CN109337365B - Composite atomic oxygen resistant polyimide film and application - Google Patents
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Abstract
The invention discloses a composite atomic oxygen resisting polyimide film and a preparation method and application thereof, wherein the film is a resin solution prepared by compounding an intrinsic atomic oxygen PI polymer shown as a formula I and TSP-POSS shown as a formula II according to a certain proportion and a composite film prepared by the resin solution; the mass percentage of the TSP-POSS in the total amount of the TSP-POSS/PI composite film is m%, wherein: m is more than 0 and less than or equal to 30. The film has the characteristic of dual atomic oxygen resistance, the PI substrate film has the characteristic of intrinsic atomic oxygen resistance because of containing phosphorus elements, and the composite film formed after the TSP-POSS is added has the characteristic of more obviously enhancing the atomic oxygen resistance. Because molecular-level recombination is formed between the TSP-POSS and the PI substrate, the composite film keeps the excellent optical transparency of the PI film substrate. The polyimide composite film disclosed by the invention covers the outer surface of a transparent aerospace device exposed in space, so that the atomic oxygen resistance of the polyimide composite film can be effectively improved.
Description
Technical Field
The invention relates to the field of functional polyimide films, in particular to a cage-type Polysilsesquioxane (POSS) composite polyimide atomic oxygen film.
Background
Most spacecraft operate on Low Earth Orbit (LEO) which is 200-700 km away from the ground. There are a number of environmental factors at this track heightAffecting the operation and working life of the spacecraft, such as thermal cycling, space debris, ultraviolet radiation, and space Atomic Oxygen (AO), among which atomic oxygen has proven to be the most important and dangerous contributor. The spacecraft running in the low earth orbit collides with atomic oxygen in the running orbit, the relative speed of the spacecraft is about 8km/s, and the impact impulse is about 1014～1015/cm2S, impact energy of about 4-5 eV is generated on the surface of the spacecraft, which is enough to cause most organic materials on the surface of the spacecraft to be chemically broken and oxidized, and the performance of the spacecraft is degraded.
In recent years, the research on the atomic oxygen effect of polymer materials is more and more focused, and the research is not only an important content in the research on the LEO space environmental effect, but also one of the key factors which must be considered in the design of spacecrafts. Polyimide (PI) is a common material in the field of aerospace, and in order to effectively reduce the corrosion of atomic oxygen on the surface of a spacecraft, the following two methods are commonly used: one is surface coating, i.e. applying a protective coating on the surface of the polymer which does not react with atomic oxygen, such as SiO2With Al2O3Etc. to improve the erosion of space material by AO; the other is a matrix strengthening method, namely elements such as silicon, phosphorus, zirconium, tin and the like with good atomic oxygen corrosion resistance are introduced into a polymer matrix, and the atomic oxygen resistance of the space material is improved by utilizing the self-healing or self-repairing function of the elements in the space atomic oxygen environment.
The surface coating method is easy to generate cracks or the coating falls off in the transportation process; when the spacecraft is in service in outer space, because the Coefficient of Thermal Expansion (CTE) of the inorganic coating on the surface is different from that of the polymer matrix in the interior, cracks are generated under the condition of thermal cycle caused by periodic solar irradiation, or the protective layer on the surface of the material generates tiny cracks or holes and the like to generate crack defects when the spacecraft is impacted by space debris in the operation process. Atomic oxygen has a certain probability to enter the defects when impacting the surface of the material, so that the atomic oxygen contacts the high polymer material under the protective layer and reacts with the high polymer material to generate a basal etching cavity. With the expansion of the undercut cavity, the protective layer on the surface of the material even falls off, the area of the high polymer material exposed in the atomic oxygen environment is increased, and the influence of the material corrosion by atomic oxygen is enhanced. Therefore, matrix strengthening research on the space material is more prone to be carried out.
In recent years, Polyhedral Oligomeric Silsesquioxanes (POSS) have attracted attention in improving the atomic oxygen resistance of materials. POSS has a three-dimensional cage-shaped inorganic silica framework structure with high spatial symmetry and has the properties of inorganic nanoparticles and organic compounds. When the POSS-PI composite material is attacked by atomic oxygen, a SiO layer is formed on the surface2The Si-O bond in the protective layer can be destroyed only at 8eV, which is far greater than the corrosion capability of atomic oxygen, thereby effectively reducing the corrosion degree of atomic oxygen and further prolonging the service life of the spacecraft. For example, in domestic patents, POSS is introduced into a PMDA-ODA polyimide film to improve the atomic oxygen resistance of the material. In another method, the structure of the polyimide itself, such as a polyimide atomic oxygen resistant film with a phosphorus-containing structure, is improved, and the atomic oxygen resistance of the material is also improved to a certain extent. For example, a kind of phosphorus-containing intrinsic antigen oxygen PI thin film is disclosed in U.S. patent. However, neither the POSS modified PI thin film nor the intrinsic atomic oxygen resistant PI thin film can satisfy the application requirements of the spacecraft on the long-life atomic oxygen resistant thin film, and a new method and technology are required to be found.
Disclosure of Invention
The invention relates to a composite type atomic oxygen resistant polyimide film designed for solving the technical problems and a preparation method and application thereof. The composite atomic oxygen resisting polyimide film has double atomic oxygen resisting characteristics and excellent optical transparency, and can be widely applied to the outer surfaces of transparent aerospace devices in space.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a composite anti-atomic oxygen polyimide film comprises a resin solution and a composite film, wherein the resin solution is prepared by compounding an intrinsic anti-atomic oxygen PI polymer shown in a formula I and TSP-POSS shown in a formula II according to a proportion;
the mass percentage of the TSP-POSS in the total amount of the TSP-POSS/PI composite film is m%, wherein: m is more than 0 and less than or equal to 30.
The intrinsic antigen atomic oxygen PI polymer is a phosphorus-containing PI film, and is synthesized by 4, 4' - [ hexafluoroisopropylidene ] diphthalic anhydride [6FDA ] and 2, 5-bis { [ 4-aminophenoxy ] phenyl } diphenyl phosphine oxide [ BADPO ].
According to the preparation method of the composite type atomic oxygen resistant polyimide film, the composite film can be prepared according to the following steps:
the first step is as follows: dissolving diphenylphosphine oxide BADPO in an aprotic strong polar solvent, stirring to form a homogeneous solution, adding a anhydride monomer 6FDA, and reacting at 15-25 ℃ for 0.5-1 h to obtain a polyamide acid PAA solution;
the second step is that: adding toluene and isoquinoline into the polyamic acid PAA solution, heating to 180-200 ℃, and reacting for 20-25 hours to obtain a soluble PI solution;
the third step: precipitating the soluble PI solution into absolute ethyl alcohol to obtain PI resin, and separating, washing and drying the resin to obtain soluble PI resin, namely the compound and polyimide resin shown in the formula I;
the fourth step: dissolving 1-25 wt% of PI resin in an aprotic strong polar solvent to prepare a PI solution;
the fifth step: dissolving TSP-POSS with the weight percentage of 1-60% in an aprotic strong polar solvent to prepare TSP-POSS solution;
and a sixth step: mixing the PI solution prepared in the fourth step with the TSP-POSS solution prepared in the fifth step according to the ratio of 1: 1 to prepare a composite resin solution;
the seventh step: uniformly coating the prepared composite resin solution on a clean glass plate, placing the glass plate in a 100-grade clean program temperature control drying box, gradually heating and solidifying, and naturally cooling to room temperature; and (3) soaking the glass plate in deionized water, and stripping to obtain the PI composite film.
In the fourth step, the PI resin is dissolved in the aprotic strong polar solvent according to the weight percentage of 10-20% to prepare a PI solution.
In the fifth step, the TSP-POSS is dissolved in an aprotic strong polar solvent according to the weight percentage of 20-30% to prepare a TSP-POSS solution.
The preparation method of the composite type atomic oxygen resistant polyimide film comprises the step of mixing an aprotic strong polar solvent selected from N-methylpyrrolidone NMP, N-dimethylacetamide DMAc and N, N-dimethylformamide DMF according to any two or three of the N-methylpyrrolidone NMP, the N, N-dimethylacetamide DMAc and the N, N-dimethylformamide DMF according to any proportion.
In the sixth step, the mixing method of the PI solution and the TSP-POSS solution comprises a mechanical stirring method and an ultrasonic dispersion method.
In the sixth step, the mixing method of the PI solution and the TSP-POSS solution is a mechanical stirring method.
In the seventh step, the temperature is gradually raised for curing, and the composite resin solution is heated and cured according to the following procedures: 0.5h at 50 ℃; 3h at 80 ℃; 1h at 120 ℃; 1h at 150 ℃; 1h at 180 ℃; 1h at 250 ℃; the temperature is 300 ℃ for 1 h.
According to the application of the composite atomic oxygen resistant polyimide film, the polyimide composite film covers the outer surface of a transparent aerospace device exposed in the space, so that the atomic oxygen resistant performance of the composite atomic oxygen resistant polyimide film can be effectively improved.
The invention has the beneficial effects that: the film has the characteristic of dual atomic oxygen resistance, the PI substrate film has the characteristic of intrinsic atomic oxygen resistance because of containing phosphorus elements, and the composite film formed after the TSP-POSS is added has the characteristic of more obviously enhancing the atomic oxygen resistance. As TSP-POSS and PI matrix resin form molecular-level composite in an organic solvent, compared with the prior art, the dispersion can be more uniform, and the problem of performance reduction caused by agglomeration of filler particles is avoided. In addition, the composite film maintains the excellent optical transparency of the PI film substrate due to the molecular level recombination between the TSP-POSS and the PI substrate. The polyimide composite film disclosed by the invention covers the outer surface of a transparent aerospace device exposed in space, so that the atomic oxygen resistance of the polyimide composite film can be effectively improved, and the transparency of the polyimide composite film is not reduced basically.
Drawings
FIG. 1 is an infrared spectrum of composite films of examples 2 to 5 of the present invention and comparative example 1.
FIG. 2 is an infrared spectrum of the composite films of comparative examples 2 to 7.
FIG. 3 is a UV-Vis plot of the composite films of examples 1-5 and comparative example 1.
Fig. 4 is a UV-Vis graph of the composite films of comparative examples 2 to 7.
Detailed Description
The invention is further illustrated with reference to the following figures and examples.
The invention relates to a composite anti-atomic oxygen polyimide film, which is a resin solution prepared by compounding an intrinsic anti-atomic oxygen PI polymer shown in a formula I and TSP-POSS shown in a formula II according to a proportion and a composite film prepared by the resin solution;
the mass percentage of the TSP-POSS in the total amount of the TSP-POSS/PI composite film is m%, wherein: m is more than 0 and less than or equal to 30.
The intrinsic antigen atomic oxygen PI polymer is a phosphorus-containing PI film, and is synthesized by 4, 4' - [ hexafluoroisopropylidene ] diphthalic anhydride [6FDA ] and 2, 5-bis { [ 4-aminophenoxy ] phenyl } diphenyl phosphine oxide [ BADPO ].
According to the preparation method of the composite type atomic oxygen resistant polyimide film, the composite film can be prepared according to the following steps:
the first step is as follows: dissolving diphenylphosphine oxide BADPO in an aprotic strong polar solvent, stirring to form a homogeneous solution, adding a anhydride monomer 6FDA, and reacting at 15-25 ℃ for 0.5-1 h to obtain a polyamide acid PAA solution;
the second step is that: adding toluene and isoquinoline into the polyamic acid PAA solution, heating to 180-200 ℃, and reacting for 20-25 hours to obtain a soluble PI solution;
the third step: precipitating the soluble PI solution into absolute ethyl alcohol to obtain PI resin, and separating, washing and drying the resin to obtain soluble PI resin, namely the compound and polyimide resin shown in the formula I;
the fourth step: dissolving 1-25 wt% of PI resin in an aprotic strong polar solvent to prepare a PI solution;
the fifth step: dissolving TSP-POSS with the weight percentage of 1-60% in an aprotic strong polar solvent to prepare TSP-POSS solution;
and a sixth step: mixing the PI solution prepared in the fourth step with the TSP-POSS solution prepared in the fifth step according to the ratio of 1: 1 to prepare a composite resin solution;
the seventh step: uniformly coating the prepared composite resin solution on a clean glass plate, placing the glass plate in a 100-grade clean program temperature control drying box, gradually heating and solidifying, and naturally cooling to room temperature; and (3) soaking the glass plate in deionized water, and stripping to obtain the PI composite film.
In the fourth step, the PI resin is dissolved in the aprotic strong polar solvent according to the weight percentage of 10-20% to prepare a PI solution.
In the fifth step, the TSP-POSS is dissolved in an aprotic strong polar solvent according to the weight percentage of 20-30% to prepare a TSP-POSS solution.
The preparation method of the composite type atomic oxygen resistant polyimide film comprises the step of mixing an aprotic strong polar solvent selected from N-methylpyrrolidone NMP, N-dimethylacetamide DMAc and N, N-dimethylformamide DMF according to any two or three of the N-methylpyrrolidone NMP, the N, N-dimethylacetamide DMAc and the N, N-dimethylformamide DMF according to any proportion.
In the sixth step, the mixing method of the PI solution and the TSP-POSS solution comprises a mechanical stirring method and an ultrasonic dispersion method.
In the sixth step, the mixing method of the PI solution and the TSP-POSS solution is a mechanical stirring method.
In the seventh step, the temperature is gradually raised for curing, and the composite resin solution is heated and cured according to the following procedures: 0.5h at 50 ℃; 3h at 80 ℃; 1h at 120 ℃; 1h at 150 ℃; 1h at 180 ℃; 1h at 250 ℃; the temperature is 300 ℃ for 1 h.
According to the application of the composite atomic oxygen resistant polyimide film, the polyimide composite film covers the outer surface of a transparent aerospace device exposed in the space, so that the atomic oxygen resistant performance of the composite atomic oxygen resistant polyimide film can be effectively improved.
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The materials are commercially available from the open literature unless otherwise specified.
The performance evaluation method of the PI film obtained in the following examples is as follows:
fourier infrared spectrum:
the method is characterized in that a Tensor 27 type Fourier transform infrared spectrometer is adopted for measurement, a thin film method is adopted for sample preparation, and the measuring range is 4000-400 cm < -1 >.
Film transparency evaluation method:
ultraviolet visible spectrum (UV-Vis). The prepared PI film is tested in an ultraviolet spectrophotometer (Nippon Hitachi, U-3210) and the test wavelength range is 190-800 nm.
Evaluation method of atomic oxygen resistance:
the prepared PI film is tested by filament discharge plasma AO effect simulation equipment, and the atomic oxygen flux is 4.02 multiplied by 1020atom/cm2。
Example 1 TSP-POSS/PI composite film having 5 wt% TSP-POSS content (m ═ 5)
Dissolving 10g of PI resin in 37.1g of DMAc to prepare PI solution A; dissolving 0.5263g of TSP-POSS in 5g of DMAc to prepare TSP-POSS solution B; and fully mixing the solution A and the solution B under mechanical stirring, filtering, standing and defoaming to prepare a TSP-POSS/Pl composite resin solution with the solid content of 20 wt%, wherein the TSP-POSS content accounts for 5 wt% of the total weight of the TSP-POSS/PI composite film. The prepared solution is uniformly coated on a clean glass plate through an automatic coating machine, and is placed in a 100-level clean program temperature control drying box, and the temperature is raised and cured according to the following program: 50 ℃/0.5 h; 80 ℃/3 h; 120 ℃/1 h; 150 ℃/1 h; 180 ℃/1 h; 250 ℃ for 1 h. Naturally cooling to room temperature. And (3) soaking the glass plate in deionized water, and stripping to obtain the PI composite film.
The TSP-POSS/PI composite film with the TSP-POSS content of 5 wt% was obtained by using 2X 2cm2Samples of size were subjected to AO erosion simulation experiments at an atomic oxygen flux of 4.02X 1020atom/cm2When the amount of the catalyst is increased, the mass loss is 0.00032g, and the atomic oxygen etching rate is 0.14015X 10-24cm3/atom。
The ultraviolet transmission spectrum is shown in FIG. 3.
Specific data are shown in table 1.
Example 2 TSP-POSS/PI composite film having a TSP-POSS content of 10 wt.% (m 10)
Dissolving 10g of PI resin in 39.4g of DMAc to prepare PI solution A; dissolving TSP-POSS1.1111g in 5g of DMAc to prepare TSP-POSS solution B; and fully mixing the solution A and the solution B under mechanical stirring, filtering, standing and defoaming to prepare a TSP-POSS/PI composite resin solution with the solid content of 20 wt%, wherein the TSP-POSS content accounts for 10 wt% of the total weight of the TSP-POSS/Pl composite film. The prepared solution is uniformly coated on a clean glass plate through an automatic coating machine, and is placed in a 100-level clean program temperature control drying box, and the temperature is raised and cured according to the following program: 50 ℃/0.5 h; 80 ℃/3 h; 120 ℃/1 h; 150 ℃/1 h; 180 ℃/1 h; 250 ℃ for 1 h. Naturally cooling to room temperature. And (3) soaking the glass plate in deionized water, and stripping to obtain the PI composite film.
The TSP-POSS/PI composite film with the TSP-POSS content of 10 wt% was obtained by using 2X 2cm2Samples of size were subjected to AO erosion simulation experiments at an atomic oxygen flux of 4.02X 1020atom/cm2When the amount of the catalyst is increased, the mass loss is 0.00021g and the atomic oxygen etching rate is 0.09197X 10-24cm3/atom。
The infrared spectrum is shown in figure 1;
the ultraviolet transmission spectrum is shown in FIG. 3.
Specific data are shown in table 1.
Example 3 TSP-POSS/PI composite film having a TSP-POSS content of 15 wt.% (m 15)
Dissolving 10g of PI resin in 42.1g of DMAc to prepare PI solution A; dissolving TSP-POSS1.7647g in 5g DMAc to prepare TSP-POSS solution B; and fully mixing the solution A and the solution B under mechanical stirring, filtering, standing and defoaming to prepare a TSP-POSS/PI composite resin solution with the solid content of 20 wt%, wherein the TSP-POSS content accounts for 15 wt% of the total weight of the TSP-POSS/PI composite film. The prepared solution is uniformly coated on a clean glass plate through an automatic coating machine, and is placed in a 100-level clean program temperature control drying box, and the temperature is raised and cured according to the following program: 50 ℃/0.5 h; 80 ℃/3 h; 120 ℃/1 h; 150 ℃/1 h; 180 ℃/1 h; 250 ℃ for 1 h. Naturally cooling to room temperature. And (3) soaking the glass plate in deionized water, and stripping to obtain the PI composite film.
The TSP-POSS/PI composite film with the TSP-POSS content of 15 wt% was obtained by using 2X 2cm2Samples of size were subjected to AO erosion simulation experiments at an atomic oxygen flux of 4.02X 1020atom/cm2When the amount of the catalyst is increased, the mass loss is 0.00045g and the atomic oxygen etching rate is 0.19708X 10-24cm3/atom。
The infrared spectrum is shown in figure 1;
the ultraviolet transmission spectrum is shown in FIG. 3.
Specific data are shown in table 1.
Example 4 TSP-POSS/PI composite film having a TSP-POSS content of 20 wt.% (m ═ 20)
Dissolving 10g of PI resin in 40.0g of DMAc to prepare PI solution A; dissolving TSP-POSS2.5000g in 10g of DMAc to prepare TSP-POSS solution B; and fully mixing the solution A and the solution B under mechanical stirring, filtering, standing and defoaming to prepare a TSP-POSS/PI composite resin solution with the solid content of 20 wt%, wherein the TSP-POSS content accounts for 20 wt% of the total weight of the TSP-POSS/PI composite film. The prepared solution is uniformly coated on a clean glass plate through an automatic coating machine, and is placed in a 100-level clean program temperature control drying box, and the temperature is raised and cured according to the following program: 50 ℃/0.5 h; 80 ℃/3 h; 120 ℃/1 h; 150 ℃/1 h; 180 ℃/1 h; 250 ℃ for 1 h. Naturally cooling to room temperature. And (3) soaking the glass plate in deionized water, and stripping to obtain the PI composite film.
The TSP-POSS/PI composite film with the TSP-POSS content of 20 wt% is obtained by using 2 x 2cm2Samples of size were subjected to AO erosion simulation experiments at an atomic oxygen flux of 4.02X 1020atom/cm2When the amount of the catalyst is increased, the mass loss is 0.00019g and the atomic oxygen etching rate is 0.08321X 10-24cm3/atom。
The infrared spectrum is shown in figure 1;
the ultraviolet transmission spectrum is shown in FIG. 3.
Specific data are shown in table 1.
Example 5 TSP-POSS/PI composite film having a TSP-POSS content of 25 wt.% (m 25)
Dissolving 10g of PI resin in 43.3g of DMAc to prepare PI solution A; dissolving TSP-POSS3.3333g in 10g DMAc to prepare TSP-POSS solution B; and fully mixing the solution A and the solution B under mechanical stirring, filtering, standing and defoaming to prepare a TSP-POSS/PI composite resin solution with the solid content of 20 wt%, wherein the TSP-POSS content accounts for 25 wt% of the total weight of the TSP-POSS/PI composite film. The prepared solution is uniformly coated on a clean glass plate through an automatic coating machine, and is placed in a 100-level clean program temperature control drying box, and the temperature is raised and cured according to the following program: 50 ℃/0.5 h; 80 ℃/3 h; 120 ℃/1 h; 150 ℃/1 h; 180 ℃/1 h; 250 ℃ for 1 h. Naturally cooling to room temperature. And (3) soaking the glass plate in deionized water, and stripping to obtain the PI composite film.
The TSP-POSS/PI composite film with 25 wt% of TSP-POSS content was obtained by using 2X 2cm2The sample of size was subjected to an AO erosion simulation experiment,at an atomic oxygen flux of 4.02X 1020atom/cm2When the amount of the catalyst is small, the mass loss is 0.00007g, and the atomic oxygen etching rate is 0.03066X 10-24cm3/atom。
The infrared spectrum is shown in figure 1;
the ultraviolet transmission spectrum is shown in FIG. 3.
Specific data are shown in table 1.
Comparative example 1 pure PI film without TSP-POSS (m ═ 0)
10g of PI resin is dissolved in 40.0g of DMAc to prepare a PI resin solution with the solid content of 20 wt%. The prepared solution is uniformly coated on a clean glass plate through an automatic coating machine, and is placed in a 100-level clean program temperature control drying box, and the temperature is raised and cured according to the following program: 50 ℃/0.5 h; 80 ℃/3 h; 120 ℃/1 h; 150 ℃/1 h; 180 ℃/1 h; 250 ℃ for 1 h. Naturally cooling to room temperature. And (3) soaking the glass plate in deionized water, and stripping to obtain the PI composite film.
The obtained PI film was used at 2X 2cm2Samples of size were subjected to AO erosion simulation experiments at an atomic oxygen flux of 4.02X 1020atom/cm2When the amount of the catalyst is increased, the mass loss is 0.00122g, and the atomic oxygen etching rate is 0.53431X 10-24cm3/atom。
The infrared spectrum is shown in figure 1;
the ultraviolet transmission spectrum is shown in FIG. 3.
Specific data are shown in table 1.
Comparative example 2 Poly (pyromellitic dianhydride-diaminodiphenyl ether) (PMDA-ODA, Kapton type film)
Commercialization
Cutting into 2 × 2cm2Samples of size were subjected to AO erosion simulation experiments at an atomic oxygen flux of 4.02X 1020atom/cm2When the amount of the catalyst is increased, the mass loss is 0.00685g, and the atomic oxygen etching rate is 3.0X 10-24cm3/atom。
The infrared spectrum is shown in figure 2;
the ultraviolet transmission spectrum is shown in FIG. 4.
Specific data are shown in table 1.
Comparative example 3 TSP-POSS/Kapton composite film having TSP-POSS content of 5 wt%
Adding 5 wt% of TSP-POSS into a polyamic acid solution of PMDA-ODA, mechanically stirring the prepared solution for 0.5h, standing for defoaming, uniformly coating the solution on a clean glass plate through an automatic coating machine, placing the glass plate in a 100-grade clean program temperature control drying oven, and heating and curing according to the following program: 50 ℃/0.5 h; 80 ℃/3 h; 120 ℃/1 h; 150 ℃/1 h; 180 ℃/1 h; 250 ℃/1 h; 300 ℃/1 h. Naturally cooling to room temperature. And (3) soaking the glass plate in deionized water, and stripping to obtain the PI composite film.
The TSP-POSS/Kapton composite film with the TSP-POSS content of 5 wt% is obtained by using 2 x 2cm2Samples of size were subjected to AO erosion simulation experiments at an atomic oxygen flux of 4.02X 1020atom/cm2When the amount of the catalyst is increased, the mass loss is 0.00245g, and the atomic oxygen etching rate is 1.07299X 10-24cm3/atom。
The infrared spectrum is shown in figure 2;
the ultraviolet transmission spectrum is shown in FIG. 4.
Specific data are shown in table 1.
Comparative example 4 TSP-POSS/Kapton composite film having TSP-POSS content of 10 wt%
Adding 10 wt% of TSP-POSS into a polyamic acid solution of PMDA-ODA, mechanically stirring the prepared solution for 0.5h, standing for defoaming, uniformly coating the solution on a clean glass plate through an automatic coating machine, placing the glass plate in a 100-grade clean program temperature control drying oven, and heating and curing according to the following program: 50 ℃/0.5 h; 80 ℃/3 h; 120 ℃/1 h; 150 ℃/1 h; 180 ℃/1 h; 250 ℃/1 h; 300 ℃/1 h. Naturally cooling to room temperature. And (3) soaking the glass plate in deionized water, and stripping to obtain the PI composite film.
The TSP-POSS/Kapton composite film with the TSP-POSS content of 10 wt% is obtained by using 2 x 2cm2Samples of size were subjected to AO erosion simulation experiments at an atomic oxygen flux of 4.02X 1020atom/cm2When the amount of the catalyst is increased, the mass loss is 0.00126g, and the atomic oxygen etching rate is 0.55182X 10-24cm3/atom。
The infrared spectrum is shown in figure 2;
the ultraviolet transmission spectrum is shown in FIG. 4.
Specific data are shown in table 1.
Comparative example 5 TSP-POSS/Kapton composite film having TSP-POSS content of 15 wt%
Adding 15 wt% of TSP-POSS into a polyamic acid solution of PMDA-ODA, mechanically stirring the prepared solution for 0.5h, standing for defoaming, uniformly coating the solution on a clean glass plate through an automatic coating machine, placing the glass plate in a 100-grade clean program temperature control drying oven, and heating and curing according to the following program: 50 ℃/0.5 h; 80 ℃/3 h; 120 ℃/1 h; 150 ℃/1 h; 180 ℃/1 h; 250 ℃/1 h; 300 ℃/1 h. Naturally cooling to room temperature. And (3) soaking the glass plate in deionized water, and stripping to obtain the PI composite film.
The TSP-POSS/Kapton composite film with the TSP-POSS content of 15 wt% is obtained by using 2 x 2cm2Samples of size were subjected to AO erosion simulation experiments at an atomic oxygen flux of 4.02X 1020atom/cm2When the amount of the catalyst is increased, the mass loss is 0.00088g, and the atomic oxygen etching rate is 0.3854X 10-24cm3/atom。
The infrared spectrum is shown in figure 2;
the ultraviolet transmission spectrum is shown in FIG. 4.
Specific data are shown in table 1.
Comparative example 6 TSP-POSS/Kapton composite film having TSP-POSS content of 20 wt%
Adding 20 wt% of TSP-POSS into a polyamic acid solution of PMDA-ODA, mechanically stirring the prepared solution for 0.5h, standing for defoaming, uniformly coating the solution on a clean glass plate through an automatic coating machine, placing the glass plate in a 100-grade clean program temperature control drying oven, and heating and curing according to the following program: 50 ℃/0.5 h; 80 ℃/3 h; 120 ℃/1 h; 150 ℃/1 h; 180 ℃/1 h; 250 ℃/1 h; 300 ℃/1 h. Naturally cooling to room temperature. And (3) soaking the glass plate in deionized water, and stripping to obtain the PI composite film.
The TSP-POSS/Kapton composite film with the TSP-POSS content of 20 wt% is obtained by using 2 x 2cm2Sample size to carry out AO etching dieTo be tested, at an atomic oxygen flux of 4.02X 1020atom/cm2When the amount of the catalyst is increased, the mass loss is 0.00062g, and the atomic oxygen etching rate is 0.27153X 10-24cm3/atom。
The infrared spectrum is shown in figure 2;
the ultraviolet transmission spectrum is shown in FIG. 4.
Specific data are shown in table 1.
Comparative example 7 TSP-POSS/Kapton composite film having TSP-POSS content of 25 wt%
Adding 25 wt% of TSP-POSS into a polyamic acid solution of PMDA-ODA, uniformly coating the prepared solution on a clean glass plate through an automatic coating machine, placing the glass plate in a 100-grade clean program temperature control drying box, and heating and curing according to the following program: 50 ℃/0.5 h; 80 ℃/3 h; 120 ℃/1 h; 150 ℃/1 h; 180 ℃/1 h; 250 ℃/1 h; 300 ℃/1 h. Naturally cooling to room temperature. And (3) soaking the glass plate in deionized water, and stripping to obtain the PI film.
The obtained POSS/Kapton composite film with TSP-POSS content of 25 wt% uses 2X 2cm2Samples of size were subjected to AO erosion simulation experiments at an atomic oxygen flux of 4.02X 1020atom/cm2When the amount of the catalyst is increased, the mass loss is 0.00049g and the atomic oxygen etching rate is 0.2146X 10-24cm3/atom。
The infrared spectrum is shown in figure 2;
the ultraviolet transmission spectrum is shown in FIG. 4.
Specific data are shown in table 1.
TABLE 1 Properties of TSP-POSS/Kapton composite films
As can be seen by comparing the data shown in Table 1, the atomic oxygen resistance of the TSP-POSS/PI composite films obtained by adding the TSP-POSS in the examples 1 to 5 is remarkably improved, wherein the atomic oxygen erosion rate of the film prepared in the example 5 is lowest, namely the atomic oxygen resistance is best, and the dual atomic oxygen protection process provided by the invention has good implementationAnd (5) effect. The light transmittance of the films of comparative examples 1-5 can show that the introduction of TSP-POSS has no significant influence on the transparency of the composite film, and the molecular-level recombination is realized. The PI film of comparative example 1 without TSP-POSS exhibited intrinsic atomic oxygen behavior with atomic oxygen etch rate comparable to that of comparative example 2
The atomic oxygen corrosion rate of the film is only one fifth of that of the film. Comparative examples 3 to 7, i.e. in the absence of atomic oxygen
After TSP-POSS is added into the base material, the atomic oxygen resistance of the composite film is also improved, but the implementation effect is weaker than that of the composite film in the examples 1-5. Therefore, the TSP-POSS/PI composite film provided by the invention has excellent atomic oxygen resistance and optical transparency, and is a film with excellent performance in the aspect of aerospace application.
The present invention is not limited to the above-mentioned preferred embodiments, and any other products similar or identical to the present invention, which can be obtained by anyone based on the teaching of the present invention, fall within the protection scope of the present invention.
Claims (3)
1. A composite atomic oxygen resistant polyimide film is characterized in that: the preparation method comprises the following steps of compounding an intrinsic antigen oxygen PI polymer shown as a formula I and TSP-POSS shown as a formula II according to a ratio to form a resin solution and preparing a composite film from the resin solution;
the mass percentage of the TSP-POSS in the total amount of the TSP-POSS/PI composite film is m%, wherein: and m is 5.
2. The composite antigenic oxy polyimide film of claim 1, wherein: the intrinsic antigen oxygen PI polymer is a phosphorus-containing PI film, and is synthesized by 4, 4' - [ hexafluoroisopropylidene ] diphthalic anhydride and 2, 5-bis { [ 4-aminophenoxy ] phenyl } diphenyl phosphine oxide.
3. The use of the composite antigenic seed oxygen polyimide film according to claim 1 or 2, wherein: the polyimide composite film covers the outer surface of the transparent aerospace equipment exposed in the outer space, so that the atomic oxygen resistance of the polyimide composite film can be effectively improved.
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| CN101531678A (en) * | 2009-04-22 | 2009-09-16 | 中国科学院化学研究所 | Phosphine-containing aromatic diamine compound, preparation method and application thereof |
| CN103435827A (en) * | 2013-08-29 | 2013-12-11 | 西北工业大学 | Preparation method of aerospace hyperbranched polysiloxane polyimide transparent hybrid thin films |
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| CN102731809A (en) * | 2012-06-04 | 2012-10-17 | 西北工业大学 | Preparation method of atomic oxygen-resistant polyimide hybrid films containing POSS (polyhedral oligomeric silsesquioxanes) structures |
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| CN101531678A (en) * | 2009-04-22 | 2009-09-16 | 中国科学院化学研究所 | Phosphine-containing aromatic diamine compound, preparation method and application thereof |
| CN103435827A (en) * | 2013-08-29 | 2013-12-11 | 西北工业大学 | Preparation method of aerospace hyperbranched polysiloxane polyimide transparent hybrid thin films |
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