CN113355910B - Polyimide film material with surface coated with silicon dioxide and preparation method thereof - Google Patents

Polyimide film material with surface coated with silicon dioxide and preparation method thereof Download PDF

Info

Publication number
CN113355910B
CN113355910B CN202010141710.1A CN202010141710A CN113355910B CN 113355910 B CN113355910 B CN 113355910B CN 202010141710 A CN202010141710 A CN 202010141710A CN 113355910 B CN113355910 B CN 113355910B
Authority
CN
China
Prior art keywords
paa
silicon dioxide
layer
thickness
nanofiber membrane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010141710.1A
Other languages
Chinese (zh)
Other versions
CN113355910A (en
Inventor
齐胜利
王芮晗
田国峰
汪晓东
武德珍
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Chemical Technology
Original Assignee
Beijing University of Chemical Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing University of Chemical Technology filed Critical Beijing University of Chemical Technology
Priority to CN202010141710.1A priority Critical patent/CN113355910B/en
Publication of CN113355910A publication Critical patent/CN113355910A/en
Application granted granted Critical
Publication of CN113355910B publication Critical patent/CN113355910B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Abstract

A polyimide film material with a surface coated with silicon dioxide is prepared by the following steps: firstly, preparing a polyamic acid (PAA) nanofiber membrane, enabling the polyamic acid (PAA) nanofiber membrane to quantitatively absorb a silicon dioxide precursor solution, flatly paving the PAA nanofiber membrane on a PAA wet membrane which is formed by coating the PAA solution and contains a large amount of solvent, enabling the PAA and the solvent in a lower layer wet membrane to permeate into an upper layer nanofiber membrane, dissolving and homogenizing a nanofiber network in situ to form an integrated structure of a silicon dioxide precursor/polyamic acid interpenetrating network loading layer and a polyamic acid base layer, and finally obtaining the polyimide film layer material with the silicon dioxide loaded on the surface through controllable hydrolysis and heat treatment. The composite membrane prepared by the method has the advantages of uniform and compact surface silicon dioxide coating layer, controllable coating layer thickness, excellent interface cohesiveness, good mechanical property and the like, and is low in cost, simple in process, wide in application range and easy to realize industrial production.

Description

Polyimide film material with surface coated with silicon dioxide and preparation method thereof
Technical Field
The present invention belongs to polyimide/silicon dioxide (SiO)2) The technical field of compounding, in particular to a surface-coated SiO2The polyimide film material and the preparation method.
Background
The electrostatic spinning is a simple and effective method for preparing the nanofiber membrane, and has the advantages of simple equipment, easiness in operation, rapidness in preparation, low cost, wide application range and the like. Meanwhile, the prepared nanofiber membrane has the characteristics of large specific surface area, large length-diameter ratio, high porosity, strong adsorption force and the like, so that the nanofiber membrane has application prospects and remarkable advantages in the fields of filter materials, biomedical functional materials, high-performance battery separators and the like.
Polyimide (PI) is a high-performance polymer containing an imide structure in a molecular structure, has excellent temperature resistance, mechanical property, dielectric property and radiation resistance, and has low thermal expansion coefficient and excellent chemical resistance, so that the PI is widely applied to a plurality of high-tech fields, such as aerospace, new energy, high-speed vehicles, protective appliances, atomic energy industry and the like. Among them, in the field of aerospace which is rapidly developing, polyimide is widely applied to thermal control materials of a space vehicle, flexible substrates of a light solar cell array, insulating protective layers of a circuit system, and the like, and is increasingly becoming one of indispensable high-performance materials in the field.
However, atomic oxygen can seriously affect the material properties of the polyimide on the surface of the spacecraft. Atomic Oxygen (AO) is one of the main components of a Low Earth Orbit (LEO), which is the main working environment of a spacecraft, and has strong oxidizing property, and meanwhile, when the spacecraft runs at an orbital speed, the AO can impact the spacecraft with relative average kinetic energy of 4-5 eV. Therefore, under the action of strong oxidation and high kinetic energy impact of atomic oxygen, polyimide generates chemical reaction and physical damage, and the electrical property, the mechanical property, the thermal property, the irradiation resistance and the like of the polyimide can be degraded or even failed over the years, thereby seriously affecting the working state and the service life of the spacecraft. Since the atomic oxygen research starts late in China before 'eleven and five', the low-orbit satellites in China all run in a short period, the satellites cannot reach the normal working level for a long time (more than 5 years), and the Su Union and number space station (Mir) and the current International Space Station (ISS) can run in the low-earth orbit for more than ten years. So far, the development of the atomic oxygen resistant material is not only a research work, but also a strong urgent need for the development of the aerospace industry in China.
At present, there are two main atomic oxygen protection methods for polyimide: firstly, a new material resistant to atomic oxygen degradation is developed, namely specific groups or atoms such as silicon, phosphorus, zirconium and POSS structures with good atomic oxygen resistance are introduced into a PI main chain; secondly, depositing a protective coating on the substrate material, namely depositing an inorganic layer (such as SiO) with excellent atomic oxygen resistance2，Al2O3Etc.) is applied to the polyimide surface. However, the methods have the defects of high research cost, complex process, difficult industrialization, easy cracking, delamination, falling off and the like of the coating.
The invention combines the electrostatic spinning preparationThe advantages of high porosity and strong adsorption capacity of the product and the advantages of low cost and easy industrialization of a coating method, and provides a method for preparing surface-coated SiO2The polyimide film material. The method can realize uniform SiO coating on the polyimide surface layer2And the integration of the coating layer and the basal layer can be realized, the problems that the coating layer is easy to break, fall off, delaminate and the like are effectively solved, and the controllability of the thickness of the loading layer can be simply realized.
Disclosure of Invention
The invention aims to provide a polyimide film material with a surface coated with silicon dioxide, and SiO on the surface of the material2The coating layer is uniform and compact, and has no defects of cracks, falling off and the like; has the advantages of controllable thickness of the cover layer, excellent interface cohesiveness, good mechanical property and the like.
The invention also aims to provide a preparation method of the polyimide film material with the surface coated with the silicon dioxide, which has the advantages of low cost, simple process, wide application range and easy realization of industrial production.
A polyimide film material with a surface coated with silicon dioxide is disclosed, wherein the thickness of the polyimide film is 20-70 μm, preferably 25-65 μm; SiO 22The thickness of the layer is 500nm to 4 μm, preferably 600nm to 3.5 μm; the transition layer is an interpenetrating network structure of polyimide and silicon dioxide, and the thickness is 300 nm-1 μm, preferably 350-800 nm.
A preparation method of a polyimide film material with a surface coated with silicon dioxide is characterized by comprising the following steps:
a: preparing a polyamide acid (PAA) solution by using polybasic acid anhydride and polyamine as monomers;
b: the PAA solution prepared in the step A is made into a PAA nanofiber membrane through electrostatic spinning;
c: coating a silicon dioxide precursor compound on the surface of the PAA nanofiber membrane in an anhydrous drying atmosphere, and standing and homogenizing to obtain the PAA nanofiber membrane adsorbing the silicon dioxide precursor compound;
d: uniformly coating the PAA solution prepared in the step A to form a film to obtain a PAA wet film containing a solvent;
e: under the anhydrous dry atmosphere, the PAA nanofiber membrane which is prepared in the step C and adsorbs the silicon dioxide precursor solution is paved on the PAA wet membrane which contains the solvent and is prepared in the step D;
f: placing the composite membrane obtained in the step E in a closed container containing hydrolysate steam atmosphere for controllable hydrolysis;
g: and F, carrying out heat treatment on the composite membrane subjected to hydrolysis treatment, thus obtaining the polyimide membrane layer material with the surface coated with silicon dioxide.
Wherein, the solid content of the PAA solution in the step A is 8-30 wt%, preferably 10-15 wt%.
The thickness of the PAA nanofiber membrane in the step B can be adjusted arbitrarily according to needs, and from the viewpoint of operability, the thickness is 10-60 μm, and preferably 15-50 μm. The larger the thickness of the nanofiber film layer is, the stronger the capability of adsorbing a silicon dioxide precursor is, and SiO2The thicker the overburden can be.
Step C, anhydrous drying atmosphere is adopted, and the humidity is required to be less than 45% RH; the silicon dioxide precursor compound is one or more of tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate and silicon tetrachloride, and the purity is preferably analytically pure. The adsorption capacity of the silicon dioxide precursor can be within the saturated adsorption capacity of the PAA nanofiber membrane, and the mass ratio of the silicon dioxide precursor to the PAA nanofiber membrane is 20-70: 1, preferably 25-65: 1. The standing time is 0.5-2.5 h.
The thickness of the PAA wet film containing the solvent in the step D can be calculated according to the thickness of the finally required polyimide layer and the solid content of the solution, and is preferably 0.1-1 mm, particularly preferably 150-600 mu m.
In step E, the humidity should be kept at less than 40% RH under the anhydrous dry atmosphere. Further, laying and standing, then placing in an anhydrous environment, and naturally volatilizing the solvent. And standing for 0.1-1 h, enabling the PAA and the solvent in the lower PAA wet film to permeate into the upper PAA nanofiber film in the standing process, and enabling the PAA nanofiber network structure to be subjected to in-situ dissolution and homogenization under the action of the solvent, so that the silicon dioxide precursor adsorbed by the nanofiber network is fixed on the shallow surface layer to form a silicon dioxide precursor/PAA interpenetrating network, namely firmly riveting a silicon compound on the shallow PAA surface layer by means of the interpenetrating network structure of the nanofibers to form the composite film with the structure of the loading layer and the PAA basal layer in an integrated manner. The time for placing the film in an anhydrous environment is 8-24 hours.
The hydrolysate used in the step F can be deionized water, a deionized water/alcohol mixed solution, or a deionized water/alcohol/acid mixed solution, wherein the alcohol can be ethanol, and the acid can be acetic acid or hydrochloric acid; wherein the volume ratio of water, alcohol and acid is VWater (W)：VAlcohol(s)：VAcid(s)1:2: 0.02-0.05. The hydrolysis process of the silicon dioxide precursor compound on the surface of the film layer is completed by utilizing the volatilization and the attachment of the hydrolysate in the closed space, and the hydrolysis process is also converted into SiO2An intermediate reaction of (1). The acid component in the hydrolysate is used as a catalyst in the hydrolysis process, and the alcohol component is used for promoting the contact of water and the silicon compound; the hydrolysis temperature is controlled to be 30-100 ℃, and the hydrolysis time is 4-12 h.
In the step G, the heat treatment condition is to heat to 300-350 ℃, preferably 310-340 ℃, and keep for 1-3 hours, preferably 1.5-2.5 hours. After heat treatment, the film is fully imidized thermally, PAA is converted into Polyimide (PI), and hydrolysis intermediate products of silicon dioxide precursor compounds are also dehydrated and converted into SiO2。
Compared with the prior art, the invention has the following technical characteristics and effects:
1. the method of the invention has simple operation and is easy for industrialized production; the application range is wide, and the method can be suitable for all PI systems for preparing PAA by solution condensation polymerization.
2. The surface of the invention is coated with SiO2The surface layer of the polyimide film material SiO2Compact structure, excellent interface combination performance and good mechanical property of materials. The core technology of the method is to form an integrated composite film structure, and the specific technical characteristics are that when a PAA nanofiber layer adsorbing a silicon dioxide precursor is uniformly spread on a PAA coating layer, the lower layer of PAA and a solvent are permeated into the PAA fiber film, and the nanofibers can maintain the original position dissolution of a net structureHomogenizing, and the silicon compounds in the pores of the nanofiber network are fixed on the shallow surface layer, i.e. the SiO is fixed by the interpenetrating network structure of the PAA nanofiber and the solubility of the PAA nanofiber with the lower PAA film2The surface layer is firmly riveted on the PAA shallow surface layer to form an integral structure of the loading layer and the basal layer in practical meaning, and the structure has quite excellent interface bonding performance and is not easy to generate defects such as cracks, falling off and the like; at the same time, it is due to the majority of SiO2The surface layer is fixed, so that the structure of the basal layer is not damaged, and the excellent mechanical property of the original PI is maintained.
3. Layer Material of the invention, SiO layer2Controllable adjustment of the thickness or the loading amount can be realized. The specific realization method is to control the thickness of the PAA nanofiber membrane and the adsorption amount of a silicon dioxide precursor compound, namely to realize the SiO of the surface layer2The quantity is adjusted and controlled, the thicker the PAA nanofiber film is, the larger the adsorption quantity of the silicon dioxide precursor is, and the SiO on the surface layer2The thicker the layer is, and the more accurately the correspondence between the thicknesses of the two layers can be established. In practical application, the thickness of the nanofiber can be simply controlled by controlling the electrostatic spinning time, and the adsorption amount of a silicon dioxide precursor compound in a nanofiber membrane can be controlled, so that SiO with different surface loading thicknesses can be obtained2The polyimide composite film of (1).
Drawings
FIG. 1 is a SiO-coated surface prepared in example 12The cross section of the polyimide film material is in a shape graph, wherein the magnification of the figure is 10000 times, and SiO on the surface layer2The thickness is 0.68 μm;
FIG. 2 is a SiO-coated surface prepared in example 22The magnification of the cross section topography of the polyimide film material is 20000 times, wherein the SiO of the surface layer2The thickness is 3.14 μm;
FIG. 3 is a SiO-coated surface prepared in example 22The magnification factor of the surface topography of the polyimide film material is 2000 times;
FIG. 4 is a SiO-coated surface prepared in example 22The cross section of the polyimide film material is provided with a Si element analysis chartThe large multiple is 3300 times;
FIG. 5 is a SiO-coated surface prepared in example 22Compared with the pure polyimide film, the tensile strength of the pure PI film is 123.1MPa, and the PI/SiO ratio is2The tensile strength of the composite film is 118.2 MPa.
FIG. 6 is a SiO-coated surface prepared in example 22The surface appearance graph of the polyimide film material and the pure polyimide film after the atomic oxygen ground simulation test has the magnification of 5000 times.
FIG. 7 is a SiO-coated surface prepared in comparative example 32The magnification factor of the surface topography of the polyimide film material is 2000 times;
FIG. 8 is a SiO-coated surface prepared in comparative example 42The magnification of the surface topography of the polyimide film material is 5000 times.
Detailed Description
The present invention will be further described with reference to specific examples. It should be noted that the following examples are only for illustrating the present invention and are not to be construed as limiting the technical solutions described in the present invention, and all modifications and equivalents that are made on the technical solutions of the present invention are included in the claims of the present invention without departing from the design spirit of the present invention.
Example 1
A: adopting pyromellitic dianhydride (PMDA) and 4, 4' -diaminodiphenyl ether (ODA) as monomers, controlling the molar ratio of the two monomers to be 1:1, and carrying out condensation polymerization in an N, N-dimethylacetamide (DMAc) solvent to obtain a polyamic acid (PAA) solution with the solid content of 12%;
b: the PAA nanofiber membrane with the thickness of 20 mu m prepared by electrostatic spinning
C: keeping the humidity at 40% RH, adsorbing a silicon dioxide precursor compound quantitatively adsorbed on the surface of the PAA nanofiber membrane at a mass ratio of TEOS/PAA nanofiber membrane of 50:1, standing for 2h, and homogenizing to obtain a PAA nanofiber membrane uniformly adsorbing the silicon dioxide precursor compound;
d: uniformly coating the PAA solution prepared in the step A to form a film to obtain a solvent-containing PAA wet film with the thickness of 180 mu m;
e: flatly spreading the PAA nanofiber membrane adsorbed with TEOS in the step C on the PAA coating film, standing for 0.5h, and standing for 12h at room temperature under the condition that the humidity is 35% RH;
f: placing the composite film in a closed container, wherein 50ml of hydrolysate is placed, and a deionized water/ethanol/acetic acid mixed solution with a volume ratio of V is selectedWater (W)：VAlcohol(s)：VAcid(s)Setting the temperature at 70 ℃ and the humidity at 20% RH as 1:2:0.02, and standing for 6 h;
g: placing the film in a heating furnace, uniformly heating to 300 ℃ from room temperature for 150min, and keeping the temperature for 120 min;
namely, the surface-coated SiO is obtained2The thickness of the surface silicon dioxide layer of the polyimide film material is 0.68 μm, the thickness of the transition layer is 0.4 μm, the thickness of the polyimide base layer is 38 μm, and the cross-sectional view is shown in FIG. 1.
Example 2
A: adopting pyromellitic dianhydride (PMDA) and 4,4 '-diaminodiphenyl ether (ODA) as monomers, controlling the molar ratio of the pyromellitic dianhydride to the 4, 4' -diaminodiphenyl ether (ODA) to be 1:1, and carrying out condensation polymerization in an N, N-dimethylacetamide (DMAc) solvent to obtain a polyamide acid (PAA) solution with the solid content of 12%;
b: preparing a PAA nanofiber membrane with the thickness of 40 mu m by electrostatic spinning;
c: keeping the humidity at 40% RH, adsorbing a silicon dioxide precursor compound quantitatively adsorbed on the surface of the PAA nanofiber membrane at a mass ratio of TEOS/PAA nanofiber membrane of 50:1, standing for 2h, and homogenizing to obtain a PAA nanofiber membrane uniformly adsorbing the silicon dioxide precursor compound;
d: uniformly coating the PAA solution prepared in the step A to form a film to obtain a solvent-containing PAA wet film with the thickness of 180 mu m;
e: flatly spreading the PAA nanofiber membrane adsorbed with TEOS in the step C on the PAA coating film, standing for 0.5h, and standing for 12h at room temperature under the condition that the humidity is 35% RH;
f: placing the composite film in a closed container, and placing hydrolysate therein50ml of deionized water/ethanol/acetic acid mixed solution with the volume ratio of VWater (W)：VAlcohol(s)：VAcid(s)Setting the temperature at 70 ℃ and the humidity at 20% RH as 1:2:0.02, and standing for 6 h;
g: placing the film in a heating furnace, uniformly heating to 300 ℃ from room temperature for 150min, and keeping the temperature for 120 min;
namely, the surface-coated SiO is obtained2The thickness of the surface silicon dioxide layer of the polyimide film material is 3.14 microns, the thickness of the transition layer is 0.6 microns, the thickness of the polyimide base layer is 37 microns, the section diagram is shown in figure 2, the surface topography is shown in figure 3, and the distribution condition of Si elements at the section is shown in figure 4;
the tensile strength is shown in fig. 5, the tensile strength of the sample prepared in example 2 is 118.2MPa, and the composite film still maintains excellent mechanical properties compared with 123.1MPa of the matrix material PI;
meanwhile, the sample prepared in example 2 was subjected to an atomic oxygen irradiation test (atomic oxygen flux 8X 10)21atoms cm-2) The results show that the mass loss is only 16% of that of the pure PI film, and the surface topography of the sample after atomic oxygen etching is shown in FIG. 6.
Comparative example 3
A: adopting pyromellitic dianhydride (PMDA) and 4,4 '-diaminodiphenyl ether (ODA) as monomers, controlling the molar ratio of the pyromellitic dianhydride to the 4, 4' -diaminodiphenyl ether (ODA) to be 1:1, and carrying out condensation polymerization in an N, N-dimethylacetamide (DMAc) solvent to obtain a polyamide acid (PAA) solution with the solid content of 12%;
b: the PAA nanofiber membrane with the thickness of 40 mu m prepared by electrostatic spinning
C: keeping the humidity at 40% RH, adsorbing a silicon dioxide precursor compound quantitatively adsorbed on the surface of the PAA nanofiber membrane at a mass ratio of TEOS/PAA nanofiber membrane of 75:1, standing for 2h, and homogenizing to obtain a PAA nanofiber membrane uniformly adsorbing the silicon dioxide precursor compound;
d: uniformly coating the PAA solution prepared in the step A to form a film to obtain a solvent-containing PAA wet film with the thickness of 180 mu m;
e: flatly spreading the PAA nanofiber membrane adsorbed with TEOS in the step C on the PAA coating film, standing for 0.5h, and standing for 12h at room temperature under the condition that the humidity is 35% RH;
f: placing the composite film in a closed container, wherein 50ml of hydrolysate is placed, and a deionized water/ethanol/hydrochloric acid mixed solution with a volume ratio of V is selectedWater (W)：VAlcohol(s)：VAcid(s)Setting the temperature at 70 ℃ and the humidity at 20% RH as 1:2:0.02, and standing for 6 h;
g: placing the film in a heating furnace, uniformly heating to 300 ℃ from room temperature for 150min, and keeping the temperature for 120 min;
namely, the surface-coated SiO is obtained2The surface topography of the sample of the polyimide film material is shown in fig. 7, and the surface topography has defects due to excessive TEOS adsorption in the experimental process, thereby seriously affecting the mechanical property (101.1 MPa).
Comparative example 4
A: adopting pyromellitic dianhydride (PMDA) and 4,4 '-diaminodiphenyl ether (ODA) as monomers, controlling the molar ratio of the pyromellitic dianhydride to the 4, 4' -diaminodiphenyl ether (ODA) to be 1:1, and carrying out condensation polymerization in an N, N-dimethylacetamide (DMAc) solvent to obtain a polyamide acid (PAA) solution with the solid content of 12%;
b: the PAA nanofiber membrane with the thickness of 40um prepared by electrostatic spinning
C: keeping the humidity at 40% RH, adsorbing a silicon dioxide precursor compound quantitatively adsorbed on the surface of the PAA nanofiber membrane at a mass ratio of TEOS/PAA nanofiber membrane of 50:1, standing for 2h, and homogenizing to obtain a PAA nanofiber membrane uniformly adsorbing the silicon dioxide precursor compound;
d: uniformly coating the PAA solution prepared in the step A to form a film to obtain a solvent-containing PAA wet film with the thickness of 180 mu m;
e: flatly spreading the PAA nanofiber membrane adsorbed with TEOS in the step C on the PAA coating film, standing for 0.5h, and standing for 12h at room temperature under the condition that the humidity is 35% RH;
f: placing the composite film in a closed container, wherein 50ml of hydrolysate is placed, and a deionized water/ethanol/hydrochloric acid mixed solution with a volume ratio of V is selectedWater (I)：VAlcohol(s)：VAcid(s)Setting the temperature at 70 ℃ and the humidity at 20% RH as 1:2:0.06,standing for 6 h;
g: placing the film in a heating furnace, uniformly heating to 300 ℃ from room temperature for 150min, and keeping the temperature for 120 min;
namely, the surface-coated SiO is obtained2The surface topography of the sample of the polyimide film material is shown in fig. 8, and the surface silicon dioxide is not uniformly formed due to overlarge acidity of the hydrolysis liquid component in the experimental process, the topography has defects, and the mechanical property (97.2MPa) is seriously influenced.
TABLE 1 composition and Property data of the films obtained in the examples
Figure BDA0002399300710000071
Experimental method for adhesion: the test of the marking of paint films of GB9286-1998 paints and varnishes;
adhesion evaluation criteria:
level 0-smooth edge of the line, there is no paint to drop off at the edge and cross point of the line;
level 1-small pieces of paint fall off at the intersection of the lines, and the total area of fall off is less than 5%;
2, small pieces of paint fall off at the edge and the intersection of the scribing line, and the total falling area is between 5 and 15 percent;
level 3-a piece of paint falls off at the edge and the intersection of the line, and the total area of the falling off is between 15 and 35 percent;
4-a piece of paint falls off at the edge and the intersection of the line, and the total area of the falling off is between 35 and 65 percent;
grade 5-there is a patch of paint falling off at the edge and intersection of the scribe, and the total area of falling off is greater than 65%.

Claims (12)

1. A preparation method of a polyimide film material with a surface coated with silicon dioxide is characterized by comprising the following steps:
a: preparing a polyamide acid (PAA) solution by using polybasic acid anhydride and polyamine as monomers;
b: the PAA solution prepared in the step A is made into a PAA nanofiber membrane through electrostatic spinning;
c: coating a silicon dioxide precursor compound on the surface of the PAA nanofiber membrane in an anhydrous drying atmosphere, and standing and homogenizing to obtain the PAA nanofiber membrane adsorbing the silicon dioxide precursor compound; the adsorption capacity of the silicon dioxide precursor is within the saturated adsorption capacity of the PAA nanofiber membrane, and the mass ratio of the silicon dioxide precursor to the PAA nanofiber membrane is 20-70: 1;
d: uniformly coating the PAA solution prepared in the step A to form a film to obtain a PAA wet film containing a solvent;
e: under the anhydrous dry atmosphere, the PAA nanofiber membrane which is prepared in the step C and adsorbs the silicon dioxide precursor solution is paved on the PAA wet membrane which contains the solvent and is prepared in the step D;
f: placing the composite membrane obtained in the step E in a closed container containing hydrolysate steam atmosphere for controllable hydrolysis; the hydrolysate is deionized water, a deionized water/alcohol mixed solution and a deionized water/alcohol/acid mixed solution, wherein the alcohol is ethanol, and the acid is acetic acid and hydrochloric acid; wherein the volume ratio of water, alcohol and acid is VWater (W)：VAlcohol(s)：VAcid(s)=1:2: 0.02-0.05; the hydrolysis temperature is 30-100 ℃, and the hydrolysis time is 4-12 h;
g: f, carrying out heat treatment on the composite membrane subjected to hydrolysis treatment, so as to obtain a polyimide membrane layer material with the surface coated with silicon dioxide;
in the polyimide film layer material with the surface coated with the silicon dioxide, the thickness of the polyimide layer is 20-70 mu m; SiO 22The thickness of the layer is 500 nm-4 μm; the transition layer is of an interpenetrating network structure of polyimide and silicon dioxide, and the thickness of the transition layer is 300 nm-1 mu m.
2. The method of claim 1, wherein in the polyimide film material with the surface coated with the silicon dioxide, the thickness of the polyimide layer is 25-65 μm; SiO 22The thickness of the layer is 600 nm-3.5 μm; the thickness of the transition layer is 350-800 nm.
3. The process of claim 1, wherein the PAA solution in step A has a solid content of 8 to 30 wt%.
4. The process of claim 3, wherein the PAA solution in step A has a solid content of 10 to 15 wt%.
5. The method of claim 1, wherein the thickness of the PAA nanofiber membrane in step B is 10-60 μm.
6. The method of claim 5, wherein the thickness of the PAA nanofiber membrane in step B is 15-50 μm.
7. The method of claim 1, wherein in step C, the atmosphere is dried without water and the humidity is less than 45% RH; the silicon dioxide precursor compound is one or more of tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate and silicon tetrachloride, and the purity is analytical purity; the mass ratio of the silicon dioxide precursor to the PAA nanofiber membrane is 25-65: 1; the standing time is 0.5-2.5 h.
8. The method of claim 1, wherein the thickness of the PAA wet film containing the solvent in step D is 0.1-1 mm.
9. The method of claim 8 wherein the wet PAA film containing solvent in step D has a thickness of 150 to 600 μm.
10. The method of claim 1, wherein the humidity is maintained at less than 40% RH in step E under an anhydrous dry atmosphere.
11. The method according to claim 1, wherein in the step G, the heat treatment is performed by heating to 300-350 ℃ for 1-3 h.
12. The method as claimed in claim 11, wherein, in the step G, the heat treatment condition is heating to 310-340 ℃ for 1.5-2.5 h.
CN202010141710.1A 2020-03-04 2020-03-04 Polyimide film material with surface coated with silicon dioxide and preparation method thereof Active CN113355910B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010141710.1A CN113355910B (en) 2020-03-04 2020-03-04 Polyimide film material with surface coated with silicon dioxide and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010141710.1A CN113355910B (en) 2020-03-04 2020-03-04 Polyimide film material with surface coated with silicon dioxide and preparation method thereof

Publications (2)

Publication Number Publication Date
CN113355910A CN113355910A (en) 2021-09-07
CN113355910B true CN113355910B (en) 2022-05-17

Family

ID=77523168

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010141710.1A Active CN113355910B (en) 2020-03-04 2020-03-04 Polyimide film material with surface coated with silicon dioxide and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113355910B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103981634A (en) * 2014-05-30 2014-08-13 北京化工大学常州先进材料研究院 Polyimide/silicon dioxide composite nanofiber film and preparation thereof
CN108774333A (en) * 2018-06-25 2018-11-09 北京化工大学 A kind of resistance to elemental oxygen polyimide film layer material and preparation method thereof
CN108909118A (en) * 2018-06-15 2018-11-30 北京化工大学常州先进材料研究院 A kind of single side polyimide composite film of resistance to elemental oxygen material and preparation method thereof
CN109651812A (en) * 2018-12-14 2019-04-19 上海卫星装备研究所 The siliceous Kapton of resistance to elemental oxygen composition and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103981634A (en) * 2014-05-30 2014-08-13 北京化工大学常州先进材料研究院 Polyimide/silicon dioxide composite nanofiber film and preparation thereof
CN108909118A (en) * 2018-06-15 2018-11-30 北京化工大学常州先进材料研究院 A kind of single side polyimide composite film of resistance to elemental oxygen material and preparation method thereof
CN108774333A (en) * 2018-06-25 2018-11-09 北京化工大学 A kind of resistance to elemental oxygen polyimide film layer material and preparation method thereof
CN109651812A (en) * 2018-12-14 2019-04-19 上海卫星装备研究所 The siliceous Kapton of resistance to elemental oxygen composition and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Thermal and mechanical properties of polyimide/nano-silica hybrid films;Mei-Hui Tsai et al.;《Thin Solid Films》;20110122;第5238-5242页 *

Also Published As

Publication number Publication date
CN113355910A (en) 2021-09-07

Similar Documents

Publication Publication Date Title
EP1832553B1 (en) Clay film product
CN103664004B (en) The preparation method of antifogging coating, antifogging coating and antifog glass
Lee et al. SiO2-coated polyimide nonwoven/Nafion composite membranes for proton exchange membrane fuel cells
EP1226589B1 (en) Infiltrated nanoporous materials and methods of producing same
Park et al. Design of multi-functional dual hole patterned carbon nanotube composites with superhydrophobicity and durability
US20110272027A1 (en) Solar photovoltaic devices and methods of making them
JP2013511601A (en) Assembly comprising polyimide film and electrode and method related thereto
CN101704957B (en) Method for preparing polymer film with continuous nanometer pore channels
WO2020082738A1 (en) Method employing aromatic fused ring molecule to modify assembly of carbon fiber surface, and method for preparing resin matrix composite material having carbon fiber reinforced interface
CN108774808B (en) Polyimide nanofiber membrane with cross-linked appearance and zirconium dioxide coated surface and preparation method thereof
CN103421444A (en) Inflaming-retarding solar cell backsheet
Wang et al. Design of a stable and methanol resistant membrane with cross-linked multilayered polyelectrolyte complexes for direct methanol fuel cells
US20110220179A1 (en) Assemblies comprising a thermally and dimensionally stable polyimide film, an electrode and an absorber layer, and methods relating thereto
CN106366791B (en) A kind of backboard that can delay failure under dry wet alternating environment
CN113355910B (en) Polyimide film material with surface coated with silicon dioxide and preparation method thereof
JP6988208B2 (en) Particle-dispersed polyimide precursor solution, method for producing porous polyimide film, and porous polyimide film
CN113354859B (en) Polyimide film with surface coated with high-cohesiveness compact silicon dioxide layer and preparation method thereof
CN110620253B (en) Method for preparing non-aqueous proton exchange membrane based on sulfonated graphene oxide by utilizing spin coating technology
CN104218205A (en) Heat-resistant porous isolating membrane and manufacturing method thereof
JPH11274536A (en) Substrate for solar cell
CN114940760A (en) Polyimide film and preparation method and application thereof
Azuta et al. Water and oxygen permeability of silica thin films containing organic polymers coated on poly (ethylene terephtalate) substrate by the sol-gel method
CN115521640B (en) Atomic oxygen-resistant micro-nano porous coating and preparation method thereof
Ahzan et al. Synthesis and Characterization of ZnO Thin Layers Using Sol-Gel Spin Coating Method
Yang et al. Superhydrophobic coatings based on thermally and chemically stable fluorinated poly (aryl ether)/SiO 2/carbon nanotube

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant