studies showed that cross-linking of 2-methylquinoxaline polymers by a Michael condensation with dimaleimides will probably occur.

Port, W. S.↗

Fabrication and evaluation of polymeric early-warning fire-alarm devices

The electrical resistivities were investigated of some polymers known to be enhanced by the presence of certain gases. This was done to make a device capable of providing early warning to fire through its response with the gases produced in the early phases of combustion. Eight polymers were investigated: poly(phenyl acetylene), poly(p-aminophenyl acetylene), poly(p-nitrophenyl acetylene), poly(p-formamidophenyl acetylene), poly(ethynyl ferrocene), poly(ethynyl carborane), poly(ethynyl pyridine), and the polymer made from 1,2,3,6 tetramethyl pyridazine. A total of 40 usable thin-film sandwich devices and a total of 70 usable interdigitated-electrode lock-and-key devices were fabricated. The sandwich devices were used for measurements of contact linearity, polymer conductivity, and polymer dielectric constant. The lock-and-key devices were used to determine the response of the polymers to a spectrum of gases that included ammonia, carbon nonoxide, carbon dioxide, sulfur dioxide, ethylene, acrolein, water vapor, and normal laboratory air. Strongest responses were to water vapor, ammonia, and acrolein, and depending on the polymer, weaker responses to carbon dioxide, sulfur dioxide, and carbon monoxide were observed. A quantitative theory of device operation, capable of accounting for observed device leakage current and sensitivity, was developed. A prototype detection/alarm system was designed and built for use in demonstrating sensor performance.

Senturia, S. D.↗

Selected fretting-wear-resistant coatings for titanium - 6-percent-aluminum - 4-percent-vanadium alloy

A titanium - 6-percent-aluminum - 4-percent-vanadium alloy (Ti-6Al-4V) was subjected to fretting-wear exposures against uncoated Ti-6Al-4V as a baseline and against various coatings and surface treatments applied to Ti-6Al-4V. The coatings evaluated included plasma-sprayed tungsten carbide with 12 percent cobalt, aluminum oxide with 13 percent titanium oxide, chromium oxide, and aluminum bronze with 10 percent aromatic polyester; polymer-bonded polyimide, polyimide with graphite fluoride, polyimide with molybdenum disulfide (MoS2), and methyl phenyl silicone bonded MoS2, preoxidation surface treatment, a nitride surface treatment, and a sputtered MoS2 coating. Results of wear measurements on both the coated and uncoated surfaces after 300,000 fretting cycles indicated that the polyimide coating was the most wear resistant and caused the least wear to the uncoated mating surface.

Bill, R. C.↗

Study of improved resins for advanced supersonic technology composites. Part 1: Heteroaromatic polymers containing ether groups. Part 2: Curing chemistry of aromatic polymers and composite studies

Fourteen ether-containing, aromatic dianhydrides have been synthesized from N-phenyl-3 or 4-nitrophthalimide and various bisphenols. The process involves nucleophilic displacement of activated nitro groups with bisphenolate ions. Ether-containing dianhydrides were indefinitely stable in the presence of atmospheric moisture. One-step, high temperature solution polymerization of the ether-containing dianhydrides with m-phenylene diamine, 4,4'-oxydianiline and 1, 3-bis(4-aminophenoxy)benzene afforded 42 polyetherimides. The polyetherimides were all soluble in m-cresol except two which were found to be crystalline. The glass transition temperatures of the polyetherimides ranged from 178 to 277 C. Soluble polybenzimidazopyrrolones containing ether groups were also prepared from the same ether-containing dianhydrides and aromatic tetraamines by one-step solution polymerization. Using low molecular weight polyetherimides, various thermoset resin systems were developed and tested as matrices for fiber-reinforced composites. The curing chemistry involving reaction of the phthalonitrile group and the o-diaminophenyl group was found to be generally applicable to crosslinking various aromatic polymers other than polyimides.

Takekoshi, T.↗

Develop Silicone Encapsulation Systems for Terrestrial Silicon Solar Arrays

The results for Task 3 of the Low Cost Solar Array Project are presented. Task 3 is directed toward the development of a cost effective encapsulating system for photovoltaic modules using silicon based materials. The technical approach of the contract effort is divided into four special tasks: (1) technology review; (2) generation of concepts for screening and processing silicon encapsulation systems; (3) assessment of encapsulation concepts; and (4) evaluation of encapsulation concepts. The candidate silicon materials are reviewed. The silicon and modified silicon resins were chosen on the basis of similarity to materials with known weatherability, cost, initial tangential modulus, accelerated dirt pick-up test results and the ratio of the content of organic phenyl substitution of methyl substitution on the backbone of the silicon resin.

Source record↗