CN114806170A - Hybrid polyimide foam material and preparation method thereof - Google Patents

Hybrid polyimide foam material and preparation method thereof Download PDF

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CN114806170A
CN114806170A CN202210385251.0A CN202210385251A CN114806170A CN 114806170 A CN114806170 A CN 114806170A CN 202210385251 A CN202210385251 A CN 202210385251A CN 114806170 A CN114806170 A CN 114806170A
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silane
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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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    • 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
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Abstract

The invention 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) preparation of polyimide syntactic foam: adding polyamic acid, graphene oxide, the silane modified zirconia prepared in the step (I) and the silane modified magnesium aluminum hydrotalcite prepared in the step (II) into water, adding triethylamine, stirring, and performing ultrasonic dispersion to obtain an aqueous dispersion; and secondly, pouring the aqueous dispersion prepared in the step I into a mould, and carrying out vacuum freeze drying and thermal imidization to obtain the composite foam material. The composite foam material prepared by the invention has excellent heat resistance, mechanical property, flame retardance and the like.

Description

Hybrid polyimide foam material and preparation method thereof
Technical Field
The invention belongs to the technical field of composite materials. More particularly, it relates 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 molecular chain. Polyimides are also classified into aliphatic polyimides and aromatic polyimides according to the type of molecular unit structure. Since the comprehensive properties of aromatic polyimide are superior to those of aliphatic polyimide, and the application thereof is more common, the aromatic polyimide is generally referred to as polyimide.
With the rapid development of high and new technologies in recent years, people have urgent needs for high-heat-resistance, high-strength and lightweight structural materials, and research on the materials is gradually heading towards multi-functionalization, high-performance and low-cost development. Polyimide contains a large amount of pi-pi conjugated structures due to the fact that a main chain contains a five-membered imide ring structure, has excellent performances such as high strength, high temperature resistance, radiation resistance and high modulus, is one of the materials with the best comprehensive performance in organic polymer materials, and has wide application in the fields of aerospace, microelectronic materials, films, separation membranes, foamed plastics, engineering plastics, biomedicine and the like.
Tian huafen and the like prepare polyimide foam (PIF) by taking pyromellitic dianhydride (PMDA) and polymethylene polyphenyl polyisocyanate (PAPI) as monomers, and then add graphene for filling modification. Dissolving PMDA and methanol in Dimethylformamide (DMF) for esterification reaction, and then respectively adding Triethanolamine (TEOA) catalyst, dibutyltin dilaurate, silicone oil and water, and uniformly stirring to obtain a precursor solution as a component A; uniformly stirring graphene with different contents and PAPI to obtain a solution serving as a component B; stirring the mixed solution of the component A and the component B at a high speed, quickly pouring the mixed solution into a mould for free foaming, and finally performing high-temperature treatment to finish the whole preparation process. The thermal stability and flame retardant properties of PIF are enhanced with increasing graphene content, which increases from 31.0% to 34.8% of pure PIF at a graphene content of 3.25% (w). The reason that the thermal stability is 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 of the graphene destroys the good interface 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 firstly 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, with greater foam density and greater compressive strength. Meanwhile, the tighter the foam holes are arranged, the higher the hardness of the PIF is, and the higher the compressive strength is, so that the strength of the wall of the foam hole is obviously improved by adding the high-modulus graphene, and the compressive strength of the PIF is improved; however, when the mass fraction of the graphene exceeds 1.98%, the excessive graphene may agglomerate, thereby decreasing the compressive strength of the composite material.
Kizilkaya et al prepared novel PI/SiO 2 The film was nanocomposite and its properties were investigated. The results show that with SiO 2 The content is increased, and the tensile strength, the tensile modulus and the elongation at break of the composite film all show the trend of increasing first and then decreasing when the SiO 2 The mass fraction is maximum at 6%. The degradation temperature of pure PI is 300 ℃, and 20% (w) of SiO is added 2 The initial decomposition temperature of the nano composite material is 550 ℃, and the thermal stability of the composite material is obviously improved.
CN106433129A discloses a graphene/SiO 2 Hybrid polyimide foam material and preparation method thereof, and graphene/SiO 2 The hybrid 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 isocyanic acid radical on the surface. graphene/SiO prepared by the invention 2 The hybrid polyimide foam material fully exerts the good reinforcing effect of graphene oxide and the good toughening effect of silicon dioxide on the one hand, and overcomes the defect that the graphene oxide and the silicon dioxide are easy to agglomerate on the other hand, so that SiO is enabled to be easily agglomerated 2 The particles can be uniformly distributed on the graphene sheet layers, the graphene sheet layers are not easy to overlap, the dispersibility is obviously improved, and the polyimide film also has the properties of good heat resistance, high mechanical property, strong flame retardance and the like.
That is, although improvement of heat resistance, flame retardancy and other properties of polyimide has been achieved to some extent by modification of polyimide, the above-mentioned properties have not yet been able to satisfy practical production requirements, and thus development of a novel polyimide foam having excellent heat resistance, mechanical properties, flame retardancy and other properties has been urgently required.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings in the prior art and provides 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) preparation of polyimide syntactic foam: adding polyamic acid, graphene oxide, the silane modified zirconia prepared in the step (I) and the silane modified magnesium aluminum hydrotalcite prepared in the step (II) into water, adding triethylamine, stirring, and performing ultrasonic dispersion to obtain an aqueous dispersion; and secondly, pouring the aqueous dispersion prepared in the step I into a mould, and carrying out vacuum freeze drying and thermal imidization to obtain the composite foam material. The composite foam material prepared by the invention has excellent heat resistance, mechanical property, flame retardance and the like.
The invention aims to provide a preparation method of a hybrid polyimide foam material.
It is another object of the present invention to provide a hybrid polyimide foam.
The above purpose of the invention is realized by the following technical scheme:
a method for preparing a hybrid polyimide foam, the method comprising the steps of:
(I) silane modified nano zirconia;
(II) silane-modified magnesium aluminum hydrotalcite;
(III) preparation of polyimide syntactic foam
Adding polyamic acid, graphene oxide, the silane modified zirconia prepared in the step (I) and the silane modified magnesium aluminum hydrotalcite prepared in the step (II) into water, adding triethylamine, stirring, and performing ultrasonic dispersion to obtain an aqueous dispersion;
and secondly, pouring the aqueous dispersion prepared in the step I into a mould, and carrying out 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 the nano zirconia into an alcohol-water mixed solution of a silane coupling agent for reaction, centrifuging, cleaning with ethanol and deionized water, and drying at 80-120 ℃ for 10-14 h to obtain the silane modified zirconium dioxide.
Preferably, the silane coupling agent is at least one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and gamma-ureidopropyltriethoxysilane; 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 alcohol-water solution of the silane coupling agent is 30-50 wt%; 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 h, and the drying is carried out at 80-120 ℃ for 10-14 h.
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 the magnesium salt and the aluminum salt in ethanol water to prepare a mixed salt solution, adding a certain amount of straws into the solution, stirring, dropwise adding alkali liquor to adjust the pH value of the solution, transferring the solution into a hydrothermal reaction kettle for reaction, centrifuging, washing, drying, calcining, and grinding to obtain magnesium-aluminum hydrotalcite; (b) and (b) adding the magnesium-aluminum hydrotalcite obtained in the step (a) into an ethanol water solution of a 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-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and gamma-ureidopropyltriethoxysilane; 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: 1 mol; 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 at 140-180 ℃ for 4-8 h; the drying is carried out for 10-14 h at the temperature of 90-120 ℃; the calcination is carried out for 10-14 h at 450-520 ℃ in an air atmosphere.
Preferably, in step (b); the concentration of the ethanol water solution of the silane coupling agent is 2-4 mol/L; the reaction is carried out for 4-8 h at the temperature of 60-80 ℃; the drying is carried out for 14-20 h at 70-90 ℃.
Preferably, in step (III), in the (r) step 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 polyamic acid to the water is (4:96) - (12: 88); the mass ratio of the polyamic acid to the triethylamine is 100 (45-65);
preferably, in the step (III), the freeze drying temperature is-45 to-35 ℃, and the drying time is 60 to 90 hours; the vacuum degree is 1-4 Pa; the thermal imidization method is to program temperature under the following conditions: 70-90 ℃ for 2-4 h, 180-220 ℃ for 1-3 h, and 260-300 ℃ for 3-6 h.
The hybrid polyimide foam material is prepared based on the preparation method of the hybrid polyimide foam material.
The invention has the following beneficial effects:
(1) the silane modified zirconia can improve the compatibility of the zirconia, so that the comprehensive performance of the polyimide is improved;
(2) in the process of preparing the hydrotalcite, the hydrotalcite is adsorbed on the surface of the straw by utilizing the adsorption performance of the straw, then the hydrotalcite loaded on the surface of the straw is obtained through hydrothermal preparation, and then the straw is removed through calcination, so that the appearance of the straw is kept, the specific surface area is improved, meanwhile, the modification of silane is facilitated, and further, the dispersion in a matrix is improved;
(3) the silane-modified zirconium oxide and the silane-modified hydrotalcite are utilized, and the synergistic effect of the two components is utilized, so that the bonding between the components is promoted, and the mechanical properties, the flame retardance and the like 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 tests conducted in examples and comparative examples.
Detailed Description
The present invention is further illustrated by the following specific examples, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
A method for preparing a hybrid polyimide foam, the method comprising the steps of:
(I) silane-modified zirconia;
adding 1g of nano zirconia into 40g of a methanol-water mixed solution of 40 mass percent of 3-aminopropyltrimethoxysilane, wherein the volume of methanol and water is 1:0.2, reacting for 5 hours at 70 ℃, then centrifuging, washing with ethanol and deionized water, and drying for 12 hours at 100 ℃ to obtain silane modified zirconium dioxide;
the grain diameter of the nano zirconia is 35 nm;
(II) silane-modified magnesium aluminum hydrotalcite;
(a) weighing 3mol of magnesium nitrate and 1mol of aluminum nitrate, dissolving 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 value of the solution is 10, wherein the concentration of the alkali is 3mol/L, and the alkali is sodium hydroxide; then transferring the mixture to 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 the air atmosphere, and grinding to obtain magnesium-aluminum hydrotalcite;
(b) then adding the magnesium-aluminum hydrotalcite obtained in the step (a) into 50mL of 2mol/L ethanol water solution of 3-aminopropyltrimethoxysilane, wherein the volume ratio of the ethanol to the water is 1: 3; then reacting for 6h at 70 ℃, centrifuging, washing with ethanol and deionized water, and drying for 18h at 80 ℃ to obtain silane modified magnesium aluminum hydrotalcite;
(III) preparation of polyimide syntactic foam
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 magnesium aluminum hydrotalcite prepared in the step (II) into 90g of water, adding 5.5g of triethylamine, stirring and uniformly dispersing by ultrasound to obtain an aqueous dispersion;
pouring the aqueous dispersion prepared in the step one into a mould, carrying out vacuum freeze drying for 80 hours at the temperature of minus 40 ℃ and under the vacuum degree of 2Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 3 hours at 80 ℃, 2 hours at 200 ℃ and 5 hours at 280 ℃.
Example 2
A method for preparing a hybrid polyimide foam, the method comprising the steps of:
(I) silane-modified zirconia;
adding 1g of nano zirconia into 40g of ethanol-water mixed solution of 50wt% of 3-aminopropyltriethoxysilane by mass fraction, wherein the volume of ethanol and water is 1: 0.3; reacting at 80 ℃ for 3h, centrifuging, washing with ethanol and deionized water, and drying at 120 ℃ for 10h to obtain silane modified zirconium dioxide;
the grain diameter of the nano zirconia is 50 nm;
(II) silane-modified magnesium aluminum hydrotalcite;
(a) weighing 4mol of magnesium acetate and 1mol of aluminum acetate, and dissolving the magnesium acetate and the aluminum acetate 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 0.3g of rice straw is added into the solution and stirred for 30 min; then, dropwise adding alkali liquor until the pH value of the solution is 10, wherein the concentration of the alkali is 4mol/L, and the alkali is potassium hydroxide; then transferring the mixture to 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 the air atmosphere, and grinding to obtain magnesium-aluminum hydrotalcite;
(b) then adding the magnesium-aluminum hydrotalcite obtained in the step (a) into 50mL of 3-aminopropyltriethoxysilane 3-aminopropyl-triethoxysilane ethanol water solution with the volume ratio of the ethanol water being 1: 2; then reacting for 4h at 80 ℃, centrifuging, washing with ethanol and deionized water, and drying for 14h at 90 ℃ to obtain silane modified magnesium aluminum hydrotalcite;
(III) preparation of polyimide syntactic foam
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 magnesium aluminum hydrotalcite prepared in the step (II) into 90mL of water, adding 6.5mg of triethylamine, stirring, and performing ultrasonic dispersion uniformly to obtain an aqueous dispersion;
pouring the aqueous dispersion prepared in the step one into a mould, freezing and drying for 60 hours at the temperature of minus 45 ℃ and under the vacuum degree of 1Pa, and performing thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 2h at 90 ℃, 1h at 220 ℃ and 3h at 300 ℃.
Example 3
A method for preparing a hybrid polyimide foam, the method comprising the steps of:
(I) silane-modified zirconia;
adding 1g of nano zirconia into 40g of methanol-water mixed solution of gamma-ureidopropyltriethoxysilane with the mass fraction of 30wt%, wherein the alcohol is methanol; the volume of the methanol and the water is 1: 0.1; reacting at 60 ℃ for 6h, centrifuging, washing with ethanol and deionized water, and drying at 80 ℃ for 14h to obtain silane modified zirconium dioxide; the grain diameter of the nano zirconia is 20 nm;
(II) silane-modified magnesium aluminum hydrotalcite;
(a) weighing 2mol of magnesium chloride and 1mol of aluminum chloride, dissolving 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 30 min; then, dropwise adding alkali liquor until the pH value of the solution is 10, wherein the alkali is 2mol/L, and the alkali is ammonia water; then transferring the mixture to 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 the air atmosphere, and grinding to obtain the magnesium-aluminum hydrotalcite;
(b) then adding the magnesium-aluminum hydrotalcite obtained in the step (a) into 25mL of 2mol/L gamma-ureidopropyltriethoxysilane ethanol water solution, wherein the volume ratio of ethanol to water is 1: 4; then reacting for 8h at 60 ℃, centrifuging, washing with ethanol and deionized water, and drying for 20h at 70 ℃ to obtain silane modified magnesium aluminum hydrotalcite;
(III) preparation of polyimide syntactic foam
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 magnesium aluminum hydrotalcite prepared in the step (II) into 90mg of water, adding 4.5mg of triethylamine, stirring, and performing ultrasonic dispersion to obtain an aqueous dispersion;
pouring the aqueous dispersion prepared in the step one into a mould, carrying out vacuum freeze drying for 90 hours at the temperature of minus 35 ℃ and under the vacuum degree of 4Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 4 hours at 70 ℃, 3 hours at 180 ℃ and 6 hours at 260 ℃.
Comparative example 1
A method for preparing a hybrid polyimide foam, the method comprising the steps of:
(I) zirconium oxide;
adding 1g of nano zirconia into 40g of methanol-water mixed solution, reacting for 5 hours at 70 ℃ with the volume of methanol and water being 1:0.2, centrifuging, washing with ethanol and deionized water, and drying for 12 hours at 100 ℃ to obtain zirconium dioxide;
the grain diameter of the nano zirconia is 35 nm;
(II) silane-modified magnesium aluminum hydrotalcite;
(a) weighing 3mol of magnesium nitrate and 1mol of aluminum nitrate, dissolving 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 value of the solution is 10, wherein the concentration of the alkali is 3mol/L, and the alkali is sodium hydroxide; then transferring the mixture to 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 the 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 trimethoxy silane with the concentration of 2mol/L, wherein the volume ratio of the ethanol water is 1: 3; then reacting for 6h at 70 ℃, centrifuging, washing with ethanol and deionized water, and drying for 18h at 80 ℃ to obtain silane modified magnesium aluminum hydrotalcite;
(III) preparation of polyimide syntactic foam
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 magnesium aluminum hydrotalcite prepared in the step (II) into 90g of water, adding 5.5g of triethylamine, stirring and uniformly dispersing by ultrasound to obtain an aqueous dispersion;
pouring the aqueous dispersion prepared in the step one into a mould, carrying out vacuum freeze drying for 80 hours at the temperature of minus 40 ℃ and under the vacuum degree of 2Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 3 hours at 80 ℃, 2 hours at 200 ℃ and 5 hours at 280 ℃.
Comparative example 2
A method for preparing a hybrid polyimide foam, the method comprising the steps of:
(I) silane-modified zirconia;
adding 1g of nano zirconia into 40g of a methanol-water mixed solution of 40 mass percent of 3-aminopropyltrimethoxysilane, wherein the volume of methanol and water is 1:0.2, reacting for 5 hours at 70 ℃, then centrifuging, washing with ethanol and deionized water, and drying for 12 hours at 100 ℃ to obtain silane modified zirconium dioxide;
the grain diameter of the nano zirconia is 35 nm;
(II) magnesium aluminum hydrotalcite;
(a) weighing 3mol of magnesium nitrate and 1mol of aluminum nitrate, dissolving 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 value of the solution is 10, wherein the concentration of the alkali is 3mol/L, and the alkali is sodium hydroxide; then transferring the mixture to 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 the 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 for 6h at 70 ℃, centrifuging, washing with ethanol and deionized water, and drying for 18h at 80 ℃ to obtain the magnalium hydrotalcite;
(III) preparation of polyimide syntactic foam
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 magnesium aluminum hydrotalcite prepared in the step (II) into 90g of water, adding 5.5g of triethylamine, stirring and uniformly dispersing by ultrasound to obtain an aqueous dispersion;
pouring the aqueous dispersion prepared in the step one into a mould, carrying out vacuum freeze drying for 80 hours at the temperature of minus 40 ℃ and under the vacuum degree of 2Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 3 hours at 80 ℃, 2 hours at 200 ℃ and 5 hours at 280 ℃.
Comparative example 3
A method for preparing a hybrid polyimide foam, the method comprising the steps of:
(I) silane-modified zirconia;
adding 1g of nano zirconia into 40g of a methanol-water mixed solution of 40 mass percent of 3-aminopropyltrimethoxysilane, wherein the volume of methanol and water is 1:0.2, reacting for 5 hours at 70 ℃, then centrifuging, washing with ethanol and deionized water, and drying for 12 hours at 100 ℃ to obtain silane modified zirconium dioxide;
the grain diameter of the nano zirconia is 35 nm;
(III) preparation of polyimide syntactic foam
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, adding 5.5g of triethylamine, stirring, and uniformly dispersing by ultrasonic waves to obtain an aqueous dispersion;
pouring the aqueous dispersion prepared in the step one into a mould, carrying out vacuum freeze drying for 80 hours at the temperature of minus 40 ℃ and under the vacuum degree of 2Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 3 hours at 80 ℃, 2 hours at 200 ℃ and 5 hours at 280 ℃.
Comparative example 4
A method for preparing a hybrid polyimide foam, the method comprising the steps of:
(II) silane-modified magnesium aluminum hydrotalcite;
(a) weighing 3mol of magnesium nitrate and 1mol of aluminum nitrate, dissolving 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 value of the solution is 10, wherein the concentration of the alkali is 3mol/L, and the alkali is sodium hydroxide; then transferring the mixture to 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 the 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 trimethoxy silane with the concentration of 2mol/L, wherein the volume ratio of the ethanol water is 1: 3; then reacting for 6h at 70 ℃, centrifuging, washing with ethanol and deionized water, and drying for 18h at 80 ℃ to obtain silane modified magnesium aluminum hydrotalcite;
(III) preparation of polyimide syntactic foam
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 waves to obtain an aqueous dispersion;
pouring the aqueous dispersion prepared in the step one into a mould, carrying out vacuum freeze drying for 80 hours at the temperature of minus 40 ℃ and under the vacuum degree of 2Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 3 hours at 80 ℃, 2 hours at 200 ℃ and 5 hours at 280 ℃.
Comparative example 5
A method for preparing a hybrid polyimide foam, the method comprising the steps of:
(I) silane-modified zirconia;
adding 1g of nano zirconia into 40g of a methanol-water mixed solution of 40 mass percent of 3-aminopropyltrimethoxysilane, wherein the volume of methanol and water is 1:0.2, reacting for 5 hours at 70 ℃, then centrifuging, washing with ethanol and deionized water, and drying for 12 hours at 100 ℃ to obtain silane modified zirconium dioxide;
the grain diameter of the nano zirconia is 35 nm;
(II) silane-modified magnesium aluminum hydrotalcite;
(a) weighing 3mol of magnesium nitrate and 1mol of aluminum nitrate, dissolving 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; then transferring the mixture to 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 the 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 trimethoxy silane with the concentration of 2mol/L, wherein the volume ratio of the ethanol water is 1: 3; then reacting for 6h at 70 ℃, centrifuging, washing with ethanol and deionized water, and drying for 18h at 80 ℃ to obtain silane modified magnesium aluminum hydrotalcite;
(III) preparation of polyimide syntactic foam
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 magnesium aluminum hydrotalcite prepared in the step (II) into 90g of water, adding 5.5g of triethylamine, stirring and uniformly dispersing by ultrasound to obtain an aqueous dispersion;
pouring the aqueous dispersion prepared in the step I into a mould, carrying out vacuum freeze drying for 80 hours at the temperature of minus 40 ℃ and under the vacuum degree of 2Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 3 hours at 80 ℃, 2 hours at 200 ℃ and 5 hours at 280 ℃.
Comparative example 6
A method for preparing a hybrid polyimide foam, the method comprising the steps of:
(I) silane-modified zirconia;
adding 1g of nano zirconia into 40g of a methanol-water mixed solution of 40 mass percent 3-aminopropyltriethoxysilane, reacting for 5h at 70 ℃, centrifuging, washing with ethanol and deionized water, and drying for 12h at 100 ℃ to obtain silane modified zirconium dioxide, wherein the volume of the methanol and the water is 1: 0.2; the grain diameter of the nano zirconia is 35 nm;
(II) silane-modified magnesium aluminum hydrotalcite;
(a) weighing 3mol of magnesium nitrate and 1mol of aluminum nitrate, dissolving 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 value of the solution is 10, wherein the concentration of the alkali is 3mol/L, and the alkali is sodium hydroxide; then transferring the mixture to 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 the 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-aminopropyltriethoxysilane with the concentration of 2mol/L, wherein the volume ratio of the ethanol water is 1: 3; then reacting for 6h at 70 ℃, centrifuging, washing with ethanol and deionized water, and drying for 18h at 80 ℃ to obtain silane modified magnesium aluminum hydrotalcite;
(III) preparation of polyimide syntactic foam
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 magnesium aluminum hydrotalcite prepared in the step (II) into 90g of water, adding 5.5g of triethylamine, stirring and uniformly dispersing by ultrasound to obtain an aqueous dispersion;
pouring the aqueous dispersion prepared in the step one into a mould, carrying out vacuum freeze drying for 80 hours at the temperature of minus 40 ℃ and under the vacuum degree of 2Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 3 hours at 80 ℃, 2 hours at 200 ℃ and 5 hours at 280 ℃.
Comparative example 7
A method for preparing a hybrid polyimide foam, the method comprising the steps of:
(I) silane-modified zirconia;
adding 1g of nano zirconia into 40g of a methanol-water mixed solution of gamma-ureidopropyltriethoxysilane with the mass fraction of 40%, wherein the volume of methanol and water is 1:0.2, reacting for 5 hours at 70 ℃, then centrifuging, washing with ethanol and deionized water, and drying for 12 hours at 100 ℃ to obtain silane modified zirconium dioxide; the grain diameter of the nano zirconia is 35 nm;
(II) silane-modified magnesium aluminum hydrotalcite;
(a) weighing 3mol of magnesium nitrate and 1mol of aluminum nitrate, dissolving 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 value of the solution is 10, wherein the concentration of the alkali is 3mol/L, and the alkali is sodium hydroxide; then transferring the mixture to 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 the 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 gamma-ureidopropyltriethoxysilane with the concentration of 2mol/L, wherein the volume ratio of the ethanol water is 1: 3; then reacting for 6h at 70 ℃, centrifuging, washing with ethanol and deionized water, and drying for 18h at 80 ℃ to obtain silane modified magnesium aluminum hydrotalcite;
(III) preparation of polyimide syntactic foam
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 magnesium aluminum hydrotalcite prepared in the step (II) into 90g of water, adding 5.5g of triethylamine, stirring and uniformly dispersing by ultrasound to obtain an aqueous dispersion;
pouring the aqueous dispersion prepared in the step one into a mould, carrying out vacuum freeze drying for 80 hours at the temperature of minus 40 ℃ and under the vacuum degree of 2Pa, and carrying out thermal imidization to obtain a composite foam material; the thermal imidization method is to program temperature under the following conditions: 3 hours at 80 ℃, 2 hours at 200 ℃ and 5 hours at 280 ℃.
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, by comparing examples 1 to 3 with comparative examples 1 to 7, the polyimide syntactic foam prepared herein has excellent flame retardancy and mechanical properties by virtue of the mutual coordination between the components.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (14)

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 syntactic foam
Adding polyamic acid, graphene oxide, the silane modified zirconia prepared in the step (I) and the silane modified magnesium aluminum hydrotalcite prepared in the step (II) into water, adding triethylamine, stirring, and performing ultrasonic dispersion to obtain an aqueous dispersion;
and secondly, pouring the aqueous dispersion prepared in the step I into a mould, and carrying out vacuum freeze drying and thermal imidization to obtain the composite foam material.
2. The preparation method of hybrid polyimide foam material according to claim 1, wherein the preparation method comprises the following steps: in the step (1), the preparation method of the silane modified nano-zirconia comprises the following steps:
adding the nano zirconia into an alcohol-water mixed solution of a silane coupling agent for reaction, centrifuging, cleaning with ethanol and deionized water, and drying at 80-120 ℃ for 10-14 h to obtain the silane modified zirconium dioxide.
3. The preparation method of hybrid polyimide foam material according to claim 2, characterized in that: the silane coupling agent is at least one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and gamma-ureidopropyltriethoxysilane; the alcohol is methanol or ethanol.
4. The preparation method of hybrid polyimide foam material according to claim 2, characterized in that: the particle size of the nano zirconia is 20-50 nm.
5. The preparation method of hybrid polyimide foam material according to claim 2, characterized in that: the volume of the alcohol and the water is 1: 0.1-0.3; the mass fraction of the alcohol-water solution of the silane coupling agent is 30-50 wt%; the mass ratio of the alcohol-water mixed solution of the nano zirconia and the silane coupling agent is 1: 40.
6. the preparation method of hybrid polyimide foam material according to claim 2, characterized in that: the reaction is carried out at the temperature of 60-80 ℃ for 3-6 h, and the drying is carried out at the temperature of 80-120 ℃ for 10-14 h.
7. The preparation method of hybrid polyimide foam material according to claim 1, wherein the preparation method comprises the following steps: 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 the magnesium salt and the aluminum salt in ethanol water to prepare a mixed salt solution, then adding a certain amount of straws into the solution, stirring, then dropwise adding alkali liquor to adjust the pH value of the solution, then transferring the solution into a hydrothermal reaction kettle for reaction, centrifuging, washing, drying, then calcining, and grinding to obtain magnesium-aluminum hydrotalcite; (b) and (b) adding the magnesium-aluminum hydrotalcite obtained in the step (a) into the added silane coupling agent ethanol water solution for reaction, centrifuging, washing with ethanol and deionized water, and drying to obtain the silane modified magnesium-aluminum hydrotalcite.
8. The preparation method of hybrid polyimide foam material according to claim 7, wherein the preparation method comprises the following steps: 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 straws are wheat straws or rice straws; .
9. The preparation method of hybrid polyimide foam material according to claim 7, wherein the preparation method comprises the following steps: 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: 1 mol; 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.
10. The method of claim 7, wherein the method comprises the following steps: in step (a); the stirring time is 10-30 min, and the pH is 10; the hydrothermal reaction is carried out at 140-180 ℃ for 4-8 h; the drying is carried out for 10-14 h at the temperature of 90-120 ℃; the calcination is carried out for 10-14 h at 450-520 ℃ in an air atmosphere.
11. The preparation method of hybrid polyimide foam material according to claim 7, wherein the preparation method comprises the following steps: in step (b); the concentration of the ethanol water solution of the silane coupling agent is 2-4 mol/L; the reaction is carried out for 4-8 h at the temperature of 60-80 ℃; the drying is carried out for 14-20 h at 70-90 ℃.
12. The preparation method of hybrid polyimide foam material according to claim 1, wherein the preparation method comprises the following steps: in step (III), in the (r) step 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 polyamic acid to the water is (4:96) - (12: 88); the mass ratio of the polyamic acid to the triethylamine is 100 (45-65).
13. The method for preparing hybrid polyimide foam according to claim 1, wherein the method comprises the following steps: in the step (III), the freeze drying temperature is-45 to-35 ℃, and the drying time is 60 to 90 hours; the vacuum degree is 1-4 Pa; the thermal imidization method is to program temperature under the following conditions: 70-90 ℃ for 2-4 h, 180-220 ℃ for 1-3 h, and 260-300 ℃ for 3-6 h.
14. A hybrid polyimide foam prepared by the process of any one of claims 1-13.
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