CN116443846A - Preparation method and application of carbon aerogel material - Google Patents
Preparation method and application of carbon aerogel material Download PDFInfo
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- CN116443846A CN116443846A CN202310225044.3A CN202310225044A CN116443846A CN 116443846 A CN116443846 A CN 116443846A CN 202310225044 A CN202310225044 A CN 202310225044A CN 116443846 A CN116443846 A CN 116443846A
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- 239000000463 material Substances 0.000 title claims abstract description 57
- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 41
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- 230000032683 aging Effects 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000000017 hydrogel Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000000499 gel Substances 0.000 claims abstract description 11
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 11
- 238000007789 sealing Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000000376 reactant Substances 0.000 claims abstract description 9
- 238000010306 acid treatment Methods 0.000 claims abstract description 5
- 239000003495 polar organic solvent Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000007259 addition reaction Methods 0.000 claims abstract description 3
- 238000010000 carbonizing Methods 0.000 claims abstract description 3
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 51
- 238000010438 heat treatment Methods 0.000 claims description 22
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000012774 insulation material Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229930003836 cresol Natural products 0.000 claims description 2
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 claims description 2
- 239000011654 magnesium acetate Substances 0.000 claims description 2
- 235000011285 magnesium acetate Nutrition 0.000 claims description 2
- 229940069446 magnesium acetate Drugs 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims 1
- 239000003623 enhancer Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 238000005336 cracking Methods 0.000 abstract description 6
- 238000004134 energy conservation Methods 0.000 abstract description 4
- 239000002893 slag Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 239000004964 aerogel Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000011734 sodium Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 229920001169 thermoplastic Polymers 0.000 description 4
- 239000004416 thermosoftening plastic Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
Abstract
The invention discloses a preparation method and application of a carbon aerogel material, comprising the following steps: (1) resin treatment: immersing the resin into a solvent for fully dissolving; (2) Mixing and fully stirring reactants, a solvent and an alkaline catalyst at room temperature, carrying out addition and polycondensation reaction to obtain 3D hydrogel, and then adding the treated resin and a reinforcing agent for fully mixing to obtain mixed sol; (3) sealing and storing the mixed sol; (4) acid treatment aging and heat aging; (5) Performing solvent replacement on the treated gel by using a polar organic solvent, and drying at normal pressure; and (6) carbonizing to obtain the carbon aerogel material. The prepared carbon aerogel material can protect the pore structure of the carbon aerogel, can resist high temperature and has lower heat conductivity coefficient, so that the cracking and slag removing condition of the material is improved; the process adopts the normal pressure drying technology, realizes energy conservation and emission reduction, reduces the cost, is safe and reliable, is suitable for industrial production, and can meet the application of various high-temperature scenes.
Description
Technical Field
The invention relates to the technical field of ultra-high temperature materials, in particular to a preparation method and application of a carbon aerogel material.
Background
The temperature of the engine, nose cone, wing front edge and other parts of the novel aerospace craft reaches over 1600 ℃, the furnace temperature design of various industrial atmosphere furnaces in the civil field is also over 1600 ℃ generally, and the application fields have higher and higher requirements on the high temperature resistance and the heat insulation performance of the heat insulation material. The traditional ultra-high temperature heat insulation materials mainly comprise zirconia fiber, carbon foam and the like, the microstructure of the traditional ultra-high temperature heat insulation materials is a micron-sized aperture, and the heat insulation performance is limited. Therefore, the development of the nano-structure aerogel material with ultrahigh temperature resistance and low thermal conductivity is one of the ways for solving the urgent demands of heat insulation of novel aerospace vehicles, energy conservation, environmental protection of industrial atmosphere furnaces and the like.
Carbon aerogels have attracted considerable attention due to their high porosity (80-98%) and adjustable pore size. The carbon aerogel is used as a novel nano porous carbon material and has ideal characteristics of low density, high electrical conductivity, high surface area, low thermal conductivity and the like. Among all the aerogel heat insulation material types, the carbon aerogel has the highest use temperature under a non-oxidizing atmosphere, has high specific extinction coefficient and high emissivity, has high heat radiation shielding capability at high temperature, and has low radiation heat conductivity. The advantages enable the carbon aerogel to have wide application prospect in the aerospace field and the civil industry field as an ultrahigh temperature heat insulation material.
However, the solution with the internal pore structure of the carbon aerogel prepared by the prior art is destroyed, so that the situation of cracking and slag falling occurs in the using process.
In view of this, the present application is specifically proposed.
Disclosure of Invention
The invention aims to provide a preparation method and application of a carbon aerogel material, wherein the prepared carbon aerogel material can protect the pore structure of the carbon aerogel, can resist high temperature and has lower heat conductivity coefficient, so that the cracking and slag-falling situation of the material is improved.
The invention is realized by the following technical scheme:
a preparation method of a carbon aerogel material comprises the following steps:
(1) Resin treatment: immersing the resin into a solvent for fully dissolving;
(2) Mixing and fully stirring reactants, a solvent and an alkaline catalyst at room temperature, carrying out addition and polycondensation reaction to obtain 3D hydrogel, and then adding the resin treated in the step (1) and the reinforcing agent for fully mixing to obtain mixed sol;
(3) Sealing and storing the mixed sol at a certain temperature for polymerization reaction;
(4) Aging and heat aging the gel after the reaction in the step (3) by acid treatment;
(5) Performing solvent replacement on the gel treated in the step (4) by using a polar organic solvent, and drying at normal pressure;
(6) Carbonizing to obtain the carbon aerogel material.
The prepared carbon aerogel material can protect the pore structure of the carbon aerogel, can resist high temperature and has lower heat conductivity coefficient, so that the cracking and slag removing condition of the material is improved; the process adopts the normal pressure drying technology, realizes energy conservation and emission reduction, reduces the cost, is safe and reliable, is suitable for industrial production, and can meet the application of various high-temperature scenes.
In the step (1), thermoplastic styrene-butadiene rubber is adopted as the resin, the resin is dissolved in an alcohol solvent at 50-60 ℃, and the molar ratio of the resin to the alcohol solvent is 1:6-10.
Further, in the step (2), the molar ratio of the solvent to the reactant is 30-100: 1, preferably 60:1, the mol ratio of the reactant to the alkaline catalyst is 300-500: 1, preferably 450:1.
further, in the step (2), the mass ratio of the resin, the reinforcing agent and the hydrogel treated in the step (1) is 1:0.03-0.05:100.
Further, in the step (2), the reactant is one or more of resorcinol and formaldehyde, melamine and formaldehyde, phenol and furfural and cresol and formaldehyde, preferably resorcinol and formaldehyde, and the molar ratio of resorcinol to formaldehyde is 1:2.5;
the solvent comprises water, an alcohol organic solvent and/or a ketone organic solvent, preferably water, methanol and/or acetone;
the alkaline catalyst comprises sodium hydroxide (NaOH), sodium carbonate (Na 2 CO 3 ) Potassium carbonate (K) 2 CO 3 ) Calcium hydroxide (Ca (OH) 2 ) One or more of magnesium acetate and hexamethylenetetramine, preferably sodium carbonate;
the reinforcing agent adopts N, N-dimethylformamide.
Further, in the step (2), the mixing temperature is room temperature, generally 20-35 ℃, the time is 20-40 min, and the stirring speed is 1000-2500 rpm/min.
Further, in the step (3), the sealing and preserving time is 24-72 hours, preferably 28-40 hours; the temperature of the sealed preservation is 60-90 ℃, preferably 85 ℃.
Further, in the step (4), the solution adopted by the acid treatment aging adopts a dilute hydrochloric acid solution, a carbonic acid solution or a trifluoroacetic acid solution of which the solvent is acetone, methanol or ethanol, preferably a mixed solution of hydrochloric acid and methanol, and the molar ratio of the hydrochloric acid to the methanol solvent is 1:1000; the temperature of the heat aging is 50-65 ℃, preferably 60-65 ℃; the heat aging time is 10 to 36 hours, preferably 20 to 30 hours.
Further, in the step (5), the polar organic solvent is an alcohol solvent, preferably anhydrous methanol or anhydrous ethanol; the solvent replacement time is 2-6 h, preferably 5h; repeating the solvent replacement for 4 times at a temperature of 50-65 ℃, preferably 60 ℃; the normal pressure drying adopts a normal pressure grading drying method, and specifically, the normal pressure drying is sequentially carried out for 2-5 hours at 55-65 ℃, 75-85 ℃, 95-105 ℃, 115-125 ℃ and 155-165 ℃.
Further, the carbonization specific steps are as follows: placing the sample treated in the step (5) into a vacuum furnace, vacuumizing to below 100Pa, heating to 150 ℃ at room temperature at a heating rate of 4 ℃/min, and keeping the temperature at 150 ℃ for continuous vacuumizing for 15min; vacuum is maintained, the carbon aerogel is heated to 1100 ℃ at a heating rate of 2 ℃/min and kept at a constant temperature for 4 hours, and then the carbon aerogel is obtained after gradually cooling to room temperature.
The invention also provides application of the carbon aerogel material in preparing the ultra-high temperature heat insulation material.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. according to the preparation method and the application of the carbon aerogel material provided by the embodiment of the invention, the prepared carbon aerogel material can protect the pore structure of the carbon aerogel, can resist ultrahigh temperature and has a lower heat conductivity coefficient, so that the cracking and slag removal condition of the material is improved;
2. the preparation method and the application of the carbon aerogel material provided by the embodiment of the invention adopt the normal pressure drying technology, realize energy conservation and emission reduction, reduce the cost, are safe and reliable, are suitable for industrial production, and can meet the application of various high-temperature scenes;
3. the preparation method and the application of the carbon aerogel material provided by the embodiment of the invention have the advantages that the prepared carbon aerogel material is used for preparing the ultrahigh-temperature heat insulation material, and has wide application prospects in the aerospace field and the civil industry field.
Drawings
In order to more clearly illustrate the technical solutions of the exemplary embodiments of the present invention, the drawings that are needed in the examples will be briefly described below, it being understood that the following drawings only illustrate some examples of the present invention and therefore should not be considered as limiting the scope, and that other related drawings may be obtained from these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a preparation process of a carbon aerogel material provided by an embodiment of the invention.
Detailed Description
For the purpose of making apparent the objects, technical solutions and advantages of the present invention, the present invention will be further described in detail with reference to the following examples and the accompanying drawings, wherein the exemplary embodiments of the present invention and the descriptions thereof are for illustrating the present invention only and are not to be construed as limiting the present invention.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. However, it will be apparent to one of ordinary skill in the art that: no such specific details are necessary to practice the invention. In other instances, well-known materials or methods have not been described in detail in order to avoid obscuring the present invention.
Throughout the specification, references to "one embodiment," "an embodiment," "one example," or "an example" mean: a particular feature, structure, or characteristic described in connection with the embodiment or example is included within at least one embodiment of the invention. Thus, the appearances of the phrases "in one embodiment," "in an example," or "in an example" in various places throughout this specification are not necessarily all referring to the same embodiment or example. Furthermore, the particular features, structures, or characteristics may be combined in any suitable combination and/or sub-combination in one or more embodiments or examples. Moreover, those of ordinary skill in the art will appreciate that the illustrations provided herein are for illustrative purposes and that the illustrations are not necessarily drawn to scale. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the description of the present invention, the terms "front", "rear", "left", "right", "upper", "lower", "vertical", "horizontal", "high", "low", "inner", "outer", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, merely to facilitate description of the present invention and simplify description, and do not indicate or imply that the devices or elements referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the scope of the present invention.
Example 1
The embodiment of the invention provides a preparation method of a carbon aerogel material, which is shown in figure 1 and comprises the following steps:
(1) Pretreatment of resin: at 50-60 ℃, isopropanol is used for dissolving resin, thermoplastic styrene-butadiene rubber is adopted for the resin, and the molar ratio of the resin to the isopropanol is 1:6;
(2) Resorcinol, methanol, solvent (water) and basic catalyst (Na 2 CO 3 ) According to 1:0.4:60: 2.2X10 -3 The mixture is fully stirred for 30min at the room temperature at 2000rpm/min to prepare mixed hydrogel;
(3) The resin treated in the step (1), the reinforcing agent (N, N-dimethylformamide) and the hydrogel prepared in the step (2) are mixed according to the following steps of 1:0.03: mixing uniformly in a mass ratio of 100, and sealing and preserving for 35 hours at 85 ℃;
(4) The prepared gel has a molar ratio of 1:1000 hydrochloric acid and a methanol solvent are prepared into a dilute acid solution for acid aging treatment, and the materials after sealed preservation are transferred into a 60 ℃ oven for heat aging for 30 hours;
(5) Immersing the aged material in absolute methanol at 60 ℃ for solvent replacement for 5 hours, and repeating the liquid replacement for 4 processes to finish the solvent replacement;
(6) Drying the replaced materials at the temperature of 60 ℃, 80 ℃, 100 ℃, 120 ℃ and 160 ℃ for 2 hours at each stage to prepare the RF aerogel material; placing the RF aerogel into a vacuum furnace, vacuumizing to below 100Pa, heating to 150 ℃ from room temperature at a heating rate of 4 ℃/min, keeping 150 ℃ for continuously vacuumizing for 15min, keeping the vacuum, heating to 1100 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 4h, and gradually cooling to room temperature to obtain the carbon aerogel.
Comparative example 1
The invention provides a preparation method of a carbon aerogel material, which comprises the following steps:
(1) Resorcinol, methanol, solvent (water) and basic catalyst (Na 2 CO 3 ) According to 1:0.4:60: 2.2X10 -3 The mixture is fully stirred for 30min at the room temperature at 2000rpm/min to prepare mixed hydrogel;
(2) Sealing and preserving the mixed hydrogel for 35 hours at the temperature of 85 ℃;
(3) The prepared gel has a molar ratio of 1:1000 hydrochloric acid and a methanol solvent are prepared into a dilute acid solution for acid aging treatment, and the materials after sealed preservation are transferred into a 60 ℃ oven for heat aging for 30 hours;
(4) Immersing the aged material in absolute methanol at 60 ℃ for solvent replacement for 5 hours, and repeating the liquid replacement for 4 processes to finish the solvent replacement;
(5) Drying the replaced materials at the temperature of 60 ℃, 80 ℃, 100 ℃, 120 ℃ and 160 ℃ for 2 hours at each stage to prepare the RF aerogel material; placing the RF aerogel into a vacuum furnace, vacuumizing to below 100Pa, heating to 150 ℃ from room temperature at a heating rate of 4 ℃/min, keeping 150 ℃ for continuously vacuumizing for 15min, keeping the vacuum, heating to 1100 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 4h, and gradually cooling to room temperature to obtain the carbon aerogel.
The comparative example differs from example 1 in that no isopropanol-dissolved resin and no reinforcing agent were added.
Comparative example 2
The invention provides a preparation method of a carbon aerogel material, which comprises the following steps:
(1) Pretreatment of resin: at 50-60 ℃, isopropanol is used for dissolving resin, thermoplastic styrene-butadiene rubber is adopted for the resin, and the molar ratio of the resin to the isopropanol is 1:6;
(2) Resorcinol, methanol, solvent (water) and basic catalyst (Na 2 CO 3 ) According to 1:0.4:60: 2.2X10 -3 The mixture is fully stirred for 30min at the room temperature at 2000rpm/min to prepare mixed hydrogel;
(3) The resin treated in the step (1), the reinforcing agent (N, N-dimethylformamide) and the hydrogel prepared in the step (2) are mixed according to the following steps of 1:0.03: mixing uniformly in a mass ratio of 100, and sealing and preserving for 35 hours at 85 ℃;
(4) The prepared gel has a molar ratio of 1:1000 hydrochloric acid and a methanol solvent are prepared into a dilute acid solution for acid aging treatment, and the materials after sealed preservation are placed under the room temperature condition for 30 hours;
(5) Immersing the materials after acid aging in absolute methanol at 60 ℃ for solvent replacement for 5 hours, and repeating the liquid replacement for 4 processes to finish the solvent replacement;
(6) Drying the replaced materials at the temperature of 60 ℃, 80 ℃, 100 ℃, 120 ℃ and 160 ℃ for 2 hours at each stage to prepare the RF aerogel material; placing the RF aerogel into a vacuum furnace, vacuumizing to below 100Pa, heating to 150 ℃ from room temperature at a heating rate of 4 ℃/min, keeping 150 ℃ for continuously vacuumizing for 15min, keeping the vacuum, heating to 1100 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 4h, and gradually cooling to room temperature to obtain the carbon aerogel.
The present comparative example differs from example 1 in that step (4) in the present comparative example was not subjected to heat aging treatment.
Comparative example 3
The invention provides a preparation method of a carbon aerogel material, which comprises the following steps:
(1) Pretreatment of resin: at 50-60 ℃, isopropanol is used for dissolving resin, thermoplastic styrene-butadiene rubber is adopted for the resin, and the molar ratio of the resin to the isopropanol is 1:6;
(2) Resorcinol, methanol, solvent (water) and basic catalyst (Na 2 CO 3 ) According to 1:0.4:60: 2.2X10 -3 The mixture is fully stirred for 30min at the room temperature at 2000rpm/min to prepare mixed hydrogel;
(3) The resin treated in the step (1), the reinforcing agent (N, N-dimethylformamide) and the hydrogel prepared in the step (2) are mixed according to the following steps of 1:0.03: mixing uniformly in a mass ratio of 100, and sealing and preserving for 35 hours at 85 ℃;
(4) Sealing and preserving the prepared gel, and transferring the gel into a 60 ℃ oven for heat aging for 30 hours;
(5) Immersing the materials after heat aging in absolute methanol at 60 ℃ for solvent replacement for 5 hours, and repeating the liquid replacement for 4 processes to finish the solvent replacement;
(6) Drying the replaced materials at the temperature of 60 ℃, 80 ℃, 100 ℃, 120 ℃ and 160 ℃ for 2 hours at each stage to prepare the RF aerogel material; placing the RF aerogel into a vacuum furnace, vacuumizing to below 100Pa, heating to 150 ℃ from room temperature at a heating rate of 4 ℃/min, keeping 150 ℃ for continuously vacuumizing for 15min, keeping the vacuum, heating to 1100 ℃ at a heating rate of 2 ℃/min, keeping the temperature for 4h, and gradually cooling to room temperature to obtain the carbon aerogel.
The present comparative example differs from example 1 in that step (4) in the present comparative example was not subjected to the acid aging treatment.
The products prepared in the above examples and comparative examples were tested for appearance, density and thermal conductivity, and the results are shown in table 1.
The heat conductivity coefficient is measured by a heat conductivity coefficient measuring instrument, and the testing method is referred to GB/T10295-2008 heat flow measuring method for measuring steady-state thermal resistance and related characteristics of insulating materials.
The high temperature thermal conductivity (1000 ℃) is the thermal conductivity of the material measured at 1000 ℃ under 0.15MPa of argon.
TABLE 1
From the results shown in table 1, it can be seen that the carbon aerogel material of the present invention is prepared by adding isopropanol-dissolved resin and reinforcing agent, and simultaneously performing acid aging and thermal aging treatment on the polymerized gel in the preparation process, so that the pore structure of the carbon aerogel can be protected, the prepared carbon aerogel can resist ultra-high temperature, has a low thermal conductivity, and even in a high temperature state, the thermal conductivity remains low, and the cracking and slag-off conditions of the material are greatly improved.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the invention, and is not meant to limit the scope of the invention, but to limit the invention to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The preparation method of the carbon aerogel material is characterized by comprising the following steps:
(1) Resin treatment: immersing the resin into a solvent for fully dissolving;
(2) Mixing and fully stirring reactants, a solvent and an alkaline catalyst at room temperature, performing addition and polycondensation reaction to obtain 3D hydrogel, and adding the resin and the reinforcing agent treated in the step (1) to obtain mixed sol;
(3) Sealing and storing the mixed sol at a certain temperature for polymerization reaction;
(4) Aging and heat aging the gel after the reaction in the step (3) by acid treatment;
(5) Performing solvent replacement on the gel treated in the step (4) by using a polar organic solvent, and drying at normal pressure;
(6) Carbonizing to obtain the carbon aerogel material.
2. The method for preparing a carbon aerogel material according to claim 1, wherein in the step (1), the resin is dissolved in an alcohol solvent at 50-60 ℃, and the molar ratio of the resin to the alcohol solvent is 1:6-10.
3. The method for preparing a carbon aerogel material according to claim 1, wherein in the step (2), the molar ratio of the solvent to the reactant is 30-100: 1, the mol ratio of the reactant to the alkaline catalyst is 300-500: 1.
4. the method for preparing a carbon aerogel material according to claim 1, wherein in the step (2), the mass ratio of the resin, the reinforcing agent and the hydrogel treated in the step (1) is 1:0.03-0.05:100.
5. The method of claim 1, wherein in step (2), the reactant is one or more of resorcinol and formaldehyde, melamine and formaldehyde, phenol and furfural, and cresol and formaldehyde; the solvent comprises water, an alcohol organic solvent and/or a ketone organic solvent; the alkaline catalyst comprises one or more of sodium hydroxide, sodium carbonate, potassium carbonate, calcium hydroxide, magnesium acetate and hexamethylenetetramine; the enhancer comprises N, N-dimethylformamide.
6. The method for preparing a carbon aerogel material according to claim 1, wherein in the step (3), the sealing and preserving time is 24-72 h, and the sealing and preserving temperature is 60-90 ℃.
7. The method for preparing a carbon aerogel material according to claim 1, wherein in the step (4), the solution adopted for the acid treatment aging is a dilute hydrochloric acid solution, a carbonic acid solution or a trifluoroacetic acid solution, wherein the solvent is acetone, methanol or ethanol;
the temperature of the heat aging is 50-65 ℃ and the time is 10-36 h.
8. The method for preparing a carbon aerogel material according to claim 1, wherein in the step (5), the polar organic solvent is an alcohol solvent, the solvent replacement time is 2-6 hours, the temperature is 50-65 ℃, and the solvent replacement is repeated for 4 times; the normal pressure drying adopts a normal pressure grading drying method, and specifically, the normal pressure drying is sequentially carried out for 2-5 hours at 55-65 ℃, 75-85 ℃, 95-105 ℃, 115-125 ℃ and 155-165 ℃.
9. The method for preparing a carbon aerogel material according to claim 1, wherein in the step (6), the specific carbonization steps are as follows: placing the sample treated in the step (5) into a vacuum furnace, vacuumizing to below 100Pa, heating to 150 ℃ at room temperature at a heating rate of 4 ℃/min, and keeping the temperature at 150 ℃ for continuous vacuumizing for 15min; vacuum is maintained, the carbon aerogel is heated to 1100 ℃ at a heating rate of 2 ℃/min and kept at a constant temperature for 4 hours, and then the carbon aerogel is obtained after gradually cooling to room temperature.
10. Use of the carbon aerogel material produced by the production method according to any one of claims 1 to 9 for producing an ultra-high temperature insulation material.
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