CN114604869B - Antioxidant expanded graphite and preparation method and application thereof - Google Patents
Antioxidant expanded graphite and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 126
- 239000010439 graphite Substances 0.000 title claims abstract description 124
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 124
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 50
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 74
- 239000007770 graphite material Substances 0.000 claims abstract description 57
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 37
- 230000003647 oxidation Effects 0.000 claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 34
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims abstract description 29
- 238000003825 pressing Methods 0.000 claims abstract description 29
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000174 gluconic acid Substances 0.000 claims abstract description 25
- 235000012208 gluconic acid Nutrition 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 21
- YIHRGKXNJGKSOT-UHFFFAOYSA-N 1,1,2,2,3,3-hexafluorobutan-1-ol Chemical compound CC(F)(F)C(F)(F)C(O)(F)F YIHRGKXNJGKSOT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims description 64
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 15
- 239000004115 Sodium Silicate Substances 0.000 claims description 14
- 230000007935 neutral effect Effects 0.000 claims description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 11
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 claims description 11
- NFMWFGXCDDYTEG-UHFFFAOYSA-N trimagnesium;diborate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]B([O-])[O-].[O-]B([O-])[O-] NFMWFGXCDDYTEG-UHFFFAOYSA-N 0.000 claims description 10
- 239000003566 sealing material Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000007800 oxidant agent Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 239000012153 distilled water Substances 0.000 description 23
- 239000000706 filtrate Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 230000006835 compression Effects 0.000 description 11
- 238000007906 compression Methods 0.000 description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000000748 compression moulding Methods 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 6
- 230000001007 puffing effect Effects 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 3
- 238000004134 energy conservation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000000138 intercalating agent Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- -1 metallurgy Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000005303 weighing 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
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/22—Intercalation
-
- 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
- C01B32/20—Graphite
- C01B32/21—After-treatment
-
- 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
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/22—Intercalation
- C01B32/225—Expansion; Exfoliation
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/02—Inorganic materials
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides oxidation-resistant expanded graphite, a preparation method and application thereof, belonging to the technical field of inorganic materials, and comprising the steps of adopting potassium permanganate as an oxidant and perchloric acid, phosphoric acid, gluconic acid and hexafluorobutanol as intercalators to prepare the expandable graphite; performing expansion pressing on expandable graphite to prepare an expanded graphite material; impregnating the expanded graphite material with an antioxidant; and drying to obtain the oxidation-resistant expanded graphite material. The oxidation-resistant expanded graphite material and the preparation method thereof provided by the invention have the advantages of environmental protection, lower cost, higher efficiency, strong oxidation resistance of products and wide application range.
Description
Technical Field
The invention belongs to the technical field of inorganic materials, and particularly relates to oxidation-resistant expanded graphite as well as a preparation method and application thereof.
Background
Expandable Graphite (EG) is a graphite intercalation compound made mainly from natural crystalline graphite by chemical oxidation or electrochemical methods. The interlayer compound of the graphite has a stage structure formed by inserting an intercalation agent, so that the distance between C-C layers of the graphite is increased, the carbon layers of the compound are peeled off under the action of external pressure and the like, and the graphite layers are mutually extruded to generate great outward expansion force, so that the graphite expands to obtain expanded graphite.
The expanded graphite has excellent properties such as high temperature resistance, electric conductivity, thermal conductivity, lubricity, plasticity, thermal shock resistance and the like of common graphite, and also has a plurality of characteristics which are obviously different from those of common graphite: 1) Soft, light, porous and good adsorption performance, and as the expanded graphite has developed pores and mainly takes mesopores and macropores, macromolecular substances, especially nonpolar macromolecules, are easy to adsorb; 2) The heat conductivity is high and is tens to hundreds times higher than that of the traditional asbestos gasket; 3) Has good radiation protection performance. Can bear long-term radiation of radioactive rays such as neutron rays, beta rays, gamma rays and the like, and the material performance and shape are not obviously changed after irradiation; 4) The self-lubricating performance is good, and the texture is soft. In actual use, the abrasion of the shaft and the shaft sleeve is very little, the device can be used for equipment with higher speed, the allowable linear speed can reach 40m/s, and the speed is improved by more than five times compared with an asbestos packing; 5) The sealing effect is good, the flexibility and the elasticity are provided, and the impermeability is good. Therefore, the graphite product made of the expanded graphite can be widely used for steel, metallurgy, petroleum and chemical machinery.
The prior art, such as Chinese patent publication No. CN 110436941A, discloses a modification method of zirconium modified expanded graphite, which comprises the following steps: and mixing the expanded graphite with a zirconium source according to a certain proportion, and carrying out carbon burying heat treatment after vacuum impregnation to obtain the modified expanded graphite. The oxidation resistance and structural integrity of the expanded graphite prepared by the method are improved, and the expanded graphite can be applied to the refractory industry. The method is simple to operate and environment-friendly.
Disclosure of Invention
The invention aims to provide an oxidation-resistant expanded graphite material and a preparation method thereof, and the method is environment-friendly, low in cost, simple and convenient to operate and high in efficiency, and the prepared oxidation-resistant expanded graphite material has good high-temperature resistance and good compression rebound resilience.
The technical scheme adopted by the invention for achieving the purpose is as follows:
provided is a method for preparing expandable graphite, comprising: adding potassium permanganate into a container filled with perchloric acid, uniformly stirring, adding natural crystalline flake graphite, uniformly stirring, sequentially adding phosphoric acid, gluconic acid and hexafluorobutanol, uniformly stirring, reacting at 25-35 ℃ for 20-40min, stirring once every 3-5min in the reaction process, washing to be neutral after the reaction is finished, carrying out suction filtration, and drying at 50-60 ℃ to obtain the expandable graphite. The expandable graphite prepared by the method can be prepared at a lower temperature, and the prepared expandable graphite has the advantages of less volatile matters and ash, energy conservation and environmental protection.
Preferably, the mass ratio of the potassium permanganate to the graphite is 0.1-0.5:1.
Preferably, the mass ratio of perchloric acid to graphite is 4-7:1.
Preferably, the mass ratio of the phosphoric acid to the graphite is 0.1-0.3:1.
Preferably, the mass ratio of the gluconic acid to the graphite is 0.4-0.6:1. More preferably, the mass ratio of the gluconic acid to the hexafluorobutanol is 1:0.3-0.8. The addition of the gluconic acid in the intercalation agent can reduce the consumption of perchloric acid and phosphoric acid, has the advantages of energy conservation and environmental protection, and when the expanded graphite is prepared, the ash content of the product is less, the expanded graphite can be prepared at a low temperature, and the expansion volume is larger. The addition of hexafluorobutanol can act synergistically with gluconic acid.
An expandable graphite is provided, which is prepared by the preparation method.
The preparation method of the oxidation-resistant expanded graphite material comprises the following steps:
1) Performing expansion pressing on the expandable graphite to obtain an expanded graphite material;
2) Preparing an antioxidant solution;
3) And (3) immersing the expanded graphite material in an antioxidant solution and drying.
Preferably, the step 1) specifically includes: and (3) expanding the expandable graphite at a high temperature of between 400 and 500 ℃ for 15 to 30 seconds, and pressing to obtain the expanded graphite material.
Preferably, the antioxidant solution comprises aluminum isopropoxide, sodium tetraborate, phosphoric acid, oxalic acid and water.
More preferably, aluminum isopropoxide in the antioxidant solution: sodium tetraborate: phosphoric acid: oxalic acid: the weight ratio of the water is 2.5-3.5:1.5-3:1.2-1.8:1.2-1.8:5-12.
Preferably, the step 3) specifically includes: adding antioxidant solution into the expanded graphite material, soaking at 70-75deg.C for 70-80min, oven drying, and gradient heating.
Further, the gradient temperature increasing process includes:
a. heat preserving at 110-120deg.C for 4-8min;
b. heating to 200-220 deg.C, and maintaining the temperature for 4-8min;
c. heating to 320-340 deg.C, and maintaining the temperature for 8-12min;
d. heating to 400-420min, and maintaining the temperature for 4-8min.
Preferably, the antioxidant solution comprises sodium silicate, magnesium borate, phosphoric acid, diethylene glycol dimethyl ether and disodium succinate. The addition of diethylene glycol dimethyl ether and disodium succinate is beneficial to the uniform distribution of the antioxidant on the surface of the expanded graphite material and improves the oxidation resistance, so that the use amount of the antioxidant can be reduced, the excessive high hardness of the expanded graphite caused by the excessive high content of sodium silicate in the expanded graphite is avoided, and the prepared oxidation-resistant expanded graphite material has good compression rebound resilience performance and expands the application range of the oxidation-resistant expanded graphite material in the field of sealing materials.
Preferably, sodium silicate in the antioxidant solution: magnesium borate: phosphoric acid: diethylene glycol dimethyl ether: the weight ratio of the disodium succinate is 12-16:6-8:20-25:3-6:4-7.
More preferably, the antioxidant solution includes an impregnating solution a and an impregnating solution B.
Further, the impregnating solution a includes sodium silicate, magnesium borate, diethylene glycol dimethyl ether, disodium succinate, and the impregnating solution B includes phosphoric acid.
Further, the concentration of sodium silicate in the impregnating solution A is 12-16wt%.
Further, the concentration of phosphoric acid in the impregnating solution B is 20-25wt%.
Preferably, the step 3) specifically includes: adding impregnating solution A into the expanded graphite material, and heating and stirring in a vacuum state; then adding the impregnating solution B, heating and stirring under vacuum, filtering and drying after the reaction is finished.
Preferably, the vacuum degree of the vacuum state is-0.02 to-0.1 MPa.
The high-temperature-resistant flexible graphite is prepared by adopting the preparation method of the oxidation-resistant expanded graphite material.
There is provided the use of expandable graphite in the preparation of flame retardant materials.
Provides the application of the high-temperature-resistant flexible graphite in preparing sealing materials.
The invention has the following beneficial effects because the intercalation agent adopted in the preparation of the expandable graphite contains gluconic acid: the addition of the gluconic acid can reduce the consumption of perchloric acid and phosphoric acid, has the advantages of energy conservation and environmental protection, and when the expanded graphite is prepared, the ash content of the product is less, the expanded graphite can be prepared at low temperature, and the expansion volume is larger. The addition of hexafluorobutanol can act synergistically with gluconic acid.
The antioxidant solution adopted in the preparation of the antioxidant expanded graphite material contains diethylene glycol dimethyl ether and disodium succinate, so the antioxidant expanded graphite material has the following beneficial effects: the oxidation resistance of the expanded graphite material can be improved, the use amount of the antioxidant is reduced, and the situation that the hardness of the expanded graphite is too high due to the fact that the sodium silicate content in the expanded graphite is too high is avoided, so that the prepared oxidation resistant expanded graphite material has good compression rebound resilience performance, and the application range of the oxidation resistant expanded graphite material in the field of sealing materials is widened.
Therefore, the invention is an oxidation-resistant expanded graphite material with environmental protection, lower cost, higher efficiency, strong oxidation resistance and wide application range and the preparation method thereof.
Drawings
FIG. 1 is a FTIR spectrum of expandable graphite according to example 1 of the present invention;
FIG. 2 shows the results of the measurement of volatile matters and ash in test example 1 of the present invention;
FIG. 3 shows the measurement result of the expansion volume in test example 1 of the present invention;
FIG. 4 is a scanning electron microscope image of test example 1 of the present invention;
FIG. 5 is a graph showing the measurement result of the oxidation weight loss ratio in test example 1 of the present invention;
FIG. 6 shows the results of measuring the compression and rebound ratios in test example 1 of the present invention.
Detailed Description
The invention is described in further detail below with reference to examples:
example 1:
1. a preparation method of expandable graphite,comprising the following steps: adding 0.6g of potassium permanganate into a beaker filled with 30g of perchloric acid, uniformly stirring, adding 5g of natural crystalline flake graphite, uniformly stirring, sequentially adding 1g of phosphoric acid, 2g of gluconic acid and 0.8g of hexafluorobutanol, uniformly stirring, reacting for 30min at 30 ℃, stirring once every 4min in the reaction process, washing with distilled water to be neutral after the reaction is finished, filtering, removing filtrate, and drying at 60 ℃ for 3h to obtain the expandable graphite. FTIR analysis of the expandable graphite obtained: adopts an AXIOS infrared spectrometer in the Netherlands, and the scanning range is 4000-500cm -1 The power was 4kW with a relative error of 0.05% and KBr pellets were used. The FTIR spectra of expandable graphite are shown in FIG. 1. As can be seen from FIG. 1, 1165cm -1 At ClO 4 - Is 1735cm -1 C=O stretching vibration peak of carboxyl at 2925cm -1 、2854cm -1 The positions are respectively an antisymmetric stretching vibration peak and a symmetrical stretching vibration peak of methylene, and 1301cm -1 The C-F stretching vibration peak is 2428cm -1 The characteristic absorption peak of phosphoric acid shows that perchloric acid, phosphoric acid, gluconic acid and hexafluorobutanol are intercalated into the interlayer structure of graphite.
2. A preparation method of an antioxidant expanded graphite material is a preparation method of antioxidant flexible graphite, and comprises the following steps:
2.1, placing 5g of the expandable graphite prepared in the step 1 in a muffle furnace at 400 ℃ for puffing for 30 seconds, pressing, setting the pressing pressure to be 2MPa, the times of pressing to be 3 times, and the single pressing time to be 2 minutes, and cutting into square sheet samples (the thickness is 0.85 mm) with the thickness of 20mm multiplied by 20mm after the compression molding to obtain an expanded graphite material;
2.2 an antioxidant solution was obtained by thoroughly mixing 18g of aluminum isopropoxide, 12g of sodium tetraborate, 10g of phosphoric acid, 8g of oxalic acid and 50g of water.
2.3 adding 60mL of an antioxidant solution prepared by 2.2 to a 20mm multiplied by 20mm expanded graphite material prepared by 2.1, soaking at 75 ℃ for 70min, drying, and then placing in a muffle furnace for gradient heating treatment: heat-preserving treatment is carried out for 4min at 120 ℃; heating to 220 ℃ and preserving heat for 4min; heating to 340 ℃ and preserving heat for 8min; heating to 420min, and heat preserving for 4min.
Example 2:
1. a method of preparing expandable graphite comprising: adding 0.6g of potassium permanganate into a beaker filled with 30g of perchloric acid, uniformly stirring, adding 5g of natural crystalline flake graphite, uniformly stirring, sequentially adding 1g of phosphoric acid, 2g of gluconic acid and 0.8g of hexafluorobutanol, uniformly stirring, reacting for 30min at 30 ℃, stirring once every 4min in the reaction process, washing with distilled water to be neutral after the reaction is finished, filtering, removing filtrate, and drying at 60 ℃ for 3h to obtain the expandable graphite.
2. A preparation method of an antioxidant expanded graphite material is a preparation method of antioxidant flexible graphite, and comprises the following steps:
2.1, placing 5g of the expandable graphite prepared in the step 1 in a muffle furnace at 400 ℃ for puffing for 30 seconds, pressing, setting the pressing pressure to be 2MPa, the times of pressing to be 3 times, and the single pressing time to be 2 minutes, and cutting into square sheet samples (the thickness is 0.85 mm) with the thickness of 20mm multiplied by 20mm after the compression molding to obtain an expanded graphite material;
2.2, adding 15g of sodium silicate, 7g of magnesium borate, 4g of diethylene glycol dimethyl ether and 6g of disodium succinate into 68g of distilled water, and uniformly mixing to obtain an impregnating solution A; adding 22g of phosphoric acid into 78g of distilled water, and uniformly mixing to obtain an impregnating solution B;
2.3 adding 60mL of impregnating solution A into the 20mm multiplied by 20mm expanded graphite material prepared in 2.1, and impregnating for 20min at the vacuum degree of-0.1 MPa, the impregnating temperature of 55 ℃ and the stirring speed of 150 rpm; then 60mL of impregnating solution B is added, the impregnation is carried out for 20min under the vacuum degree of minus 0.1MPa, the impregnation temperature is 55 ℃ and the stirring speed is 150rpm, and after the reaction is finished, the filtration is carried out, and the drying is carried out for 3h at 60 ℃.
Example 3:
1. a method of preparing expandable graphite comprising: adding 0.6g of potassium permanganate into a beaker filled with 30g of perchloric acid, uniformly stirring, adding 5g of natural crystalline flake graphite, uniformly stirring, sequentially adding 1g of phosphoric acid, 2g of gluconic acid and 0.7g of hexafluorobutanol, uniformly stirring, reacting at 30 ℃ for 30min, stirring once every 4min in the reaction process, washing with distilled water to be neutral after the reaction is finished, filtering, removing filtrate, and drying at 60 ℃ for 3h to obtain the expandable graphite.
2. A preparation method of an antioxidant expanded graphite material is a preparation method of antioxidant flexible graphite, and is the same as in example 1.
Example 4:
1. a method of preparing expandable graphite comprising: adding 0.6g of potassium permanganate into a beaker filled with 30g of perchloric acid, uniformly stirring, adding 5g of natural crystalline flake graphite, uniformly stirring, sequentially adding 1g of phosphoric acid, 2g of gluconic acid and 1.4g of hexafluorobutanol, uniformly stirring, reacting for 30min at 30 ℃, stirring once every 4min in the reaction process, washing with distilled water to be neutral after the reaction is finished, filtering, removing filtrate, and drying at 60 ℃ for 3h to obtain the expandable graphite.
2. A preparation method of an antioxidant expanded graphite material is a preparation method of antioxidant flexible graphite, and is the same as in example 1.
Example 5:
1. a method of preparing expandable graphite comprising: adding 0.6g of potassium permanganate into a beaker filled with 30g of perchloric acid, uniformly stirring, adding 5g of natural crystalline flake graphite, uniformly stirring, sequentially adding 1g of phosphoric acid and 2g of gluconic acid, uniformly stirring, reacting for 30min at 30 ℃, stirring once every 4min in the reaction process, washing with distilled water to be neutral after the reaction is finished, carrying out suction filtration, removing filtrate, and drying at 60 ℃ for 3h to obtain the expandable graphite.
2. A preparation method of an antioxidant expanded graphite material is a preparation method of antioxidant flexible graphite, and is the same as in example 1.
Example 6:
1. a method of preparing expandable graphite comprising: adding 0.6g of potassium permanganate into a beaker filled with 30g of perchloric acid, uniformly stirring, adding 5g of natural crystalline flake graphite, uniformly stirring, sequentially adding 1g of phosphoric acid and 0.8g of hexafluorobutanol, uniformly stirring, reacting for 30min at 30 ℃, stirring once every 4min in the reaction process, washing to be neutral by using distilled water after the reaction is finished, filtering, removing filtrate, and drying at 60 ℃ for 3h to obtain the expandable graphite.
2. A preparation method of an antioxidant expanded graphite material is a preparation method of antioxidant flexible graphite, and is the same as in example 1.
Example 7:
1. a method of preparing expandable graphite comprising: adding 0.6g of potassium permanganate into a beaker filled with 30g of perchloric acid, uniformly stirring, adding 5g of natural crystalline flake graphite, uniformly stirring, sequentially adding 1g of phosphoric acid, uniformly stirring, reacting at 30 ℃ for 30min, stirring once every 4min in the reaction process, washing with distilled water to be neutral after the reaction is finished, filtering, removing filtrate, and drying at 60 ℃ for 3h to obtain the expandable graphite.
2. A preparation method of an antioxidant expanded graphite material is a preparation method of antioxidant flexible graphite, and is the same as in example 1.
Example 8:
1. a method of preparing expandable graphite comprising: adding 0.6g of potassium permanganate into a beaker filled with 40g of perchloric acid, uniformly stirring, adding 5g of natural crystalline flake graphite, uniformly stirring, sequentially adding 3g of phosphoric acid, uniformly stirring, reacting at 30 ℃ for 30min, stirring once every 4min in the reaction process, washing with distilled water to be neutral after the reaction is finished, filtering, removing filtrate, and drying at 60 ℃ for 3h to obtain the expandable graphite.
2. A preparation method of an antioxidant expanded graphite material is a preparation method of antioxidant flexible graphite, and is the same as in example 1.
Example 9:
1. a method of preparing expandable graphite comprising: adding 0.6g of potassium permanganate into a beaker filled with 30g of perchloric acid, uniformly stirring, adding 5g of natural crystalline flake graphite, uniformly stirring, sequentially adding 1g of phosphoric acid, 2g of gluconic acid and 0.8g of hexafluorobutanol, uniformly stirring, reacting for 30min at 30 ℃, stirring once every 4min in the reaction process, washing with distilled water to be neutral after the reaction is finished, filtering, removing filtrate, and drying at 60 ℃ for 3h to obtain the expandable graphite.
2. A preparation method of an antioxidant expanded graphite material is a preparation method of antioxidant flexible graphite, and comprises the following steps:
2.1, placing 5g of the expandable graphite prepared in the step 1 in a muffle furnace at 400 ℃ for puffing for 30 seconds, pressing, setting the pressing pressure to be 2MPa, the times of pressing to be 3 times, and the single pressing time to be 2 minutes, and cutting into square sheet samples (the thickness is 0.85 mm) with the thickness of 20mm multiplied by 20mm after the compression molding to obtain an expanded graphite material;
2.2, adding 15g of sodium silicate, 7g of magnesium borate and 6g of disodium succinate into 68g of distilled water, and uniformly mixing to obtain an impregnating solution A; adding 22g of phosphoric acid into 78g of distilled water, and uniformly mixing to obtain an impregnating solution B; the remainder is the same as in example 2.
Example 10:
1. a method of preparing expandable graphite comprising: adding 0.6g of potassium permanganate into a beaker filled with 30g of perchloric acid, uniformly stirring, adding 5g of natural crystalline flake graphite, uniformly stirring, sequentially adding 1g of phosphoric acid, 2g of gluconic acid and 0.8g of hexafluorobutanol, uniformly stirring, reacting for 30min at 30 ℃, stirring once every 4min in the reaction process, washing with distilled water to be neutral after the reaction is finished, filtering, removing filtrate, and drying at 60 ℃ for 3h to obtain the expandable graphite.
2. A preparation method of an antioxidant expanded graphite material is a preparation method of antioxidant flexible graphite, and comprises the following steps:
2.1, placing 5g of the expandable graphite prepared in the step 1 in a muffle furnace at 400 ℃ for puffing for 30 seconds, pressing, setting the pressing pressure to be 2MPa, the times of pressing to be 3 times, and the single pressing time to be 2 minutes, and cutting into square sheet samples (the thickness is 0.85 mm) with the thickness of 20mm multiplied by 20mm after the compression molding to obtain an expanded graphite material;
2.2, adding 15g of sodium silicate, 7g of magnesium borate and 4g of diethylene glycol dimethyl ether into 68g of distilled water, and uniformly mixing to obtain an impregnating solution A; adding 22g of phosphoric acid into 78g of distilled water, and uniformly mixing to obtain an impregnating solution B; the remainder is the same as in example 2.
Example 11:
1. a method of preparing expandable graphite comprising: adding 0.6g of potassium permanganate into a beaker filled with 30g of perchloric acid, uniformly stirring, adding 5g of natural crystalline flake graphite, uniformly stirring, sequentially adding 1g of phosphoric acid, 2g of gluconic acid and 0.8g of hexafluorobutanol, uniformly stirring, reacting for 30min at 30 ℃, stirring once every 4min in the reaction process, washing with distilled water to be neutral after the reaction is finished, filtering, removing filtrate, and drying at 60 ℃ for 3h to obtain the expandable graphite.
2. A preparation method of an antioxidant expanded graphite material is a preparation method of antioxidant flexible graphite, and comprises the following steps:
2.1, placing 5g of the expandable graphite prepared in the step 1 in a muffle furnace at 400 ℃ for puffing for 30 seconds, pressing, setting the pressing pressure to be 2MPa, the times of pressing to be 3 times, and the single pressing time to be 2 minutes, and cutting into square sheet samples (the thickness is 0.85 mm) with the thickness of 20mm multiplied by 20mm after the compression molding to obtain an expanded graphite material;
2.2, adding 15g of sodium silicate and 7g of magnesium borate into 68g of distilled water, and uniformly mixing to obtain an impregnating solution A; adding 22g of phosphoric acid into 78g of distilled water, and uniformly mixing to obtain an impregnating solution B; the remainder is the same as in example 2.
Example 12:
1. a method of preparing expandable graphite comprising: adding 0.6g of potassium permanganate into a beaker filled with 30g of perchloric acid, uniformly stirring, adding 5g of natural crystalline flake graphite, uniformly stirring, sequentially adding 1g of phosphoric acid, 2g of gluconic acid and 0.8g of hexafluorobutanol, uniformly stirring, reacting for 30min at 30 ℃, stirring once every 4min in the reaction process, washing with distilled water to be neutral after the reaction is finished, filtering, removing filtrate, and drying at 60 ℃ for 3h to obtain the expandable graphite.
2. A preparation method of an antioxidant expanded graphite material is a preparation method of antioxidant flexible graphite, and comprises the following steps:
2.1, placing 5g of the expandable graphite prepared in the step 1 in a muffle furnace at 400 ℃ for puffing for 30 seconds, pressing, setting the pressing pressure to be 2MPa, the times of pressing to be 3 times, and the single pressing time to be 2 minutes, and cutting into square sheet samples (the thickness is 0.85 mm) with the thickness of 20mm multiplied by 20mm after the compression molding to obtain an expanded graphite material;
2.2, adding 15g of sodium silicate, 7g of magnesium borate and 12g of ethylene glycol into 68g of distilled water, and uniformly mixing to obtain an impregnating solution A; adding 22g of phosphoric acid into 78g of distilled water, and uniformly mixing to obtain an impregnating solution B;
2.3 adding 80mL of impregnating solution A into the expanded graphite material with 20mm multiplied by 20mm prepared by 2.1, and impregnating for 60min at the vacuum degree of-0.1 MPa, the impregnating temperature of 55 ℃ and the stirring speed of 150 rpm; then 80mL of impregnating solution B is added, the impregnation is carried out for 40min under the vacuum degree of minus 0.1MPa, the impregnation temperature is 55 ℃ and the stirring speed is 150rpm, and after the reaction is finished, the filtration is carried out, and the drying is carried out for 3h at 60 ℃.
Test example 1:
1.1 the expandable graphite volatiles and ash were determined as described above in accordance with GB 10698-89. The results of the volatile and ash determinations are shown in FIG. 2.
1.2 measurement of the expansion volume: 1g of expandable graphite is weighed, a quartz beaker is placed in a muffle furnace at 400 ℃ for preheating for 5min, a sample is placed in the beaker, the sample is rapidly placed in the muffle furnace at a set temperature, a furnace door is opened until the sample is not expanded any more, the test is repeated for 5 times, and an arithmetic average value is taken as an expansion volume. The measurement results of the expansion volume are shown in FIG. 3.
1.3 scanning electron microscope analysis is carried out on the antioxidant expanded graphite material prepared by the method. The scanning electron microscope is shown in fig. 4.
1.4 measurement of oxidation weight loss ratio of oxidation-resistant expanded graphite material:
the experiment is carried out in a muffle furnace, the oxidizing atmosphere is static air, and the test temperature point selected in the experiment process is 900 ℃. The experimental procedure was as follows:
(1) Firstly, cleaning a square boat with distilled water, putting the square boat into an oven to be dried at 100 ℃, then putting the square boat into a muffle furnace to be burned at 900 ℃ for 1h, and measuring the dry weight of the square boat on an electronic precision balance after the square boat is cooled;
(2) Placing an oxidation-resistant expanded graphite material into a square boat, and measuring the total weight of the oxidation-resistant expanded graphite material and the square boat;
(3) Raising the temperature of the muffle furnace, after the muffle furnace is stabilized at a certain temperature point, putting the ark and the oxidation-resistant expanded graphite material into the muffle furnace, half-opening the furnace door, firing for a certain time, taking out, cooling to room temperature, and weighing.
The weight loss ratio w of the oxidation-resistant expanded graphite material is calculated by an oxidation weight loss method, and the calculation formula is as follows:
wherein: m is the dry weight of the ark, unit g;
m 1 the unit g is the dry weight of the oxidation-resistant expanded graphite material and the ark before firing;
m 2 the unit g is the dry weight of the oxidation-resistant expanded graphite material and the ark after firing. The measurement results of the oxidation weight loss rate are shown in FIG. 5.
1.5 compression resilience performance test of antioxidant expanded graphite material: and (3) superposing antioxidant expanded graphite materials, wherein the superposition thickness is 1.7mm, measuring the compression rate and the rebound rate by using a compression rebound tester, measuring three different points, and taking the arithmetic average value as the compression rate and the rebound rate of the graphite plate. The measurement results of the compression ratio and the rebound ratio are shown in FIG. 6.
As can be seen from fig. 2 and 3, the volatile components and ash content of examples 1, 3 and 4 are not much different from those of examples 5, 6 and 7, but are significantly smaller than those of example 8, the expansion volume of example 5 is significantly larger than those of examples 6 and 7, and the expansion volume of examples 1, 3 and 4 is not much different from those of example 8, but is significantly larger than those of examples 5, 6 and 7, which shows that the addition of gluconic acid in the intercalating agent can reduce the use amount of perchloric acid and phosphoric acid, and when the expanded graphite is prepared, the ash content of the product is small, and the expansion volume is large. The addition of hexafluorobutanol is capable of acting synergistically with gluconic acid, presumably in the presence of hexafluorobutanol to facilitate the incorporation of gluconic acid into the interlayer structure.
As can be seen from fig. 4, compared with example 11, the oxidation-resistant expanded graphite prepared in example 2 has a more uniform and more dense impregnation solution distribution on the surface of the expanded graphite, which indicates that the addition of diethylene glycol dimethyl ether and disodium succinate is beneficial to the uniform distribution of the antioxidant on the surface.
As can be seen from fig. 5, the oxidation weight loss ratio of example 2 is significantly smaller than that of example 9, example 10, example 11 and example 12, and as can be seen from fig. 6, the compression rate and rebound rate of example 2 are significantly larger than those of example 9, example 10, example 11 and example 12, which means that the addition of diethylene glycol dimethyl ether and disodium succinate can improve the oxidation resistance of the expanded graphite, and at the same time can reduce the amount of antioxidant used, and has good compression set elastic properties.
The conventional technology in the above embodiments is known to those skilled in the art, and thus is not described in detail herein.
The above embodiments are merely for illustrating the present invention and not for limiting the same, and various changes and modifications may be made by one of ordinary skill in the art without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions are also within the scope of the present invention, which is defined by the claims.
Claims (4)
1. The preparation method of the oxidation-resistant expanded graphite material is characterized by comprising the following steps of:
1) Adding potassium permanganate into a container filled with perchloric acid, uniformly stirring, adding natural crystalline flake graphite, uniformly stirring, sequentially adding phosphoric acid, gluconic acid and hexafluorobutanol, uniformly stirring, reacting at 25-35 ℃ for 20-40min, stirring once every 3-5min in the reaction process, washing to be neutral after the reaction is finished, carrying out suction filtration, and drying at 50-60 ℃ to obtain expandable graphite; performing expansion pressing on expandable graphite to obtain an expanded graphite material;
2) Preparing an antioxidant solution, wherein the antioxidant solution comprises an impregnating solution A and an impregnating solution B; the impregnating solution A comprises sodium silicate, magnesium borate, diethylene glycol dimethyl ether and disodium succinate, the impregnating solution B comprises phosphoric acid, and the sodium silicate: magnesium borate: phosphoric acid: diethylene glycol dimethyl ether: the weight ratio of the disodium succinate is 12-16:6-8:20-25:3-6:4-7;
3) Adding the impregnating solution A into the expanded graphite material, and heating and stirring the material in a vacuum state; adding the impregnating solution B, heating and stirring in a vacuum state, filtering and drying after the reaction is finished;
in the step 1), the mass ratio of the potassium permanganate to the graphite is 0.1-0.5:1; the mass ratio of perchloric acid to graphite is 4-7:1; the mass ratio of phosphoric acid to graphite is 0.1-0.3:1; the mass ratio of the gluconic acid to the graphite is 0.4-0.6:1; the mass ratio of the gluconic acid to the hexafluorobutanol is 1:0.3-0.8;
in the step 2), the concentration of sodium silicate in the impregnating solution A is 12-16wt percent, and the concentration of phosphoric acid in the impregnating solution B is 20-25wt percent;
in the step 3), the vacuum degree of the vacuum state is minus 0.02 to minus 0.1MPa.
2. The method of claim 1, wherein said step 1) comprises: and (3) expanding the expandable graphite at a high temperature of between 400 and 500 ℃ for 15 to 30 seconds, and pressing to obtain the expanded graphite material.
3. A high temperature resistant flexible graphite, characterized in that: prepared by the method of claim 1.
4. Use of the high temperature resistant flexible graphite of claim 3 in the preparation of a sealing material.
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