CN109626954A - A kind of heatproof damp-proof silicon dioxide silica aerogel composite material and its preparation method and application - Google Patents
A kind of heatproof damp-proof silicon dioxide silica aerogel composite material and its preparation method and application Download PDFInfo
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- CN109626954A CN109626954A CN201811506605.2A CN201811506605A CN109626954A CN 109626954 A CN109626954 A CN 109626954A CN 201811506605 A CN201811506605 A CN 201811506605A CN 109626954 A CN109626954 A CN 109626954A
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- catalyst
- fluorine
- composite material
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- silicon dioxide
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 45
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 26
- 239000004965 Silica aerogel Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 84
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 47
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 42
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 40
- 239000011737 fluorine Substances 0.000 claims abstract description 38
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000004964 aerogel Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000000835 fiber Substances 0.000 claims abstract description 20
- 230000008878 coupling Effects 0.000 claims abstract description 18
- 238000010168 coupling process Methods 0.000 claims abstract description 18
- 238000005859 coupling reaction Methods 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 238000006073 displacement reaction Methods 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 8
- 230000002787 reinforcement Effects 0.000 claims abstract description 7
- 239000007822 coupling agent Substances 0.000 claims abstract description 6
- 238000006482 condensation reaction Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 55
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 26
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- 230000002378 acidificating effect Effects 0.000 claims description 14
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 13
- 235000019253 formic acid Nutrition 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- 241001502050 Acis Species 0.000 claims description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 235000011054 acetic acid Nutrition 0.000 claims description 9
- 238000001994 activation Methods 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims description 7
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 6
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 6
- NYTYVZFFEIBDBZ-UHFFFAOYSA-N CO[SiH](OC)OC.[Ru].[F] Chemical class CO[SiH](OC)OC.[Ru].[F] NYTYVZFFEIBDBZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 5
- -1 trifluoro octyl Chemical group 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 230000002708 enhancing effect Effects 0.000 claims description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 4
- 125000004407 fluoroaryl group Chemical group 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 239000003365 glass fiber Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 238000005507 spraying Methods 0.000 claims description 3
- 229920002748 Basalt fiber Polymers 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 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 2
- 229910052863 mullite Inorganic materials 0.000 claims description 2
- 238000003908 quality control method Methods 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 235000002639 sodium chloride Nutrition 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000011017 operating method Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000010410 layer Substances 0.000 description 9
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000012545 processing Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- DHGUOKRCSSAAPM-UHFFFAOYSA-N dimethoxy-octyl-(trifluoromethoxy)silane Chemical class FC(O[Si](OC)(OC)CCCCCCCC)(F)F DHGUOKRCSSAAPM-UHFFFAOYSA-N 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910002012 Aerosil® Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000002210 supercritical carbon dioxide drying Methods 0.000 description 2
- 238000000352 supercritical drying Methods 0.000 description 2
- GZBAUYZREARCNR-UHFFFAOYSA-N C(CCCCCCCCC)[Si](OC)(OC)OC.[F] Chemical compound C(CCCCCCCCC)[Si](OC)(OC)OC.[F] GZBAUYZREARCNR-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 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
- C04B30/00—Compositions for artificial stone, not containing binders
- C04B30/02—Compositions for artificial stone, not containing binders containing fibrous materials
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
-
- 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/20—Mortars, concrete or artificial stone characterised by specific physical values for the density
-
- 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
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/30—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values
- C04B2201/32—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values for the thermal conductivity, e.g. K-factors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Silicon Compounds (AREA)
Abstract
The present invention relates to a kind of preparation methods of heatproof damp-proof silicon dioxide silica aerogel composite material, include the following steps: that (1) prepares silicon dioxide gel by hydrolysis-condensation reaction using siliceous coupling reagent in the presence of the first catalyst of catalytic amount, and the siliceous coupling reagent includes fluorine-containing coupling agent；(2) existing for the second catalyst of catalytic amount fibre reinforcement is impregnated using the silicon dioxide gel under the conditions of, through sol-gel, aging, solvent displacement, dry, obtains hydrophobic type fibre-reinforced aerogel composite material.The present invention also provides heatproof damp-proof silicon dioxide silica aerogel composite material and its applications.The method of the present invention the method for the present invention simple process, operating procedure is few, and equipment cost is low；Composite material heat resistance especially high temperature resistance of the invention is good, and humidity resistance is excellent, and room temperature thermal conductivity is low, and thermal conductivity is stablized, and density is adjustable, and impurity content is stably and controllable.
Description
Technical field
The invention belongs to thermal protection technology fields, more specifically to a kind of heatproof damp-proof aerosil
Composite material and preparation method and application.
Background technique
Aeroge is a kind of light material with unique nanometer three-dimensional porous network structure, is to be currently known thermal conductivity
Minimum solid matter, referred to as super insulating material.Aerosil is a kind of most common aerogel material,
Body has the characteristics that the moisture that porosity is high, specific surface is huge and surface hydrophilic group content is abundant, is easy in absorption air
And influence material heat-proof quality.Therefore, it usually requires to carry out at hydrophobization during silica aerogel material produces
Reason, to increase its aerial stability and service life.
At present, it is thus proposed that realize hydrophobic modification by following methods: (1) by using trimethylchloro-silicane
Alkane, hexamethyldisilazane or hexamethyldisiloxane etc. are used as modifying agent, gel obtained are carried out in atent solvent molten
Modifying agent is added after agent displacement to be modified (for example, see CN107337424A).In addition, somebody proposes to pass through estersil forerunner
Body and siloxanes containing hydrophobic grouping (such as methyltrimethoxysilane etc.) are cogelled or directly adopt siloxanes containing hydrophobic grouping
Gel carries out hydrophobic modification (for example, see CN104016360A and CN106745004A).However, above scheme is being used
The material hydrophobic layer group of moisture-proof hydrophobic scheme constructs become alkanes group, temperature tolerance is usually no more than 350 DEG C.Moreover,
Due to the imperfection of solgel reaction, the alkoxy of suitable content is still contained on the aeroge surface after hydrophobic treatment, this
Class group temperature tolerance is lower than 300 DEG C.This is allowed under air conditions, and after primary more than 350 DEG C high/low temperatures are recycled, material is
Lose humidity resistance.The easily moisture absorption that losing the silica aerogel material of humidity resistance can become (is tried in related constant temperature and humidity
It tests middle hydroscopicity to be even greater than 30%), to lose the use reliability as the reusable heat-barrier material of high-performance.Always
For it, current silicic acid anhydride mode, which cannot achieve, to be met expected stability and repeatability and improves.Therefore, mesh
Preceding urgent need develops one kind can high/low temperature recycling and the silica gas with good humidity resistance and excellent heat-proof quality
Gel complex material.
Summary of the invention
In order to overcome the shortage of prior art, the present invention provides one kind to be used to prepare heatproof damp-proof aerosil
The method of composite material, described method includes following steps: (1) using and contain in the presence of the first catalyst of catalytic amount
Silicon coupling reagent prepares silicon dioxide gel by hydrolysis-condensation reaction, and the siliceous coupling reagent includes fluorine-containing coupling
Agent；(2) existing for the second catalyst of catalytic amount fibre reinforcement is impregnated using the silicon dioxide gel under the conditions of, through molten
Glue-gel, aging, solvent displacement, drying, obtain hydrophobic type fibre-reinforced aerogel composite material.
The present invention provides a kind of heatproof damp-proof silicon dioxide silica aerogel composite material in second aspect, and the heatproof is anti-
Tidal stencils silicon dioxide silica aerogel composite material includes fluorine-containing hydrophobic layer structure；
Third aspect present invention provides the described in any item composite materials of first aspect present invention or second party of the present invention
Composite material described in face is preparing the application in composite element；Preferably, the composite element is selected from by putting down
Plate type member, hemispherical member, class hemispherical member, the group of cone-shaped component and Special-Shaped Surface component composition.
Compared with prior art, the present invention at least has the following beneficial effects:
(1) the method for the present invention simple process, operating procedure is few, and equipment cost is low.
(2) composite material heat resistance of the invention is good, can within the scope of 25 to 600 DEG C Reusability.
(3) composite material high temperature resistance of the invention is good, can up to 600 DEG C at a temperature of reuse.
(4) composite material humidity resistance of the invention is excellent, can be within the scope of 600 DEG C after Reusability 10 times or more
Hydroscopicity is not more than 6%, even no greater than 2%.
(5) the room temperature thermal conductivity of composite material of the invention is low, can be for no more than 0.025W/mK.
(6) thermal conductivity of composite material of the invention is stablized, and 10 times or more material thermal conductivities afterwards are reused at 25 to 600 DEG C
Rate variation is not more than 6%.
(7) density can be in 0.20g/cm3~0.40g/cm3In the range of it is adjustable.
(8) impurity content is stably and controllable, still has good humidity resistance after being used for multiple times, hence it is evident that is better than common airsetting
Glue.
To sum up, aerogel composite prepared by the present invention has heat resistance especially high temperature resistance good, prevent
Tide is had excellent performance, and breaches existing aerogel material hydrophobicity resistance to extreme temperature, can satisfy that reusable performance is stable to be wanted
Ask, can long-time storage and performance is unaffected in humid conditions, can be used as big in High Mach number and long endurance aircraft
Heat-insulated thermally protective materials use in area.Such as plate shaped, hemispherical, class hemisphere are made by aerogel composite of the invention
Shape, taper and various large-sized special-shaped surface members, particularly under complicated high/low temperature alternation environment be on active service use abnormal shape rigidity every
The production of hot component has directive significance.
Specific embodiment
Illustrate the present invention in detail further below, but the present invention is not therefore subject to any restriction.
As described above, the present invention in first aspect provides one kind, to be used to prepare heatproof damp-proof aerosil multiple
The method of condensation material, described method includes following steps: (1) using siliceous in the presence of the first catalyst of catalytic amount
Coupling reagent prepares silicon dioxide gel by hydrolysis-condensation reaction, and the siliceous coupling reagent includes fluorine-containing coupling agent；
(2) existing for the second catalyst of catalytic amount fibre reinforcement is impregnated using the silicon dioxide gel under the conditions of, through colloidal sol-
Gel, aging, solvent displacement, drying, obtain hydrophobic type fibre-reinforced aerogel composite material.
The inventors discovered that the hydrophobicity of aerogel material can be substantially improved by using fluoro-containing group even full-fluorine group
Temperature resistant range.
In some preferred embodiments, the method also includes following steps: (3) are fine to the hydrophobic type in high temperature
Dimension enhancing aerogel composite carries out surface activation process, obtains surface active fiber enhancing aerogel composite.It is preferred that
, the activation temperature of the surface active is 400~600 DEG C (such as 400,450,500,550 or 600 DEG C), preferably 450
~550 DEG C (such as 500 DEG C), activation time is 0.5h~1.5h (such as 0.5,1 or 1.5 hour).The inventors discovered that needle
The problem of to unstable residue is locally present after material drying and moulding, it is unstable remaining living can to remove surface by high-temperature process
Property group and moisture obtain the hydrophobic of the better more moisture-proof surface local activation of more heat resistance to realize surface active
The aerogel composite of fiber type enhancing.
In some preferred embodiments, the method also includes following steps: (4) are using hydrophobic reagent to described
Surface active fiber enhances aerogel composite and carries out silicic acid anhydride and drying, obtains hydrophobization aerogel composite.
The inventors discovered that if being formed by material and carrying out after surface active carrying out further modification using hydrophobic reagent outstanding
It is fluoro-containing group modification, the distribution and content of fluoro group in hydrophobic layer can be further strengthened, to further enhance material
Heatproof humidity resistance.
In some preferred embodiments, the silicic acid anhydride is in the presence of the third catalyst of catalytic amount
It carries out.It is further preferred that the quality control of the hydrophobic reagent is 5~20 mass % of total amount of material.Further preferred
It is that the silicic acid anhydride is carried out using stifling or/and spraying method in vacuum or the state of normal pressure, and silicic acid anhydride temperature is
40~120 DEG C (such as 40,60,80,100 or 120 DEG C), the silicic acid anhydride time is 6~72h (such as 12,24,36,48 or 60
Hour).
In some embodiments, in step (1), the fluorine-containing coupling agent includes fluorine containing silane coupling agent；And/or
In step (3), the hydrophobic reagent is fluorine containing silane hydrophobic reagent.Preferably, the fluorine containing silane coupling agent and/or
The fluorine containing silane hydrophobic reagent is selected from molecular formula R4-n-(Si)-(O-R’)nIncluded in reagent composition group, wherein n=
1-3 (such as 1,2 or 3), R, which are selected from, contains fluoroalkyl, 6-12 (example by 1-10 (such as 1,2,3,4,5,6,7,8,9 or 10) a carbon
Such as 6,7,8,9,10,11 or the 12) group of a carbon formed containing fluoro aryl or single fluorine atom, wherein the fluorine-containing atomicity containing fluoroalkyl
It is a for 1-19 (such as 1,2,3,4,5,6,7,8,9,10,12,14,16 or 18), it is 1-10 (examples containing the fluorine-containing atomicity of fluoro aryl
Such as 1,2,3,4,5,6,7,8,9 or 10)；O-R ' is selected from the alkoxy by carbon atom number for 1-5 (such as 1,2,3,4 or 5) a carbon
The group of composition.It may further be preferable that the fluorine containing silane coupling agent and/or fluorine containing silane hydrophobic reagent are pungent selected from ten trifluoros
Base trimethoxy silane, 17 fluorine ruthenium trimethoxysilanes or pentafluorophenyl group trimethoxy silane are (as example, but not with this
Three kinds are limited) composition group.
In some embodiments, first catalyst is acidic catalyst.Preferably, first catalyst from
One of group being made of oxalic acid, acetic acid, formic acid and hydrochloric acid solution is a variety of.It may further be preferable that first catalysis
The concentration of agent is 0.01~0.1M；It is even furthermore preferable that the molar ratio of first catalyst and siliceous coupling reagent is
1:20~10000 (such as 1:20,1:50,1:100,1:1000 or 1:10000).
In other some embodiments, second catalyst is acidic catalyst or basic catalyst.Preferably
Be, second catalyst be acidic catalyst in the case where, second catalyst be selected from by oxalic acid, acetic acid, formic acid and
One of group of hydrochloric acid solution composition is a variety of.In the case where second catalyst is basic catalyst, described second
Catalyst is selected from one of group being made of ammonium hydroxide, sodium hydroxide and ammonium fluoride or a variety of.
The dosage of catalyst is not particularly limited in the present invention, as long as flower forcing expected from capable of playing the role of (such as be catalyzed
Amount).It is preferred that the molar ratio of second catalyst and siliceous coupling reagent be 1:20~10000 (such as 1:
20,1:50,1:100,1:1000 or 1:10000).In addition, the present invention is not particularly limited the concentration of the second catalyst, example
Such as can be 0.01~0.1M (such as 0.01M, 0.02M, 0.04M, 0.06M, 0.08M, 0.1M).
In some embodiments, the third catalyst can be acid catalyst.Preferably, the third catalyst
It can be one or more selected from the group being made of trifluoroacetic acid, acetic acid, formic acid and hydrochloric acid.It is further preferred that the third catalysis
The concentration of agent is 0.01~0.1M (such as 0.01M, 0.02M, 0.04M, 0.06M, 0.08M, 0.1M), it is further preferred that,
The molar ratio of the third catalyst and hydrophobic reagent be 1:5000~10000 (such as 1:5000,1:7500 or 1:
10000)。
The present invention can adjust the surface active time by adjusting catalyst type or additive amount and optionally, surface is repaired
It adorns reagent type and catalyst type or additive amount and optionally adjusts the ratio of fluorine containing silane coupling agent and positive esters of silicon acis reagent
Example effectively adjusts material hydrophobic layer structure and content, guarantees that the heat-insulated heat resistance of material is excellent, and repeatedly using
Still there are good heat-proof quality and moisture barrier properties afterwards.
The present invention is not particularly limited the fiber in fibre reinforcement, it is preferred that the fibre in the fibre reinforcement
Dimension selected from one of group for being made of basalt fibre, glass fibre, quartz fibre, mullite fiber or alumina fibre or
It is a variety of.
In preferred some embodiments, first catalyst is acidic catalyst, and second catalyst
For basic catalyst.In other some embodiments, first catalyst, second catalyst and the third are urged
Agent is each independently acidic catalyst.First catalyst, second catalyst and the third catalyst can be with
It is identical to can also be different, on condition that the first catalyst cannot use basic catalyst.
In preferred some embodiments, the fluorine-containing coupling reagent also includes positive esters of silicon acis；
Preferably, the molar ratio of positive esters of silicon acis and fluorine containing silane coupling agent be 0~100:1 (such as 0:1,0.5:1,1:
1,5:1,10:1,20:1,50:1 or 100:1).It is further preferred that positive esters of silicon acis and fluorine containing silane coupling agent first will when in use
The two stirs 6h-24h (for example, 12 or 18 hours) at room temperature.
In some more specifically embodiments, the method for the present invention includes above-mentioned steps (1) to (4).Specifically, institute
The method of stating includes the following steps:
Step (1)
Using fluorine containing silane coupling reagent and optional positive esters of silicon acis under the acidic catalysis conditions as the first catalyst
The hydrolysis-condensation reaction that 6h-24h is carried out in such as alcohols solvent constructs heatproof hydrophobic layer structure, shape on sol particle surface
At heatproof hydrophobic layer structure.
It, can be by fluorine containing silane coupling agent and positive esters of silicon acis under acidic catalysis conditions there are positive esters of silicon acis
Be blended with alcohols (such as ethyl alcohol, methanol) solvent, mixed proportion as described above can for 1:0~100 (such as 1:0,1:
0.5,1:1,1:5,1:10,1:20,1:50 or 1:100), and (for example, 12 or 18 is small by stirring 6h-24h at room temperature
When).Wherein first catalyst is selected from the group that is made of oxalic acid, acetic acid, formic acid and hydrochloric acid solution, concentration can for 0.01~
0.1M (such as 0.01M, 0.02M, 0.04M, 0.06M, 0.08M, 0.1M), the molar ratio with siliceous coupling reagent can be 1:20
~10000 (such as 1:20,1:50,1:100,1:1000 or 1:10000).
Step (2)
The second catalyst is added in silicon dioxide gel after the treatment, and (it can be urged for acidic catalyst or alkalinity
Agent), and impregnating reinforcing fiber matrix, impregnation method can for vacuum impregnation, suppress dipping or vacuum-suppresses dipping.Wherein,
In the case where the second catalyst is acidic catalyst, second catalyst can be selected from by oxalic acid, acetic acid, formic acid and hydrochloric acid
One of group of solution composition is a variety of；Preferably, the concentration of second catalyst is 0.01~0.1M；More preferably
Be, the molar ratio of the second catalyst and siliceous coupling reagent be 1:20~10000 (such as 1:20,1:50,1:100,1:1000 or
1:10000).It is further preferred that in the case that second catalyst is basic catalyst, the second selected catalyst can be with
Selected from by the group that forms of ammonium hydroxide, sodium hydroxide and ammonium fluoride solution that concentration is 0.001~0.1M, concentration can for 0.01~
0.1M (such as 0.01M, 0.02M, 0.04M, 0.06M, 0.08M, 0.1M), the molar ratio with siliceous coupling reagent can be 1:20
~10000 (such as 1:20,1:50,1:100,1:1000 or 1:10000).By sol gel reaction, completed to its aging
Afterwards, solvent displacement and drying are carried out.Sol gel reaction, aging and the solvent displacement of silicon dioxide gel are all this field skills
Technology known to art personnel.The displacement solvent such as acetone can be used for example to carry out in solvent displacement.The present invention does not have drying mode
There is special limitation, it is preferred that supercritical carbon dioxide drying mode is especially preferably used using supercritical drying mode,
These drying modes are all techniques known in the art.
Step (3)
In step (3), surface active temperature can be 400~600 DEG C, preferably 450~550 DEG C (for example, 500),
The total time of surface active can be 0.5h~1.5h (such as 0.5,1 or 1.5h).It in some embodiments, can be using not
The aerogel material that same temperature control program obtains above-mentioned steps carries out high-temperature activation, obtains the composite wood of surface active
Material.The temperature programming stage can be, for example, 400 DEG C of (a), soaking time be 0.5~1h or (b) 500 DEG C, soaking time be 1~
1.5h or (c) 600 DEG C, soaking time is one of 0.5~1h or a variety of, so that material surface is sufficiently activated
And significant change does not occur for surface texture composition.
Step (4)
In step (4), hydrophobic reagent be can include but is not limited to: ten trifluoro octyl trimethoxy silanes, 17 fluorine
Ruthenium trimethoxysilane or pentafluorophenyl group trimethoxy silane.To being down to the aerogel material of room temperature after surface active in container
During middle carry out silicic acid anhydride, hydrophobic reagent and third catalyst, the third catalysis can be added thereto
Agent can be acidic catalyst, such as selected from the group being made of trifluoroacetic acid, acetic acid, formic acid and hydrochloric acid solution, concentration can be
0.01~0.1M (such as 0.01M, 0.02M, 0.04M, 0.06M, 0.08M, 0.1M) is dredged with hydrophobic reagent such as fluorine containing silane
The molar ratio of aquation reagent can be 1:5000~10000 (such as 1:5000,1:7500 or 1:10000), control hydrophobic agents
Quality is 5~20% (such as 5%, 10%, 15% or 20%) of material gross mass, hydrophobic mode can using it is stifling or/
And spraying, the state progress of vacuum or normal pressure is hydrophobic, and drain temperature is 40~120 DEG C (such as 40,60,80,100 or 120 DEG C),
The hydrophobic time is 6~72h (such as 6,12,24,48 or 72h).It after silicic acid anhydride, can be dried, drying can adopt
Take and vacuumize or drying dedoping step to material can be realized in the mode of 150 DEG C of air blast, obtain high temperature insulating excellent effect and
Moisture-proof heat-barrier material of good performance after multiple high/low temperature circulation.
The present invention constructs the fluorine-containing hydrophobic layer structure in aeroge nanoparticle surface layer by way of copolycondensation, and passes through fiber
The mode of dioxide composite silica aerogel obtains resistance to 600 DEG C of moisture-proof aerogel composites.In some preferred embodiments,
Material realizes the further of fluorine-containing heatproof hydrophobic layer structure by the mode for being catalyzed hydrophobic by high-temperature activation processing sufficiently removal of impurities
It is perfect, finally obtain the resistance to 600 DEG C reusable moisture-proof silicon dioxide silica aerogel composite materials with excellent thermal insulation performance.
The present invention provides a kind of heatproof damp-proof silicon dioxide silica aerogel composite material in second aspect, and the heatproof is anti-
Tidal stencils silicon dioxide silica aerogel composite material includes fluorine-containing hydrophobic layer structure.Preferably, the heatproof damp-proof silica
Aerogel composite has following performance: (1) room temperature thermal conductivity≤0.025W/mK；(2) 600 DEG C reuse 10 times with
Material hydroscopicity≤2% after upper, and/or (3) reuse 10 times or more at 600 DEG C after material thermal conductivity change≤5%.It is more excellent
Choosing, the composite material are made using method described in any item of the claim 1 to 8.
The present invention provides composite material made from method described in first aspect present invention or the present invention in the third aspect
Composite material described in second aspect is preparing the application in composite element；Preferably, the composite element choosing
Free flat plate-shaped member, hemispherical member, class hemispherical member, the group of cone-shaped component and Special-Shaped Surface component composition.
Embodiment
Below in conjunction with specific embodiment, the present invention will be described in detail, but protection scope of the present invention is not limited to these implementations
Example.Reagent employed in embodiment such as ten trifluoro octyl trimethoxy silanes, pentafluorophenyl group trimethoxy silane, 17 fluorine
Ruthenium trimethoxysilane and methyl orthosilicate etc. can be commercially available from Beijing Yi Nuokai Science and Technology Ltd.；Fibrofelt is prefabricated
Body can be commercially available by Nanjing Glass Fibre Research and Design Institute.
Embodiment 1
By ten trifluoro octyl trimethoxy silanes, methyl orthosilicate, formic acid, deionized water 10:50:4.8 in molar ratio:
240 ratio is dissolved in the ethanol solution of 600 molar equivalents, stirs 12h at room temperature.It is 0.1g/cm by density3Quartz fibre
Felt precast body is put into mold, using (control under the conditions of base catalysis by above-mentioned silicon dioxide gel of vacuum compaction molding mode
PH value is between 8~9) with precast body composite molding, aged at room temperature 36h, 90 DEG C of high temperature ageing 36h, aging are carried out after gel
Acetone solvent is carried out after the completion to replace 3 times, then carries out supercritical carbon dioxide drying, obtains fiber-reinforcement silicon dioxide aerogel
Composite material.Through detecting, the density of obtained material is 0.25g/cm3, 600 DEG C of heatproof, room temperature thermal conductivity is 0.021W/
M.K (establishing criteria GB/T 10295-2008), the 5.5% (establishing criteria of hydroscopicity after 600 DEG C of spherical heat shield reuses
GB/T 21655.1-2008), material repeat performance is substantially better than the aerogel material of common silicic acid anhydride, and high temperature makes
Existing aerogel material is much smaller than with rear hydroscopicity.
Embodiment 2
It is carried out using mode substantially the same manner as Example 1, the difference is that it is pungent to be added without ten trifluoros in step (1)
Base trimethoxy silane, but methyl orthosilicate is used to replace ten trifluoro octyl trimethoxy silanes, so that ten trifluoro octyls three
The ratio of methoxy silane, methyl orthosilicate, formic acid, deionized water 0:60:4.8:240 in molar ratio are dissolved in 600 molar equivalents
Ethanol solution in；In addition, without surface modification.As a result, it has been found that product hydrophobic effect is poor, sample does not have dampproof effect
(establishing criteria GB/T 21655.1-2008).After the present inventor has also observed 600 DEG C/3600s/10 times use of compound exemplar
Constant temperature and humidity examines hydroscopicity, as a result as shown in table 1 below.
Embodiment 3
It is carried out by the way of substantially the same manner as Example 1, the difference is that, further by treated, material is placed
Room temperature is placed in closed container, and catalytic amount formic acid solution is added and accounts for 5 mass % pentafluorophenyl group trimethoxies of total amount of material
Base silane carries out silicic acid anhydride after vacuumizing, treatment temperature is 50 DEG C, and the processing time is 8h, then using the side vacuumized
Formula is dried, and obtains fiber-reinforcement silicon dioxide aerogel composite material.Through detecting, the density of resulting materials is 0.24g/
cm3, 600 DEG C of heatproof, room temperature thermal conductivity is 0.022W/m.K (establishing criteria GB/T 10295-2008), 600 DEG C of spherical heat shield
Hydroscopicity after reuse is 3.6% (establishing criteria GB/T 21655.1-2008), and material repeat performance is substantially better than
The aerogel material of common silicic acid anhydride, hydroscopicity is much smaller than existing aerogel material after applied at elevated temperature.
Embodiment 4
It is carried out by the way of substantially the same manner as Example 3, the difference is that, after supercritical drying and putting
It sets before room temperature is placed in closed container, material is put into 500 DEG C of Muffle furnace and carries out processing 0.5h.
Embodiment 5
It is carried out by the way of substantially the same manner as Example 4, the difference is that, use 17 fluorine decyl trimethoxy silicon
Alkane replaces ten trifluoro octyl trimethoxy silanes, replaces formic acid using oxalic acid, uses the ethanol solution of 600 molar equivalents, room temperature
Lower stirring 10h.Processing 1h is carried out in the Muffle furnace for being put into 500 DEG C.Through detecting, the density of resulting materials is 0.24g/cm3, resistance to
600 DEG C of temperature, room temperature thermal conductivity are 0.024W/m.K (establishing criteria GB/T 10295-2008), and the 600 DEG C of repetitions of taper heat shield make
Hydroscopicity < 2% (establishing criteria GB/T21655.1-2008) after, material repeat performance are substantially better than common hydrophobic
Change the aerogel material of processing, hydroscopicity is much smaller than existing aerogel material after applied at elevated temperature.
Embodiment 6
It is carried out by the way of substantially the same manner as Example 4, the difference is that, by 17 fluorine decyl trimethoxy silicon
The ethyl alcohol that the ratio of alkane, methyl orthosilicate, hydrochloric acid, deionized water 60:0:2.4:240 in molar ratio are dissolved in 600 molar equivalents is molten
In liquid, 6h is stirred at room temperature.It is put into 450 DEG C of Muffle furnace and carries out processing 1.5h.Through detecting, the density of resulting materials is
0.22g/cm3, 600 DEG C of heatproof, room temperature thermal conductivity is 0.021W/m.K (establishing criteria GB/T 10295-2008), spherical heat-insulated
Hydroscopicity < 2% (establishing criteria GB/T21655.1-2008) after covering 600 DEG C of reuses, material repeat performance are obvious
Better than the aerogel material of common silicic acid anhydride, hydroscopicity is much smaller than existing aerogel material after applied at elevated temperature.
Embodiment 7
It is carried out by the way of substantially the same manner as Example 6, the difference is that, using ten trifluoro octyl trimethoxy silicon
Alkane replaces 17 fluorine ruthenium trimethoxysilanes.Through detecting, the density of resulting materials is 0.23g/cm3, 600 DEG C of heatproof, room temperature
Thermal conductivity is 0.023W/m.K (establishing criteria GB/T 10295-2008), the hydroscopicity after 600 DEG C of taper heat shield reuses
< 2% (establishing criteria GB/T 21655.1-2008), material repeat performance is substantially better than the airsetting of common silicic acid anhydride
Glue material, hydroscopicity is much smaller than existing aerogel material after applied at elevated temperature.
Table 1
Finally, it should be noted that unspecified part of the present invention is known to the skilled person technology, and more than
Embodiment is merely illustrative of the technical solution of the present invention, rather than its limitations；Although being carried out with reference to the foregoing embodiments to the present invention
Detailed description, those skilled in the art should understand that: it still can be to skill documented by foregoing embodiments
Art scheme is modified or equivalent replacement of some of the technical features；And these are modified or replaceed, and do not make phase
The essence of technical solution is answered to be detached from the purport of technical solution of various embodiments of the present invention.
Claims (10)
1. a kind of method for being used to prepare heatproof damp-proof silicon dioxide silica aerogel composite material, which is characterized in that the method
Include the following steps:
(1) it is prepared using siliceous coupling reagent by hydrolysis-condensation reaction in the presence of the first catalyst of catalytic amount
Silicon dioxide gel, and the siliceous coupling reagent includes fluorine-containing coupling agent；
(2) existing for the second catalyst of catalytic amount fibre reinforcement, warp are impregnated using the silicon dioxide gel under the conditions of
Sol-gel, aging, solvent displacement, drying, obtain hydrophobic type fibre-reinforced aerogel composite material.
2. the method according to claim 1, wherein the method also includes following steps:
(3) surface activation process is carried out to the hydrophobic type fibre-reinforced aerogel composite material in high temperature, obtains surface active
Fibre-reinforced aerogel composite material；Preferably, the activation temperature of the surface active be 400~600 DEG C, preferably 450
~550 DEG C, activation time is 0.5h~1.5h.
3. according to the method described in claim 2, it is characterized in that, the method also includes following steps:
(4) silicic acid anhydride is carried out to surface active fiber enhancing aerogel composite using hydrophobic reagent and done
It is dry, obtain hydrophobization aerogel composite；
Preferably, the silicic acid anhydride carries out in the presence of the third catalyst of catalytic amount；
It is further preferred that the quality control of the hydrophobic reagent is 5~20 mass % of total amount of material；
It may further be preferable that the silicic acid anhydride is carried out using stifling or/and spraying method in vacuum or the state of normal pressure,
Silicic acid anhydride temperature is 40~120 DEG C, and the silicic acid anhydride time is 6~72h.
4. according to the method in any one of claims 1 to 3, it is characterised in that:
In step (1), the fluorine-containing coupling agent includes fluorine containing silane coupling agent；And/or in step (3), the hydrophobization
Reagent is fluorine containing silane hydrophobic reagent；
Preferably, the fluorine containing silane coupling agent and/or the fluorine containing silane hydrophobic reagent are selected from molecular formula R4-n-(Si)-
(O-R’)nIncluded in reagent composition group, wherein n=1-3, R, which are selected from, to be contained by 1-10 carbon containing fluoroalkyl, 6-12 carbon
The group of fluoro aryl or single fluorine atom composition, wherein be 1-19 containing the fluorine-containing atomicity of fluoroalkyl, the fluorine-containing atomicity containing fluoro aryl
It is 1-10；O-R ' is selected from the group being made of the alkoxy that carbon atom number is 1-5 carbon；
It is further preferred that the fluorine containing silane coupling agent and/or fluorine containing silane hydrophobic reagent are selected from ten trifluoro octyl trimethoxies
The group of base silane, 17 fluorine ruthenium trimethoxysilanes or pentafluorophenyl group trimethoxy silane composition.
5. preparation method according to any one of claim 1 to 4, it is characterised in that:
First catalyst is acidic catalyst；Preferably, the free oxalic acid of first catalyst, acetic acid, formic acid and salt
One of group of acid solution composition is a variety of；It may further be preferable that the concentration of first catalyst is 0.01~0.1M；
It is even furthermore preferable that the molar ratio of first catalyst and siliceous coupling reagent is 1:20~10000；And/or
Second catalyst is acidic catalyst or basic catalyst；Preferably, it is urged in second catalyst for acidity
In the case where agent, second catalyst is selected from one of group being made of oxalic acid, acetic acid, formic acid and hydrochloric acid solution or more
Kind, in the case where second catalyst is basic catalyst, second catalyst is selected from by ammonium hydroxide, sodium hydroxide and fluorine
Change one of group of ammonium composition or a variety of；It is further preferred that the concentration of second catalyst is 0.01~0.1M；Further
Preferably, the molar ratio of second catalyst and siliceous coupling reagent is 1:20~10000；And/or
The third catalyst is acid catalyst, it is preferred that the third catalyst is selected from by trifluoroacetic acid, acetic acid, formic acid
It is one or more with the group of hydrochloric acid composition, it is further preferred that the concentration of the third catalyst is 0.01~0.1M, it is further excellent
The molar ratio of choosing, the third catalyst and hydrophobic reagent is 1:5000~10000.
6. the method according to any one of claims 1 to 5, it is characterised in that: the fiber choosing in the fibre reinforcement
One of group of free basalt fibre, glass fibre, quartz fibre, mullite fiber or alumina fibre composition is more
Kind.
7. method according to any one of claim 1 to 6, it is characterised in that:
First catalyst is acidic catalyst, and second catalyst is basic catalyst；
First catalyst, second catalyst and the third catalyst are each independently acidic catalyst.
8. method according to any one of claim 1 to 7, it is characterised in that:
The fluorine-containing coupling reagent also includes positive esters of silicon acis；
Preferably, the molar ratio of positive esters of silicon acis and fluorine containing silane coupling agent is 0~100:1；
It is further preferred that the two is first stirred 6h- when in use by positive esters of silicon acis and fluorine containing silane coupling agent at room temperature
24h。
9. a kind of heatproof damp-proof silicon dioxide silica aerogel composite material, which is characterized in that the heatproof damp-proof silica
Aerogel composite includes fluorine-containing hydrophobic layer structure；
Preferably, the heatproof damp-proof silicon dioxide silica aerogel composite material have following performance: (1) room temperature thermal conductivity≤
0.025W/mK；(2) material hydroscopicity≤2% after reusing 10 times or more at 600 DEG C, and/or (3) in 600 DEG C of reuses
Material thermal conductivity variation≤5% after 10 times or more；
It is further preferred that the composite material is made using method described in any item of the claim 1 to 8.
10. composite wood described in composite material made from method described in any item of the claim 1 to 8 or claim 9
Material is preparing the application in composite element；Preferably, the composite element is selected from by flat plate-shaped member, hemispherical
Component, class hemispherical member, the group of cone-shaped component and Special-Shaped Surface component composition.
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| CN113830772A (en) * | 2021-09-02 | 2021-12-24 | 南京工业大学 | In-situ fluorinated modified super-amphiphobic flexible SiO2Method for producing aerogels |
| CN114751718A (en) * | 2022-04-01 | 2022-07-15 | 巩义市泛锐熠辉复合材料有限公司 | Method for preparing hydrophobic silica aerogel felt under normal pressure |
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| CN110963820A (en) * | 2019-12-09 | 2020-04-07 | 航天特种材料及工艺技术研究所 | Moisture-proof treatment method for heat-insulating material and application thereof |
| CN113830772A (en) * | 2021-09-02 | 2021-12-24 | 南京工业大学 | In-situ fluorinated modified super-amphiphobic flexible SiO2Method for producing aerogels |
| CN113830772B (en) * | 2021-09-02 | 2023-09-26 | 南京工业大学 | In-situ fluorination modified super-amphiphobic flexible SiO 2 Method for preparing aerogel |
| CN114751718A (en) * | 2022-04-01 | 2022-07-15 | 巩义市泛锐熠辉复合材料有限公司 | Method for preparing hydrophobic silica aerogel felt under normal pressure |
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