CN114806170B - Hybrid polyimide foam material and preparation method thereof - Google Patents

Hybrid polyimide foam material and preparation method thereof Download PDF

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CN114806170B
CN114806170B CN202210385251.0A CN202210385251A CN114806170B CN 114806170 B CN114806170 B CN 114806170B CN 202210385251 A CN202210385251 A CN 202210385251A CN 114806170 B CN114806170 B CN 114806170B
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foam material
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water
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silane modified
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刘培礼
张茂伟
陶刚
国晓军
霍行
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Qingdao Advanced Marine Material Technology Co ltd
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/048—Elimination of a frozen liquid phase
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    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract

The application belongs to the technical field of composite materials, and particularly relates to a hybrid polyimide foam material and a preparation method thereof. The preparation method comprises the following steps: (I) silane modified nano zirconia; (II) silane modified magnesium aluminum hydrotalcite; (III) preparing polyimide composite foam material: (1) adding polyamide acid, graphene oxide, silane modified zirconia prepared in the step (I) and silane modified magnesium aluminum hydrotalcite prepared in the step (II) into water, adding triethylamine, stirring, and uniformly dispersing by ultrasonic to obtain an aqueous dispersion; (2) pouring the aqueous dispersion prepared in the step (1) into a mold, and performing vacuum freeze drying and thermal imidization to obtain the composite foam material. The composite foam material prepared by the application has excellent heat resistance, mechanical property, flame retardance and other properties.

Description

Hybrid polyimide foam material and preparation method thereof
Technical Field
The application belongs to the technical field of composite materials. More particularly, to a hybrid polyimide foam material and a preparation method thereof.
Background
Polyimide (PI) is a high molecular polymer having an imide ring structure in the main chain. Polyimide can be classified into aliphatic polyimide and aromatic polyimide according to the kind of molecular unit structure. Aromatic polyimides are more commonly used because they have better overall properties than aliphatic polyimides, and therefore the term "polyimide" is used generically to refer to aromatic polyimides.
With the rapid development of high and new technologies in recent years, urgent demands for high-heat-resistant, high-strength and light-weight structural materials are met, and research on materials is gradually going to multi-functionalization, high-performance and low-cost. The polyimide contains a five-membered imide ring structure on the main chain, so that the polyimide contains a large number of pi-pi conjugated structures and has excellent performances such as high strength, high temperature resistance, radiation resistance, high modulus and the like, so that the polyimide becomes one of materials with the best comprehensive performance in organic high polymer materials, and has wide application in various fields such as aerospace, microelectronic materials, films, separation films, foamed plastics, engineering plastics, biological medicines and the like.
Tian Huafeng et al prepared polyimide foam (PIF) with pyromellitic dianhydride (PMDA) and polymethylene polyphenyl polyisocyanate (PAPI) as monomers, and then added graphene for filling modification. PMDA and methanol are dissolved in Dimethylformamide (DMF) for esterification reaction, and Triethanolamine (TEOA) catalyst, dibutyltin dilaurate, silicone oil and water are respectively added and uniformly stirred to obtain a precursor solution which is a component A; uniformly stirring graphene with different contents and PAPI to obtain a solution serving as a component B; and (3) stirring the mixed solution of the component A and the component B at a high speed, rapidly pouring the mixed solution into a mold for free foaming, and finally performing high-temperature treatment to complete the whole preparation process. With the increase of the graphene content, the thermal stability and flame retardant performance of the PIF are enhanced, and when the graphene content is 3.25% (w), the Limiting Oxygen Index (LOI) is increased from 31.0% to 34.8% of the pure PIF. The reason why the thermal stability is firstly increased and then reduced is that the high thermal stability of the graphene endows the composite material with better thermal stability, but the high content damages good interfacial compatibility and order between the matrix and the polymer to a certain extent, so that the thermal stability is reduced. The compressive strength is increased and then reduced, and the maximum value is reached when the mass fraction of the graphene is 1.98%. This is because the density of PIF increases with increasing graphene content, the greater the foam density, the greater the compressive strength. Meanwhile, the more compact the cell arrangement is, the greater the hardness and the higher the compressive strength of the PIF are, so that the addition of the high-modulus graphene remarkably improves the strength of the cell wall, thereby improving the compressive strength of the PIF; however, when the mass fraction of graphene exceeds 1.98%, excessive graphene is agglomerated, so that the compressive strength of the composite material is reduced.
Kizilkaya et al prepared a novel PI/SiO 2 Nanocomposite films and their properties were studied. The results show that with SiO 2 The tensile strength, tensile modulus and elongation at break of the composite film all show the trend of increasing and then decreasing when the content is increased, and when the SiO is 2 The mass fraction is the largest at 6%. The degradation temperature of the pure PI is 300 ℃, and 20% (w) of SiO is added 2 The initial decomposition temperature of the nanocomposite is 550 ℃, and the thermal stability of the composite is obviously improved.
CN106433129A discloses a graphene/SiO 2 Hybrid polyimide foam material and preparation method thereof, and graphene/SiO (silicon dioxide) 2 The hybridized polyimide foam material is prepared from modified graphene oxide, benzophenone tetracarboxylic dianhydride, diaminodiphenyl ether, 3-aminopropyl triethoxysilane, tetraethoxysilane and the like through amidation reaction and sol-gel reaction, wherein the modified graphene oxide is modified graphene oxide with isocyanate groups on the surface. graphene/SiO prepared by the method 2 On one hand, the hybridized polyimide foam material fully exerts the good reinforcing effect of graphene oxide and the good toughening effect of silicon dioxide, and on the other hand, overcomes the defect that the graphene oxide and the silicon dioxide are easy to agglomerate, so that SiO 2 The particles can be uniformly distributed on the graphene sheets, the graphene sheets are not easy to overlap, the dispersibility is obviously improved, and the polyimide has the properties of good heat resistance, high mechanical property, strong flame retardance and the like.
Namely, the polyimide is modified to improve the heat resistance, the flame retardance and other properties of the polyimide to a certain degree, but the polyimide still cannot meet the actual production requirements, so that development of a novel polyimide foam with excellent heat resistance, mechanical properties, flame retardance and other properties is urgently needed.
Disclosure of Invention
The application aims to overcome the defects and the shortcomings in the prior art and provide a hybrid polyimide foam material and a preparation method thereof. The preparation method comprises the following steps: (I) silane modified nano zirconia; (II) silane modified magnesium aluminum hydrotalcite; (III) preparing polyimide composite foam material: (1) adding polyamide acid, graphene oxide, silane modified zirconia prepared in the step (I) and silane modified magnesium aluminum hydrotalcite prepared in the step (II) into water, adding triethylamine, stirring, and uniformly dispersing by ultrasonic to obtain an aqueous dispersion; (2) pouring the aqueous dispersion prepared in the step (1) into a mold, and performing vacuum freeze drying and thermal imidization to obtain the composite foam material. The composite foam material prepared by the application has excellent heat resistance, mechanical property, flame retardance and other properties.
The application aims to provide a preparation method of a hybrid polyimide foam material.
It is another object of the present application to provide a hybrid polyimide foam.
The above object of the present application is achieved by the following technical scheme:
a method for preparing a hybrid polyimide foam material, the method comprising the steps of:
(I) Silane modified nano zirconia;
(II) silane modified magnesium aluminum hydrotalcite;
(III) preparation of polyimide composite foam Material
(1) Adding polyamide acid, graphene oxide, silane modified zirconia prepared in the step (I) and silane modified magnesium aluminum hydrotalcite prepared in the step (II) into water, adding triethylamine, stirring, and uniformly dispersing by ultrasonic to obtain an aqueous dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mold, and performing vacuum freeze drying and thermal imidization to obtain the composite foam material.
Preferably, in the step (1), the preparation method of the silane modified nano zirconia comprises the following steps:
adding nano zirconia into an alcohol-water mixed solution of a silane coupling agent for reaction, centrifuging, washing with ethanol and deionized water, and drying at 80-120 ℃ for 10-14 h to obtain silane modified zirconium dioxide.
Preferably, the silane coupling agent is at least one of 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane and gamma-ureido propyl triethoxysilane; the alcohol is methanol or ethanol.
Preferably, the particle size of the nano zirconia is 20-50 nm.
Preferably, the volume of the alcohol and the water is 1:0.1-0.3; the mass fraction of the aqueous alcohol solution of the silane coupling agent is 30-50wt%; the mass ratio of the alcohol-water mixed solution of the nano zirconia and the silane coupling agent is 1:40.
preferably, the reaction is carried out at 60-80 ℃ for 3-6 hours, and the drying is carried out at 80-120 ℃ for 10-14 hours.
Preferably, in the step (II), the preparation method of the silane-modified magnesium aluminum hydrotalcite is as follows: (a) Weighing magnesium salt and aluminum salt, dissolving in ethanol water to prepare mixed salt solution, adding a certain amount of straw into the solution, stirring, dripping alkaline solution to adjust the pH of the solution, transferring to a hydrothermal reaction kettle for reaction, centrifuging, washing, drying, calcining, and grinding to obtain magnesium-aluminum hydrotalcite; (b) And (c) adding the magnesium aluminum hydrotalcite obtained in the step (a) into an ethanol water solution of the silane coupling agent for reaction, centrifuging, washing with ethanol and deionized water, and drying to obtain the silane modified magnesium aluminum hydrotalcite.
Preferably, the magnesium salt is at least one of magnesium nitrate, magnesium acetate and magnesium chloride; the aluminum salt is at least one of aluminum nitrate, aluminum chloride and aluminum acetate; the alkali is one of sodium hydroxide, potassium hydroxide, sodium carbonate and ammonia water; the straw is wheat straw or rice straw; the silane coupling agent is at least one of 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane and gamma-ureido propyl triethoxy silane; the alcohol is methanol or ethanol.
Preferably, in the step (a), the molar ratio of magnesium to aluminum is 1:2-4: the volume ratio of the ethanol to the water is 1:3-7; the ratio of the straw to the aluminum salt is 0.1-0.3 g:1mol; the concentration of the alkali is 2-4 mol/L, and in the step (b), the molar ratio of the aluminum to the silane is 1:0.05-0.15; the volume ratio of the ethanol water is 1:2-4.
Preferably, in step (a); the stirring time is 10-30 min, and the pH is 10; the hydrothermal reaction is carried out for 4-8 hours at 140-180 ℃; the drying is carried out for 10-14 hours at the temperature of 90-120 ℃; the calcination is carried out for 10-14 hours in an air atmosphere at 450-520 ℃.
Preferably, in step (b); the concentration of the ethanol aqueous solution of the silane coupling agent is 2-4 mol/L; the reaction is carried out for 4-8 hours at the temperature of 60-80 ℃; and the drying is carried out at 70-90 ℃ for 14-20 h.
Preferably, in step (III), in step (1) in step (III), the mass ratio of the polyamic acid, the silane-modified zirconia, and the silane-modified magnesium aluminum hydrotalcite is 100: 5-12:2-4:6-10; the mass ratio of the polyamide acid to the water is (4:96) - (12:88); the mass ratio of the polyamide acid to the triethylamine is 100 (45-65);
preferably, in the step (III), in the step (2) in the step (III), the freeze-drying temperature is-45 to-35 ℃ and the drying time is 60-90 hours; the vacuum degree is 1-4 Pa; the thermal imidization method is to program the temperature under the following conditions: 2-4 h at 70-90 ℃, 1-3 h at 180-220 ℃ and 3-6 h at 260-300 ℃.
The hybrid polyimide foam material prepared based on the preparation method of the hybrid polyimide foam material is provided.
The application has the following beneficial effects:
(1) The compatibility of the zirconia can be improved by modifying the zirconia by silane, so that the comprehensive performance of polyimide is improved;
(2) In the process of preparing hydrotalcite, hydrotalcite is adsorbed on the surface of straw by utilizing the adsorption property of the straw, then the hydrotalcite is loaded on the surface of the straw by hydrothermal preparation, and then the straw is removed by calcination, so that the morphology of the straw is reserved, the specific surface area is improved, and the modification of silane is facilitated, so that the dispersion in a matrix is improved;
(3) The silane modified zirconia and the silane modified hydrotalcite are utilized, and the synergistic effect between the two components is utilized to promote the bonding between the components, so that the mechanical property, the flame retardance and other properties of the polyimide foam are further improved.
(4) The preparation method is simple, and the prepared polyimide foam has excellent performance.
Drawings
FIG. 1 shows the results of the test of examples and comparative examples.
Detailed Description
The present application is further illustrated below with reference to specific examples, which are not intended to limit the application in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present application are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1
A method for preparing a hybrid polyimide foam material, the method comprising the steps of:
(I) Silane modified zirconia;
adding 1g of nano zirconia into 40g of a 40% mass fraction methanol-water mixed solution of 3-aminopropyl trimethoxy silane, reacting at 70 ℃ for 5 hours, centrifuging, washing with ethanol and deionized water, and drying at 100 ℃ for 12 hours to obtain silane modified zirconia;
the grain diameter of the nanometer zirconia is 35nm;
(II) silane modified magnesium aluminum hydrotalcite;
(a) 3mol of magnesium nitrate and 1mol of aluminum nitrate are weighed and dissolved in 40mL of ethanol water to prepare a mixed salt solution, wherein the volume ratio of the ethanol to the water is 1:5; then adding 0.2g of wheat straw into the solution, stirring for 20min, and then dropwise adding alkali liquor until the pH of the solution is 10, wherein the concentration of the alkali is 3mol/L, and the alkali is sodium hydroxide; transferring the mixture into a hydrothermal reaction kettle, reacting for 6 hours at 160 ℃, centrifuging, washing, drying for 12 hours at 110 ℃, calcining for 12 hours at 480 ℃ in an air atmosphere, and grinding to obtain magnesium aluminum hydrotalcite;
(b) Then adding the magnesium aluminum hydrotalcite obtained in the step (a) into 50mL of ethanol water solution of 3-aminopropyl trimethoxysilane with the concentration of 2mol/L, wherein the volume ratio of ethanol water is 1:3; then reacting at 70 ℃ for 6 hours, centrifuging, washing with ethanol and deionized water, and drying at 80 ℃ for 18 hours to obtain silane modified magnesium aluminum hydrotalcite;
(III) preparation of polyimide composite foam Material
(1) Adding 10mg of polyamic acid, 1mg of graphene oxide, 0.3mg of silane modified zirconia prepared in the step (I) and 0.8mg of silane modified magnesia-alumina hydrotalcite prepared in the step (II) into 90g of water, adding 5.5g of triethylamine, stirring, and uniformly dispersing by ultrasonic to obtain an aqueous dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mold, and performing vacuum freeze drying for 80 hours at the vacuum degree of 2Pa at the temperature of minus 40 ℃ to obtain a composite foam material through thermal imidization; the thermal imidization method is to program the temperature under the following conditions: 80 ℃ for 3 hours, 200 ℃ for 2 hours and 280 ℃ for 5 hours.
Example 2
A method for preparing a hybrid polyimide foam material, the method comprising the steps of:
(I) Silane modified zirconia;
adding 1g of nano zirconia into 40g of ethanol-water mixed solution of 3-aminopropyl triethoxysilane with the mass fraction of 50wt%, wherein the volume of ethanol and water is 1:0.3; reacting at 80 ℃ for 3 hours, centrifuging, washing with ethanol and deionized water, and drying at 120 ℃ for 10 hours to obtain silane modified zirconium dioxide;
the grain diameter of the nanometer zirconia is 50nm;
(II) silane modified magnesium aluminum hydrotalcite;
(a) Weighing 4mol of magnesium acetate and 1mol of aluminum acetate, and dissolving in 40mL of ethanol water to prepare a mixed salt solution, wherein the volume ratio of the ethanol to the water is 1:3; then adding 0.3g of rice straw into the solution, and stirring for 30min; then dropwise adding alkali liquor to the pH value of the solution to be 10, wherein the concentration of the alkali is 4mol/L, and the alkali is potassium hydroxide; transferring the mixture into a hydrothermal reaction kettle, reacting for 4 hours at 180 ℃, centrifuging, washing, drying for 10 hours at 120 ℃, calcining for 10 hours at 520 ℃ in an air atmosphere, and grinding to obtain magnesium aluminum hydrotalcite;
(b) Then adding the magnesium aluminum hydrotalcite obtained in the step (a) into 50mL of ethanol water solution of 3-aminopropyl triethoxysilane with the concentration of 3mol/L, wherein the volume ratio of ethanol water is 1:2; then reacting for 4 hours at 80 ℃, centrifuging, washing with ethanol and deionized water, and drying for 14 hours at 90 ℃ to obtain silane modified magnesium aluminum hydrotalcite;
(III) preparation of polyimide composite foam Material
(1) Adding 10mg of polyamic acid, 1.2mg of graphene oxide, 0.2mg of silane modified zirconia prepared in the step (I) and 1mg of silane modified magnesia-alumina hydrotalcite prepared in the step (II) into 90mL of water, adding 6.5mg of triethylamine, stirring, and uniformly dispersing by ultrasonic to obtain an aqueous dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mold, and freeze-drying for 60 hours at the vacuum degree of 1Pa at the temperature of-45 ℃ to obtain a composite foam material through thermal imidization; the thermal imidization method is to program the temperature under the following conditions: 90 ℃ for 2 hours, 220 ℃ for 1 hour and 300 ℃ for 3 hours.
Example 3
A method for preparing a hybrid polyimide foam material, the method comprising the steps of:
(I) Silane modified zirconia;
adding 1g of nano zirconia into 40g of a 30wt% mixed solution of gamma-ureido propyl triethoxysilane and methanol water, wherein the alcohol is methanol; the volume of the methanol and the water is 1:0.1; reacting at 60 ℃ for 6 hours, centrifuging, washing with ethanol and deionized water, and drying at 80 ℃ for 14 hours to obtain silane modified zirconium dioxide; the grain diameter of the nanometer zirconia is 20nm;
(II) silane modified magnesium aluminum hydrotalcite;
(a) 2mol of magnesium chloride and 1mol of aluminum chloride are weighed and dissolved in 40mL of ethanol water to prepare a mixed salt solution, wherein the volume ratio of the ethanol to the water is 1:7; then 0.1g of wheat straw is added into the solution and stirred for 30min; then dropwise adding alkali liquor to the pH value of the solution to be 10, wherein the concentration of the alkali is 2mol/L, and the alkali is ammonia water; transferring the mixture into a hydrothermal reaction kettle, reacting for 8 hours at 140 ℃, centrifuging, washing, drying for 14 hours at 90 ℃, calcining for 14 hours at 450 ℃ in an air atmosphere, and grinding to obtain magnesium aluminum hydrotalcite;
(b) Then adding the magnesium aluminum hydrotalcite obtained in the step (a) into 25mL of gamma-ureido propyl triethoxysilane ethanol water solution with the concentration of 2mol/L, wherein the volume ratio of ethanol water is 1:4; then reacting at 60 ℃ for 8 hours, centrifuging, washing with ethanol and deionized water, and drying at 70 ℃ for 20 hours to obtain silane modified magnesium aluminum hydrotalcite;
(III) preparation of polyimide composite foam Material
(1) Adding 10mg of polyamic acid, 0.5mg of graphene oxide, 0.4mg of silane modified zirconia prepared in the step (I) and 0.6g of silane modified magnesia-alumina hydrotalcite prepared in the step (II) into 90mg of water, adding 4.5mg of triethylamine, stirring, and uniformly dispersing by ultrasonic to obtain an aqueous dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mold, and performing vacuum freeze drying for 90 hours at the vacuum degree of 4Pa at the temperature of minus 35 ℃ to obtain a composite foam material through thermal imidization; the thermal imidization method is to program the temperature under the following conditions: 4h at 70 ℃, 3h at 180 ℃ and 6h at 260 ℃.
Comparative example 1
A method for preparing a hybrid polyimide foam material, the method comprising the steps of:
(I) Zirconium oxide;
adding 1g of nano zirconia into 40g of methanol-water mixed solution, wherein the volume of methanol and water is 1:0.2, reacting for 5 hours at 70 ℃, centrifuging, washing with ethanol and deionized water, and drying for 12 hours at 100 ℃ to obtain zirconium dioxide;
the grain diameter of the nanometer zirconia is 35nm;
(II) silane modified magnesium aluminum hydrotalcite;
(a) 3mol of magnesium nitrate and 1mol of aluminum nitrate are weighed and dissolved in 40mL of ethanol water to prepare a mixed salt solution, wherein the volume ratio of the ethanol to the water is 1:5; then adding 0.2g of wheat straw into the solution, stirring for 20min, and then dropwise adding alkali liquor until the pH of the solution is 10, wherein the concentration of the alkali is 3mol/L, and the alkali is sodium hydroxide; transferring the mixture into a hydrothermal reaction kettle, reacting for 6 hours at 160 ℃, centrifuging, washing, drying for 12 hours at 110 ℃, calcining for 12 hours at 480 ℃ in an air atmosphere, and grinding to obtain magnesium aluminum hydrotalcite;
(b) Then adding the magnesium aluminum hydrotalcite obtained in the step (a) into an ethanol water solution containing 50mL of 3-aminopropyl trimethoxysilane with the concentration of 2mol/L, wherein the volume ratio of ethanol water is 1:3; then reacting at 70 ℃ for 6 hours, centrifuging, washing with ethanol and deionized water, and drying at 80 ℃ for 18 hours to obtain silane modified magnesium aluminum hydrotalcite;
(III) preparation of polyimide composite foam Material
(1) Adding 10mg of polyamic acid, 1mg of graphene oxide, 0.3mg of silane modified zirconia prepared in the step (I) and 0.8mg of silane modified magnesia-alumina hydrotalcite prepared in the step (II) into 90g of water, adding 5.5g of triethylamine, stirring, and uniformly dispersing by ultrasonic to obtain an aqueous dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mold, and performing vacuum freeze drying for 80 hours at the vacuum degree of 2Pa at the temperature of minus 40 ℃ to obtain a composite foam material through thermal imidization; the thermal imidization method is to program the temperature under the following conditions: 80 ℃ for 3 hours, 200 ℃ for 2 hours and 280 ℃ for 5 hours.
Comparative example 2
A method for preparing a hybrid polyimide foam material, the method comprising the steps of:
(I) Silane modified zirconia;
adding 1g of nano zirconia into 40g of a 40% mass fraction methanol-water mixed solution of 3-aminopropyl trimethoxy silane, reacting at 70 ℃ for 5 hours, centrifuging, washing with ethanol and deionized water, and drying at 100 ℃ for 12 hours to obtain silane modified zirconia;
the grain diameter of the nanometer zirconia is 35nm;
(II) magnesium aluminum hydrotalcite;
(a) 3mol of magnesium nitrate and 1mol of aluminum nitrate are weighed and dissolved in 40mL of ethanol water to prepare a mixed salt solution, wherein the volume ratio of the ethanol to the water is 1:5; then adding 0.2g of wheat straw into the solution, stirring for 20min, and then dropwise adding alkali liquor until the pH of the solution is 10, wherein the concentration of the alkali is 3mol/L, and the alkali is sodium hydroxide; transferring the mixture into a hydrothermal reaction kettle, reacting for 6 hours at 160 ℃, centrifuging, washing, drying for 12 hours at 110 ℃, calcining for 12 hours at 480 ℃ in an air atmosphere, and grinding to obtain magnesium aluminum hydrotalcite;
(b) Then adding the magnesium aluminum hydrotalcite obtained in the step (a) into 50mL of ethanol water solution, wherein the volume ratio of the ethanol water is 1:3; then reacting at 70 ℃ for 6 hours, centrifuging, washing with ethanol and deionized water, and drying at 80 ℃ for 18 hours to obtain magnesium aluminum hydrotalcite;
(III) preparation of polyimide composite foam Material
(1) Adding 10mg of polyamic acid, 1mg of graphene oxide, 0.3mg of silane modified zirconia prepared in the step (I) and 0.8mg of silane modified magnesia-alumina hydrotalcite prepared in the step (II) into 90g of water, adding 5.5g of triethylamine, stirring, and uniformly dispersing by ultrasonic to obtain an aqueous dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mold, and performing vacuum freeze drying for 80 hours at the vacuum degree of 2Pa at the temperature of minus 40 ℃ to obtain a composite foam material through thermal imidization; the thermal imidization method is to program the temperature under the following conditions: 80 ℃ for 3 hours, 200 ℃ for 2 hours and 280 ℃ for 5 hours.
Comparative example 3
A method for preparing a hybrid polyimide foam material, the method comprising the steps of:
(I) Silane modified zirconia;
adding 1g of nano zirconia into 40g of a 40% mass fraction methanol-water mixed solution of 3-aminopropyl trimethoxy silane, reacting at 70 ℃ for 5 hours, centrifuging, washing with ethanol and deionized water, and drying at 100 ℃ for 12 hours to obtain silane modified zirconia;
the grain diameter of the nanometer zirconia is 35nm;
(III) preparation of polyimide composite foam Material
(1) Adding 10mg of polyamic acid, 1mg of graphene oxide and 1.1mg of silane modified zirconia prepared in the step (I) into 90g of water, and then adding 5.5g of triethylamine, stirring and uniformly dispersing by ultrasonic to obtain an aqueous dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mold, and performing vacuum freeze drying for 80 hours at the vacuum degree of 2Pa at the temperature of minus 40 ℃ to obtain a composite foam material through thermal imidization; the thermal imidization method is to program the temperature under the following conditions: 80 ℃ for 3 hours, 200 ℃ for 2 hours and 280 ℃ for 5 hours.
Comparative example 4
A method for preparing a hybrid polyimide foam material, the method comprising the steps of:
(II) silane modified magnesium aluminum hydrotalcite;
(a) 3mol of magnesium nitrate and 1mol of aluminum nitrate are weighed and dissolved in 40mL of ethanol water to prepare a mixed salt solution, wherein the volume ratio of the ethanol to the water is 1:5; then adding 0.2g of wheat straw into the solution, stirring for 20min, and then dropwise adding alkali liquor until the pH of the solution is 10, wherein the concentration of the alkali is 3mol/L, and the alkali is sodium hydroxide; transferring the mixture into a hydrothermal reaction kettle, reacting for 6 hours at 160 ℃, centrifuging, washing, drying for 12 hours at 110 ℃, calcining for 12 hours at 480 ℃ in an air atmosphere, and grinding to obtain magnesium aluminum hydrotalcite;
(b) Then adding the magnesium aluminum hydrotalcite obtained in the step (a) into an ethanol water solution containing 50mL of 3-aminopropyl trimethoxysilane with the concentration of 2mol/L, wherein the volume ratio of ethanol water is 1:3; then reacting at 70 ℃ for 6 hours, centrifuging, washing with ethanol and deionized water, and drying at 80 ℃ for 18 hours to obtain silane modified magnesium aluminum hydrotalcite;
(III) preparation of polyimide composite foam Material
(1) Adding 10mg of polyamic acid, 1mg of graphene oxide and 1.1mg of silane modified magnesium aluminum hydrotalcite prepared in the step (II) into 90g of water, adding 5.5g of triethylamine, stirring, and uniformly dispersing by ultrasonic to obtain an aqueous dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mold, and performing vacuum freeze drying for 80 hours at the vacuum degree of 2Pa at the temperature of minus 40 ℃ to obtain a composite foam material through thermal imidization; the thermal imidization method is to program the temperature under the following conditions: 80 ℃ for 3 hours, 200 ℃ for 2 hours and 280 ℃ for 5 hours.
Comparative example 5
A method for preparing a hybrid polyimide foam material, the method comprising the steps of:
(I) Silane modified zirconia;
adding 1g of nano zirconia into 40g of a 40% mass fraction methanol-water mixed solution of 3-aminopropyl trimethoxy silane, reacting at 70 ℃ for 5 hours, centrifuging, washing with ethanol and deionized water, and drying at 100 ℃ for 12 hours to obtain silane modified zirconia;
the grain diameter of the nanometer zirconia is 35nm;
(II) silane modified magnesium aluminum hydrotalcite;
(a) 3mol of magnesium nitrate and 1mol of aluminum nitrate are weighed and dissolved in 40mL of ethanol water to prepare a mixed salt solution, wherein the volume ratio of the ethanol to the water is 1:5; stirring for 20min, and then dropwise adding alkali liquor until the pH value of the solution is 10, wherein the concentration of the alkali is 3mol/L, and the alkali is sodium hydroxide; transferring the mixture into a hydrothermal reaction kettle, reacting for 6 hours at 160 ℃, centrifuging, washing, drying for 12 hours at 110 ℃, calcining for 12 hours at 480 ℃ in an air atmosphere, and grinding to obtain magnesium aluminum hydrotalcite;
(b) Then adding the magnesium aluminum hydrotalcite obtained in the step (a) into an ethanol water solution containing 50mL of 3-aminopropyl trimethoxysilane with the concentration of 2mol/L, wherein the volume ratio of ethanol water is 1:3; then reacting at 70 ℃ for 6 hours, centrifuging, washing with ethanol and deionized water, and drying at 80 ℃ for 18 hours to obtain silane modified magnesium aluminum hydrotalcite;
(III) preparation of polyimide composite foam Material
(1) Adding 10mg of polyamic acid, 1mg of graphene oxide, 0.3mg of silane modified zirconia prepared in the step (I) and 0.8mg of silane modified magnesia-alumina hydrotalcite prepared in the step (II) into 90g of water, adding 5.5g of triethylamine, stirring, and uniformly dispersing by ultrasonic to obtain an aqueous dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mold, and performing vacuum freeze drying for 80 hours at the vacuum degree of 2Pa at the temperature of minus 40 ℃ to obtain a composite foam material through thermal imidization; the thermal imidization method is to program the temperature under the following conditions: 80 ℃ for 3 hours, 200 ℃ for 2 hours and 280 ℃ for 5 hours.
Comparative example 6
A method for preparing a hybrid polyimide foam material, the method comprising the steps of:
(I) Silane modified zirconia;
adding 1g of nano zirconia into 40g of a 40% mass fraction methanol-water mixed solution of 3-aminopropyl triethoxysilane, reacting at 70 ℃ for 5 hours, centrifuging, washing with ethanol and deionized water, and drying at 100 ℃ for 12 hours to obtain silane modified zirconia; the grain diameter of the nanometer zirconia is 35nm;
(II) silane modified magnesium aluminum hydrotalcite;
(a) 3mol of magnesium nitrate and 1mol of aluminum nitrate are weighed and dissolved in 40mL of ethanol water to prepare a mixed salt solution, wherein the volume ratio of the ethanol to the water is 1:5; then adding 0.2g of wheat straw into the solution, stirring for 20min, and then dropwise adding alkali liquor until the pH of the solution is 10, wherein the concentration of the alkali is 3mol/L, and the alkali is sodium hydroxide; transferring the mixture into a hydrothermal reaction kettle, reacting for 6 hours at 160 ℃, centrifuging, washing, drying for 12 hours at 110 ℃, calcining for 12 hours at 480 ℃ in an air atmosphere, and grinding to obtain magnesium aluminum hydrotalcite;
(b) Then adding the magnesium aluminum hydrotalcite obtained in the step (a) into an ethanol water solution containing 50mL of 3-aminopropyl triethoxysilane with the concentration of 2mol/L, wherein the volume ratio of ethanol water is 1:3; then reacting at 70 ℃ for 6 hours, centrifuging, washing with ethanol and deionized water, and drying at 80 ℃ for 18 hours to obtain silane modified magnesium aluminum hydrotalcite;
(III) preparation of polyimide composite foam Material
(1) Adding 10mg of polyamic acid, 1mg of graphene oxide, 0.3mg of silane modified zirconia prepared in the step (I) and 0.8mg of silane modified magnesia-alumina hydrotalcite prepared in the step (II) into 90g of water, adding 5.5g of triethylamine, stirring, and uniformly dispersing by ultrasonic to obtain an aqueous dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mold, and performing vacuum freeze drying for 80 hours at the vacuum degree of 2Pa at the temperature of minus 40 ℃ to obtain a composite foam material through thermal imidization; the thermal imidization method is to program the temperature under the following conditions: 80 ℃ for 3 hours, 200 ℃ for 2 hours and 280 ℃ for 5 hours.
Comparative example 7
A method for preparing a hybrid polyimide foam material, the method comprising the steps of:
(I) Silane modified zirconia;
adding 1g of nano zirconia into 40g of 40% gamma-ureidopropyl triethoxysilane methanol-water mixed solution, wherein the volume of methanol and water is 1:0.2, reacting for 5 hours at 70 ℃, centrifuging, washing with ethanol and deionized water, and drying for 12 hours at 100 ℃ to obtain silane modified zirconia; the grain diameter of the nanometer zirconia is 35nm;
(II) silane modified magnesium aluminum hydrotalcite;
(a) 3mol of magnesium nitrate and 1mol of aluminum nitrate are weighed and dissolved in 40mL of ethanol water to prepare a mixed salt solution, wherein the volume ratio of the ethanol to the water is 1:5; then adding 0.2g of wheat straw into the solution, stirring for 20min, and then dropwise adding alkali liquor until the pH of the solution is 10, wherein the concentration of the alkali is 3mol/L, and the alkali is sodium hydroxide; transferring the mixture into a hydrothermal reaction kettle, reacting for 6 hours at 160 ℃, centrifuging, washing, drying for 12 hours at 110 ℃, calcining for 12 hours at 480 ℃ in an air atmosphere, and grinding to obtain magnesium aluminum hydrotalcite; (b) Then adding the magnesium aluminum hydrotalcite obtained in the step (a) into an ethanol water solution containing 50mL of gamma-ureido propyl triethoxysilane with the concentration of 2mol/L, wherein the volume ratio of ethanol water is 1:3; then reacting at 70 ℃ for 6 hours, centrifuging, washing with ethanol and deionized water, and drying at 80 ℃ for 18 hours to obtain silane modified magnesium aluminum hydrotalcite;
(III) preparation of polyimide composite foam Material
(1) Adding 10mg of polyamic acid, 1mg of graphene oxide, 0.3mg of silane modified zirconia prepared in the step (I) and 0.8mg of silane modified magnesia-alumina hydrotalcite prepared in the step (II) into 90g of water, adding 5.5g of triethylamine, stirring, and uniformly dispersing by ultrasonic to obtain an aqueous dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mold, and performing vacuum freeze drying for 80 hours at the vacuum degree of 2Pa at the temperature of minus 40 ℃ to obtain a composite foam material through thermal imidization; the thermal imidization method is to program the temperature under the following conditions: 80 ℃ for 3 hours, 200 ℃ for 2 hours and 280 ℃ for 5 hours.
The limiting oxygen index and mechanical properties of the polyimide foams obtained in examples 1 to 3 and comparative examples 1 to 7 are shown in FIG. 1.
As can be seen from FIG. 1, the polyimide composite foam materials prepared by the present application have excellent flame retardant properties and mechanical properties by the mutual coordination between the components through the comparison of examples 1 to 3 and comparative examples 1 to 7.
The above examples are preferred embodiments of the present application, but the embodiments of the present application are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present application should be made in the equivalent manner, and the embodiments are included in the protection scope of the present application.

Claims (9)

1. A preparation method of a hybrid polyimide foam material is characterized by comprising the following steps: the preparation method comprises the following steps:
(I) Silane modified nano zirconia;
(II) silane modified magnesium aluminum hydrotalcite;
(III) preparation of polyimide composite foam Material
(1) Adding polyamide acid, graphene oxide, silane modified zirconia prepared in the step (I) and silane modified magnesium aluminum hydrotalcite prepared in the step (II) into water, adding triethylamine, stirring, and uniformly dispersing by ultrasonic to obtain an aqueous dispersion;
(2) pouring the aqueous dispersion prepared in the step (1) into a mold, and performing vacuum freeze drying and thermal imidization to obtain a composite foam material;
in the step (I), the preparation method of the silane modified nano zirconia comprises the following steps:
adding nano zirconia into an alcohol-water mixed solution of a silane coupling agent for reaction, centrifuging, washing with ethanol and deionized water, and drying at 80-120 ℃ for 10-14 h to obtain silane modified zirconium dioxide;
the volume ratio of the alcohol to the water is 1:0.1-0.3; the mass fraction of the aqueous alcohol solution of the silane coupling agent is 30-50wt%; the mass ratio of the alcohol-water mixed solution of the nano zirconia and the silane coupling agent is 1:40, a step of performing a;
in the step (II), the preparation method of the silane modified magnesium aluminum hydrotalcite comprises the following steps: (a) Weighing magnesium salt and aluminum salt, dissolving in ethanol water to prepare mixed salt solution, adding a certain amount of straw into the solution, stirring, dripping alkaline solution to adjust the pH of the solution, transferring to a hydrothermal reaction kettle for reaction, centrifuging, washing, drying, calcining, and grinding to obtain magnesium-aluminum hydrotalcite; (b) Then adding the magnesium aluminum hydrotalcite obtained in the step (a) into an ethanol aqueous solution of a silane coupling agent for reaction, centrifuging, washing with ethanol and deionized water, and drying to obtain silane modified magnesium aluminum hydrotalcite;
in the step (a), the molar ratio of magnesium to aluminum is 1:2-4: the volume ratio of the ethanol to the water is 1:3-7; the ratio of the straw to the aluminum salt is 0.1-0.3 g:1mol; the concentration of the alkali is 2-4 mol/L, and in the step (b), the molar ratio of the aluminum to the silane is 1:0.05-0.15; the volume ratio of the ethanol water is 1:2-4;
in the step (III), in the step (1) in the step (III), the mass ratio of the polyamic acid to water is (4:96) to (12:88); the mass ratio of the polyamide acid to the triethylamine is 100 (45-65).
2. The method for preparing the hybridized polyimide foam material according to claim 1, wherein the method comprises the following steps: in the step (I), the silane coupling agent is at least one of 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane and gamma-ureido propyl triethoxysilane; the alcohol is methanol or ethanol.
3. The method for preparing the hybridized polyimide foam material according to claim 1, wherein the method comprises the following steps: in the step (I), the particle size of the nano zirconia is 20-50 nm.
4. The method for preparing the hybridized polyimide foam material according to claim 1, wherein the method comprises the following steps: in the step (I), the reaction is carried out at 60-80 ℃ for 3-6 h, and the drying is carried out at 80-120 ℃ for 10-14 h.
5. The method for preparing the hybridized polyimide foam material according to claim 1, wherein the method comprises the following steps: in the step (II), the magnesium salt is at least one of magnesium nitrate, magnesium acetate and magnesium chloride; the aluminum salt is at least one of aluminum nitrate, aluminum chloride and aluminum acetate; the alkali is one of sodium hydroxide, potassium hydroxide, sodium carbonate and ammonia water; the straw is wheat straw or rice straw.
6. The method for preparing the hybridized polyimide foam material according to claim 1, wherein the method comprises the following steps: in step (II), in step (a); the stirring time is 10-30 min, and the pH is 10; the hydrothermal reaction is carried out for 4-8 hours at 140-180 ℃; the drying is carried out for 10-14 hours at the temperature of 90-120 ℃; the calcination is carried out for 10-14 hours in an air atmosphere at 450-520 ℃.
7. The method for preparing the hybridized polyimide foam material according to claim 1, wherein the method comprises the following steps: in step (II), in step (b); the concentration of the ethanol aqueous solution of the silane coupling agent is 2-4 mol/L; the reaction is carried out for 4-8 hours at the temperature of 60-80 ℃; and the drying is carried out at 70-90 ℃ for 14-20 h.
8. The method for preparing the hybridized polyimide foam material according to claim 1, wherein the method comprises the following steps: in the step (III), in the step (2) in the step (III), the freeze-drying temperature is-45 to-35 ℃ and the drying time is 60-90 hours; the vacuum degree is 1-4 Pa; the thermal imidization method is to program the temperature under the following conditions: 2-4 h at 70-90 ℃, 1-3 h at 180-220 ℃ and 3-6 h at 260-300 ℃.
9. A hybrid polyimide foam prepared by the method of preparing a hybrid polyimide foam according to any one of claims 1 to 8.
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