CN113842843A - Preparation method of alumina aerogel material derived by taking polyimide as template - Google Patents
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- CN113842843A CN113842843A CN202111152986.0A CN202111152986A CN113842843A CN 113842843 A CN113842843 A CN 113842843A CN 202111152986 A CN202111152986 A CN 202111152986A CN 113842843 A CN113842843 A CN 113842843A
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Abstract
The invention relates to an alumina aerogel material derived by taking polyimide as a template, a preparation method and application thereof, wherein the preparation method specifically comprises the following steps: s1: dissolving inorganic metal aluminum salt and polyamic acid salt solution in water in sequence, adding epoxypropane after stirring uniformly, and standing to obtain alumina-polyamic acid salt composite wet gel; s2: carrying out solvent replacement on the alumina-polyamic acid salt composite wet gel for multiple times to remove impurities, and then carrying out alcohol supercritical drying to obtain alumina-polyimide composite aerogel; s3: and calcining the alumina-polyimide composite aerogel to obtain the alumina aerogel material. Compared with the prior art, the alumina aerogel material prepared by the invention has the advantages of low density, excellent compressibility, outstanding thermal stability, outstanding high-temperature heat-insulating property, mechanical compressibility and ultrahigh temperature resistance, and the related preparation method has the advantages of low energy consumption, low cost and simple process, and is beneficial to promoting the large-scale production of the material.
Description
Technical Field
The invention relates to the technical field of aerogel preparation, in particular to an alumina aerogel material derived by taking polyimide as a template, a preparation method and application thereof.
Background
Among the many types of oxide aerogels, alumina aerogels are the most temperature resistant aerogel materials.
However, the ultra-high porosity causes alumina aerogel to have a defect of poor mechanical properties. The alumina aerogel is easy to break and crack under the action of external force. In addition, under the condition of ultra-high temperature (1000 ℃ -1300 ℃), the alumina aerogel is easy to sinter due to the crystal orientation transformation of the internal structure, and the specific surface area is greatly reduced.
In order to further improve the heat resistance of the alumina aerogel, researchers have attempted to add additives such as silica, barium oxide, and SiC whiskers to the framework of the alumina aerogel, or to modify the alumina aerogel framework in a gas phase or a liquid phase, thereby suppressing the crystal orientation transition of the alumina aerogel at high temperatures. Although the two methods can improve the heat resistance of the alumina aerogel to a certain extent, the defect of poor mechanical property is not obviously improved all the time. In addition, some researchers try to introduce organic components into the alumina aerogel framework, so that although the mechanical property of the alumina aerogel can be effectively improved, the introduction of the organic components can greatly reduce the thermal stability of the aerogel material, and thus the aerogel material cannot be applied to the high-temperature field. Therefore, the synthesis of the aerogel material with excellent mechanical property and ultrahigh temperature resistance has extremely important practical significance.
Disclosure of Invention
The invention aims to provide an alumina aerogel material derived by taking polyimide as a template, a preparation method and application thereof.
The purpose of the invention is realized by the following technical scheme:
a preparation method of an alumina aerogel material derived by taking polyimide as a template specifically comprises the following steps:
s1: dissolving inorganic metal aluminum salt and polyamic acid salt solution in water in sequence, adding epoxypropane after stirring uniformly, and standing to obtain the alumina-polyamic acid salt composite wet gel
S2: carrying out solvent replacement for many times on the alumina-polyamic acid salt composite wet gel obtained in the step S1 to remove impurities, and then carrying out alcohol supercritical drying to realize thermal imidization of polyamic acid salt to obtain alumina-polyimide composite aerogel, wherein a reaction equation is shown below;
s3: and (4) calcining the alumina-polyimide composite aerogel obtained in the step S2 to obtain an alumina aerogel material.
Further, the preparation method further includes step S0, which is located before step S1:
s0: dissolving a diamine compound and a dianhydride compound in a solvent in sequence, stirring, adding water, collecting precipitated polyamic acid, washing, freeze-drying to obtain a pure polyamic acid solid, dissolving the pure polyamic acid solid in water, and adding ammonia water to obtain a polyamic acid salt solution, wherein the ammonia water has the function of dissolving the pure polyamic acid solid so as to form the polyamic acid salt solution, and the chemical reaction generated in the step is shown in the following formula I (4, 4 ' -diaminodiphenyl ether represents a diamine compound, and 3,3 ', 4,4 ' -biphenyltetracarboxylic dianhydride represents a dianhydride compound):
in step S0, the dianhydride compound is selected from one or more of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, or 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride.
In step S0, the diamine compound is one or more selected from 4,4 ' -diaminodiphenyl ether, p-phenylenediamine, 2 ' -dimethylbenzidine and 2,2 ' -bis [4- (4-aminophenoxy) phenyl ] propane.
In step S0, the solvent is selected from one or more of 1-methyl-2-pyrrolidone or dimethylacetamide.
In step S0, the molar ratio of diamine compound to dianhydride compound is 1: 1.
In the step S0, the temperature of freeze drying is-80 to-60 ℃, and the freeze drying is carried out twice, wherein the time of freeze drying is 15-20 h each time.
In step S0, the ratio of the amount of polyamic acid, water and ammonia water is (0.1-0.5) g (20-28) ml (0.5-1.0) ml when preparing the polyamic acid salt solution.
In step S1, the inorganic metal aluminum salt is selected from one or more of aluminum chloride, aluminum nitrate, or aluminum sulfate. In particular, a crystalline hydrate of an inorganic metal aluminum salt may be used.
In step S1, when preparing the alumina-polyamic acid salt composite wet gel, the adding amount ratio of the inorganic metal aluminum salt, the polyamic acid salt solution, the water and the propylene oxide is (3.0-8.0) g, (1.0-9.0) ml, (20-27) ml and (9.0-12.0) ml. The specific concentration of polyamic acid salt in the polyamic acid salt solution can be obtained according to the addition amounts of pure polyamic acid solid, water, and ammonia in step S0, and the equilibrium constant of the reaction.
In the step S1, the standing temperature is 20-30 ℃, and the standing time is 12-36 h.
In step S2, solvent replacement is performed with alcohol.
In the step S2, the temperature of alcohol supercritical drying is 265-300 ℃, the time of alcohol supercritical drying is 13-16 h, and the pressure of alcohol supercritical drying is 11.0-14 MPa.
In step S3, the calcination temperature is 600-1000 ℃ and the calcination time is 0.5-2.0 h.
An alumina aerogel material obtained by the preparation method. In terms of mechanical properties, the compressibility of the alumina aerogel material of the invention is as high as 80%. In terms of thermal properties, the material can still keep porous shape after being subjected to heat treatment at 1300 DEG CThe density is 0.09-0.12 g/cm3The specific surface area is 431.5-630.3 cm3(ii)/g; after being burned for 300s by flame at 1300 ℃, the average back temperature is as low as 50-65 ℃, and the material is an ultra-high temperature resistant material with excellent performance.
The application of the alumina aerogel material is to use the alumina aerogel material as a heat insulating material and a catalyst carrier used at high temperature.
The method comprises the steps of firstly, uniformly mixing polyamic acid salt and an inorganic metal aluminum salt solution by adopting a precursor blending method, then adding propylene oxide into the mixed solution, wherein the propylene oxide serving as a proton capture agent can be combined with hydrogen ions generated by hydrolysis of aluminum ions in the solution, so that the hydrolysis reaction of the aluminum ions is accelerated to form aluminum hydroxyl groups, the aluminum hydroxyl groups are dehydrated through a polycondensation reaction to form Al-O-Al bonds, and finally an alumina gel framework is formed. Then, carrying out alcohol supercritical drying on the obtained alumina-polyamic acid salt composite wet gel to obtain alumina-polyimide composite aerogel, wherein in the alcohol supercritical drying process, liquid in holes of the wet gel is converted into a supercritical state and is discharged out of the gel, so that the wet gel forms aerogel; meanwhile, the polyamic acid salt can be dehydrated to form polyimide by thermal imidization reaction at the supercritical temperature of alcohol. And finally, calcining the obtained alumina-polyimide composite aerogel at high temperature, and decomposing the polyimide at high temperature to finally obtain the alumina aerogel material. The polyimide in the invention is used as a template to generate an alumina nanobelt structure, an alumina gel framework directly synthesized by propylene oxide is formed by particle accumulation and is not formed by nanobelt winding synthesis, and the belt-shaped structure can be formed only by using the polyimide as the template alumina gel framework.
Compared with the prior art, the invention has the following advantages: the alumina aerogel material prepared by the invention successfully overcomes the defects that the existing aerogel material is not resistant to ultra-high temperature or resistant to ultra-high temperature and not resistant to ultra-high temperature, is an aerogel material with good endurance and ultra-high temperature resistance, and is low in density, excellent in compressibility, outstanding in thermal stability and high-temperature heat insulation performance, and is an aerogel material with mechanical compressibility and ultra-high temperature resistance. These excellent properties make the material potentially very useful as heat insulating material and catalyst carrier for high temperature applications in the future. The preparation method provided by the invention has the advantages of simple process, low equipment requirement, strong operability, low energy consumption and low cost, and is beneficial to promoting large-scale production and practical application of the material.
Drawings
FIG. 1 is a graph of compressive stress versus compressive strain for an alumina aerogel material made in accordance with example 1 of the present invention;
FIG. 2 is a comparison graph of the apparent morphology of the alumina aerogel material prepared by example 2 of the present invention before and after heat treatment at 1300 ℃ for 2 hours;
FIG. 3 is a graph showing the temperature change with time after the alumina aerogel material, the commercial mullite fiber mat, and the commercial alumina silicate fiber mat, which are manufactured in example 3 of the present invention, are burned with a flame at 1300 ℃ for 300 s.
Detailed Description
The invention is described in detail below with reference to the accompanying drawings and specific examples, all of which are commercially available.
Example 1
The preparation method of the alumina aerogel material derived by taking polyimide as the template comprises the following specific steps:
(1) 1.8g of 3,3 ', 4,4 ' -biphenyltetracarboxylic dianhydride and 2.5g of 2,2 ' -bis [4- (4-aminophenoxy) phenyl ] propane are sequentially dissolved in 30ml of dimethylacetamide, and a large amount of deionized water is added after uniform stirring to precipitate polyamic acid. Washing the obtained polyamic acid for several times, freezing, and freeze-drying at-80 deg.C twice for 15 hr to obtain pure polyamic acid solid. 0.3g of polyamic acid solid is dissolved in 23ml of deionized water, 0.6ml of ammonia water is added, and the solution is stirred for a certain time to obtain the polyamic acid salt solution.
(2) 4.0g AlCl3·6H2O is dissolved in 20ml of deionized water, and 3ml of polyamic acid salt solution is added thereto after stirring uniformly. After stirring again uniformly, 10ml of propylene oxide was added to the resulting solution. Standing at 25 deg.C for 12 hr to obtain the final product.
(3) And (3) replacing the composite wet gel obtained in the step (2) with alcohol for several times, and then placing the composite wet gel into a high-pressure kettle for alcohol supercritical drying, wherein the drying temperature is 270 ℃, the drying pressure is 11.0MPa, and the drying time is 15 h. And (3) after the alcohol supercritical drying is finished, the alumina-polyimide composite aerogel can be prepared.
(4) And (4) calcining the alumina-polyimide composite aerogel obtained in the step (3) at the temperature of 1000 ℃ for 1.5h to obtain the alumina aerogel material. The alumina aerogel material has a density of 0.11g/cm3(ii) a Compressibility of 80% and specific surface area of 431.5cm3The average back temperature is 50 ℃ after being burned for 300s by flame at 1300 ℃.
Example 2
The preparation method of the alumina aerogel material derived by taking polyimide as the template comprises the following specific steps:
(1) 1.1g of pyromellitic dianhydride and 0.54g of p-phenylenediamine are sequentially dissolved in 18ml of 1-methyl-2-pyrrolidone, and a large amount of deionized water is added after uniform stirring to precipitate polyamic acid. Washing the obtained polyamic acid for several times, freezing, and freeze-drying at-70 deg.C twice for 20 hr to obtain pure polyamic acid solid. 0.2g of polyamic acid solid is dissolved in 25ml of deionized water, 0.7ml of ammonia water is added, and the solution is stirred for a certain time to obtain the polyamic acid salt solution.
(2) Adding 5.0g of Al (NO)3)3·9H2O is dissolved in 25ml of deionized water, and 3ml of polyamic acid salt solution is added thereto after stirring uniformly. Stirring again, adding into the obtained solution11ml of propylene oxide. Standing at 30 deg.C for 24 hr to obtain the final product.
(3) And (3) replacing the composite wet gel obtained in the step (2) with alcohol for several times, and placing the composite wet gel into an autoclave for alcohol supercritical drying. The drying temperature is 285 ℃, the drying pressure is 12.5MPa, and the drying time is 14 h. And (3) after the alcohol supercritical drying is finished, the alumina-polyimide composite aerogel can be prepared.
(4) And (4) calcining the alumina-polyimide composite aerogel obtained in the step (3) at the temperature of 900 ℃ for 0.5h to obtain the alumina aerogel material. The alumina aerogel material has a density of 0.10g/cm3(ii) a Compressibility of 85% and specific surface area of 482.6cm3The average back temperature of the mixture is 60 ℃ after the mixture is burned for 300s by flame at 1300 ℃.
Example 3
The preparation method of the alumina aerogel material derived by taking polyimide as the template comprises the following specific steps:
(1) 1.6g of 3,3 ', 4,4 ' -benzophenone tetracarboxylic dianhydride and 1.1g of 2,2 ' -dimethylbenzidine are sequentially dissolved in 23ml of dimethylacetamide, and a large amount of deionized water is added after uniform stirring to precipitate polyamic acid. The obtained polyamic acid is washed for a plurality of times, frozen and then freeze-dried, wherein the temperature of freeze-drying is-70 ℃, and the freeze-drying is carried out twice, and the time of each freeze-drying is 18 hours, so that pure polyamic acid solid is prepared. 0.5g of polyamic acid solid is dissolved in 28ml of deionized water, 1.0ml of ammonia water is added into the solution, and the solution is stirred for a certain time to obtain the polyamic acid salt solution.
(2) Adding 8.0g of Al2(SO4)3·6H2O was dissolved in 27ml of deionized water, and 9.0ml of polyamic acid salt solution was added thereto after stirring uniformly. After stirring again uniformly, 12ml of propylene oxide was added to the resulting solution. Standing at 20 deg.C for 36 hr to obtain the final product.
(3) And (3) replacing the composite wet gel obtained in the step (2) with alcohol for several times, and placing the composite wet gel into an autoclave for alcohol supercritical drying. The drying temperature is 300 ℃, the drying pressure is 14MPa, and the drying time is 13 h. And (3) after the alcohol supercritical drying is finished, the alumina-polyimide composite aerogel can be prepared.
(4) And (4) calcining the alumina-polyimide composite aerogel obtained in the step (3) at the temperature of 750 ℃ for 1.0h to obtain the alumina aerogel material. The alumina aerogel material has a density of 0.12g/cm3(ii) a Compressibility of 80% and specific surface area of 510.7cm3The average back temperature of the mixture is 65 ℃ after the mixture is burned for 300s by flame at 1300 ℃.
Example 4
The preparation method of the alumina aerogel material derived by taking polyimide as the template comprises the following specific steps:
(1) 1.5g of 3,3 ', 4,4 ' -biphenyl tetracarboxylic dianhydride and 1.0g of 4,4 ' -diaminodiphenyl ether are sequentially dissolved in 20ml of 1-methyl-2-pyrrolidone, and a large amount of deionized water is added after uniform stirring to precipitate polyamic acid. Washing the obtained polyamic acid for several times, freezing, and freeze-drying at-75 deg.C twice for 15 hr to obtain pure polyamic acid solid. 0.1g of polyamic acid solid is dissolved in 20ml of deionized water, 0.6ml of ammonia water is added, and the solution is stirred for a certain time to obtain the polyamic acid salt solution.
(2) 4.0g AlCl3·6H2O is dissolved in 20ml of deionized water, and 5ml of polyamic acid salt solution is added thereto after stirring uniformly. After stirring again uniformly, 9.5ml of propylene oxide was added to the resulting solution. Standing at 28 deg.C for 24 hr to obtain the final product.
(3) And (3) replacing the composite wet gel obtained in the step (2) with alcohol for several times, and placing the composite wet gel into an autoclave for alcohol supercritical drying. The drying temperature is 265 ℃, the drying pressure is 13MPa, and the drying time is 16 h. And (3) after the alcohol supercritical drying is finished, the alumina-polyimide composite aerogel can be prepared.
(4) And (4) calcining the alumina-polyimide composite aerogel obtained in the step (3) at the temperature of 600 ℃ for 2.0h to obtain the alumina aerogel material. The oxidation is carried outThe density of the aluminum aerogel material is 0.11g/cm3(ii) a Compressibility of 85% and specific surface area of 506.2cm3The average back temperature of the mixture is 55 ℃ after the mixture is burned for 300s by flame at 1300 ℃.
Comparative example 1
A commercial mullite fiber mat.
Comparative example 2
A commercial aluminum silicate fiber felt.
Fig. 1 is a compression test of the alumina aerogel material prepared in example 1, and it can be seen that the strain of the alumina aerogel material increases with the increase of the stress, the maximum bearing stress is 1.1MPa, and the compressibility of the alumina aerogel material (compressibility refers to the deformation amount corresponding to the stress-strain curve that does not break after the material is compressed to a certain deformation amount) is as high as 80%, which indicates that the alumina aerogel material has good mechanical properties.
Fig. 2 is a comparison graph of the apparent morphology of the alumina aerogel material prepared in example 2 before heat treatment at 1300 ℃ and after heat treatment for 2 hours (wherein, a represents before heat treatment, and b represents after heat treatment, the scale bar is 500nm), it can be seen that the alumina aerogel material still maintains the porous apparent morphology before heat treatment after heat treatment at 1300 ℃, and the skeleton structure is formed by intertwining the nanobelt elements, which indicates that the alumina aerogel material has good thermal stability.
FIG. 3 is a graph showing the change of the back temperature of the alumina aerogel material obtained in example 3, the commercial mullite fiber mat in comparative example 1, and the commercial alumina silicate fiber mat in comparative example 2 after flame ignition at 1300 ℃ for 300 seconds as a function of time (the back temperature refers to the condition in which one end of the sample is heat-treated and the temperature change of the other end is measured). It can be seen that the average back temperature of the alumina aerogel material of the invention after being burned by flame at 1300 ℃ for 300s is as low as 70 ℃ which is far lower than the average back temperature of the commercial mullite fiber felt (202 ℃) and the commercial alumina silicate fiber felt (212 ℃), which indicates that the alumina aerogel material prepared by the invention has outstanding heat insulation performance at high temperature.
Example 5
The preparation method of the alumina aerogel material derived by taking polyimide as the template comprises the following specific steps:
(1) 1.5g of 3,3 ', 4,4 ' -biphenyl tetracarboxylic dianhydride and 1.0g of 4,4 ' -diaminodiphenyl ether are sequentially dissolved in 20ml of 1-methyl-2-pyrrolidone, and a large amount of deionized water is added after uniform stirring to precipitate polyamic acid. Washing the obtained polyamic acid for several times, freezing, and freeze-drying at-60 deg.C twice for 20 hr to obtain pure polyamic acid solid. 0.1g of polyamic acid solid is dissolved in 20ml of deionized water, 0.5ml of ammonia water is added, and the solution is stirred for a certain time to obtain the polyamic acid salt solution.
(2) 3.0g AlCl3·6H2O was dissolved in 20ml of deionized water, and 1.0ml of polyamic acid salt solution was added thereto after stirring uniformly. After stirring again uniformly, 9.0ml of propylene oxide was added to the resulting solution. Standing at 20 deg.C for 24 hr to obtain the final product.
(3) And (3) replacing the composite wet gel obtained in the step (2) with alcohol for several times, and placing the composite wet gel into an autoclave for alcohol supercritical drying. The drying temperature is 265 ℃, the drying pressure is 13MPa, and the drying time is 16 h. And (3) after the alcohol supercritical drying is finished, the alumina-polyimide composite aerogel can be prepared.
(4) And (4) calcining the alumina-polyimide composite aerogel obtained in the step (3) at the temperature of 600 ℃ for 2.0h to obtain the alumina aerogel material. The alumina aerogel material has a density of 0.90g/cm3(ii) a Compressibility of 80% and specific surface area of 630.3cm3The average back temperature of the mixture is 65 ℃ after the mixture is burned for 300s by flame at 1300 ℃.
Example 6
In this example, the alumina aerogel materials obtained in examples 1 to 5 were used as a heat insulator and a catalyst carrier for use at high temperatures.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A preparation method of an alumina aerogel material derived by taking polyimide as a template is characterized by comprising the following steps:
s1: dissolving inorganic metal aluminum salt and polyamic acid salt solution in water in sequence, adding epoxypropane after stirring uniformly, and standing to obtain alumina-polyamic acid salt composite wet gel;
s2: carrying out solvent replacement on the alumina-polyamic acid salt composite wet gel obtained in the step S1 for multiple times, and then carrying out alcohol supercritical drying to obtain alumina-polyimide composite aerogel;
s3: and (4) calcining the alumina-polyimide composite aerogel obtained in the step S2 to obtain an alumina aerogel material.
2. The method of preparing a polyimide template derived alumina aerogel material according to claim 1, further comprising step S0 before step S1:
s0: dissolving a diamine compound and a dianhydride compound in a solvent in sequence, stirring, adding water, collecting precipitated polyamic acid, washing, freeze-drying to obtain a pure polyamic acid solid, dissolving the pure polyamic acid solid in water, and adding ammonia water to obtain a polyamic acid salt solution.
3. The method of claim 2, wherein in step S0, the dianhydride compound is selected from one or more of 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, pyromellitic dianhydride, or 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride;
in step S0, the diamine compound is one or more selected from 4,4 ' -diaminodiphenyl ether, p-phenylenediamine, 2 ' -dimethylbenzidine or 2,2 ' -bis [4- (4-aminophenoxy) phenyl ] propane;
in step S0, the solvent is selected from one or more of 1-methyl-2-pyrrolidone or dimethylacetamide.
4. The method for preparing the polyimide template derived alumina aerogel material according to claim 2, wherein in step S0, the molar ratio of the diamine compound to the dianhydride compound is 1: 1;
in step S0, the ratio of the amount of polyamic acid, water and ammonia water is (0.1-0.5) g (20-28) ml (0.5-1.0) ml when preparing the polyamic acid salt solution.
5. The method for preparing the alumina aerogel material derived by taking the polyimide as the template according to claim 2, wherein in the step S0, the temperature of freeze drying is-80 to-60 ℃, and the freeze drying is carried out twice, and the time of each freeze drying is 15 to 20 hours.
6. The method of claim 1, wherein in step S1, the inorganic metal aluminum salt is selected from one or more of aluminum chloride, aluminum nitrate, and aluminum sulfate;
in step S1, when preparing the alumina-polyamic acid salt composite wet gel, the adding amount ratio of the inorganic metal aluminum salt, the polyamic acid salt solution, the water and the propylene oxide is (3.0-8.0) g, (1.0-9.0) ml, (20-27) ml, (9.0-12.0) ml;
in the step S1, the standing temperature is 20-30 ℃, and the standing time is 12-36 h.
7. The method for preparing the polyimide-templated derived alumina aerogel material according to claim 1, wherein in step S2, the solvent is replaced with alcohol;
in the step S2, the temperature of alcohol supercritical drying is 265-300 ℃, the time of alcohol supercritical drying is 13-16 h, and the pressure of alcohol supercritical drying is 11.0-14 MPa.
8. The method for preparing the polyimide-templated derived alumina aerogel material according to claim 1, wherein the calcination temperature is 600 to 1000 ℃ and the calcination time is 0.5 to 2.0 hours in step S3.
9. An alumina aerogel material obtainable by the process of any of claims 1 to 8.
10. Use of the alumina aerogel material of claim 9.
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| CN116351469A (en) * | 2023-03-08 | 2023-06-30 | 石河子大学 | Nonmetal catalyst and preparation method and application thereof |
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| CN113842843B (en) | 2022-07-29 |
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