CN110483994B - Silicon oxide reinforced polyimide aerogel micro powder and preparation method thereof - Google Patents
Silicon oxide reinforced polyimide aerogel micro powder and preparation method thereof Download PDFInfo
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Abstract
The invention provides a silicon oxide reinforced polyimide aerogel micro powder and a preparation method thereof, belonging to the technical field of nano porous materials and heat insulation. The preparation method comprises the following steps: respectively dissolving a methyl ethyl vinyl ether-maleic anhydride copolymer, 3-aminopropyl triethoxysilane and aromatic diamine in a solvent; mixing the three solutions according to a certain proportion, stirring uniformly, standing for reaction to form gel, preparing micro powder gel by adopting a mechanical crushing method, and soaking the gel in a dehydrating agent; and finally, replacing the dehydrated gel solvent, and performing supercritical drying to obtain the silicon oxide nanoparticle reinforced linear polyimide aerogel micro powder. The polyimide aerogel micro powder obtained by the invention is brown, has an organic-inorganic double-network structure, has the rigidity of silicon oxide and the toughness of polyimide, and has low density (0.03-0.3 g/cm)3) High specific surface area (200-600 m)2(g), good high temperature resistance and the like.
Description
Technical Field
The invention relates to a silicon oxide reinforced linear polyimide aerogel micro powder and a preparation method thereof, belonging to the technical field of nano porous materials and heat insulation.
Background
Aerogel is a porous nano material, and is the lightest solid material with the best heat insulation performance in the world at present. The silica aerogel has a high specific surface area (400-1500 m)2A/g), a high porosity (80-99.8%), a low density (0.003-0.6 g/cm)3) And low thermal conductivity (0.013-0.038W/mk), and the like, so that the material has very important application in the fields of high-temperature resistance, heat insulation, ultralow density, acoustic impedance coupling, gas adsorption and filtration, catalyst carriers, drug carriers and the like. Various types of aerogels have been prepared so far by chemical crosslinking methods, including silica aerogel (CN 102424538A; CN102633269A), chitosan aerogel (CN102417606A), carbon aerogel (CN 102423668A; CN102430369A), metal oxide and its composite aerogel (CN102513041A), multi-element composite aerogel (CN102584010A), graphene and carbon nanotube aerogel (CN102674315A), titanium oxide aerogel (CN102671587A), and the like. The aerogel mentioned above has weak mechanical strength and large brittleness, and is not flame retardant, radiation resistant, and the like, so that the invention of the aerogel with excellent mechanical properties, and simultaneously has excellent radiation resistance, weather resistance, non-combustion, and the like is urgently needed to realize the application of the aerogel in the aviation and civil fields.
Polyimide is an organic polymer with an imide ring in the main chain, and has the advantages of high mechanical strength, good thermal stability, wear resistance and the like. The significant advantages of either as a structural or functional material have been fully appreciated. In recent years, research on polyimide aerogel is receiving attention, and compared with other polymer aerogels, polyimide aerogel has unique properties such as excellent strength, adjustable rigidity, high temperature resistance, very low temperature resistance, radiation resistance, flame retardance and the like, so that the polyimide aerogel has attracted much attention since 2006 (USP7074880, 2006) for the first time. As such, NASA in the united states has conducted a great deal of research on the preparation and application of polyimide aerogels (document ACS appl. However, the existing polyimide aerogel is difficult to prepare powder due to high toughness and cannot be used as a powder filler, the traditional polyimide aerogel is high in cost, the skeleton structure is organic components, and the traditional polyimide aerogel is poor in light degree and low in strength.
Disclosure of Invention
Aiming at the defects and material limitations of the prior art, the invention mainly aims to provide a silicon oxide reinforced linear polyimide aerogel micro powder and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of silicon oxide reinforced polyimide aerogel micro powder comprises the following steps:
respectively dissolving a methyl vinyl ether-maleic anhydride copolymer, 3-aminopropyltriethoxysilane and aromatic diamine in a solvent to obtain a methyl vinyl ether-maleic anhydride copolymer solution, a 3-aminopropyltriethoxysilane solution and an aromatic diamine solution;
step (2), stirring and mixing the methyl vinyl ether-maleic anhydride copolymer solution, the 3-aminopropyl triethoxysilane solution and the aromatic diamine solution according to a certain proportion, standing to form gel, and soaking the formed gel in a dehydrating agent for chemical imidization to obtain imidized gel;
and (3) crushing the imidized gel, replacing the solvent and drying to obtain the silicon oxide nanoparticle reinforced linear polyimide aerogel micropowder.
In an alternative embodiment, the aromatic diamine in step (1) includes any one or a combination of two or more of p-phenylenediamine, m-phenylenediamine, 4' -diaminobiphenyl, 4' -methylenedianiline, and 4,4' -diaminodiphenyl ether.
In an alternative embodiment, the number average molecular weight of the methyl vinyl ether-maleic anhydride copolymer of step (1) is 50000-200000. 4. The method for preparing a silica-reinforced polyimide aerogel micropowder according to claim 1, wherein the solvent in step (1) comprises at least one of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, or N-methylpyrrolidone.
In an alternative embodiment, the methylethenyl group in step (1)The concentration of the ether-maleic anhydride copolymer solution is 0.1-0.3 g/cm3The concentration of the 3-aminopropyltriethoxysilane solution is 0.01-0.2 g/cm3The concentration of the aromatic diamine solution is 0.05 to 0.2g/cm3The volume ratio of the methyl vinyl ether-maleic anhydride copolymer solution, the 3-aminopropyltriethoxysilane solution and the aromatic diamine solution in the step (2) is 100: 4-6: 25 to 35.
In an optional embodiment, the gel is formed by standing at 0-80 ℃ in the step (2), and the dehydrating agent is at least one of pyridine, triethylamine, acetic anhydride, picoline, acetyl chloride, thionyl chloride, a phosphorus halide or dicyclohexylcarbodiimide.
In an alternative embodiment, the pulverizing in step (3) comprises: extruding at 20-50 deg.C under 0.5-3MPa for 1-5h, and stirring at 800-.
In an alternative embodiment, the solvent displacement of step (3) comprises: replacing the pulverized gel with methanol, ethanol or acetone for at least two times.
In an optional embodiment, the drying method in step (3) adopts carbon dioxide, ethanol or methanol as supercritical fluid, and performs supercritical drying at 40-250 deg.C and under pressure of 8MPa or more for 2-10 h.
The silica-reinforced polyimide aerogel micropowder prepared by the preparation method is brown, has an organic-inorganic double-network structure, has a density of 0.03-0.3 g/cm3 and a specific surface area of 200-600 m2(ii) in terms of/g. Compared with the prior art, the invention has the following beneficial effects:
the invention adopts linear polyanhydride as monomer, which has the advantages of low cost, numerous functional groups and the like, so that organic siloxane and the like can be introduced to form an organic second gel network while the polyimide gel is formed by crosslinking diamine, and the two networks are chemically bonded to form the synergistic effect of mechanical enhancement and thermal stability enhancement.
Drawings
FIG. 1 is a scanning electron microscope photograph of a polyimide aerogel fine powder obtained in example 1 of the present invention.
FIG. 2 is a scanning electron microscope photograph of the polyimide aerogel fine powder obtained in example 2 of the present invention.
FIG. 3 is a scanning electron microscope photograph of the polyimide aerogel fine powder obtained in example 3 of the present invention.
FIG. 4 is a scanning electron microscope photograph of the polyimide aerogel fine powder obtained in example 4 of the present invention.
FIG. 5 is a scanning electron microscope photograph of the polyimide aerogel fine powder obtained in example 5 of the present invention.
FIG. 6 is a scanning electron microscope photograph of the polyimide aerogel fine powder obtained in example 6 of the present invention.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The invention is described in further detail below with reference to the following figures and examples:
a preparation method of silicon oxide reinforced linear polyimide aerogel micro powder comprises the following steps:
respectively dissolving a methyl vinyl ether-maleic anhydride copolymer, 3-aminopropyltriethoxysilane and aromatic diamine in a solvent to obtain a methyl vinyl ether-maleic anhydride copolymer solution, a 3-aminopropyltriethoxysilane solution and an aromatic diamine solution;
step (2), stirring and mixing the methyl vinyl ether-maleic anhydride copolymer solution, the 3-aminopropyl triethoxysilane solution and the aromatic diamine solution according to a certain proportion, standing to form gel, and soaking the formed gel in a dehydrating agent for chemical imidization to obtain imidized gel;
and (3) crushing the imidized gel, replacing the solvent and drying to obtain the silicon oxide nanoparticle reinforced linear polyimide aerogel micropowder.
Wherein, the aromatic diamine in the step (1) is preferably any one or the combination of more than two of p-phenylenediamine, m-phenylenediamine, 4,4' -diaminobiphenyl, 4,4' -methylenedianiline and 4,4' -diaminodiphenyl ether; the number average molecular weight of the methyl vinyl ether-maleic anhydride copolymer in the step (1) is preferably 50000-200000, more preferably 80000; the solvent in the step (1) is preferably at least one of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone;
in an optional embodiment, the concentration of the methyl vinyl ether-maleic anhydride copolymer solution in the step (1) is 0.1-0.3 g/cm3The concentration of the 3-aminopropyltriethoxysilane solution is 0.01-0.2 g/cm3The concentration of the aromatic diamine solution is 0.05 to 0.2g/cm3The volume ratio of the methyl vinyl ether-maleic anhydride copolymer solution, the 3-aminopropyltriethoxysilane solution and the aromatic diamine solution in the step (2) is 100: 4-6: 25 to 35. Under the reaction condition, 3-aminopropyltriethoxysilane reacts with methyl ethyl thin ether-maleic anhydride copolymer to generate alkoxysilane modified functional high molecular polymer, which is further hydrolyzed and condensed into a molecular-level double-network system, the high molecular network and the silicon oxide network are directly combined through chemical bonds, the interface between the high molecular network and the silicon oxide network is eliminated, and the strength is greatly improved.
In an optional embodiment, the gel is formed by standing at 0-80 ℃ in the step (2), and the dehydrating agent is at least one of pyridine, triethylamine, acetic anhydride, picoline, acetyl chloride, thionyl chloride, a phosphorus halide or dicyclohexylcarbodiimide.
In an alternative embodiment, the pulverizing in step (3) comprises: extruding at 20-50 deg.C under 0.5-3MPa for 1-5h, and stirring at 800-. The inventor conducts a great deal of experimental research throughout the year in the process of implementing the invention, and researches show that when crushing is carried out under the condition, the uneven and large granularity caused by the factors such as too small extrusion pressure, too slow stirring speed and the like can be avoided, the damage of the internal structure of the gel caused by the factors such as the inappropriate extrusion pressure or the too fast stirring speed and the like can be avoided, and the high-quality aerogel is ensured to be obtained.
Specifically, the solvent replacement in step (3) comprises: replacing the crushed gel with methanol, ethanol or acetone for at least two times; the drying method in the step (3) adopts carbon dioxide, ethanol or methanol as supercritical fluid, and carries out supercritical drying under the conditions that the temperature is 40-250 ℃ and the pressure is not less than 8MPa, and the drying time is 2-10 h.
The embodiment of the invention also provides the silicon oxide reinforced polyimide aerogel micropowder prepared by the preparation method, which is brown, has an organic-inorganic double-network structure and has a density of 0.03-0.3 g/cm3The specific surface area is 200 to 600m2/g。
The following are some specific examples of the present invention, and the raw materials used in the examples of the present invention are all commercially available products:
wherein the number average molecular weight of the methyl vinyl ether-maleic anhydride copolymer used in examples 1 to 6 is 80000;
example 1
(1) Preparation of monomer solution: 10g of methyl vinyl ether-maleic anhydride copolymer, 1g of 3-aminopropyltriethoxysilane and 5g of p-phenylenediamine were dissolved in 100ml of N-methylpyrrolidone to give a solution having a concentration of 0.1, 0.01 and 0.05g/cm3The solution of (1).
(2) Synthesis of gel: respectively taking 100ml, 5 ml and 30ml of the solution, mixing uniformly, forming gel at 0 ℃, and soaking the gel in a mixed solution of pyridine and acetic anhydride (volume ratio is 1: 1) for dehydration.
(3) Preparation of polyimide aerogel micropowder-pulverization, solvent replacement and drying: the dehydrated gel (imidized gel) is extruded for 3h at 30 ℃ under the pressure of 2MPa, then is stirred for 3h at the rotating speed of 1000 r/min to obtain wet gel micro powder, and then is soaked in methanol with the volume 2 times of that of the wet gel micro powder for solvent replacement, and the methanol is replaced once every 5 hours for 3 times. And drying the gel after replacement in supercritical carbon dioxide at 40 ℃ and 10MPa for 10 hours to prepare the silicon oxide reinforced linear polyimide aerogel micro powder with the average particle size of 9.8 um. According to the characteristics of BET isothermal adsorption, SEM and the like, the polyimide aerogel micro powder has a nano porous structure, a scanning electron micrograph of the polyimide aerogel micro powder refers to figure 1, and other physical parameters such as specific surface area, density and the like refer to Table 1.
Example 2
(1) Preparation of monomer solution: 30g of methyl vinyl ether-maleic anhydride copolymer, 5g of 3-aminopropyltriethoxysilane and 20g of p-phenylenediamine were dissolved in 100ml of N, N-dimethylacetamide to give a solution with a concentration of 0.3, 0.05 and 0.2g/cm3The solution of (1).
(2) Synthesis of gel: respectively taking 100ml, 5 ml and 30ml of the solution, mixing uniformly, forming gel at 40 ℃, and soaking the gel in a mixed solution of triethylamine and acetic anhydride (the volume ratio is 1: 1) for dehydration.
(3) Preparation of polyimide aerogel micropowder-pulverization, solvent replacement and drying: extruding the dehydrated gel at 50 deg.C under 3MPa for 1 hr, stirring at 2000 r/min for 2 hr to obtain wet gel micropowder, soaking in 2 times volume of ethanol for solvent replacement, and replacing with ethanol every 10 hr for 3 times. And drying the replaced gel in supercritical carbon dioxide at 45 ℃ and 8MPa for 10 hours to prepare the silicon oxide reinforced linear polyimide aerogel micro powder with the average particle size of 64.6 um. According to the characteristics of BET isothermal adsorption, SEM and the like, the polyimide aerogel micro powder has a nano porous structure, a scanning electron micrograph of the polyimide aerogel micro powder is shown in figure 2, and other physical parameters such as specific surface area, density and the like are shown in Table 1.
Example 3
(1) Preparation of monomer solution: 30g of methyl vinyl ether-maleic anhydride copolymer, 10g of 3-aminopropyltriethoxysilane and 15g of p-phenylenediamine were dissolved in 100ml of dimethyl sulfoxide to give solutions having concentrations of 0.3, 0.1 and 0.15g/cm3The solution of (1).
(2) Synthesis of gel: respectively taking 100ml, 5 ml and 30ml of the above solutions, mixing uniformly, forming gel at 40 ℃, and soaking the gel in acetyl chloride for dehydration.
(3) Preparation of polyimide aerogel micropowder-pulverization, solvent replacement and drying: extruding the dehydrated gel at 30 deg.C under 2MPa for 3 hr, stirring at 1000 r/min for 3 hr to obtain wet gel micropowder, soaking in 1 volume of ethanol for solvent replacement, and replacing with ethanol every 9 hr for 3 times. And drying the replaced gel in 9MPa supercritical ethanol at 245 ℃ for 10 hours to prepare the silica-reinforced linear polyimide aerogel micro powder with the average particle size of 86.8 um. According to the characterization of BET isothermal adsorption, SEM, etc., the polyimide aerogel fine powder has a nanoporous structure, a scanning electron micrograph of the polyimide aerogel fine powder is shown in fig. 3, and other physical parameters such as specific surface area and density are shown in table 1.
Example 4
(1) Preparation of monomer solution: 30g of methyl vinyl ether-maleic anhydride copolymer, 20g of 3-aminopropyltriethoxysilane and 10g of p-phenylenediamine were dissolved in 100ml of dimethyl sulfoxide to give solutions having concentrations of 0.3, 0.2 and 0.1g/cm3The solution of (1).
(2) Synthesis of gel: respectively taking 100ml, 5 ml and 30ml of the solution, mixing uniformly, forming gel at 60 ℃, and soaking the gel in a mixed solution of picoline and acetic anhydride (1: 1) for dehydration.
(3) Preparation of polyimide aerogel micropowder-pulverization, solvent replacement and drying: and (3) extruding the dehydrated gel at 30 ℃ under the pressure of 2MPa for 3h, stirring at the rotating speed of 1000 r/min for 3h to obtain wet gel micro powder, soaking in acetone with the volume of 1 time for solvent replacement, and replacing the acetone once every 8 hours for 3 times. And drying the gel after replacement in supercritical carbon dioxide at 42 ℃ and 9MPa for 10 hours to prepare the silica-reinforced linear polyimide aerogel micro powder with the average particle size of 164.4 um. According to the characterization of BET isothermal adsorption, SEM, etc., the polyimide aerogel fine powder has a nanoporous structure, a scanning electron micrograph of the polyimide aerogel fine powder is shown in fig. 4, and other physical parameters such as specific surface area and density are shown in table 1.
Example 5
(1) Preparation of monomer solution:30g of methyl vinyl ether-maleic anhydride copolymer, 20g of 3-aminopropyltriethoxysilane and 20g of p-phenylenediamine were dissolved in 100ml of N-methylpyrrolidone to give a solution having a concentration of 0.3, 0.2 and 0.2g/cm3The solution of (1).
(2) Synthesis of gel: respectively taking 100ml, 5 ml and 30ml of the solution, mixing uniformly, forming gel at 80 ℃, and soaking the gel in dicyclohexylcarbodiimide for dehydration.
(3) Preparation of polyimide aerogel micropowder-pulverization, solvent replacement and drying: extruding the dehydrated gel at 30 deg.C under 2MPa for 3 hr, stirring at 1000 rpm for 3 hr to obtain wet gel micropowder, soaking in 1 times volume of methanol for solvent replacement, and replacing with methanol every 8 hr for 3 times. And drying the replaced gel in supercritical methanol at 245 ℃ and 9MPa for 10 hours to prepare the silica-reinforced linear polyimide aerogel micro powder with the average particle size of 200.5 um. According to the characterization of BET isothermal adsorption, SEM, etc., the polyimide aerogel fine powder has a nanoporous structure, a scanning electron micrograph of the polyimide aerogel fine powder is shown in fig. 5, and other physical parameters such as specific surface area and density are shown in table 1.
Example 6
(1) Preparation of monomer solution: 20g of methyl vinyl ether-maleic anhydride copolymer, 10g of 3-aminopropyltriethoxysilane and 10g of p-phenylenediamine were dissolved in 100ml of N-methylpyrrolidone to give a solution having a concentration of 0.2, 0.1 and 0.1g/cm3The solution of (1).
(2) Synthesis of gel: respectively taking 100ml, 5 ml and 30ml of the solution, mixing uniformly, forming gel at 70 ℃, and soaking the gel in thionyl chloride for dehydration.
(3) Preparation of polyimide aerogel micropowder-pulverization, solvent replacement and drying: extruding the dehydrated gel at 30 deg.C under 2MPa for 3 hr, stirring at 1000 rpm for 3 hr to obtain wet gel micropowder, soaking in 1 volume times of methanol for solvent replacement, and replacing with methanol every 8 hr for 3 times. And drying the replaced gel in supercritical carbon dioxide at 40 ℃ and under 10MPa for 10 hours to prepare the silicon oxide reinforced linear polyimide aerogel micro powder with the average particle size of 268.6 um. According to the characterization of BET isothermal adsorption, SEM, etc., the polyimide aerogel fine powder has a nanoporous structure, a scanning electron micrograph of the polyimide aerogel fine powder is shown in fig. 6, and other physical parameters such as specific surface area and density are shown in table 1.
Example 7
The preparation was identical to example 3, except that the methyl vinyl ether-maleic anhydride copolymer used in example 7 had a number average molecular weight of 50000; the average particle size of the obtained silicon oxide reinforced linear polyimide aerogel micro powder is 156.4 um. See table 1 for other physical parameters such as specific surface area, density, etc.
Example 8
The procedure is as in example 3, except that the methyl vinyl ether-maleic anhydride copolymer used in example 7 has a number average molecular weight of 150000. The average particle size of the obtained silica-reinforced linear polyimide aerogel micro powder is 298.4 um. See table 1 for other physical parameters such as specific surface area, density, etc.
TABLE 1 structural and performance parameters of silica-reinforced polyimide aerogel micropowder obtained in examples 1-8
The above description is only one embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
The invention has not been described in detail in part of the common general knowledge of those skilled in the art.
Claims (7)
1. A preparation method of silicon oxide reinforced polyimide aerogel micropowder is characterized by comprising the following steps:
respectively dissolving a methyl vinyl ether-maleic anhydride copolymer, 3-aminopropyltriethoxysilane and aromatic diamine in a solvent to obtain a methyl vinyl ether-maleic anhydride copolymer solution, a 3-aminopropyltriethoxysilane solution and an aromatic diamine solution;
step (2), stirring and mixing the methyl vinyl ether-maleic anhydride copolymer solution, the 3-aminopropyl triethoxysilane solution and the aromatic diamine solution according to a certain proportion, standing to form gel, and soaking the formed gel in a dehydrating agent for chemical imidization to obtain imidized gel;
step (3), the imidized gel is subjected to crushing, solvent replacement and supercritical drying treatment to obtain silicon oxide nanoparticle reinforced linear polyimide aerogel micro powder;
the aerogel micro powder has an organic-inorganic double-network structure, the density is 0.03-0.3 g/cm3, and the specific surface area is 200-600 m2/g；
The concentration of the methyl vinyl ether-maleic anhydride copolymer solution in the step (1) is 0.1-0.3 g/cm3The concentration of the 3-aminopropyltriethoxysilane solution is 0.01-0.2 g/cm3The concentration of the aromatic diamine solution is 0.05 to 0.2g/cm3；
The volume ratio of the methyl vinyl ether-maleic anhydride copolymer solution, the 3-aminopropyltriethoxysilane solution and the aromatic diamine solution in the step (2) is 100: 4-6: 25-35;
the number average molecular weight of the methyl vinyl ether-maleic anhydride copolymer in the step (1) is 50000-200000.
2. The method for producing a silica-reinforced polyimide aerogel fine powder according to claim 1, wherein the aromatic diamine in step (1) comprises any one or a combination of two or more of p-phenylenediamine, m-phenylenediamine, 4' -diaminobiphenyl, 4' -methylenedianiline, and 4,4' -diaminodiphenyl ether.
3. The method for preparing a silica-reinforced polyimide aerogel micropowder according to claim 1, wherein the solvent in step (1) comprises at least one of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, or N-methylpyrrolidone.
4. The method for preparing the silica-reinforced polyimide aerogel micropowder according to claim 1, wherein the gel is formed by standing at 0-80 ℃ in the step (2), and the dehydrating agent is at least one of pyridine, triethylamine, acetic anhydride, picoline, acetyl chloride, thionyl chloride, phosphorus halide or dicyclohexylcarbodiimide.
5. The method for preparing silica-reinforced polyimide aerogel micropowder according to claim 1, wherein the pulverization in the step (3) comprises: extruding at 20-50 deg.C under 0.5-3MPa for 1-5h, and stirring at 800-.
6. The method for preparing silica-reinforced polyimide aerogel micropowder according to claim 1, wherein the solvent substitution in the step (3) comprises: replacing the pulverized gel with methanol, ethanol or acetone for at least two times.
7. The preparation method of the silica-reinforced polyimide aerogel micropowder according to claim 1, wherein the drying method in the step (3) adopts carbon dioxide, ethanol or methanol as a supercritical fluid, and supercritical drying is carried out at 40-250 ℃ and under the pressure of not less than 8MPa for 2-10 h.
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| CN104211881B (en) * | 2013-06-03 | 2017-04-12 | 联茂电子股份有限公司 | Organic-inorganic hybrid material film and making method thereof |
| US20150038039A1 (en) * | 2013-08-01 | 2015-02-05 | Iteq Corporation | Organic-inorganic hybrid material film and method for manufacturing the same |
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