CN111675826A - Method for improving oxidation resistance of phenolic aerogel composite material and modified phenolic aerogel composite material prepared by method - Google Patents
Method for improving oxidation resistance of phenolic aerogel composite material and modified phenolic aerogel composite material prepared by method Download PDFInfo
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- 239000004964 aerogel Substances 0.000 title claims abstract description 138
- 239000002131 composite material Substances 0.000 title claims abstract description 138
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims abstract description 50
- 230000003647 oxidation Effects 0.000 title claims abstract description 31
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 31
- 239000002243 precursor Substances 0.000 claims abstract description 107
- -1 phenolic aldehyde Chemical class 0.000 claims abstract description 73
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 53
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 52
- 238000001035 drying Methods 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 239000011240 wet gel Substances 0.000 claims abstract description 32
- 239000000835 fiber Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000013329 compounding Methods 0.000 claims abstract description 15
- 239000000499 gel Substances 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 229920002050 silicone resin Polymers 0.000 claims description 37
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 15
- 239000004917 carbon fiber Substances 0.000 claims description 15
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052863 mullite Inorganic materials 0.000 claims description 7
- 229920001709 polysilazane Polymers 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- 238000000643 oven drying Methods 0.000 claims description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 claims description 4
- 229960001553 phloroglucinol Drugs 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 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 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- 229920006282 Phenolic fiber Polymers 0.000 claims description 3
- 239000003377 acid catalyst Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000005456 alcohol based solvent Substances 0.000 claims description 3
- 229920013822 aminosilicone Polymers 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 229930003836 cresol Natural products 0.000 claims description 3
- 239000011094 fiberboard Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 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
- BTQAJGSMXCDDAJ-UHFFFAOYSA-N phloroglucinol aldehyde Natural products OC1=CC(O)=C(C=O)C(O)=C1 BTQAJGSMXCDDAJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920001225 polyester resin Polymers 0.000 claims description 3
- 239000004645 polyester resin Substances 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000000352 supercritical drying Methods 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- CCDWGDHTPAJHOA-UHFFFAOYSA-N benzylsilicon Chemical compound [Si]CC1=CC=CC=C1 CCDWGDHTPAJHOA-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000003973 paint Substances 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 229920000441 polyisocyanide Polymers 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 11
- 238000009413 insulation Methods 0.000 abstract description 8
- 238000007605 air drying Methods 0.000 abstract description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 230000003064 anti-oxidating effect Effects 0.000 description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 230000004580 weight loss Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 230000002787 reinforcement Effects 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000004966 Carbon aerogel Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
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- 238000004321 preservation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/42—Impregnation with macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
- C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
- C08J2205/026—Aerogel, i.e. a supercritically dried gel
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- Phenolic Resins Or Amino Resins (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention relates to a method for improving the oxidation resistance of a phenolic aerogel composite material and a modified phenolic aerogel composite material prepared by the method. The method comprises the following steps: (1) preparing a precursor solution containing a phenolic aldehyde precursor, a catalyst and an organic solvent, compounding the precursor solution and a fiber product in situ, and then carrying out sol-gel reaction to obtain a phenolic aldehyde wet gel composite material; (2) airing the phenolic aldehyde wet gel composite material at normal temperature, and then drying to prepare a phenolic aldehyde aerogel composite material; (3) compounding an antioxidant precursor solution with a certain depth on the surface of the phenolic aerogel composite material, and then sequentially carrying out an air-drying step and a high-temperature drying step to prepare the antioxidant modified phenolic aerogel composite material. The phenolic aerogel composite material prepared by the method has the advantages of excellent oxidation resistance, low cost, short period and simple process. The phenolic aerogel prepared by the invention has the advantages of excellent oxidation resistance, good heat insulation performance and the like, and has excellent comprehensive performance.
Description
Technical Field
The invention belongs to the technical field of phenolic aldehyde aerogel preparation, relates to a method for improving the oxidation resistance of aerogel, and particularly relates to a method for improving the oxidation resistance of a phenolic aldehyde aerogel composite material and a modified phenolic aldehyde aerogel composite material prepared by the method.
Background
Aerogel materials have high specific strength, large specific surface area and fine and uniform pore diameters, so that the aerogel materials have good heat insulation and noise reduction performances and become one of the research hotspots which are concerned by the research institutions all over the world. Aerogel materials are mainly classified into two categories, namely inorganic aerogels and organic aerogels, wherein the main component of the inorganic aerogels is silicon dioxide, the service temperature of the aerogels is not more than 700 ℃, and when the temperature is higher, such as the temperature of high-temperature parts of rocket motors reaches thousands of degrees or even higher, the inorganic aerogels can be sintered to cause shrinkage and microstructure damage, so that the heat insulation performance is lost. Compared with inorganic aerogel, the organic aerogel, especially phenolic aldehyde aerogel contains carbon element, has better capacity of absorbing heat radiation, and the effect is particularly obvious at high temperature, the phenolic aldehyde aerogel can not be sintered and shrunk under the high-temperature effect, but is subjected to carbonization reaction to generate carbon aerogel, and the carbon aerogel can meet the requirement of thousands of degrees of temperature preservation. Therefore, the high-temperature heat insulation performance of the phenolic aerogel material is obviously superior to that of the inorganic aerogel material.
The phenolic aerogel composite material can be carbonized and further oxidized in a high-temperature aerobic environment, and after long-time work, the phenolic aerogel is subjected to invalidation and loses heat-insulating property due to oxidation. Therefore, how to improve the oxidation resistance of the phenolic aerogel is a technical problem to be solved urgently in the field.
Disclosure of Invention
The invention aims to provide a method for improving the oxidation resistance of a phenolic aerogel composite material and a modified phenolic aerogel composite material prepared by the method, so as to at least solve the problems that the phenolic aerogel in the prior art is poor in oxidation resistance and fails when the phenolic aerogel is used at a high temperature for a long time. The method can obtain the phenolic aerogel composite material with excellent oxidation resistance and has simple process; the phenolic aerogel composite material prepared by the invention has excellent comprehensive performance.
In order to achieve the above object, the present invention provides in a first aspect a method for improving the oxidation resistance of a phenolic aerogel composite, the method comprising the steps of:
(1) preparing a precursor solution containing a phenolic aldehyde precursor, a catalyst and an organic solvent, and carrying out sol-gel reaction after the precursor solution and a fiber product are compounded in situ to obtain a phenolic aldehyde wet gel composite material;
(2) airing the phenolic aldehyde wet gel composite material at normal temperature, and then drying to obtain a phenolic aldehyde aerogel composite material; and
(3) compounding an antioxidant precursor solution with a certain depth on the surface of the phenolic aerogel composite material, and then sequentially carrying out an airing step and a high-temperature drying step to prepare the antioxidant modified phenolic aerogel composite material.
Preferably, the antioxidant precursor contained in the antioxidant precursor solution is one or more of methyl phenyl silicone resin, methyl silicone resin, low phenyl methyl silicone resin, epoxy modified silicone resin, silicone polyester modified resin, benzyl silicone resin, polymethyl silicone resin, amino silicone resin, fluorosilicone resin, silicone polyester resin, methyl MQ silicone resin, vinyl MQ silicone resin, silicone acrylic resin paint, polysilazane, silica sol, alumina sol and mullite sol; preferably, the antioxidant precursor contained in the antioxidant precursor solution is one or more of methyl silicone resin, low phenyl silicone resin, polymethyl silicone resin, polysilazane, silica sol, aluminum sol and mullite sol.
Preferably, the depth of the antioxidant precursor solution is 0.5-3 mm; and/or the concentration of the antioxidant precursor in the antioxidant precursor solution is 5-25 wt%, preferably 8-20 wt%.
Preferably, the airing step is carried out for 12-96 hours at normal temperature and normal pressure; and/or the drying temperature of the high-temperature drying step is 60-150 ℃, and the drying time is 24-72 h.
Preferably, the phenolic precursor is one or more of resorcinol and formaldehyde, melamine and formaldehyde, phenolic resin and formaldehyde, mixed cresol and formaldehyde, polyisocyanolate, phloroglucinol and formaldehyde, poly-N-methylol acrylamide and resorcinol; and/or the catalyst is a basic catalyst or an acidic catalyst; the alkaline catalyst is selected from the group consisting of sodium carbonate solution, potassium hydroxide solution and sodium hydroxide solution; the acid catalyst is hydrochloric acid solution; and/or the organic solvent is an alcohol solvent; the alcohol solvent is selected from one or more of alcohol solvents with the boiling point lower than 150 ℃; preferably, the alcohol solvent is selected from the group consisting of ethanol, propanol and butanol.
Preferably, the concentration of the phenolic aldehyde precursor in the precursor solution is 10-25 wt%; and/or the molar ratio of the phenolic aldehyde precursor to the catalyst is (20-100): 1.
preferably, the fiber product is a fiber felt, a fiber blanket or a fiber board made of one or more fibers selected from carbon fibers, quartz fibers, high silica fibers, glass fibers, phenolic fibers and silicon carbide fibers.
Preferably, in the step (1), the temperature of the sol-gel reaction is 60-160 ℃, and the time of the sol-gel reaction is 24-120 h; and/or in the step (2), the normal-temperature airing time is 24-48 h.
Preferably, in step (2), the drying is oven drying or supercritical drying; the drying temperature of the drying oven is 60-100 ℃, and the drying time of the drying oven is 18-30 h.
In a second aspect, the present invention provides an oxidation-resistant modified phenolic aerogel composite prepared by the method of the invention described in the first aspect.
Compared with the prior art, the method of the invention at least has the following beneficial effects:
(1) the invention realizes the anti-oxidation technology of the phenolic aerogel composite material, greatly reduces the complexity of the anti-oxidation operation of the phenolic aerogel composite material, and is beneficial to low-cost anti-oxidation modification and large-scale application of the phenolic aerogel composite material.
(2) According to the invention, the antioxidant precursor with a certain depth is compounded on the surface of the phenolic aerogel composite material, so that the phenolic aerogel composite material can be effectively prevented from losing effectiveness due to oxidation in a long-time working process in a high-temperature aerobic environment; in addition, the reasonable antioxidant process is beneficial to obtaining the phenolic aerogel composite material with excellent antioxidant performance.
(3) The phenolic aerogel prepared by the method has excellent oxidation resistance and simple process; the phenolic aerogel prepared by the invention has excellent comprehensive performance.
Drawings
FIG. 1 is a flow chart of the preparation of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The present invention provides in a first aspect a method of improving the oxidation resistance of a phenolic aerogel composite, the method comprising the steps of:
(1) preparing a precursor solution (phenolic aldehyde precursor solution) containing a phenolic aldehyde precursor, a catalyst and an organic solvent, compounding the precursor solution and a fiber product (fiber reinforcement) in situ, and then carrying out sol-gel reaction to obtain a phenolic aldehyde wet gel composite material; in the present invention, the fiber article is immersed in the precursor solution so that the precursor solution is compounded with the fiber article (fiber reinforcement) in situ;
(2) airing the phenolic aldehyde wet gel composite material at normal temperature, and then drying to obtain a phenolic aldehyde aerogel composite material; and
(3) compounding an antioxidant precursor solution with a certain depth on the surface of the phenolic aerogel composite material, and then sequentially carrying out an air-drying step and a high-temperature drying step to prepare an antioxidant modified phenolic aerogel composite material (modified phenolic aerogel composite material); in the invention, the phenolic aerogel composite material is soaked in the antioxidant precursor solution so as to compound the antioxidant precursor solution with a certain depth on the surface of the phenolic aerogel composite material; in the invention, the antioxidant precursor solution contains an antioxidant precursor and a precursor solvent, wherein the precursor solvent is an organic solvent, and can be a common solvent such as toluene, xylene, ethanol, propylene glycol and the like; in the invention, for example, the phenolic aerogel composite material is aired at normal temperature (for example, 20-30 ℃) and normal pressure (for example, atmospheric pressure) until the weight of the phenolic aerogel composite material is not increased.
At present, the antioxidant performance of the phenolic aerogel is improved by adopting an inorganic hybridization mode, but the situation of improving the antioxidant performance is not described in detail, and the inorganic hybridization method makes the forming mechanism and the gelling process of the phenolic aerogel more complicated, increases factors influencing the performance of a phenolic aerogel system, and has poor controllability. According to the phenolic aerogel composite material and the preparation method thereof, the phenolic aerogel composite material is soaked in the antioxidant precursor solution with a certain depth, and then the steps of airing and high-temperature drying are sequentially carried out, so that the antioxidant precursor is compounded on the surface of the phenolic aerogel composite material, the antioxidant treatment is completed, and the antioxidant performance of the phenolic aerogel composite material is improved; the invention belongs to an oxidation resistant mode of physical plugging, is simple and convenient to operate, and has small influence on the performance of the phenolic aerogel; the antioxidation treatment of the invention can improve the antioxidation performance of the phenolic aerogel composite material, because the antioxidation precursor reacts at high temperature to lead the surface of the phenolic aerogel to be compact, thereby effectively playing the role of blocking oxygen, and the antioxidation treatment of the invention can not change the main structure of the phenolic aerogel, and basically can not reduce the heat insulation performance of the phenolic aerogel, for example, the room temperature heat conductivity coefficient of the antioxidation modified phenolic aerogel composite material prepared by the invention is about 0.058W/m.K, while the room temperature heat conductivity coefficient of the phenolic aerogel composite material before modification is about 0.055W/m.K.
The method realizes the anti-oxidation technology of the phenolic aerogel composite material, greatly reduces the complexity of the anti-oxidation operation of the phenolic aerogel composite material, and is beneficial to low-cost anti-oxidation modification and large-scale application of the phenolic aerogel composite material. According to the method, the antioxidant precursor with a certain depth is compounded on the surface of the phenolic aerogel composite material, so that the phenolic aerogel composite material can be effectively prevented from losing effectiveness due to oxidation in the high-temperature aerobic long-time working process.
According to some preferred embodiments, the antioxidant precursor contained in the antioxidant precursor solution is one or more of methylphenyl silicone resin, methyl silicone resin, low-phenyl methyl silicone resin, epoxy modified silicone resin, silicone polyester modified resin, benzyl silicone resin, polymethyl silicone resin, amino silicone resin, fluoro silicone resin, silicone polyester resin, methyl MQ silicone resin, vinyl MQ silicone resin, silicone acrylic resin coating, polysilazane, silica sol, alumina sol, mullite sol; preferably, the antioxidant precursor contained in the antioxidant precursor solution is one or more of methyl silicone resin, low phenyl silicone resin, polymethyl silicone resin, polysilazane, silica sol, aluminum sol and mullite sol.
According to some preferred embodiments, the depth of the antioxidant precursor solution is 0.5 to 3mm (e.g., 0.5, 1, 1.5, 2, 2.5, or 3 mm); and/or the concentration of the antioxidant precursor in the antioxidant precursor solution is 5-25 wt% (e.g., 5, 10, 15, 20, or 25 wt%), preferably 8-20 wt% (e.g., 8, 10, 12, 14, 16, 18, or 20 wt%). In the invention, the depth of the antioxidant precursor solution is preferably 0.5-3 mm, and the concentration of the antioxidant precursor contained in the antioxidant precursor solution is preferably 5-25 wt%, and in the invention, the antioxidant precursor solution with certain depth and concentration matched with each other can further ensure that a better oxygen isolation effect is obtained, so that the effect of improving the oxidation resistance of the phenolic aerogel composite material is better played; if the depth and the concentration of the antioxidant precursor solution are not in the above preferred ranges, the effect of improving the antioxidant performance of the phenolic aerogel composite material is not obvious, the heat insulation performance is greatly reduced when the depth or the concentration is too high, and the obvious antioxidant effect cannot be achieved when the depth or the concentration is too low.
According to some preferred embodiments, in step (3): the air-drying step is to air-dry for 12-96 h (for example, 12, 18, 24, 36, 48, 60, 72, 80 or 96h) at normal temperature and normal pressure, and in the invention, the air-drying step is preferably to air-dry for 12-96 h at normal temperature and normal pressure until the weight of the phenolic aerogel composite material is not reduced any more; and/or the drying temperature for the high-temperature drying step is 60-150 ℃ (for example, 60, 70, 80, 90, 100, 110, 120, 130, 140 or 150 ℃), and the drying time is 24-72 h (for example, 24, 36, 48, 60 or 72 h). In the anti-oxidation treatment process, the phenolic aerogel is preferably dried at normal temperature and normal pressure for 12-96 hours and then dried at the high temperature of 60-150 ℃ for 24-72 hours, so that the stability of the microstructure of the phenolic aerogel in the drying process is improved, and the heat insulation performance is improved. In the invention, an antioxidant precursor solution with the depth of 0.5-3 mm and the antioxidant precursor-containing concentration of 5-25 wt% and more preferably 8-20 wt% is preferably compounded on the surface of the phenolic aerogel composite material, and the phenolic aerogel composite material is dried at normal temperature and normal pressure for 12-96 h and then dried at the high temperature of 60-150 ℃ for 24-72 h to complete the antioxidant treatment of the phenolic aerogel composite material.
According to some preferred embodiments, the phenolic precursor is one or more of resorcinol and formaldehyde, melamine and formaldehyde, phenolic resin and formaldehyde, mixed cresols and formaldehyde, polyisocyanoates, phloroglucinol and formaldehyde, poly-N-methylol acrylamide and resorcinol; in the present invention, for example, the phenolic precursor is a resorcinol + formaldehyde system or a melamine + formaldehyde system or a phenolic resin + formaldehyde system or a mixed cresol + formaldehyde system or a phloroglucinol + formaldehyde system or a poly N-methylol acrylamide + resorcinol system, or the phenolic precursor is a polyiso-nitrile acid ester. In particular, when the phenolic precursor is a system comprising two components, for example, when the phenolic precursor is a system comprising resorcinol and formaldehyde, the molar ratio of resorcinol to formaldehyde is preferably (0.1 to 1): 1, more preferably the molar ratio of resorcinol to formaldehyde is 0.5: 1.
According to some preferred embodiments, the catalyst is a basic catalyst or an acidic catalyst; the alkaline catalyst is selected from the group consisting of sodium carbonate solution, potassium hydroxide solution and sodium hydroxide solution; the acid catalyst is hydrochloric acid solution; in the invention, the concentration of the catalyst is preferably 0.1-1 mol/L.
According to some preferred embodiments, the organic solvent is an alcoholic solvent; the alcohol solvent is selected from one or more of alcohol solvents with the boiling point lower than 150 ℃; preferably, the alcohol solvent is selected from the group consisting of ethanol, propanol (e.g., isopropanol), and butanol.
According to some preferred embodiments, the precursor solution contains a concentration of phenolic precursor of 10 to 25 wt.% (e.g., 10 wt.%, 12 wt.%, 15 wt.%, 18 wt.%, 20 wt.%, 22 wt.%, or 25 wt%); and/or the molar ratio of the phenolic aldehyde precursor to the catalyst is (20-100): 1 (e.g., 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 90:1, or 100: 1). In the invention, the concentration of the phenolic aldehyde precursor in the precursor solution refers to the initial concentration of the phenolic aldehyde precursor at the moment of preparing the precursor solution, and refers to the concentration of the phenolic aldehyde precursor which does not participate in any reaction; when the phenolic precursor comprises two components, the molar ratio of the phenolic precursor to the catalyst refers to the ratio of the sum of the amounts of the two components of the material (the total amount of the phenolic precursor) contained in the phenolic precursor to the amount of the material of the catalyst. In particular, when the catalyst is in the form of a solution, the amount of the substance of the catalyst is the amount of the substance of the solute contained in the catalyst, for example, when the catalyst is a potassium hydroxide solution (e.g., an aqueous potassium hydroxide solution), the amount of the substance of the catalyst is the amount of the substance of potassium hydroxide contained in the catalyst.
According to some preferred embodiments, the fiber product is a fiber mat, fiber blanket or fiber board made of one or more fibers selected from the group consisting of carbon fibers, quartz fibers, high silica fibers, glass fibers, phenolic fibers, silicon carbide fibers.
According to some preferred embodiments, in step (1), the temperature of the sol-gel reaction is 60 ℃ to 160 ℃ (e.g., 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃ or 160 ℃), and the time of the sol-gel reaction is 24 to 120 hours (e.g., 24, 36, 48, 60, 72, 84, 96, 108 or 120 hours); and/or in the step (2), the normal-temperature air-drying time is 24-48 h (for example, 24, 30, 36, 42 or 48 h).
According to some preferred embodiments, in step (2), the drying is oven drying or supercritical drying; the temperature of the oven drying is 60-100 ℃ (60, 70, 80, 90 or 100 ℃), and the time of the oven drying is 18-30 h (18, 24 or 30 h).
The present invention provides in a second aspect an oxidation-resistant modified phenolic aerogel composite (modified phenolic aerogel composite) obtainable by the method of the invention described in the first aspect. The modified phenolic aerogel composite material prepared by the method has the advantages of excellent oxidation resistance, low cost, short period and simple process; the modified phenolic aerogel composite material prepared by the invention has the advantages of excellent oxidation resistance, good heat insulation performance and the like, and has excellent comprehensive performance.
The invention will be further illustrated by way of example, but the scope of protection is not limited to these examples.
Example 1
Adopting a resorcinol and formaldehyde phenolic aldehyde precursor system, wherein a catalyst is 0.1mol/L hydrochloric acid solution, and an organic solvent is isopropanol; wherein the concentration of the phenolic aldehyde precursor is 10 wt%, the phenolic aldehyde precursor is: the molar ratio of the catalyst is 50: 1; and mixing the raw materials, and uniformly stirring to obtain a precursor solution. Selecting a carbon fiber felt as a reinforcement, compounding the precursor solution and the carbon fiber felt, placing the precursor solution and the carbon fiber felt in a sealed die, closing the die, placing the die in a 60 ℃ oven, and reacting (sol-gel reaction) for 96 hours to obtain the phenolic aldehyde wet gel composite material.
And secondly, taking the phenolic aldehyde wet gel composite material out of the sealing mould, placing the phenolic aldehyde wet gel composite material in air, airing the phenolic aldehyde wet gel composite material for 36 hours at normal temperature, then placing the phenolic aldehyde wet gel composite material in an oven, and drying the phenolic aldehyde wet gel composite material in the oven for 24 hours at the temperature of 80 ℃ to obtain the phenolic aldehyde aerogel composite material.
Thirdly, compounding a methyl silicone resin toluene solution with the depth of 1mm and the concentration of 10 wt% on the surface of the phenolic aerogel composite material, airing at normal temperature for 48 hours, and finally drying at 150 ℃ for 24 hours to obtain the phenolic aerogel composite material (modified phenolic aerogel composite material) with excellent oxidation resistance.
It was determined that the weight loss rate of the modified phenolic aerogel composite material prepared in this example was only 1.1% after being treated at 600 ℃ for 10min in an aerobic environment at a high temperature.
Example 2
Adopting a resorcinol and formaldehyde phenolic aldehyde precursor system, wherein a catalyst is 0.1mol/L hydrochloric acid solution, and an organic solvent is isopropanol; wherein the concentration of the phenolic aldehyde precursor is 10 wt%, the phenolic aldehyde precursor is: the molar ratio of the catalyst is 50: 1; and mixing the raw materials, and uniformly stirring to obtain a precursor solution. Selecting a carbon fiber felt as a reinforcement, compounding the precursor solution and the carbon fiber felt, placing the precursor solution and the carbon fiber felt in a sealed die, closing the die, placing the die in a 60 ℃ oven, and reacting (sol-gel reaction) for 96 hours to obtain the phenolic aldehyde wet gel composite material.
And secondly, taking the phenolic aldehyde wet gel composite material out of the sealing mould, placing the phenolic aldehyde wet gel composite material in air, airing the phenolic aldehyde wet gel composite material for 36 hours at normal temperature, then placing the phenolic aldehyde wet gel composite material in an oven, and drying the phenolic aldehyde wet gel composite material in the oven for 24 hours at the temperature of 80 ℃ to obtain the phenolic aldehyde aerogel composite material.
Thirdly, compounding a propylene glycol solution of 12 wt% polysilazane with the depth of 0.5mm on the surface of the phenolic aerogel composite material, airing at normal temperature for 48 hours, and finally drying at 150 ℃ for 24 hours to obtain the phenolic aerogel composite material (modified phenolic aerogel composite material) with excellent oxidation resistance.
It was determined that the weight loss rate of the modified phenolic aerogel composite material prepared in this example was only 1.0% after being treated at 600 ℃ for 10min in an aerobic environment at a high temperature.
Example 3
Adopting a resorcinol and formaldehyde phenolic aldehyde precursor system, wherein a catalyst is 0.1mol/L hydrochloric acid solution, and an organic solvent is isopropanol; wherein the concentration of the phenolic aldehyde precursor is 10 wt%, the phenolic aldehyde precursor is: the molar ratio of the catalyst is 50: 1; and mixing the raw materials, and uniformly stirring to obtain a precursor solution. Selecting a carbon fiber felt as a reinforcement, compounding the precursor solution and the carbon fiber felt, placing the precursor solution and the carbon fiber felt in a sealed die, closing the die, placing the die in a 60 ℃ oven, and reacting (sol-gel reaction) for 96 hours to obtain the phenolic aldehyde wet gel composite material.
And secondly, taking the phenolic aldehyde wet gel composite material out of the sealing mould, placing the phenolic aldehyde wet gel composite material in air, airing the phenolic aldehyde wet gel composite material for 36 hours at normal temperature, then placing the phenolic aldehyde wet gel composite material in an oven, and drying the phenolic aldehyde wet gel composite material in the oven for 24 hours at the temperature of 80 ℃ to obtain the phenolic aldehyde aerogel composite material.
Thirdly, compounding an ethanol solution of 10 wt% mullite sol with the depth of 2mm on the surface of the phenolic aerogel composite material, airing at normal temperature for 48 hours, and finally drying at 120 ℃ for 24 hours to obtain the phenolic aerogel composite material (modified phenolic aerogel composite material) with excellent oxidation resistance.
It was determined that the weight loss rate of the modified phenolic aerogel composite material prepared in this example was only 0.9% after the modified phenolic aerogel composite material was treated at 800 ℃ for 10min in an aerobic environment at a high temperature.
Example 4
Example 4 is essentially the same as example 1, except that:
in the third step, a 20 wt% methyl silicone resin toluene solution with the depth of 0.5mm is compounded on the surface of the phenolic aerogel composite material, the phenolic aerogel composite material is dried at normal temperature for 48 hours, and finally the phenolic aerogel composite material (the modified phenolic aerogel composite material) with excellent oxidation resistance is obtained after drying at 150 ℃ for 24 hours.
It was determined that the weight loss rate of the modified phenolic aerogel composite material prepared in this example was only 1.2% after being treated at 600 ℃ for 10min in an aerobic environment at a high temperature.
Example 5
Example 5 is essentially the same as example 1, except that:
in the third step, a methyl silicone resin toluene solution with the depth of 3mm and the concentration of 8 wt% is compounded on the surface of the phenolic aerogel composite material, the phenolic aerogel composite material is dried at normal temperature for 48 hours, and finally the phenolic aerogel composite material (the modified phenolic aerogel composite material) with excellent oxidation resistance is obtained after the phenolic aerogel composite material is dried at 150 ℃ for 24 hours.
It was determined that the weight loss rate of the modified phenolic aerogel composite material prepared in this example was only 1.0% after being treated at 600 ℃ for 10min in an aerobic environment at a high temperature.
Example 6
Example 6 is essentially the same as example 1, except that:
and step three, compounding a methyl silicone resin toluene solution with the depth of 5mm and the concentration of 4 wt% on the surface of the phenolic aerogel composite material, airing at normal temperature for 48 hours, and finally drying at 150 ℃ for 24 hours to obtain the modified phenolic aerogel composite material.
It was determined that the modified phenolic aerogel composite material prepared in this example had a weight loss rate of 3.7% after being treated at 600 ℃ for 10min in an aerobic environment at a high temperature.
Example 7
Example 7 is essentially the same as example 1, except that:
and step three, compounding a 30 wt% methyl silicone resin toluene solution with the depth of 0.5mm on the surface of the phenolic aerogel composite material, airing at normal temperature for 48 hours, and finally drying at 150 ℃ for 24 hours to obtain the modified phenolic aerogel composite material.
It was determined that the weight loss rate of the modified phenolic aerogel composite material prepared in this example was 0.8% after being treated at 600 ℃ for 10min in an aerobic environment at a high temperature.
Although the weight loss rate of the modified phenolic aerogel composite material prepared in this embodiment is low, the room-temperature thermal conductivity coefficient of the modified phenolic aerogel composite material is obviously increased, and the room-temperature thermal conductivity coefficient is measured to be increased to 0.061W/m.K, while the room-temperature thermal conductivity coefficients of the modified phenolic aerogel composite materials prepared in embodiments 1 to 6 are only measured to be 0.055-0.058W/m.K.
Comparative example 1
Adopting a resorcinol and formaldehyde phenolic aldehyde precursor system, wherein a catalyst is 0.1mol/L hydrochloric acid solution, and an organic solvent is isopropanol; wherein the concentration of the phenolic aldehyde precursor is 10 wt%, the phenolic aldehyde precursor is: the molar ratio of the catalyst is 50: 1; and mixing the raw materials, and uniformly stirring to obtain a precursor solution. Selecting a carbon fiber felt as a reinforcement, compounding the precursor solution and the carbon fiber felt, placing the precursor solution and the carbon fiber felt in a sealed die, closing the die, placing the die in a 60 ℃ oven, and reacting (sol-gel reaction) for 96 hours to obtain the phenolic aldehyde wet gel composite material.
And secondly, taking the phenolic aldehyde wet gel composite material out of the sealing mould, placing the phenolic aldehyde wet gel composite material in air, airing the phenolic aldehyde wet gel composite material for 36 hours at normal temperature, then placing the phenolic aldehyde wet gel composite material in an oven, and drying the phenolic aldehyde wet gel composite material in the oven for 24 hours at the temperature of 80 ℃ to obtain the phenolic aldehyde aerogel composite material.
The weight loss rate of the phenolic aerogel composite material prepared by the comparative example is 5.0 percent after being treated for 10min at the high temperature of 600 ℃ in an aerobic environment; the thermal conductivity coefficient at room temperature of the phenolic aerogel composite material prepared by the comparative example is measured to be 0.055W/m.K.
As can be seen from the results of the examples and comparative examples in Table 1, the phenolic aerogel composite material prepared by the invention has excellent oxidation resistance.
In conclusion, the method adopts an anti-oxidation treatment method to improve the performance of the phenolic aerogel composite material, simplifies the modification process, and prepares the phenolic aerogel composite material with more excellent anti-oxidation performance, namely comprehensive performance, under the normal pressure drying condition; in addition, the method has the advantages of low cost, short period, simple process and the like.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for improving the oxidation resistance of a phenolic aerogel composite, which is characterized by comprising the following steps:
(1) preparing a precursor solution containing a phenolic aldehyde precursor, a catalyst and an organic solvent, and carrying out sol-gel reaction after the precursor solution and a fiber product are compounded in situ to obtain a phenolic aldehyde wet gel composite material;
(2) airing the phenolic aldehyde wet gel composite material at normal temperature, and then drying to obtain a phenolic aldehyde aerogel composite material; and
(3) compounding an antioxidant precursor solution with a certain depth on the surface of the phenolic aerogel composite material, and then sequentially carrying out an airing step and a high-temperature drying step to prepare the antioxidant modified phenolic aerogel composite material.
2. The method of claim 1, wherein:
the antioxidant precursor contained in the antioxidant precursor solution is one or more of methyl phenyl silicone resin, methyl silicone resin, low phenyl methyl silicone resin, epoxy modified silicone resin, silicone polyester modified resin, benzyl silicone resin, polymethyl silicone resin, amino silicone resin, fluorine silicone resin, silicone polyester resin, methyl MQ silicone resin, vinyl MQ silicone resin, silicone acrylic resin paint, polysilazane, silica sol, aluminum sol and mullite sol;
preferably, the antioxidant precursor contained in the antioxidant precursor solution is one or more of methyl silicone resin, low phenyl silicone resin, polymethyl silicone resin, polysilazane, silica sol, aluminum sol and mullite sol.
3. The method of claim 1, wherein:
the depth of the antioxidant precursor solution is 0.5-3 mm; and/or
The concentration of the antioxidant precursor in the antioxidant precursor solution is 5-25 wt%, preferably 8-20 wt%.
4. The method of claim 1, wherein in step (3):
the airing step is airing at normal temperature and normal pressure for 12-96 h; and/or
The drying temperature of the high-temperature drying step is 60-150 ℃, and the drying time is 24-72 hours.
5. The method according to any one of claims 1 to 4, characterized in that:
the phenolic aldehyde precursor is one or more of resorcinol and formaldehyde, melamine and formaldehyde, phenolic resin and formaldehyde, mixed cresol and formaldehyde, polyisocyanide ester, phloroglucinol and formaldehyde, poly-N-methylol acrylamide and resorcinol; and/or
The catalyst is a basic catalyst or an acidic catalyst;
the alkaline catalyst is selected from the group consisting of sodium carbonate solution, potassium hydroxide solution and sodium hydroxide solution;
the acid catalyst is hydrochloric acid solution; and/or
The organic solvent is an alcohol solvent;
the alcohol solvent is selected from one or more of alcohol solvents with the boiling point lower than 150 ℃;
preferably, the alcohol solvent is selected from the group consisting of ethanol, propanol and butanol.
6. The method according to any one of claims 1 to 4, characterized in that:
the concentration of the phenolic aldehyde precursor in the precursor solution is 10-25 wt%; and/or
The molar ratio of the phenolic aldehyde precursor to the catalyst is (20-100): 1.
7. the method according to any one of claims 1 to 4, characterized in that:
the fiber product is a fiber felt, a fiber blanket or a fiber board made of one or more fibers selected from carbon fibers, quartz fibers, high silica fibers, glass fibers, phenolic fibers and silicon carbide fibers.
8. The method according to any one of claims 1 to 4, characterized in that:
in the step (1), the temperature of the sol-gel reaction is 60-160 ℃, and the time of the sol-gel reaction is 24-120 h; and/or
In the step (2), the normal-temperature airing time is 24-48 h.
9. The method according to any one of claims 1 to 4, characterized in that:
in the step (2), the drying is oven drying or supercritical drying;
the drying temperature of the drying oven is 60-100 ℃, and the drying time of the drying oven is 18-30 h.
10. An oxidation-resistant modified phenolic aerogel composite made by the method of any of claims 1 to 9.
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| CN113929962B (en) * | 2021-10-22 | 2023-02-17 | 航天特种材料及工艺技术研究所 | Aerogel surface high-temperature-resistant composite coating and preparation method thereof |
| CN114045004A (en) * | 2021-11-25 | 2022-02-15 | 航天特种材料及工艺技术研究所 | Phase-change composite thermal protection material and preparation method thereof |
| CN114455978A (en) * | 2022-03-09 | 2022-05-10 | 长沙思云新材料科技有限公司 | Fiber-reinforced mullite-proportioned oxide-modified phenolic resin aerogel composite material and preparation method thereof |
| CN114479602B (en) * | 2022-03-15 | 2023-01-31 | 航天特种材料及工艺技术研究所 | Repair coating for aerogel surface defects and preparation method and application thereof |
| CN114479602A (en) * | 2022-03-15 | 2022-05-13 | 航天特种材料及工艺技术研究所 | Repair coating for aerogel surface defects and preparation method and application thereof |
| CN115181393B (en) * | 2022-07-01 | 2023-06-23 | 蚌埠凌空科技有限公司 | Modified resin matrix composite material for heat insulation and preparation method thereof |
| CN115678090A (en) * | 2022-09-07 | 2023-02-03 | 航天特种材料及工艺技术研究所 | Ablation-resistant phenolic aerogel and preparation method thereof |
| CN115678090B (en) * | 2022-09-07 | 2024-04-02 | 航天特种材料及工艺技术研究所 | Ablation-resistant phenolic aerogel and preparation method thereof |
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