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A method of preparing insoluble thermoplastic aromatic polyimides is described, having uniquely low softening temperatures by reacting, in a suitable solvent, an aromatic dianhydride, and a meta-substituted aromatic diamine.

Polyimides have found broad application in fiber-reinforced composites for aerospace components and as thin films for electronics packaging. Typical routes to processing these materials require temperatures above 200 C. As a result, tooling costs for fabricating components from these composites can be quite high. Recent efforts within the Polymers Branch at the NASA Lewis Research Center have been aimed at developing radiationcurable (with light or electron beams) polyimides. Such materials may enable the processing of polymers and composites at or near room temperature, leading to reduced tooling requirements and costs. A new Diels-Alder route to polyimides has been developed that employs ultraviolet light (UV), rather than heat, to effect polymerization. This approach, which can be carried out at room temperature, is based on a well-known photochemical reaction--the photoenolization of o-methylphenyl ketones. Irradiation of o-methylphenyl ketones, such as 1 in the preceding figure, with UV wavelengths above 300 nm produces a photoenol, 2. This photoenol is unstable, but it persists long enough to undergo Diels-Alder reactions with good dienophiles, such as maleimide, 3. By utilizing a diketone, such as 2,5-dibenzoylp-xylene, 5, and a bismalemide, 6, this chemistry has been used to make a number of polyimides, 7.

Kapton(registered name) is used extensively in spacecraft thermal blankets, solar arrays, and space inflatable structures. Atomic oxygen (AO) in low Earth orbit (LEO) causes severe degradation of Kapton. SiO2 coatings impart remarkable oxidation resistance to Kapton, yet imperfections in the SiO2 application process and micrometeoroid / debris impact in orbit damage the SiO2 coating leading to Kapton erosion. Polyhedral oligomeric silsesquioxane (POSS) is a silicon and oxygen cage-like structure surrounded by organic groups which can be polymerizable. POSS-diamine was polymerized with the Kapton monomers, pyromellitic dianhydride and 4.4'-oxydianiline. The resulting POSS-Kapton polyimide (PI) is self-passivating by the formation of a silica layer upon exposure to AO. Evidence of a SiO2 passivation layer has been shown by X-Ray Photoelectron Spectroscopy studies on AO exposed samples, and erosion yields of 3.5, 7.0, and 8.75 weight % Si8O11 MC-POSS-PI samples which were 3.7, 0.98, and 0.3 percent, respectively, of the erosion yield for Kapton H at a fluence of 8.5 x 10 to the 20th power oxygen atoms per square cm. The self-passivation of POSS-Kapton-PIs has also been demonstrated by monitoring a 1 micron deep scratch in MC-POSS-PI after exposure to AO. Kapton H(trade mark), SiO2 coated Kapton HN(trade mark) and 8.75 wt % Si8O11 MC-POSS-PI samples were exposed to AO, scratched, and re-exposed to AO. Upon the first exposure, these samples eroded 5.0 micron, 0 micron, and 200 nm respectively. Upon the second exposure the samples eroded, respectively, an additional 5.0 micron within and outside of the scratch, and 7.0 micron and 200 nm within the scratch only. Physical property characterization of POSS-PIs exposed to AO, and samples flown in LEO on the Materials International Space Station Experiment (MISSE), evidence that POSS-PIs are a viable Kapton replacement material.

Azobenzene-functionalized polyimide materials can directly transduce light into mechanical force. Here, we examine the impact of polymer backbone rigidity on the photomechanical response in a series of linear, azobenzene-functionalized polymers. The rigidity of the backbone was varied by the polymerization of five dianhydride monomers with a newly synthesized diamine (azoBPA-diamine). The azobenzene-functionalized linear polymers exhibit glass transition temperatures (Tg) ranging from 276 to 307 C and maintain excellent thermal stability. The photomechanical response of these materials was characterized by photoinduced cantilever bending as well as direct measurement of photogenerated stress upon exposure to linearly polarized, 445 nm light. Increasing the rigidity of the polymer backbone increases the magnitude of stress that is generated but decreases the angle of cantilever deflection.

This research project addressed two fundamental aspects of carbon fiber reinforced high temperature polyimide composites, namely the curing chemistry involved for polyimide formation and then, the thermal oxidative stability of the polyimide structure so produced. The latter played a key role in controlling the composite long-term service temperature when the composite was targeted for aircraft and aerospace applications. The TGA/FTIR and TGA/MS evolved gas analysis provided a convenient means to study these two features by monitoring the off-gas reaction products during cure in the former and following the off-gas degradation products in the latter. TGA served as a curing reactor in the former while FTIR and MS identified the reaction products in real time. Similarly, TGA provided the means of aging a composite in a controlled environment while FTIR and MS were used to detect the degradation products given off, also in real time. According to TGA/FTIR/MS study, the thermal curing of polyimides including AFR700B/T650-35, LARC RP-46/IM7 and VCAP-75/Glass fiber prepregs proceeded essentially by: (1) the elimination of methanol from amic-acid prepolymer formation, (2) the release of water from subsequent imidization, and (3) finally, the thermal crosslinking via a reverse Diels-Alder reaction when a NE end capping monomer was used. Thus, this polyimide curing reaction sequence confirmed the literature findings. However, the FTIR/MS data obtained could also accommodate the alternative that the elimination of water from amide-ester formation occurred first, which was followed by the release of methanol from subsequent imidization. In the case of AFR700B/T650-35 prepreg, most off-gases were released by 430 deg F (221 deg C), thereby marking this temperature as the time for both vacuum cut-off and application of consolidation during autoclaving to produce low void content parts. Again, this coincided with industrial autoclaving practice.

A series of four new end-capped and hydroxymethyl-functionalized polyimides were prepared. Through a two-step chemical modification process 3- aminopropylisobutyl-POSS was covalently attached to the polymer backbone. POSS loading levels as high as 40 wt-% could be obtained while maintaining excellent processability and optical clarity of thin films. Concurrent attachment of either a cyanate ester or hydroxyethyl methacrylate (HEMA) group afforded processable POSS-polyimides that underwent thermal curing to yield solvent resistant films, both having final Tg?s of 251 ?C. Kinetic analysis of the cure reactions yielded energy of activations of 93 kJ/mol (cyanate ester) and 103 kJ/mol (HEMA). Exposure of a POSS polyimide containing 31 wt-% POSS to atomic oxygen displayed no measurable level of erosion relative to a Kapton? standard.

Evidence for the formation of a protective silica layer on the surface of POSS-Kapton(Registered)-PIs upon exposure to AO was found in X-Ray Photoelectron Spectroscopy (XPS) studies of POSS-Kapton(R)-PIs flown on the Materials International Space Station Experiment (MISSE1), and in separate studies of POSS-Kapton(R)-PIs exposed to AO in a ground-based facility. To directly compare the effect of AO on Kapton H(R), SiO2 coated Kapton HN(R), and 8.75 weight % Si8O11 cage main-chain POSS-Kapton(R)-polyimide (8.75 wt % Si8O11 MC-POSS-PI), these materials were exposed to AO, scratched, and exposed to a second equivalent AO fluence. The erosion of the three materials, inside and outside of the scratched area, was monitored by stylus surface profilometry. The results of this study indicate that the POSS Kapton(R) PI reproducibly eroded about 200 nm before forming a silica layer. A thin film of 7 wt % Si8O11 survived a 3.9 year flight on the MISSE1, on the International Space Station which resides at 500 km in LEO. The effects of temperature, physical property characterizations, and the MISSE1 flight will be discussed.

Evidence for the formation of a protective silica layer on the surface of POSS-Kapton(Registered)-PIs upon exposure to AO was found in X-Ray Photoelectron Spectroscopy (XPS) studies of POSS-Kapton(R)-PIs flown on the Materials International Space Station Experiment (MISSE1), and in separate studies of POSS-Kapton(R)-PIs exposed to AO in a ground-based facility. To directly compare the effect of AO on Kapton H(R), SiO2 coated Kapton HN(R), and 8.75 weight % Si8O11 cage main-chain POSS-Kapton(R)-polyimide (8.75 wt % Si8O11 MC-POSS-PI), these materials were exposed to AO, scratched, and exposed to a second equivalent AO fluence. The erosion of the three materials, inside and outside of the scratched area, was monitored by stylus surface profilometry. The results of this study indicate that the POSS Kapton(R) PI reproducibly eroded about 200 nm before forming a silica layer. A thin film of 7 wt % Si8O11 survived a 3.9 year flight on the MISSE1, on the International Space Station which resides at 500 km in LEO. The effects of temperature, physical property characterizations, and the MISSE1 flight will be discussed.

Amorphous polyimides containing polar functional groups have been synthesized and investigated for potential use as high temperature piezoelectric sensors. The thermal stability of the piezoelectric effect of one polyimide was evaluated as a function of various curing and poling conditions under dynamic and static thermal stimuli. First, the polymer samples were thermally cycled under strain by systematically increasing the maximum temperature from 50 C to 200 C while the piezoelectric strain coefficient was being measured. Second, the samples were isothermally aged at an elevated temperature in air, and the isothermal decay of the remanent polarization was measured at room temperature as a function of time. Both conventional and corona poling methods were evaluated. This material exhibited good thermal stability of the piezoelectric properties up to 100 C.

This invention relates the novel diamines, the polyimide oligomers and the polyimides derived therefrom and to the method of preparing the diamines, oligomers and the polyimides. The thermoplastic polyimides derived from the aromatic diamines of this invention are characterized as having a high glass transition temperature, good mechanical properties and improved processability in the manufacture of adhesives, electronic and composite materials for use in the automotive and aerospace industry. The distinction of the novel aromatic diamines of this invention is the 2,2',6,6'-substituted biphenyl radicals which exhibit noncoplanar conformation that enhances the solubility of the diamine as well as the processability of the polyimides, while retaining a realatively high glass transition temperature and improved mechanical properties at useful temperature ranges.

Polyimides from cyclobutane dianhydrides have been prepared and have been shown to be sensitive to electron beams as well as to deep UV irradiation. Synthesis, thermal properties and sensitivity data are presented. Keywords: Imides; Polymers.

Thianthrene-2,3,7,8-tetracarboxylic dianhydride was synthesized via nucleophilic aromatic substitution of N-phenyl-4,5-dichlorophthalimide with thiobenzamide, thioacetamide and sodium sulfide. This monomer was then polymerized with aromatic diamines by the conventional low temperature technique in N, N-dimethylacetamide (DMAc) to yield soluble poly(amic acid)s. Polyimides were obtained by thermal cyclization of the poly(amic acid) films. Polymers obtained formed creasable thin films and had excellent thermal stability in air and nitrogen. The bent thianthrene structure limited crystallization and chain- packing as indicated by X-ray analysis. The highly amorphous thianthrene containing polyimides were only soluble in H2SO4.

A study has been in progress for several years at Syracuse University on the relationships between the chemical structure of polymers and their permeability and selectivity to different gases. A better understanding of these relationships is of great importance for the development of new processes for the separation of gases by selective permeation through polymer membranes. Two classes of polymers have been investigated up to now for this purpose, namely silicone polymers (poly(organosiloxanes) and polyimides (1-5). Therefore, it was of interest also to study the structure/permeability relationships of silicon-containing polyimides. Accordingly, the following types of polymers were used in this study: (1) silicone-polyimide copolymers, and (2) 'silicon- modified polyimides.', i.e., polyimides containing silicon atoms in the backbone chains. These polymers were employed in the form of thin, nonporous membranes, and their permeability to H2, 02, N2, CO2, and CH4 was determined at 35.O'C and at pressures up to about 120 psig (- 8.2 atm.). The results of the study are discussed below.

The concept of intramolecular cycloaddition (IMC) curing of polymers for use as matrix resins, previously established for polyphenylquinoxalines, has been extended to polyimides. Two novel aromatic diamines incorporating a 2,2'- bis (phenylethynyl) diphenyl moiety were synthesized and then polymerized with various bis-anhydrides. In the optimum combination, a polyimide was obtained which was soluble in aprotic solvents, softened at 185 deg. C, underwent a cure at 233 deg C wherein the 2,2'-bis(phenylethynyl) diphenyl moiety was converted to a much more rigid dibenzoanthracene structure, and the resultant polymer displayed a softening point of 310-325 deg C after cure.

A research area of high activity in connection with aerospace engineering has been the development of polymer thermosetting resins that can resist temperature as high as 300 C while maintaining adequate toughness, and providing ease of processing to enable low temperature and low cost composite fabrication methods. In order to meet such requirements, sequential interpenetrating polymer networks (IPNs) based on bismaleimide (BMI) and cyanate ester (CE) monomers were investigated. In these systems, a polycyanurate network is first formed in the presence of BMI and appropriate reactive diluent monomers and in a second step, a network based on the BMI is created in the presence of a fully formed polycyanurate network. The materials developed can be processed at relatively low temperature (less than 150 C) and with the aid of electron beam (EB) curing. Of major importance to the success of this work was the identification of a reactive diluent that improves ease of processing and has tailored reactivity to allow for the controlled synthesis of CE-BMI sequential IPNs. Based on solubility and reactivity of a number of reactive diluents, N-acryloylmorpholine (AMP) was selected as a comonomer for BMI copolymerization. A donor-acceptoreaction mechanism was suggested to explain the relative reactivity of a variety of reactive diluents towards maleimide functionality. The optimum processing parameters for the formation of the first network were determined through the study of metal catalyzed cure and hydrolysis of cyanate esters, whereas the reaction behavior for second network formation in terms of the influence of EB dose rate and temperature was elucidated through an in-situ kinetics study of maleimide and AMP copolymerization. Structure-property relationships were developed which allowed for the design of improved resin systems. In particular, appropriate network coupler possessing cyanate ester and maleimide functionality was synthesized to link the polycyanurate first network to the BMI/AMP second network and thus form linked sequential IPNs (LIPNs). Consequently, Tg as high as 370 C was achieved and a fracture toughness of 120 Joules per square meters was obtained for resin systems that possess adequately low viscosity for processing using liquid molding techniques at low temperature.

The N-CYCAP polyimides utilize a (2,2) paracyclophane endcap that polymerizes and does not generate volatile gases during the cure process. These polyimides have both high glass temperatures (390 C) and an onset of decomposition in air of 560 C. Thermal oxidative stability (TOS) weight loss studies show that replacing 25 percent by weight of the paraphenylene diamine in the polymer backbone with metaphenylene diamine improves the weight loss characteristics. N-CYCAP neat resin samples performed better than PMR-II-50 when exposed at 343 and 371 C in air for up to 1000 hours. Preliminary composite studies show that both PMR-II-50 and N-CYCAP have better thermal stability when fabricated on T-40R. Higher isothermal aging temperatures of longer aging times are needed to determine the differences in TOS between composite samples of PMR-II-50 and N-CYCAP polyimides.

The monomeric reactants approach was used to fabricate addition-type polyimide/graphite fiber composites with improved mechanical properties and thermal stability characteristics over those of composites derived from addition-type amide acid prepolymers. A screening study of 24 different monomer combinations was performed. The results of a more extensive investigation of a selected number of monomer combinations showed that the combination providing the best thermomechanical properties was 5-norbornene-2.3-dicarboxylic acid monomethyl ester/4,4(')-methylenedianiline/3,3(')4,4(')-benzophenonetetracarboxylic acid dimethyl ester at a molar ratio of 2/3.09/2.09.

Preparation of thermally stable polyimides from solutions of monomeric reactions

The presumed relationship of chemical impurities to final composite properties was investigated for PMR-polyimide resin. Ester/acid solutions of one monomer were aged at selected temperatures and chemical changes were monitored spectroscopically. At selected intervals, graphite fiber reinforced composite panels were fabricated. Changes in resin processing characteristics and composite properties were determined. The correlation of these data are discussed as are related characterization studies of PMR-polyimide resin.

The use of polymer matrix composites (PMC's) in aircraft engines can lead to substantial weight savings over metals. This weight reduction correlates into better fuel economy, increased speed, and increased passenger load. Typically, high performance PMC's possess high thermal-oxidative stabilities (TOS) and high glass transition temperatures (Tg's) to withstand temperatures up to 316 C (600 F). One of the leading high temperature resins system available today is PMR-15 (Polymerization of Monomeric Reactants, MW=1500). This thermosetting polyimide utilizes addition curing through polymer endcaps which enables hand lay-up processing of carbon fiber composite parts with low void contents. However, the large amount of hand labor raises manufacturing costs and prohibits the use of PMR-15 in many aerospace applications. Resin Transfer Molding (RTM) provides an economical alternative, but it requires a melt Viscosity of less than 10(exp 3) centipoise (cP). This is much lower than the minimum melt viscosity of PMR-15 (about 10(exp 6) cP). To improve the processability of polyimides, the polymer backbone can be modified by incorporating flexible linkages, such as branching. bulky pendant groups, kinked structures, and twisted or non-coplanar moietes . The focus of this paper will be the introduction of non-coplanar biaryls into the PMR polyimide backbone to increase processability while maintaining high temperature performance.

Studies were performed to achieve a lower-curing-temperature PMR polyimide. The use of m-aminostyrene as the end-cap instead of the monoalkyl ester of 5-normbornene-2,3 dicarboxylic acid was investigated in typical PMR formulations. Model compound studies were also performed. Differential scanning calorimetry studies were performed on model compounds and neat resins to establish their melting and curing characteristics. The elevated temperature weight loss characteristics of neat resins and graphite fiber composites were determined. The room temperature and short-time 260 C (500 F) mechanical properties of the composites were also determined. The use of m-aminostyrene end-caps reduced the final cure temperature of PMR resins by about 55 C (100 F), but the composites prepared with these resins are limited to use temperatures of about 260 C (500 F).

By electron spectroscopy it was shown that aromatic polyimides containing electron-donor residues of diamines -C6H4-X-C6H-(X=NH, NCH3, NC6H5, O, S, and CH2) form charge transfer complexes with low-molecular-weight electron acceptors. Based on the data obtained, the hypothesis was advanced that the coloration of the polyimides per se is due to the formation of charge transfer complexes between the electron-acceptor imide fragments and the electron-donor residues of the diamines.

The present invention relates generally to polyimides. It relates particularly to novel polyimides prepared from 2,3, 3',4' -biphenyltetracarboxylic dianhydride and aromatic diamines. These novel polyimides have low color, good solubility, high thermal emissivity, low solar absorptivity and high tensile strength.

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.

The photogeneration of free amines or diamines from soluble organic precursors such as photoactive 2-nitrobenzyl carbamates is useful for the imidization of polymers containing amic acid or amic ester groups as part of their main-chain or their side-chain. The base-catalyzed reaction occurs at lower temperatures than the noncatalyzed thermal process and is applicable to the patterning of thin film coatings.

The field of hybrid organic-inorganic materials has grown drastically over the last several years. This interest stems from our ever-increasing ability to custom-build and control molecular structure at several length scales. This ability to control both the composition and structure of hybrid materials is sometimes broadly referred to as nanocomposite systems. One class of hybrid (organic-inorganic) nanostructured material is polyhedral oligomeric silsesquioxane (POSS), shown in the preceding diagram. The hybrid composition gives POSS materials dramatically enhanced properties relative to traditional hydrocarbons and inorganics. An important benefit of this technology is that it makes possible the formulations of nanostructured chemicals with excellent thermal and oxidative stability. This is largely due to the inorganic component.

In the present invention, linear aromatic polyimides containing the cyclobutene-3,4-dione moiety were produced from the reaction of a substituted or unsubstituted 1,2-bis(4-aminoanilino) cyclobutene-3,4-dione (SQDA) with various aromatic dianhydrides. These polymers had high molecular weights and their glass transition temperatures (Tgs) were greater than 500 C. Despite the very high Tg, these polymers exhibited excellent adhesion to glass. In addition, the films of these polyimides increased in flexibility with increasing cure temperatures. The novelty of this invention lies in the linear aromatic polyimide containing the cyclobutene-3,4-dione moiety. The presence of this moiety causes such changes in properties as Tgs greater than 500 C, excellent adhesion to glass, and increased flexibility with increasing cure temperatures.

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.

An improvement of addition polyimides wherein an essentially solventless, high viscosity laminating resin is synthesized from low cost liquid monomers is disclosed. The improved process takes advantage of a reactive, liquid plasticizer such as monoethylphthalate (MEP) which is used in lieu of an alcohol solvent, and helps solve a major problem of maintaining good prepreg tack and drape, or the ability of the prepreg to adhere to adjacent plies and conform to a desired shape during the layup process. This improvement results in both longer life of the polymer prepreg and the processing of low void laminate and appears to be applicable to all addition polyimide systems.

The development of new composite resins for various aerospace applications is attempted. Although it is highly desirable that these polymers be soluble in order to facilitate processing, they must display considerable solvent-resistance in use. A recent approach has involved the synthesis of a new series of polyimides containing flexible linkages. The polymers were prepared by the polymerization of aromatic dianhydrides with diamines containing oxyethylene linkages. For example, the polymerization of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) with 1,2-bis(4-aminophenoxy)ethane (1a) and bis2-(4-aminophenoxy)ethylether (lb), afforded highly crystalline polyimides that were completely insoluble. However, a polyimide that was amorphous and soluble was obtained from the polymerization of BTDA and an isomer of lb, i.e., bis2-(3-aminophenoxy)ethyl ether (4b). In an attempt to obtain a soluble, amorphous polyimide that could be annealed into a crysalline state, block copolymers of 1b and 4b and BTDA were prepared. Copolymers containing less than 20 weight % 1b were soluble in organic solvents. However, these polymers did not crystallize when heated above their Tg's. Copolymers containing higher levels of 1b were semicrystalline and insoluble. The polymerization of the diamines containing oxyethylene linkages with 4,4'-oxydiphthalic anhydride (ODPA) and a new dianhydride, i.e., 4,4'-oxyethyleneoxyethyleneoxydiphthalic anhydride (OEDA) was investigated. It was postulated that the use of these more flexible dianhydrides would result in more processable polyimides.

A poly(Diels-Alder) (PDA) resin approach was investigated as a means to achieve autoclavability of high temperature resistant resin/fiber composites under mild fabrication procedures. Low void content Type A-S graphite reinforced composites were autoclave fabricated from a PDA resin/fiber prepared from an acetone:methanol:dioxane varnish. Autoclave conditions were 477K (400F) and 0.7 MN/sq m (100 psi) for up to two hours duration. After postcure at temperatures up to 589K (600F), the composites demonstrated high initial mechanical properties at temperatures up to 561K (550F). The results from isothermal aging studies in air for 1000 hours indicated potential for long-term ( 1000 hours) use at 533K (500F) and shorter-term (up to 1000 hours) at 561K (550F).

The monomeric reactants approach was used to fabricate addition-type polyimide/graphite fiber composites with improved mechanical properties and thermal stability characteristics over those of composites derived from addition-type amide acid prepolymers. A screening study of 24 different monomer combinations was performed. The results of a more extensive investigation of a selected number of monomer combinations showed that the combination providing the best thermomechanical properties was 5-norbornene -2,3 -dicarboxylic acid monomethyl ester/4, 4'-methylenedianiline /3, 3'4, 4' -benzophenonetetracarboxylic acid dimethyl ester at a molar ratio of 2/3.09/2.09.

Polyimides (PIs) such as Kapton are used extensively in spacecraft thermal blankets, solar arrays, and space inflatable structures. Atomic oxygen (AO) in low Earth orbit (LEO) causes severe degradation of Kapton. SiO2 coatings impart remarkable oxidation resistance and have been widely used to protect Kapton, yet imperfections in the SiO2 application process and micro-meteoroid/debris impact in orbit damage the SiO2 coating leading to Kapton erosion. A polyimide that is self-passivating by the formation of a silica layer upon exposure to AO has been achieved by the copolymerization of a polyhedral oligomeric silsesquioxane (POSS) diamine. The self-passivating properties have been shown by monitoring a 1 micron deep scratch in POSS-PIs after exposure to AO. During the first AO exposure and outside of the scratch, these samples eroded 5.0 microns, 0 microns, and less than 200 nm respectively. During the second AO exposure, the samples eroded an additional 5.0 microns within the scratch and outside of the scratch, 7.0 microns within the scratch and 0 microns outside of the scratch, and 200 nm within the scratch and 0 microns outside of the scratch respectively.

Kapton polyimide (PI) is extensively used in solar arrays, spacecraft thermal blankets, and space inflatable structures. Upon exposure to atomic oxygen (AO) in low Earth orbit (LEO), Kapton is severely degraded. An effective approach to prevent this erosion is chemically bonding polyhedral oligomeric silsesquioxane (POSS) into the polyimide matrix by copolymerization of POSS-diamine with the polyimide monomers. POSS is a silicon and oxygen cage-like structure surrounded by organic groups and can be polymerizable. The copolymerization of POSS provides Si and O in the polymer matrix on the nano level. During POSS polyimide exposure to atomic oxygen, organic material is degraded and a silica passivation layer is formed. This silica layer protects the underlying polymer from further degradation. Ground-based studies and MISSE-1 and MISSE-5 flight results have shown that POSS polyimides are resistant to atomic-oxygen attack in LEO.

Partial contents; This Study will, WHat is a thin film?, An application of Thin Film polyimides, Typical Solar Thermal Rocket Configuration, Benefits of 6FDA +APB Thin Films, Design Parameters for Articles constructed with thin film polyimides, theory, thin film test appartus, unlaxial test appartus, toggle grip design, computer test panel, experimental procedure, Modulus of Elasticity results, Coefficient of Thermal Expansion results, Conclusions and Recommendations, Acknowledgement.

Kapton polyimide (PI) is widely used on the exterior of spacecraft as a thermal insulator. Atomic oxygen (AO) in lower earth orbit (LEO) causes severe degradation in Kapton resulting in reduced spacecraft lifetimes. One solution is to coat the polymer surface with SiO2 since this coating is known to impart remarkable oxidation resistance. Imperfections in the SiO2 application process and micrometeoroid/debris impact in orbit damage the SiO2 coating, leading to erosion of Kapton. A self passivating, self healing silica layer protecting underlying Kapton upon exposure to AO may result from the nanodispersion of silicon and oxygen within the polymer matrix. Polyhedral oligomeric silsesquioxane (POSS) is composed of an inorganic cage structure with a 2:3 Si:O ratio surrounded by tailorable organic groups and is a possible delivery system for nanodispersed silica. A POSS dianiline was copolymerized with pyromellitic dianhydride and 4,4΄-oxydianiline resulting in POSS Kapton Polyimide. The glass transition temperature (Tg) of 5 to 25 weight % POSS Polyimide was determined to be slightly lower, 5 - 10 %, than that of unmodified polyimides (414 C). Furthermore the room temperature modulus of polyimide is unaffected by POSS, and the modulus at temperatures greater than the Tg of the polyimide is doubled by the incorporation of 20 wt % POSS. To simulate LEO conditions, POSS PI films underwent exposure to a hyperthermal O-atom beam. Surface analysis of exposed and unexposed films conducted with X-ray photoelectron spectroscopy, atomic force microscopy, and surface profilometry support the formation of a SiO2 self healing passivation layer upon AO exposure. This is exemplified by erosion rates of 10 and 20 weight % POSS PI samples which were 3.7 and 0.98 percent, respectively, of the erosion rate for Kapton H at a fluence of 8.5 x 1020 O atoms/sq cm.

One of the most important contributions of theoretical chemistry is the correct prediction of properties of materials before any costly experimental work begins. This is especially true in the field of electrically conducting polymers. Development of the Valence Effective Hamiltonian (VEH) technique for the calculation of the band structure of polymers was initiated. The necessary VEH potentials were developed for the sulfur and oxygen atoms within the particular molecular environments and the explanation explored for the success of this approximate method in predicting the optical properties of conducting polymers.

The differences in the radiation durabilities of two polyimide materials, Du Pont Kapton and General Electric Ultem, are compared. An explanation of the basic mechanisms which occur during exposure to electron radiation from analyses of infrared (IR) and electron paramagnetic resonance (EPR) spectroscopic data for each material is provided. The molecular model for Kapton was, in part, established from earlier modeling for Ultem (pp. 1293-1298 of IEEE Transactions on Nuclear Science, December 1984). Techniques for understanding the durability of one complex polymer based on the understanding of a different and equally complex polymer are demonstrated. The spectroscopic data showed that the primary radiation-generated change in the tensile properties of Ultem (a large reduction in tensile elongation) was due to crosslinking, which followed the capture by phenyl radicals of hydrogen atoms removed from gem-dimethyl groups. In contrast, the tensile properties of Kapton remained unchanged because radical-radical recombination, a self-mending process, took place.

Nine new condensation polyimides containing the trifluorophenylethylidene linkage were synthesized by the amic-acid route. Several other polyimides, including some with the hexafluoroisopropylidene linkage, were also prepared as controls. Amic-acid solutions were characterized by determining their inherent viscosities prior to thermal conversion into polyimide films. Glass transition temperatures (T sug g), thermogravimetric analysis (TGA), and isothermal weight loss data were obtained for the films. The films were pulverized into molding powders which, in turn, were thermally processed under pressure into neat resin discs. The discs were also characterized by T sub gs and 316 C and 371 C isothermal weight losses. The film study identified two new polyimides with T sub gs greater that 371 C and two new polyimides with low rates of weight loss. The resin discs exhibited the same overall trends in T sub g and weight loss as the respective films, however the weight loss per unit surface area was always greater, presumably due to voids or to mechanical degradation induced during preparation of the molding powders.

The effect of atomic oxygen flux and VUV radiation alone and in combination on the surface of fluorinated polyimide films was studied using XPS spectroscopy. Exposure of fluorinated polyimides to VUV radiation alone caused no observable damage to the polymer surface, while an atomic oxygen flux resulted in substantial oxidation of the surface. On the other hand, exposure to VUV radiation and atomic oxygen in combination caused extensive oxidation of the polymer surface after only 2 minutes of exposure. The amount of oxidized carbon on the polymer surface indicated that there is aromatic ring opening oxidation. The changes in the O1s/C1s, N1s/C1s, and F1s/C1s ratios suggested that an ablative degradation process is highly favorable. A synergistic effect of VUV radiation in the presence of atomic oxygen is clearly evidenced from the XPS study. The atomic oxygen could be considered as the main factor in the degradation process of fluorinated polyimide films exposed to a low earth orbit environment.

A high temperature semi-interpenetrating polymer network (semi-IPN) was developed which had significantly improved processability, damage tolerance and mechanical performance, when compared to the commercial Thermid.RTM. materials. This simultaneous semi-IPN was prepared by mixing a thermosetting polyimide with a thermoplastic monomer precursor solution (NR-15082) and allowing them to react upon heating. This reaction occurs at a rate which decreases the flow and broadens the processing window. Upon heating at a higher temperature, there is an increase in flow. Because of the improved flow properties, broadened processing window and enhanced toughness, high strength polymer matrix composites, adhesives and molded articles can now be prepared from the acetylene endcapped polyimides which were previously inherently brittle and difficult to process.

Polyimides have found broad application in fiber-reinforced composites for aerospace components and as thin films for electronics packaging. Typical routes to processing these materials require temperatures above 200 C. As a result, tooling costs for fabricating components from these composites can be quite high. Recent efforts within the Polymers Branch at the NASA Lewis Research Center have been aimed at developing radiationcurable (with light or electron beams) polyimides. Such materials may enable the processing of polymers and composites at or near room temperature, leading to reduced tooling requirements and costs. A new Diels-Alder route to polyimides has been developed that employs ultraviolet light (UV), rather than heat, to effect polymerization. This approach, which can be carried out at room temperature, is based on a well-known photochemical reaction--the photoenolization of o-methylphenyl ketones. Irradiation of o-methylphenyl ketones, such as 1 in the preceding figure, with UV wavelengths above 300 nm produces a photoenol, 2. This photoenol is unstable, but it persists long enough to undergo Diels-Alder reactions with good dienophiles, such as maleimide, 3. By utilizing a diketone, such as 2,5-dibenzoylp-xylene, 5, and a bismalemide, 6, this chemistry has been used to make a number of polyimides, 7.

The Gabriel method allows preparation of imide derivatives from methyl iodide in good yields. The 1H T1S' were approximately 65-78 s for all protons, including the aromatic protons. 13C CP/MAS NMR spectra of the model N- methylphthalimides showed multiplet peaks for the aromatic carbons which may be due to differences in crystal packing. However, the 15N spectra show a single peak for imides 2 and 3. A procedure has been developed for incorporating 15N and 13C isotopic labelling into N-methylphthalimide, a model imide. From solid- state 15N NMR spectroscopic methods the values and orientation of the delta shift tensor with respect to the N-CH3 bond as well as the N-CH3 bond length have been determined.

Briefing charts on a Study of the Self-Passivation of Space-Survivable POSS Kapton Polyimides.

The overall objective of this study is to expand the performance space of carbon-fiber reinforced polyimide composites using a synergistic combination of hybrid inorganic-organic, nano-structured chemicals and state-of-the-art oligoimide chemistry. The addition of nano-structured chemicals both retains the light-weight nature of organic polymers and imparts substantially improved erosion resistance to high energy atomic oxygen and vacuum ultraviolet radiation, as well as high temperature mechanical performance and oxidative stability. In particular, this study will formulate hybrid, nano-structured polyimide composites, from the molecular to the macroscopic level, while tailoring their properties to the service durability requirements of Air Force-related applications.

This invention relates to the compositions and processes for preparing thermoset and thermoplastic polyimides derived from novel asymmetrical dianhydrides: specifically 2,3,3',4' benzophenone dianhydride (a-BTDA), and 3,4'-(hexafluoroisopropylidene)diphthalic anhydride (a-6FDA). The a-BTDA anhydride is prepared by Suzuki coupling with catalysts from a mixed anhydride of 3,4-dimethylbenzoic acid or 2,3-dimethylbenzoic acid with 2,3-dimethylphenylboronic acid or 3,4-dimethylphenylboronic acid respectively, to form 2,3,3',4'-tetramethylbenzophenone which is oxidized to form 2,3,3',4'-benzophenonetetracarboxylic acid followed by cyclodehydration to obtain a-BTDA. The a-6FDA is prepared by nucleophilic triflouoromethylation of 2,3,3',4'-tetramethylbenzophenone with trifluoromethyltrimethylsilane to form 3,4'-(trifluoromethylmethanol)-bis(o-xylene) which is converted to 3,4'-(hexafluoroisopropylidene-bis(o-xylene). The 3,4'-(hexafluoroisopropylidene)-bis(o-xylene) is oxidized to the corresponding tetraacid followed by cyclodehydration to yield a-6FDA.

Polyimide films made from diarylanhydrides with oxygen, carbonyl, and hexafluoroisopropylidene 6F bridging groups are photolabile when irradiated with unfiltered light from a medium pressure mercury lamp. The presence of oxygen is necessary to the photolytic degradation process, which results in the ultimate oxidative ablation of thin polyimide films. Films based on the 6F dianhydride containing a hexafluoroisopropylidene hinge group are the most unstable. However, photolysis of 6F dianhydride based polyimides in an inert atmosphere with either the unfiltered medium pressure mercury lamp or an electron beam results in no detectable changes even after long exposure times.

Studies were performed to investigate the effect of substituting a hexafluoro isopropyl idene connecting group for a carbonyl group of a PMR polyimide monomeric reactant on the thermo-mechanical properties processability of graphite fiber reinforced PMR polyimide composites. Composites were fabricated utilizing PMR methodology. Monomeric reactant solutions of various stoichiometric ratios were used to impregnate Hercules HTS graphite fiber. The processing characteristics and elevated temperature (600 F) mechanical properties of the composites are described.

The process of the present invention includes first treating a polyamide acid (such as LARC-TPI polyamide acid) in an amide-containing solvent (such as N-methyl pyrrolidone) with an aprotic organic base (such as triethylamine), followed by dehydrating with an organic dehydrating agent (such as acetic anhydride). The level of crystallinity in the linear aromatic polyimide so produced is maximized without any degradation in the molecular weight thereof.

Aromatic polyimides are a class of polymers that show remarkable thermal stability, strength, and toughness. These properties make them attractive candidates for use in high-performance carbon fiber composites for airborne and spaceborne structural components. Our research centered on the development of an understanding of the underlying process of crystallite formation in a particular class of aryl polyimides for which there are some x-ray crystallographic data available. The ultimate aim of the project is to be able to develop a model sufficiently flexible to be able, on the basis of the chemical structure of a polymer in this class, to predict: (1) whether it will be prone to form crystallites; (2) crystallographic features of the crystallites; and (3) synthesis and/or processing conditions that will be favorable or unfavorable to crystallite formation. This will provide guidance to the laboratory chemists in their choice of candidate polymers and processing methods.