CN112646220B - Atomic oxygen prevention polyimide composite film and preparation method thereof - Google Patents

Atomic oxygen prevention polyimide composite film and preparation method thereof Download PDF

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CN112646220B
CN112646220B CN202010436176.7A CN202010436176A CN112646220B CN 112646220 B CN112646220 B CN 112646220B CN 202010436176 A CN202010436176 A CN 202010436176A CN 112646220 B CN112646220 B CN 112646220B
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polyamic acid
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atomic oxygen
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polyimide
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徐阳
齐振一
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Shanghai Institute of Ceramics of CAS
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Abstract

The invention relates to an atomic oxygen prevention polyimide composite film and a preparation method thereof, wherein the preparation method of the atomic oxygen prevention polyimide film comprises the following steps: (1) coating a polyamic acid resin solution on the surface of a bearing body to obtain a polyamic acid liquid film, drying at 60-220 ℃ for 1-20 minutes, and then stripping from the bearing body to obtain a polyamic acid gel film; (2) coating a solution of polyamic acid/polysiloxane block copolymer on at least one side of the polyamic acid gel film, and drying at 50-100 ℃ for 10-180 seconds to form a transition layer on at least one side of the polyamic acid gel film; (3) continuously coating a self-crosslinking trapezoidal polysilsesquioxane solution on the surface of the transition layer, and drying at 60-120 ℃ for 10-120 seconds to obtain a multilayer composite film; (4) and carrying out multi-stage drying treatment on the obtained multilayer composite film in a clamping state to obtain the anti-atomic oxygen polyimide film.

Description

Atomic oxygen prevention polyimide composite film and preparation method thereof
Technical Field
The invention relates to an atomic oxygen prevention coating and an integrated forming method thereof, in particular to a polyimide-based atomic oxygen prevention composite film and a preparation method thereof, and belongs to the field of film preparation.
Background
Polyimide (PI) is excellent in tensile strength, thermal stability, insulation properties, and resistance to spatial irradiation, and is widely used for flexible thermal control materials for spacecraft, substrates for flexible solar cell arrays, and the like. However, when the polyimide film is applied to a low-earth orbit, the polyimide film is severely corroded by Atomic Oxygen (AO), and the optical, thermal and mechanical properties of the material are rapidly attenuated due to the loss of quality, so that the service life of the film is greatly limited. Therefore, improving the atomic oxygen resistance of polyimide films has been an important research topic at home and abroad.
The improvement of the atomic oxygen resistance of the polyimide film is mainly realized by introducing atomic oxygen resistant molecules, molecular chains or aggregates into the interior (bulk modification) or the surface (surface modification) of the polyimide. The surface modification is to add a protective layer on the surface of a commercial polyimide film, and the mechanical property of the film is hardly changed. However, the polyimide film is insoluble, infusible and chemically resistant (except for strong alkali), so that the interface between the protective surface layer and the polyimide substrate is sharp and is difficult to form stable physical or chemical interaction, the protective layer has low adhesive force on the surface of the polyimide film and is easy to peel off, or the protective layer is easy to crack or peel off due to the existence of interface stress in space environments such as cold-heat cycle, atomic oxygen corrosion, particle irradiation and the like, and further atomic oxygen undercut occurs.
Disclosure of Invention
In order to solve the problems, the invention provides an atomic oxygen resistant polyimide film and an integrated forming method thereof.
In one aspect, the invention provides a method for preparing an atomic oxygen resistant polyimide film, comprising the following steps:
(1) coating the polyamic acid resin solution on the surface of a bearing body to obtain a polyamic acid liquid film, and then drying the polyamic acid liquid film for 1-20 minutes at the temperature of 60-220 ℃ to obtain a polyamic acid gel film;
(2) coating a polyamic acid/polysiloxane block copolymer on at least one side of a polyamic acid gel film, and drying at 50-100 ℃ for 10-180 seconds to form a transition layer on at least one side of the polyamic acid gel film;
(3) continuously coating a self-crosslinking trapezoidal polysilsesquioxane solution on the surface of the transition layer, and drying at 60-120 ℃ for 10-120 seconds to obtain a multilayer composite film;
(4) carrying out multi-stage drying treatment on the obtained multilayer composite film in a clamping state to obtain the atomic oxygen resistant polyimide film; the temperature gradient of the multi-stage drying treatment is distributed between 120 ℃ and 400 ℃, and the drying time of each stage is 30 seconds to 120 seconds.
In the invention, the preparation of the atomic oxygen prevention layer is carried out when the molecular chain of the polyimide film in the initial stage of forming (polyamide acid gel film) still has solubility, and meanwhile, the special polyamide acid/polysiloxane block copolymer is adopted as the transition layer between the polyimide substrate and the atomic oxygen prevention surface layer, so that the interface compatibility is improved, and the problem of mismatching of the thermal expansion coefficients of the substrate and the surface layer is solved.
Preferably, the solid content of the polyamic acid resin solution is 10-30 wt%; the thickness of the polyamic acid liquid film coated on the bearing body is 20-500 mu m.
Preferably, the preparation method of the polyamic acid/polysiloxane block copolymer comprises the following steps:
(1) dissolving a diamine monomer in a mixed solvent, adding at least two batches of a first dianhydride monomer in the stirring process, and reacting for 2-3 hours at room temperature;
(2) continuously adding amino double-end-sealed polysiloxane, stirring for 1-2 hours, adding a second part of dianhydride monomer, and reacting at room temperature for 6-12 hours to obtain the polyamic acid/polysiloxane segmented copolymer solution;
the structural formula of the amino double-terminated polysiloxane is as follows:
Figure BDA0002502358350000021
r is an active group, preferably at least one of vinyl, acryloyloxyalkyl, methacryloyloxyalkyl, alkynyl, phenylethynyl and alkynylphenyl;
t is an inert group, preferably at least one of methyl, ethyl, propyl, isopropyl and phenyl;
and a and b are statistical averages of two kinds of repeating units, wherein a + b is 10-500, and b/(a + b) is 5-40%.
In addition, the molar ratio of the total diamine to the total dianhydride is preferably 100 (101-103), the total diamine comprises a diamine monomer and amino double-end-capped polysiloxane, and the total dianhydride comprises a first part and a second part of dianhydride monomer; the first part of dianhydride accounts for 50-80 mol% of the total molar amount of diamine monomers.
Further, preferably, the mixed solvent includes at least one of dioxane or tetrahydrofuran, and at least one of dimethylacetamide, dimethylformamide or N-methylpyrrolidone.
In addition, the solid content of the polyamic acid/polysiloxane block copolymer is preferably 5-30 wt%, and the polysiloxane in the block copolymer accounts for 10-50 wt%.
Also, it is preferable that the polyamic acid/polysiloxane block copolymer has a wet coating amount of 1 to 50g/m2。
Preferably, the self-crosslinking trapezoid polysilsesquioxane solution has a solid content of 10-70 wt% and a wet coating amount of 1-20 g/m2。
Preferably, the structural formula of the self-crosslinking ladder-shaped polysilsesquioxane is as follows:
Figure BDA0002502358350000031
wherein R is1、R2……RnIndependently selected from active functional groups or/and inert functional groups, and n is an even number of 50-1000; the active functional group is selected from at least one of vinyl, allyl, methacryloxypropyl, acryloxypropyl, methacryloxymethyl, ethynyl, phenylethynyl and maleimide propyl; the inert functional group is at least one selected from methyl, phenyl, propyl, butyl, isobutyl, hexyl, cyclohexyl and cyclopentyl1～T4Independently selected from hydrogen and/or Si (CH)3)2A silicon group of the structure Y, wherein Y is R1～RnOne of the groups; preferably, R1、R2……RnThe content of the medium active functional groups is 5-60%, and more preferably 10-40%.
In another aspect, the present invention also provides an atomic oxygen resistant polyimide composite film prepared according to the above preparation method, comprising: the composite material comprises a polyimide substrate, and a polyimide/polysiloxane block copolymer transition layer and a cross-linked trapezoidal polysilsesquioxane atomic oxygen protective layer which are sequentially formed on the surface of the polyimide substrate.
Compared with the prior polyimide film atomic oxygen prevention surface modification technology, the invention has the following advantages:
(1) the integrated forming process provided by the invention is used for preparing the transition layer and the protective surface layer when the polyimide base film is still in a gel/solution state, and solves the problem of poor binding force between the atomic oxygen protective surface layer and the polyimide base material by utilizing the physical entanglement and chemical bonding of polymer chains at an interface;
(2) the anti-atomic oxygen polyimide film prepared by the invention has good flexibility and high and low temperature cycle resistance, and maintains the mechanical property of the polyimide substrate;
(3) the thickness of the film layer is controllable, and the atomic oxygen protective surface layer has a compact structure and no crack defect;
(4) the integrated molding process provided by the invention has strong universality and is suitable for the integrated preparation of almost all soluble atomic oxygen protective materials and polyimide films;
(5) the integrated forming process provided by the invention is simple, compact in process, high in efficiency and suitable for continuous production.
Drawings
FIG. 1 is a photograph showing the bending state of the atomic oxygen resistant polyimide film obtained in example 1, and it can be seen that the integrated composite film was repeatedly wound on a cylinder having a diameter of 8mm 100 times without any peeling of the film layer, and had good flexibility and firm bonding of the film layer;
FIG. 2 is an electron micrograph of the atomic oxygen resistant polyimide film obtained in example 1, from which it can be seen that the integrated composite film has a smooth and dense surface without any scratch or crack;
FIG. 3 is an EDS chart of the surface of the atomic oxygen prevention polyimide film obtained in example 1, from which it can be seen that the protective surface layer comprises three elements of carbon, oxygen and silicon, wherein the silicon element accounts for 10.16 atom%, and the nitrogen element contained in the transition layer is not detected at this time, which indicates that the protective surface layer has a certain thickness;
FIG. 4 is a photograph showing the appearance of the composite film (only comprising the polyimide base layer and the protective surface layer) obtained in comparative example 3, from which it is clearly seen that the protective surface layer is not well bonded to the polyimide base layer, and the protective surface layer is seriously warped and has an orange peel shape;
FIG. 5 is a flow chart of the process for integrally forming the atomic oxygen resistant polyimide film of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In order to solve the problems of sharp interface, poor firmness and weak cold and hot alternation resistance of the existing polyimide film and an atomic oxygen protective surface layer, the invention provides a novel forming process.
The integrated molding method of the polyimide film and the atomic oxygen protective layer comprises a polymer solution preparation and integrated molding process.
Preparing a polymer solution.
Preparation of polyamic acid resin solution. Under the stirring condition, diamine is dissolved in an organic solvent, dianhydride monomer is added in batches (at least twice), and stirring is continued for 3-12 hours at room temperature (15-30 ℃) to obtain polyamic acid resin solution. The solid content of the obtained polyamic acid resin solution can be 10-25 wt%. Wherein the diamine is at least one of 4,4 '-diaminodiphenyl ether (4,4' -ODA), p-phenylenediamine (p-PDA), m-phenylenediamine (m-PDA), 2-bis [4- (4-aminophenoxy) phenyl ] propane (BAPP), 3 '-diaminodiphenyl ether (3,3' -ODA), or 1, 3-bis (4-aminophenoxy) benzene (TPER). The dianhydride may be at least one of pyromellitic dianhydride (PMDA), 2,3',3,4' -biphenyltetracarboxylic dianhydride (a-BPDA), 3',4,4' -biphenyltetracarboxylic dianhydride (s-BPDA), 4,4 '-oxydiphthalic anhydride (ODPA), 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (6FDA), 4,4'- (4,4' isopropyldiphenoxy) bis (phthalic anhydride) (BPADA), or 3,3',4,4' -diphenylsulfone tetracarboxylic dianhydride (DSDA). The organic solvent may be dimethylacetamide, dimethylformamide, N-methylpyrrolidone, or a mixture thereof. The molar ratio of diamine to dianhydride can be 100: 99-101.
Preparation of polyamic acid/polysiloxane block copolymer solution. Weighing diamine monomers, dissolving the diamine monomers in a mixed solvent, slowly adding a first part of dianhydride monomers in two batches under a stirring state, and reacting for 2-3 hours at room temperature (15-30 ℃). And then adding amino double-end-blocked polysiloxane and stirring for 1-2 hours, then adding a second part of dianhydride monomer at one time, and reacting for 6-12 hours at room temperature) to obtain a polyamic acid/polysiloxane block copolymer solution, wherein the solid content is 5-30 wt%, and the mass fraction of polysiloxane in the copolymer is 10-50 wt%. The molar ratio of the total diamine to the total dianhydride is 100 (101-103), the total diamine comprises a diamine monomer and amino double-end-capped polysiloxane, and the total dianhydride comprises a first part and a second part of dianhydride monomer; the first part of dianhydride monomer accounts for 50-80 mol% of the total molar amount of the diamine monomer. The structural formula of the amino double-end-blocked polysiloxane is shown as II:
Figure BDA0002502358350000051
r is an active group, including: vinyl, acryloxyalkyl, alkynyl, and the like; t is an inert group comprising: alkyl groups such as methyl, ethyl, propyl, and phenyl; and a and b are statistical averages of two kinds of repeating units, wherein a + b is 10-500, and b/(a + b) is 5-40%. The mixed solvent comprises at least one of dioxane or tetrahydrofuran and at least one of dimethylacetamide, dimethylformamide or N-methylpyrrolidone.
And preparing a self-crosslinking ladder-shaped polysilsesquioxane solution. Dissolving the self-crosslinking trapezoidal polysilsesquioxane in an organic solvent, and stirring overnight to obtain a self-crosslinking trapezoidal polysilsesquioxane solution, wherein the solid content can be 10-70 wt%. The organic solvent can be dimethylacetamide, dimethylformamide, N-methylpyrrolidone, dioxane, tetrahydrofuran, or a mixture of at least any two thereof. The structural formula of the self-crosslinking ladder-shaped polysilsesquioxane is shown as I:
Figure BDA0002502358350000052
R1、R2……Rnindependently selected from reactive functional groups (including vinyl, allyl, methacryloxypropyl, acryloxypropyl, methacryloxymethyl, ethynyl, phenylethynyl, maleimidopropyl) and inert functional groups (including methyl, phenyl, propyl, butyl, isobutyl, hexyl, cyclohexyl, cyclopentyl). T is1～T4Independently selected from hydrogen and/or Si (CH)3)2A silicon group of the structure Y, wherein Y is R1～RnOne of the groups. R1、R2……RnThe number of the medium active functional groups accounts for 5-60%, preferably 10-40%; n is an even number of 50 to 1000.
In one embodiment of the present invention, a method for preparing self-crosslinking ladder polysilsesquioxane comprises: (1) selecting and mixing at least two silane monomers to obtain a silane mixed solution; (2) adding an organic solvent into an alkali metal salt aqueous solution to obtain a catalyst solution, wherein the alkali metal salt is carbonate or/and bicarbonate, preferably at least one selected from sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate; (3) dripping the silane mixed solution into a catalyst solution, and stirring and reacting for 1-4 days at 20-30 ℃ to obtain a viscous solution; (4) and diluting, washing and drying the obtained viscous solution to obtain the self-crosslinking ladder-shaped polysilsesquioxane. The silane monomer is selected from trimethoxy silane containing a reactive functional group or/and an inert functional group, or/and triethoxy silane containing a reactive functional group or/and an inert functional group. The active functional group is selected from at least one of vinyl, allyl, methacryloxypropyl, acryloxypropyl, methacryloxymethyl, ethynyl, phenylethynyl and maleimide propyl; the inert functional group is selected from at least one of methyl, phenyl, propyl, butyl, isobutyl, hexyl, cyclohexyl and cyclopentyl. The water in the metal salt aqueous solution is 3-10 times of the total mole number of the silane monomers, and the alkali metal salt is 1-20 per mill of the total mole number of the silane monomers. The metal salt aqueous solution contains alcohol, and the addition amount of the alcohol is 0-5 mol% of water. The organic solvent is at least one selected from toluene, dioxane, tetrahydrofuran, dimethylformamide, dimethylacetamide and dimethyl sulfoxide; the dosage of the organic solvent is such that the mole number of the silane monomer/volume of the organic solvent is within the range of 1-20 mol/L. The dropping rate of the silane mixed liquid is 0.1-50 mL/min.
The integrated forming process of the atomic oxygen resistant polyimide film mainly comprises the following steps: before the polyimide film is formed (or a polyamic acid gel film), the transition layer and the atomic oxygen protective layer are directly superposed, the high molecular solution is mutually permeated at the interface of the film layer, and the high molecular chains between the layers are mutually entangled, so that the interface bonding force is enhanced. At the same time, the use of block copolymers of specific composition further promotes the interpenetration of the macromolecular solutions at the interface.
Referring to fig. 5, the following is an exemplary description of the integrated molding process of the atomic oxygen resistant polyimide film.
The polyamic acid resin solution is cast on a carrier (such as a clean steel belt) to obtain a polyamic acid liquid film with a thickness of 20-500 μm. And then drying the polyamide acid gel film for 1-20 min in a drying tunnel 1 at the temperature of 60-220 ℃ to obtain a polyamide acid gel film with low imidization degree, and stripping the polyamide acid gel film from a steel belt for later use. The polyamic acid gel film is cured in a subsequent multi-stage drying treatment to form a polyimide substrate, and the thickness of the polyimide substrate is about 2-150 μm.
In polyamic acid gelCoating the polyamide acid/polysiloxane block copolymer solution on one side or two sides of the film, and drying for 10-180 seconds through a drying tunnel 2 at 50-100 ℃ to obtain the transition layer. The wet coating amount of the polyamic acid/polysiloxane block copolymer solution on each side can be controlled within 1-50 g/m2. The polyamic acid/polysiloxane block copolymer solution forms a transition layer connecting the polyimide substrate and the atomic oxygen protective layer after multi-stage drying treatment, and the thickness of the transition layer can be 50 nm-15 μm.
And coating a self-crosslinking trapezoidal polysilsesquioxane solution (a protective surface layer) on the transition layer, and drying at the temperature of 60-120 ℃ for 10-120 s to obtain the multilayer composite film. The wet coating amount of the self-crosslinking trapezoidal polysilsesquioxane solution on each surface is 1-20 g/m2. The thickness of the atomic oxygen protective layer formed by the self-crosslinking ladder-shaped polysilsesquioxane solution after multi-stage drying treatment can be 100 nm-14 mu m.
And carrying out multi-stage drying treatment on the multilayer composite film in a clamping state to obtain the anti-atomic oxygen polyimide film. Here, the temperature gradient of the multi-stage drying treatment is distributed between 120 and 400 ℃, and the drying time of each stage is 30 to 120 seconds. For example, the polyimide composite film (namely the anti-atomic oxygen polyimide film) with single or double surfaces resistant to atomic oxygen is obtained by sequentially passing through a drying tunnel 3 with the temperature of 120 ℃/160 ℃/200 ℃/280 ℃/350 ℃/400 ℃/200 ℃ and the retention time of each section is 30-120 s.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Preparation of self-crosslinking ladder polysilsesquioxane:
weighing 841.3g of phenyltriethoxysilane and393.6g of methacryloxymethyltriethoxysilane were mixed for use. Taking 316ml of deionized water, 25ml of ethanol and KHCO34.00g in a reaction flask protected by nitrogen, stirring for 10min to KHCO3Completely dissolving; adding 250ml of dioxane and 250ml of tetrahydrofuran, and stirring for 20 min; then dropwise adding a silane mixed solution while stirring, wherein the dropping speed is 10ml/min, and the temperature of the solution is controlled to be 20-30 ℃; after the dropwise addition, the reaction was stirred for two days. Adding 500ml of n-hexane into the viscous reaction solution, oscillating with 300ml of deionized water, standing to remove water phase liquid, repeatedly washing for 3 times, and evaporating under reduced pressure to remove the organic solvent to obtain 625.46g of self-crosslinking trapezoidal polysilsesquioxane with the yield of 92%, wherein R1～nThe radicals containing both phenyl and methacryloxymethyl radicals, T1～T4Is hydrogen.
Example 1
1) Adding 80kg of Dimethylacetamide (DMAC) solvent and 9.57kg of 4,4' -diaminodiphenyl ether (ODA) into a dry reaction kettle, stirring until the ODA is completely dissolved, sequentially and slowly adding 5kg, 3kg, 2kg and 0.43kg of pyromellitic dianhydride (PMDA) at the interval of 1 hour every time, and continuously stirring for 8 hours at room temperature to obtain polyamide acid resin (base material solution) with the solid content of 20%;
2) weighing 518 g of 4,4' -diaminodiphenyl ether (ODA) and dissolving in a mixed solvent consisting of 2.63kg of dioxane and 3.95kg of Dimethylacetamide (DMAC), weighing 367 g of pyromellitic dianhydride (PMDA) and adding into the solution in two times, and stirring at room temperature for 2 hours; continuously adding 500 g of amino double-end-blocked polysiloxane (wherein R is vinyl, T is methyl, a is 10.3, and b is 3.2), stirring for 1 hour, slowly adding 295.4 g of PMDA, and stirring overnight at room temperature to obtain a polyamic acid/polysiloxane block copolymer solution (transition layer solution) with 20 wt% of solid content, wherein the mass fraction of polysiloxane in the copolymer molecule is 30%;
3) 500 grams of self-crosslinking ladder polysilsesquioxane (where, R is1～nThe groups comprise phenyl and methacryloxymethyl, the methacryloxymethyl accounts for about 30mol percent, and n is about 400) is dissolved in a mixed solution consisting of 250 g of dioxane and 250 g of DMAC to obtain the self-crosslinking trapezoid with the solid content of 50 weight percentPolysilsesquioxane solution (overcoat solution);
4) casting a liquid film of the substrate solution with the thickness of about 250 mu m on a clean steel belt, drying the liquid film for 10min through a drying tunnel at the temperature of 130 ℃, and then stripping a polyamic acid gel film from the steel belt;
5) coating a transition layer solution on one surface of the polyamic acid gel film, wherein the wet coating amount is controlled to be about 10g/m2Drying at 80 deg.C for 80 s;
6) continuing to apply the protective layer solution on the transition layer, and controlling the wet coating amount to about 10g/m2Drying at 90 deg.C for 60 s;
7) the multilayer composite film passes through a drying channel with the temperature of 120 ℃/160 ℃/200 ℃/240 ℃/280 ℃/320 ℃/200 ℃ under the clamping state, the retention time of each section is 90s, the single-side atomic oxygen-proof polyimide composite film is obtained, and the total thickness is about 36 mu m. Wherein the thickness of the base material is about 30 μm, the thickness of the transition layer is about 1.5 μm, and the thickness of the atomic oxygen prevention layer is about 4.5 μm.
Example 2
The preparation process of the method for preparing the atomic oxygen resistant polyimide film in the embodiment 2 is referred to as the embodiment 1, and the difference is only that: the wet coating amount of the transition layer in the step 5) is about 50g/m2The coating weight of the atomic oxygen protective layer in the step 6) is about 20g/m2. In the obtained atomic oxygen prevention polyimide film, the thickness of the base material is about 30 μm, the thickness of the transition layer is about 7.5 μm, and the thickness of the atomic oxygen prevention layer is about 9 μm.
Comparative example 1
The method for preparing the thin film in this comparative example 1 includes steps 1), 4) and 7) in example 1. Wherein, the thickness of the substrate solution salivation in the step 4) is about 300 μm. The finished film is a single-layer structure and only comprises a polyimide substrate, and the thickness of the finished film is about 36 mu m.
Comparative example 2
The method for preparing the thin film in this comparative example 2 includes the steps 1), 2), 4), 5), and 7) of example 1. Wherein the thickness of the substrate solution salivation in the step 4) is about 200 μm, and the wet coating amount of the transition layer in the step 5) is about 100g/m2. The resulting finished film was a two-layer structure comprising only the polyimide substrate and the transition layer, with a total thickness of about 39 μm. Wherein the thickness of the substrate is about 24 μmThe thickness of the transition layer is about 15 μm.
Comparative example 3
The method for preparing the thin film in this comparative example 3 includes the steps 1), 3), 4), 6), and 7) of example 1. Wherein the thickness of the salivation of the base material solution in the step 4) is about 250 mu m, and the coating weight of the atomic oxygen protective layer in the step 6) is about 20g/m2. The obtained film finished product is of a two-layer structure, only comprises a polyimide substrate and an atomic oxygen protective layer, and has the total thickness of about 39 mu m. Wherein the thickness of the substrate is about 30 μm, and the thickness of the atomic oxygen protective layer is about 9 μm.
The film products obtained in example 1, example 2, comparative example 1, comparative example 2 and comparative example 3 were subjected to high and low temperature alternation test (100 cycles at + -100 ℃), and the silicon content on the film surface before and after high and low temperature was analyzed by EDS, see table 1. The silicon content on the surface of the film is almost unchanged before and after the high and low temperature tests in example 1 and comparative example 2, which shows that the integrally formed composite film using the copolymer as the transition layer has strong interlayer bonding force. Comparative example 3 contains no copolymer transition layer, and the film layer was peeled off severely after high and low temperatures, with a surface silicon content of only 0.16 atom%.
Table 1:
surface silicon content (atom%) High and low temperature rear surface silicon content (atom%)
Example 1 10.16 10.59
Example 2 10.28 10.38
Comparative example 1 0 0
Comparative example 2 2.77 2.85
Comparative example 3 10.23 0.16
The film products obtained in example 1, example 2, comparative example 1, comparative example 2 and comparative example 3 were subjected to an atomic oxygen etching test, respectively, and the beam current density was 5.0X 1015atoms/(cm2S), cumulative flux 5.04X 1020atoms/cm2The results are shown in Table 2.
Table 2:
mass loss (mg) Atomic oxygen erosion Rate (cm)3/atom)
Example 1 0.19 6.79×10-26
Example 2 0.20 7.14×10-26
Comparative example 1 8.59 3.00×10-24
Comparative example 2 0.66 2.31×10-25
Comparative example 3 - -
. As is clear from Table 2, the atomic oxygen corrosion ratios of the atomic oxygen resistant polyimide films (examples 1 and 2) having the transition layer were 6.79 to 7.14X 10-26cm3The erosion rate was two orders of magnitude less than that of the polyimide substrate (comparative example 1). Comparative example 2 without protective surface layer but transition layer contains silicon, oxygen element, its atomic oxygen erosion rate is an order of magnitude less than polyimide substrate (comparative example 1), possess certain atomic oxygen resistance ability. Comparative example 3 the atomic oxygen resistant skin cracked and peeled severely due to the absence of the transition layer, and the mass loss data was not valid.

Claims (11)

1. A preparation method of an atomic oxygen prevention polyimide film is characterized by comprising the following steps:
(1) coating a polyamic acid resin solution on the surface of a bearing body to obtain a polyamic acid liquid film, drying at 60-220 ℃ for 1-20 minutes, and then stripping from the bearing body to obtain a polyamic acid gel film;
(2) coating a solution of polyamic acid/polysiloxane block copolymer on at least one side of the polyamic acid gel film, and drying at 50-100 ℃ for 10-180 seconds to form a transition layer on at least one side of the polyamic acid gel film;
(3) continuously coating a self-crosslinking trapezoidal polysilsesquioxane solution on the surface of the transition layer, and drying at 60-120 ℃ for 10-120 seconds to obtain a multilayer composite film;
(4) carrying out multi-stage drying treatment on the obtained multilayer composite film in a clamping state to obtain the atomic oxygen resistant polyimide film; the temperature gradient of the multi-stage drying treatment is distributed between 120 ℃ and 400 ℃, and the drying time of each stage is 30 seconds to 120 seconds.
2. The method according to claim 1, wherein the polyamic acid resin solution has a solid content of 10 to 30 wt%; the thickness of the polyamic acid liquid film is 20-500 μm.
3. The method according to claim 1, wherein the polyamic acid/polysiloxane block copolymer solution is prepared by a method comprising:
(1) dissolving a diamine monomer in a mixed solvent, adding at least two batches of a first dianhydride monomer in the stirring process, and reacting for 2-3 hours at room temperature;
(2) continuously adding amino double-end-sealed polysiloxane, stirring for 1-2 hours, adding a second part of dianhydride monomer, and reacting at room temperature for 6-12 hours to obtain the polyamic acid/polysiloxane segmented copolymer solution;
the structural formula of the amino double-terminated polysiloxane is as follows:
Figure DEST_PATH_IMAGE001
；
r is an active group and is at least one of vinyl, acryloyloxyalkyl, methacryloyloxyalkyl, alkynyl, phenylethynyl and alkynylphenyl;
t is an inert group and is at least one of methyl, ethyl, propyl, isopropyl and phenyl;
a and b are statistical averages of two kinds of repeating units, a + b = 10-500, and b/(a + b) = 5-40%.
4. The preparation method of claim 3, wherein the molar ratio of the total diamine to the total dianhydride is 100 (101-103), the total diamine comprises diamine monomers and amino double-terminated polysiloxane, and the total dianhydride comprises a first part and a second part of dianhydride monomers; the first part of dianhydride accounts for 50-80 mol% of the total molar amount of diamine monomers.
5. The production method according to claim 3, wherein the mixed solvent includes at least one of dioxane and tetrahydrofuran, and at least one of dimethylacetamide, dimethylformamide, and N-methylpyrrolidone.
6. The method according to claim 3, wherein the polyamic acid/polysiloxane block copolymer solution has a solid content of 5 to 30wt%, and the polysiloxane in the block copolymer is 10 to 50 wt%.
7. The method according to claim 3, wherein the polyamic acid/polysiloxane block copolymer solution has a wet coating amount of 1 to 50g/m2。
8. The method according to claim 1, wherein the self-crosslinking ladder-type polysilsesquioxane solution has a solid content of 10 to 70wt% and a wet coating amount of 1 to 20g/m2。
9. The method of any one of claims 1-8, wherein the self-crosslinking ladder-type polysilsesquioxane has the formula:
Figure 830700DEST_PATH_IMAGE002
；
wherein R is1、R2……RnIndependent of each otherSelected from active functional groups or/and inert functional groups, and n is an even number of 50-1000; the active functional group is selected from at least one of vinyl, allyl, methacryloxypropyl, acryloxypropyl, methacryloxymethyl, ethynyl, phenylethynyl and maleimide propyl; the inert functional group is at least one selected from methyl, phenyl, propyl, butyl, isobutyl, hexyl, cyclohexyl and cyclopentyl1～T4Is hydrogen and/or Si (CH)3)2A silicon group of the structure Y, wherein Y is R1～RnOne of the radicals R1、R2……RnThe number of the medium active functional groups accounts for 5-60%.
10. The method of claim 9, wherein R is1、R2……RnThe number of the medium active functional groups accounts for 10-40%.
11. An atomic oxygen resistant polyimide composite film prepared according to the preparation method of any one of claims 1 to 10, comprising: the self-crosslinking polyimide/polysiloxane block copolymer composite material comprises a polyimide base material, and a polyimide/polysiloxane block copolymer transition layer and a self-crosslinking trapezoidal polysilsesquioxane atomic oxygen protective layer which are sequentially formed on the surface of the polyimide base material.
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