CN113480336A - Preparation and use method of graphite antioxidant - Google Patents
Preparation and use method of graphite antioxidant Download PDFInfo
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- CN113480336A CN113480336A CN202110673934.1A CN202110673934A CN113480336A CN 113480336 A CN113480336 A CN 113480336A CN 202110673934 A CN202110673934 A CN 202110673934A CN 113480336 A CN113480336 A CN 113480336A
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- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 73
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 68
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000010439 graphite Substances 0.000 title claims abstract description 43
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 93
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 38
- 239000007770 graphite material Substances 0.000 claims abstract description 35
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 alkoxy silane Chemical compound 0.000 claims abstract description 10
- 229910000077 silane Inorganic materials 0.000 claims abstract description 10
- 238000007598 dipping method Methods 0.000 claims abstract description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 19
- 239000004327 boric acid Substances 0.000 claims description 19
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 6
- 229910000831 Steel Inorganic materials 0.000 abstract description 2
- 230000002378 acidificating effect Effects 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 239000010959 steel Substances 0.000 abstract description 2
- 239000012855 volatile organic compound Substances 0.000 abstract description 2
- 230000001680 brushing effect Effects 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 238000010992 reflux Methods 0.000 description 12
- 230000004580 weight loss Effects 0.000 description 8
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 6
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- XYYQWMDBQFSCPB-UHFFFAOYSA-N dimethoxymethylsilane Chemical compound COC([SiH3])OC XYYQWMDBQFSCPB-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a preparation method and a using method of a graphite antioxidant, relating to the technical field of graphite antioxidants, wherein the preparation method of the graphite antioxidant comprises the following steps: s1, adding 30-100 parts of alkoxy silane into the reaction kettle, then adding aqueous solution of acetic acid, hydrochloric acid and the like, wherein the proportion of the aqueous solution of the acetic acid, the hydrochloric acid and the like is 10-50 parts, the acetic acid and the hydrochloric acid are dissolved in 100 parts of water, and uniformly stirring to obtain the aqueous solution of the acetic acid or the hydrochloric acid. The boron-silicon-based antioxidant can be completely dissolved in water, a common organic solvent is not adopted, VOCs are not discharged when the antioxidant is used, the antioxidant is weakly acidic or neutral, and basically does not corrode a reaction vessel or other steel materials, a network structure such as Si-O-B-O-C can be formed by dipping or brushing the graphite material with the antioxidant and then carrying out heat treatment, pores or active sites of the graphite material can be better protected, and the antioxidant temperature of the graphite material is increased to 1000-1100 ℃.
Description
Technical Field
The invention relates to a graphite antioxidant, in particular to a preparation method and a use method of the graphite antioxidant.
Background
The graphite material has the advantages of corrosion resistance, self lubrication, high temperature resistance and the like, and has extremely wide application in national production and life.
However, when the graphite material is used under an aerobic condition exceeding 400 ℃, the graphite material is quickly oxidized by oxygen, so that the graphite material is quickly worn at a high temperature, the service life is reduced, and great waste is caused.
At present, silica sol, water-soluble phosphate and the like are mostly adopted as an immersion type graphite antioxidant in the antioxidation treatment of graphite materials, and the method of immersion and surface brush coating is mostly adopted to ensure that the surface or the interior of graphite obtains the antioxidation performance; however, the silica sol is a suspension of nano-silica in water or other solvents, and is difficult to enter the graphite product, so that the graphite product is subjected to oxidation resistance protection at high temperature in the presence of oxygen; although the phosphate series antioxidants can completely enter the interior of the graphite product as aqueous solutions and further play a role in protecting the graphite from being oxidized by oxygen at high temperature, the phosphates capable of dissolving in water generally have strong acidity, the pH value of the phosphates is generally below 2, the phosphates have great pressure on containers and surrounding environments of the antioxidants when in use, the optimal use temperature of the phosphate series antioxidants does not exceed 900 ℃, and the antioxidant capacity of the phosphate series antioxidants is sharply reduced when the temperature exceeds 900 ℃.
Disclosure of Invention
The invention aims to provide a preparation method and a using method of a graphite antioxidant, aiming at the defects of the conventional graphite product impregnated antioxidant: if the graphite product is not easy to enter the interior of the graphite product, the acidity is too strong, the environmental pollution is great, the protection temperature of the graphite product is not high, and the like, a preparation method and a use method of a water-soluble and near-neutral graphite antioxidant impregnant are provided, and the antioxidant temperature of the graphite product can be increased to 1000-1100 ℃.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation of a graphite antioxidant, comprising the steps of:
s1, adding 30-100 parts of alkoxy silane into a reaction kettle, then adding aqueous solution of acetic acid, hydrochloric acid and the like, wherein the proportion of the aqueous solution of the acetic acid, the hydrochloric acid and the like is 10-50 parts, the acetic acid and the hydrochloric acid are dissolved in 100 parts of water, and uniformly stirring to obtain aqueous solution of the acetic acid or the hydrochloric acid;
s2, slowly dripping a certain amount of water-soluble silane coupling agent on the basis of the step S1, wherein the adding proportion of the water-soluble silane coupling agent is 40-100 parts, and the water-soluble silane coupling agent is required to be dripped during stirring;
s3, adding a certain amount of boric acid in batches on the basis of the step S2, wherein the adding proportion is 20-60 parts, the boric acid is added in batches under stirring, then the temperature is raised to 40-70 ℃, the stirring is carried out for 2-5 hours under heat preservation, and the water-soluble boron-silicon-based graphite antioxidant can be obtained after the cooling and discharging;
the use method of the graphite antioxidant comprises the following steps: the prepared boron-silicon-based graphite antioxidant can be used for treating a graphite material by adopting a brush coating or dipping method, drying the graphite material after brush coating or dipping, and treating the graphite material for 1 to 3 hours at the temperature of 800 ℃ in a protective atmosphere to obtain the graphite material subjected to antioxidant treatment.
In a preferred embodiment of the present invention, the alkoxysilane meansThe silane having X- (Si-OR) after the hydrogen atom in the Si-H bond has been replaced by an alkoxy groupnIn the compound with the structure, X groups can be H, methyl, ethyl, propyl, butyl, phenyl, Cl, Br and other groups, R groups can be methoxy, ethoxy, propoxy and the like, and the number of n can be an integer from 1 to 3.
In a preferred embodiment of the present invention, the alkoxysilane may be ethyl orthosilicate, methyltriethoxysilane, methyldiethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, or the like.
In a preferred embodiment of the present invention, the silane coupling agent in step S2 may be selected from 3-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, and vinyltriethoxysilane.
As a preferable technical scheme of the invention, the proportion of adding the aqueous solution of acetic acid or hydrochloric acid into the reaction kettle in the step S1 is 0-120 parts.
As a preferable technical scheme of the invention, the boric acid in the step S3 can be common industrial pure boric acid or analytically pure boric acid.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the boron-silicon-based antioxidant can be completely dissolved in water, a common organic solvent is not adopted, VOCs are not discharged when the antioxidant is used, and the antioxidant is weakly acidic or neutral and basically does not corrode a reaction container or other steel materials.
2. According to the invention, after the graphite material is soaked or coated with the antioxidant, a network structure such as Si-O-B-O-C can be formed through heat treatment, pores or active sites of the graphite material can be better protected, and the antioxidant temperature of the graphite material is increased to 1000-1100 ℃.
3. The prepared near-neutral or weakly-acidic water-soluble antioxidant can well protect the graphite material under the high-temperature and aerobic conditions, and reduces the loss caused by oxidation.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a technical scheme of a preparation method and a use method of a graphite antioxidant, which comprises the following steps: the preparation of the graphite antioxidant comprises the following steps:
s1, adding 30-100 parts of alkoxy silane into a reaction kettle, then adding aqueous solution of acetic acid, hydrochloric acid and the like, wherein the proportion of the aqueous solution of the acetic acid, the hydrochloric acid and the like is 10-50 parts, the acetic acid and the hydrochloric acid are dissolved in 100 parts of water, and uniformly stirring to obtain aqueous solution of the acetic acid or the hydrochloric acid;
s2, slowly dripping a certain amount of water-soluble silane coupling agent on the basis of the step S1, wherein the adding proportion of the water-soluble silane coupling agent is 40-100 parts, and the water-soluble silane coupling agent is required to be dripped during stirring;
s3, adding a certain amount of boric acid in batches on the basis of the step S2, wherein the adding proportion is 20-60 parts, the boric acid is added in batches under stirring, then the temperature is raised to 40-70 ℃, the stirring is carried out for 2-5 hours under heat preservation, and the water-soluble boron-silicon-based graphite antioxidant can be obtained after the cooling and discharging;
the use method of the graphite antioxidant comprises the following steps: the prepared boron-silicon-based graphite antioxidant can be used for treating a graphite material by adopting a brush coating or dipping method, drying the graphite material after brush coating or dipping, and treating the graphite material for 1 to 3 hours at the temperature of 800 ℃ in a protective atmosphere to obtain the graphite material subjected to antioxidant treatment.
The alkoxysilane means a silane in which a hydrogen atom in an Si-H bond is replaced with an alkoxy group and which contains X- (Si-OR)nIn the compound with the structure, X groups can be H, methyl, ethyl, propyl, butyl, phenyl, Cl, Br and other groups, R groups can be methoxy, ethoxy, propoxy and the like, and the number of n can be an integer from 1 to 3.
The alkoxy silane can be selected from ethyl orthosilicate, methyl triethoxysilane, methyl diethoxy silane, ethyl triethoxysilane, phenyl triethoxysilane, etc.
In the step S2, the silane coupling agent can be selected from 3-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane and vinyltriethoxysilane.
In the step S1, the acetic acid or hydrochloric acid aqueous solution is added into the reaction kettle in a proportion of 0-120 parts.
In the step S3, the boric acid can be ordinary industrial pure boric acid or analytically pure boric acid.
Example one
Adding 8.915Kg of methyltriethoxysilane into a reaction kettle with a reflux device at room temperature, weighing 1Kg of acetic acid, adding 6Kg of water to prepare an acetic acid aqueous solution, adding the acetic acid aqueous solution into the reaction kettle while stirring, stirring for 10min, then slowly adding 11.205Kg of 3-aminopropyltrimethoxysilane at a constant speed, wherein the adding speed is 200g/min and the stirring speed is 50rpm, then adding 3Kg of boric acid in three batches, heating to 60 ℃, refluxing and stirring for 2h, finally heating to 70 ℃, stirring and refluxing for 3h, stopping stirring and cooling to room temperature to obtain a water-soluble boron-silicon antioxidant, wherein the Ph of the antioxidant is 5.5;
completely immersing graphite material to be subjected to oxidation resistance treatment in the prepared water-soluble boron-silicon antioxidant, vacuumizing to-0.9 Mpa in a vacuum container, keeping for 1h, breaking vacuum, pressurizing to 2Mpa, maintaining pressure for 1h, relieving pressure, removing graphite material, wiping off residual antioxidant on the surface, and wiping in N2Raising the temperature to 800 ℃ under protection, and preserving the temperature for 1h to obtain the graphite material subjected to oxidation resistance treatment. The material is oxidized and weightless than 10% in an air atmosphere at 900 ℃ for 2 h; the oxidation weight loss is lower than 17 percent in the air atmosphere of 1000 ℃ for 2 h; the oxidation weight loss is lower than 25 percent in the air atmosphere of 1100 ℃ for 2 h.
Example two
Adding 12.01Kg of phenyltriethoxysilane into a reaction kettle with a reflux device at room temperature, weighing 3Kg of acetic acid, adding 8Kg of water to prepare an acetic acid aqueous solution, adding the acetic acid aqueous solution into the reaction kettle while stirring, stirring for 10min, then slowly adding 22.27Kg of gamma-glycidoxypropyltrimethoxysilane at a constant speed, adding 380g/min at a stirring speed of 60rpm, then adding 4Kg of boric acid in three batches, heating to 55 ℃, stirring under reflux for 2h, finally heating to 70 ℃, stirring under reflux for 2h, stopping stirring, cooling to room temperature to obtain a water-soluble boron-silicon antioxidant, wherein the Ph of the antioxidant is 3.2;
completely immersing the graphite material needing antioxidant treatment in the prepared water-soluble boron-silicon antioxidant, vacuumizing to-0.9 Mpa in a vacuum container, keeping for 1h, breaking vacuum, pressurizing to 2Mpa, keeping pressure for 1h, relieving pressure, removing the graphite material, wiping off the residual antioxidant on the surface, heating to 800 ℃ under the protection of N2, and keeping the temperature for 1h to obtain the graphite material needing antioxidant treatment. The material is oxidized and weightless than 8% in an air atmosphere at 900 ℃ for 2 h; the oxidation weight loss is lower than 14 percent in the air atmosphere of 1000 ℃ for 2 h; the oxidation weight loss is lower than 21 percent in the air atmosphere of 1100 ℃ for 2 h.
EXAMPLE III
At room temperature, adding 5.3Kg of dimethoxymethylsilane into a reaction kettle with a reflux device, weighing 3Kg of acetic acid, adding 8Kg of water to prepare an acetic acid aqueous solution, adding the acetic acid aqueous solution into the reaction kettle while stirring, stirring for 10min, then slowly adding 27.8Kg of gamma-methacryloxypropyltrimethoxysilane at a constant speed, wherein the adding speed is 470g/min and the stirring speed is 100rpm, then adding 3Kg of boric acid in three batches, heating to 70 ℃, refluxing and stirring for 2h, finally heating to 80 ℃, stirring and refluxing for 2h, stopping stirring and cooling to room temperature to obtain the water-soluble boron-silicon antioxidant;
completely immersing the graphite material needing antioxidant treatment in the prepared water-soluble boron-silicon antioxidant, vacuumizing to-0.9 Mpa in a vacuum container, keeping for 1h, breaking vacuum, pressurizing to 2Mpa, keeping pressure for 1h, relieving pressure, removing the graphite material, wiping off the residual antioxidant on the surface, heating to 800 ℃ under the protection of N2, and keeping the temperature for 1h to obtain the graphite material needing antioxidant treatment. The material is oxidized and weightless than 11% in an air atmosphere at 900 ℃ for 2 h; the oxidation weight loss is lower than 16 percent in the air atmosphere of 1000 ℃ for 2 h; the oxidation weight loss is less than 26 percent in the air atmosphere of 1100 ℃ for 2 h.
Example four
Adding 12.01Kg of phenyltriethoxysilane into a reaction kettle with a reflux device at room temperature, weighing 0.1Kg of acetic acid, adding 8Kg of water to prepare an acetic acid aqueous solution, adding the acetic acid aqueous solution into the reaction kettle under stirring, stirring for 20min, slowly adding 11.07Kg of gamma-aminopropyltriethoxysilane at a constant speed, adding 200g/min at a stirring speed of 50rpm, adding 2Kg of boric acid in three batches, heating to 55 ℃, stirring under reflux for 2h, finally heating to 75 ℃, stirring under reflux for 2h, stopping stirring, cooling to room temperature to obtain a water-soluble boron-silicon antioxidant with a Ph of 6.2;
stirring the prepared water-soluble boron-silicon antioxidant and alumina micro powder into slurry according to the weight ratio of 1:0.3, completely immersing the graphite material needing antioxidant treatment in the slurry for 30min, taking out and draining the slurry, heating to 800 ℃ under the protection of N2, and preserving heat for 1h to obtain the graphite material needing antioxidant treatment. The material is oxidized and weightless than 3% in an air atmosphere at 900 ℃ for 2 h; the oxidation weight loss is lower than 8 percent in the air atmosphere of 1000 ℃ for 2 h; the oxidation weight loss is lower than 13 percent in the air atmosphere of 1100 ℃ for 2 h.
In the present invention, unless otherwise explicitly specified or limited, for example, it may be fixedly attached, detachably attached, or integrated; can be mechanically or electrically connected; the terms may be directly connected or indirectly connected through an intermediate, and may be communication between two elements or interaction relationship between two elements, unless otherwise specifically limited, and the specific meaning of the terms in the present invention will be understood by those skilled in the art according to specific situations.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. The preparation method of the graphite antioxidant is characterized by comprising the following steps: the preparation of the graphite antioxidant comprises the following steps:
s1, adding 30-100 parts of alkoxy silane into a reaction kettle, then adding aqueous solution of acetic acid, hydrochloric acid and the like, wherein the proportion of the aqueous solution of the acetic acid, the hydrochloric acid and the like is 10-50 parts, the acetic acid and the hydrochloric acid are dissolved in 100 parts of water, and uniformly stirring to obtain aqueous solution of the acetic acid or the hydrochloric acid;
s2, slowly dripping a certain amount of water-soluble silane coupling agent on the basis of the step S1, wherein the adding proportion of the water-soluble silane coupling agent is 40-100 parts, and the water-soluble silane coupling agent is required to be dripped during stirring;
s3, adding a certain amount of boric acid in batches on the basis of the step S2, wherein the adding proportion is 20-60 parts, the boric acid is added in batches under stirring, then the temperature is raised to 40-70 ℃, the stirring is carried out for 2-5 hours under heat preservation, and the water-soluble boron-silicon-based graphite antioxidant can be obtained after the cooling and discharging;
the use method of the graphite antioxidant comprises the following steps: the prepared boron-silicon-based graphite antioxidant can be used for treating a graphite material by adopting a brush coating or dipping method, drying the graphite material after brush coating or dipping, and treating the graphite material for 1 to 3 hours at the temperature of 800 ℃ in a protective atmosphere to obtain the graphite material subjected to antioxidant treatment.
2. The method for preparing and using a graphite antioxidant as claimed in claim 1, wherein the graphite antioxidant comprises the following components: the alkoxy silane refers to the silane containing X- (Si-OR) after the hydrogen atom in the Si-H bond is replaced by alkoxynIn the compound with the structure, X groups can be H, methyl, ethyl, propyl, butyl, phenyl, Cl, Br and other groups, R groups can be methoxy, ethoxy, propoxy and the like, and the number of n can be an integer from 1 to 3.
3. The method for preparing and using a graphite antioxidant as claimed in claim 2, wherein: said alkoxy silane can be selected from ethyl orthosilicate, methyl triethoxysilane, methyl diethoxy silane, ethyl triethoxysilane, phenyl triethoxysilane, etc.
4. The method for preparing and using a graphite antioxidant as claimed in claim 1, wherein the graphite antioxidant comprises the following components: the silane coupling agent in the step S2 can be selected from 3-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane and vinyltriethoxysilane.
5. The method for preparing and using a graphite antioxidant as claimed in claim 1, wherein the graphite antioxidant comprises the following components: and in the step S1, the acetic acid or hydrochloric acid aqueous solution is added into the reaction kettle in a proportion of 0-120 parts.
6. The method for preparing and using a graphite antioxidant as claimed in claim 1, wherein the graphite antioxidant comprises the following components: in the step S3, the boric acid can be ordinary industrial pure boric acid or analytically pure boric acid.
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Citations (4)
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| US4301026A (en) * | 1978-12-02 | 1981-11-17 | Teruhisa Kondo | Antioxidant for carbonaceous material and method |
| JPH10195381A (en) * | 1997-01-13 | 1998-07-28 | Daihachi Chem Ind Co Ltd | Composition for coating film formation |
| CN104163657A (en) * | 2014-07-21 | 2014-11-26 | 中国矿业大学(北京) | Graphite mould antioxidant impregnation liquid, preparation method and application method thereof |
| CN110452019A (en) * | 2019-09-02 | 2019-11-15 | 广东省材料与加工研究所 | A kind of anti-oxidant maceration extract of graphite jig, preparation method and application |
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2021
- 2021-06-17 CN CN202110673934.1A patent/CN113480336A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4301026A (en) * | 1978-12-02 | 1981-11-17 | Teruhisa Kondo | Antioxidant for carbonaceous material and method |
| JPH10195381A (en) * | 1997-01-13 | 1998-07-28 | Daihachi Chem Ind Co Ltd | Composition for coating film formation |
| CN104163657A (en) * | 2014-07-21 | 2014-11-26 | 中国矿业大学(北京) | Graphite mould antioxidant impregnation liquid, preparation method and application method thereof |
| CN110452019A (en) * | 2019-09-02 | 2019-11-15 | 广东省材料与加工研究所 | A kind of anti-oxidant maceration extract of graphite jig, preparation method and application |
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