CN115678426A - Super-temperature-resistant organic silicon ablation-resistant anti-sagging heat-insulating coating and preparation method thereof - Google Patents
Super-temperature-resistant organic silicon ablation-resistant anti-sagging heat-insulating coating and preparation method thereof Download PDFInfo
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000010703 silicon Substances 0.000 title claims abstract description 85
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 85
- 238000000576 coating method Methods 0.000 title claims abstract description 73
- 239000011248 coating agent Substances 0.000 title claims abstract description 71
- 238000002679 ablation Methods 0.000 title claims abstract description 48
- 238000007665 sagging Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 191
- 229910000077 silane Inorganic materials 0.000 claims abstract description 97
- 239000002245 particle Substances 0.000 claims abstract description 91
- 239000000919 ceramic Substances 0.000 claims abstract description 89
- -1 phenolic aldehyde Chemical class 0.000 claims abstract description 74
- 229920005989 resin Polymers 0.000 claims abstract description 65
- 239000011347 resin Substances 0.000 claims abstract description 65
- 239000000843 powder Substances 0.000 claims abstract description 62
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 55
- 150000004645 aluminates Chemical class 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 238000009413 insulation Methods 0.000 claims abstract description 36
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 31
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052796 boron Inorganic materials 0.000 claims abstract description 31
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 31
- 239000005011 phenolic resin Substances 0.000 claims abstract description 31
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 29
- 239000004917 carbon fiber Substances 0.000 claims abstract description 29
- 239000010445 mica Substances 0.000 claims abstract description 20
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 84
- 238000003756 stirring Methods 0.000 claims description 76
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 72
- 239000000203 mixture Substances 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 239000000413 hydrolysate Substances 0.000 claims description 54
- 238000002156 mixing Methods 0.000 claims description 53
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 49
- 235000019441 ethanol Nutrition 0.000 claims description 46
- 239000007864 aqueous solution Substances 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 44
- 239000006185 dispersion Substances 0.000 claims description 34
- 239000011259 mixed solution Substances 0.000 claims description 33
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 28
- 239000000377 silicon dioxide Substances 0.000 claims description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 27
- 235000012239 silicon dioxide Nutrition 0.000 claims description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 21
- 239000011521 glass Substances 0.000 claims description 19
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 18
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 18
- 239000005543 nano-size silicon particle Substances 0.000 claims description 18
- 239000004005 microsphere Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 14
- 239000000440 bentonite Substances 0.000 claims description 14
- 229910000278 bentonite Inorganic materials 0.000 claims description 14
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 14
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 14
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 14
- 239000011787 zinc oxide Substances 0.000 claims description 14
- 230000008878 coupling Effects 0.000 claims description 13
- 238000010168 coupling process Methods 0.000 claims description 13
- 238000005859 coupling reaction Methods 0.000 claims description 13
- ADMWVBXCJSMQLF-UHFFFAOYSA-N C(C)O.[Si] Chemical compound C(C)O.[Si] ADMWVBXCJSMQLF-UHFFFAOYSA-N 0.000 claims description 12
- 229910021485 fumed silica Inorganic materials 0.000 claims description 12
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 claims description 9
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 9
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 9
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 6
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical group CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 125000003944 tolyl group Chemical group 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 6
- 108010009736 Protein Hydrolysates Proteins 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229920002379 silicone rubber Polymers 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004447 silicone coating Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Paints Or Removers (AREA)
Abstract
The invention discloses a super-temperature-resistant organic silicon ablation-resistant anti-sagging heat-insulation coating and a preparation method thereof, wherein the coating comprises nano-silica dispersion liquid, phenolic aldehyde modified alcohol-soluble organic silicon resin, mica powder, silane modified carbon fiber, aluminate-coated foamed ceramic particles, absolute ethyl alcohol and the like; the super-temperature-resistant organic silicon ablation-resistant anti-sagging heat-insulating coating adopts the boron phenolic resin modified alcohol-soluble organic silicon resin with a specific methyl phenyl ratio as a base material, and the heat resistance, the adhesive force and the impact resistance of the heat-insulating coating are obviously superior to those of the prior art; the carbon fiber pretreated by silane can reduce the viscosity of the coating, reduce the thickness of a paint film and reduce the weight of the coating on the rocket shell; according to the super-temperature-resistant organic silicon ablation-resistant anti-sagging heat-insulation coating, the foamed ceramic particles are coated by the aluminate, and the binding force and affinity between the foamed ceramic particles and resin are improved through the bonding effect; obviously reduces the viscosity of the system and improves the manufacturability of the paint production.
Description
Technical Field
The invention relates to the technical field of special coatings, in particular to a super-temperature-resistant organic silicon ablation-resistant anti-sagging heat-insulation coating and a preparation method thereof.
Background
The ablation-resistant heat-insulating coating is widely applied to the fields of metallurgy, power generation and the like, the ablation-resistant heat-insulating coating needs to utilize self phase change heat absorption and mass exchange to achieve the purpose of heat prevention, and the ablation-resistant heat-insulating coating is also widely used for rocket outer shell body heat protection in the field of aerospace, because the flying speed of a rocket is very high, a serious surface pneumatic heating phenomenon can be generated under the action of atmospheric retardation and friction, the surface temperature of the rocket is increased to be more than 1000 ℃, and therefore the ablation-resistant heat-insulating coating needs to carry out heat protection on the rocket, and the flight failure of the rocket is avoided.
The ablation-resistant heat-insulating coating can play a good role in corrosion resistance and heat insulation for coated equipment, and can also provide reliable guarantee for normal operation of the equipment. The smaller the density is, the smaller the gravity load on the used equipment is, and the requirements on the high and low temperature alternating environment are higher due to the variable use environment, so that the cracking is avoided under the high and low temperature alternating environment.
The ablation-resistant heat-insulating material can be classified into epoxy resin, silicon rubber light and organic silicon resin; the ablation-resistant heat-insulating material taking the epoxy resin as the matrix has the characteristics of high ablation efficiency, good bonding performance and low cost, but the coating has poor toughness, is easy to crack and peel and has poor adaptability to high-low temperature alternating environments; although the silicon rubber light heat insulation coating has low density and small gravity load on equipment in aerospace, the silicon rubber light heat insulation coating is easy to crack in a high-temperature and low-temperature alternating environment and cannot meet a complicated and changeable use environment; in addition, the temperature resistance of the conventional organic silicon high-temperature-resistant heat-insulating coating is generally below 700 ℃, the high-temperature ablation cannot meet the requirements in the aerospace field, a coating needs multiple constructions, and the coating process is relatively complicated.
Disclosure of Invention
In order to solve the problems, the invention aims to provide the super-temperature-resistant organic silicon ablation-resistant anti-sagging heat-insulation coating and the preparation method thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the super-temperature-resistant organic silicon anti-ablation anti-sagging heat-insulation coating comprises the following raw materials in parts by weight: 10-15 parts of nano silicon dioxide dispersion liquid, 20-25 parts of phenolic aldehyde modified alcohol soluble organic silicon resin, 30-35 parts of mica powder, 8-10 parts of silane modified carbon fiber, 5-8 parts of ceramic powder, 10-13 parts of aluminate coated foamed ceramic particles, 3.5-5 parts of zinc oxide, 3.5-5 parts of silicon carbide, 0.5-0.8 part of expanded microspheres, 3.2-5 parts of glass powder, 0.2-0.6 part of fumed silica, 0.1-0.4 part of organic bentonite and 10-20 parts of absolute ethyl alcohol;
the phenolic aldehyde modified alcohol-soluble organic silicon resin is prepared by the following steps:
(1) adding tetraethoxysilane and ethanol into a reaction kettle, adding a hydrochloric acid aqueous solution into an overhead tank under stirring, dropwise adding the hydrochloric acid aqueous solution into the reaction kettle at a speed of 60-70 ml/min, and controlling the reaction temperature to be 35-45 ℃ to obtain tetraethoxysilane hydrolysate; ethyl orthosilicate hydrolysate and morpholine are mixed according to a volume ratio of 9:1, detecting the gel time after mixing, and stopping dripping the hydrochloric acid aqueous solution when the gel time is 4-6 minutes to obtain tetraethoxysilane hydrolysate for later use;
the mass ratio of the ethyl orthosilicate to the ethanol is 30:60 to 70 percent; the content of silicon dioxide in the tetraethoxysilane is 35 to 40 percent;
the mass concentration of the hydrochloric acid aqueous solution is 0.8-1.2%;
(2) adding 34-36 parts by weight of methyltriethoxysilane, 5-6 parts by weight of dimethyldiethoxysilane and 10-15 parts by weight of diphenyldiethoxysilane into a batching tank in sequence, cooling to-5-0 ℃, adding 10-15 parts by weight of toluene and 8-10 parts by weight of butanone into the batching tank in sequence, controlling the temperature of the batching tank below 5 ℃ in the adding process, and dispersing for 30-40 minutes to obtain a silane mixed solution;
adding 60-65 parts of ethanol aqueous solution with the mass concentration of 30-35% into a reaction kettle, dropwise adding silane mixed solution into the reaction kettle while stirring, wherein the dropwise adding speed is 2-2.5L/min, and the temperature of the reaction kettle is controlled to be 10-15 ℃ in the dropwise adding process to obtain silane hydrolysate;
(3) adding the silane hydrolysate obtained in the step (2) into 20-25 parts of the n-silane ethyl ester hydrolysate obtained in the step (1), distilling under reduced pressure to remove the solvent, heating to 110 ℃, dropwise adding 0.02-0.03 part of catalyst mixed solution, adding 20-25 parts of absolute ethyl alcohol, stirring, uniformly mixing, and cooling to 20-30 ℃ to obtain alcohol-soluble organic silicon resin;
the catalyst mixed liquid is prepared from n-butyl titanate, zinc naphthenate and absolute ethyl alcohol according to the mass ratio of 2-3: 1 to 2:7, mixing to obtain;
(4) and (3) mixing the alcohol-soluble organic silicon resin obtained in the step (3) with the boron phenolic resin ethanol solution according to a mass ratio of 4-6: 1, mixing, heating to 60-65 ℃, stirring and dispersing to obtain phenolic aldehyde modified alcohol-soluble organic silicon resin;
the mass concentration of the boron phenolic resin in the boron phenolic resin ethanol solution is 45-55%;
the silane modified carbon fiber is prepared by the following steps:
adding chopped carbon fibers with the length of 8-10 mm into a silane coupling agent-ethanol solution with the mass concentration of 5-10%, uniformly stirring, drying at the temperature of 140-150 ℃ for 2-3 hours, and sieving by a 120-mesh sieve after ball milling to obtain silane modified carbon fibers; the silane coupling agent is vinyl triethoxysilane, a silane coupling agent KH550 or a silane coupling agent KH560;
the mass ratio of the chopped carbon fibers to the silane coupling agent-ethanol solution is 1:1 to 3;
the foamed ceramic particles coated with the aluminate are prepared according to the following steps:
baking the foamed ceramic particles in an oven at 115-120 ℃ for 1.5-2 hours, placing the foamed ceramic particles to 20-30 ℃, adding the foamed ceramic particles into a mixer, starting stirring, adding aluminate ester into a dry powder mixer in batches, heating the mixture to 75-80 ℃, dispersing the mixture for 1-2 hours, cooling the mixture to below 40 ℃, stopping stirring, placing the mixture to 20-30 ℃, and discharging the materials to obtain the foamed ceramic particles coated with the aluminate ester; the adding times of the aluminate can be adjusted according to actual needs, generally 3-5 times, the aluminate can be more uniformly distributed in the foamed ceramic particles by adding the aluminate for a plurality of times, the dispersing speed is accelerated, otherwise, the aluminate is easy to agglomerate;
wherein the mass ratio of the foamed ceramic particles to the aluminate is 100:2 to 4.
Preferably, the nano-silica dispersion is prepared according to the following steps:
drying silicon dioxide with the particle size of 15-20 nm, adding the silicon dioxide into a silane-ethanol solution at the temperature of 55-60 ℃, and ultrasonically dispersing for 1-1.5 hours to obtain a dispersion liquid for later use;
the silane-ethanol solution is prepared by mixing gamma-methacryloxypropyltrimethoxysilane and ethanol according to a mass ratio of 1-1.2: 100, obtaining;
adding anhydrous ethanol into a dispersion kettle, starting stirring, adding citric acid into the dispersion kettle, then adding the dispersion liquid obtained in the step, adding triethanolamine into the dispersion kettle after the dispersion is dispersed for 1-2 hours, adjusting the pH value to 6-7, and filtering the dispersion liquid by using a vibrating screen of 360 meshes to obtain the nano-silica dispersion liquid;
wherein the mass volume ratio of the silicon dioxide, the silane-ethanol solution, the absolute ethyl alcohol and the citric acid is 1kg: 2-2.1L: 2-2.2L: 0.02-0.03 kg.
Preferably, the particle size of the mica powder is 300-400 meshes.
Preferably, the particle size of the glass powder is 5000-8000 meshes.
The invention also comprises a preparation method of the super-heat-resistant organosilicon anti-ablation anti-sagging heat-insulation coating, wherein 20-25 parts by weight of phenolic modified alcohol-soluble organosilicon resin, 30-35 parts by weight of mica powder, 8-10 parts by weight of silane modified carbon fiber, 3.5-5 parts by weight of zinc oxide, 3.5-5 parts by weight of silicon carbide, 10-13 parts by weight of aluminate coated foamed ceramic particles, 5-8 parts by weight of ceramic powder, 3.2-5 parts by weight of glass powder and 10-20 parts by weight of absolute ethyl alcohol are sequentially added into a ball mill and stirred to obtain a mixture, the mixture is ground to 30-40 micrometers, 10-15 parts by weight of nano-silica dispersion liquid, 0.5-0.8 part by weight of expanded microspheres, 0.2-0.6 part by weight of fumed silica and 0.1-0.4 part by weight of organic bentonite are added into the mixture, and stirred and dispersed for 25-30 minutes to obtain the super-heat-resistant organosilicon anti-ablation anti-sagging heat-insulation coating;
the phenolic aldehyde modified alcohol-soluble organic silicon resin is prepared by the following steps:
(1) adding tetraethoxysilane and ethanol into a reaction kettle, adding a hydrochloric acid aqueous solution into an overhead tank under stirring, dropwise adding the hydrochloric acid aqueous solution into the reaction kettle at a speed of 60-70 ml/min, and controlling the reaction temperature to be 35-45 ℃ to obtain tetraethoxysilane hydrolysate; mixing tetraethoxysilane hydrolysate and morpholine according to a volume ratio of 9:1, detecting the gel time after mixing, and stopping dripping the hydrochloric acid aqueous solution when the gel time is 4-6 minutes to obtain tetraethoxysilane hydrolysate for later use;
the mass ratio of the ethyl orthosilicate to the ethanol is 30:60 to 70 percent; the content of silicon dioxide in the tetraethoxysilane is 35 to 40 percent;
the mass concentration of the hydrochloric acid aqueous solution is 0.8-1.2%;
(2) adding 34-36 parts by weight of methyltriethoxysilane, 5-6 parts by weight of dimethyldiethoxysilane and 10-15 parts by weight of diphenyldiethoxysilane into a batching tank in sequence, cooling to-5-0 ℃, adding 10-15 parts by weight of toluene and 8-10 parts by weight of butanone into the batching tank in sequence, controlling the temperature of the batching tank below 5 ℃ in the adding process, and dispersing for 30-40 minutes to obtain a silane mixed solution;
adding 60-65 parts of ethanol aqueous solution with the mass concentration of 30-35% into a reaction kettle, dropwise adding silane mixed solution into the reaction kettle while stirring, wherein the dropwise adding speed is 2-2.5L/min, and the temperature of the reaction kettle is controlled to be 10-15 ℃ in the dropwise adding process to obtain silane hydrolysate;
(3) adding the silane hydrolysate obtained in the step (2) into 20-25 parts of the n-silane ethyl ester hydrolysate obtained in the step (1), distilling under reduced pressure to remove the solvent, heating to 110 ℃, dropwise adding 0.02-0.03 part of catalyst mixed solution, adding 20-25 parts of absolute ethyl alcohol, stirring, uniformly mixing, and cooling to 20-30 ℃ to obtain alcohol-soluble organic silicon resin;
the catalyst mixed liquid is prepared from n-butyl titanate, zinc naphthenate and absolute ethyl alcohol according to the mass ratio of 2-3: 1 to 2:7, mixing to obtain;
(4) and (3) mixing the alcohol-soluble organic silicon resin obtained in the step (3) with the boron phenolic resin ethanol solution according to a mass ratio of 4-6: 1, mixing, heating to 60-65 ℃, stirring and dispersing to obtain phenolic aldehyde modified alcohol-soluble organic silicon resin;
the mass concentration of the boron phenolic resin in the boron phenolic resin ethanol solution is 45-55%;
the silane modified carbon fiber is prepared by the following steps:
adding chopped carbon fibers with the length of 8-10 mm into a silane coupling agent-ethanol solution with the mass concentration of 5-10%, uniformly stirring, drying for 2-3 hours at the temperature of 140-150 ℃, and sieving by using a 120-mesh screen after ball milling to obtain silane modified carbon fibers; the silane coupling agent is vinyl triethoxysilane, a silane coupling agent KH550 or a silane coupling agent KH560;
the mass ratio of the chopped carbon fibers to the silane coupling agent-ethanol solution is 1:1 to 3;
the foamed ceramic particles coated with the aluminate are prepared according to the following steps:
baking the foamed ceramic particles in an oven at 115-120 ℃ for 1.5-2 hours, placing the foamed ceramic particles to 20-30 ℃, adding the foamed ceramic particles into a mixer, starting stirring, adding aluminate ester into a dry powder mixer in batches, heating the mixture to 75-80 ℃, dispersing the mixture for 1-2 hours, cooling the mixture to below 40 ℃, stopping stirring, placing the mixture to 20-30 ℃, and discharging the materials to obtain the foamed ceramic particles coated with the aluminate ester;
wherein the mass ratio of the foamed ceramic particles to the aluminate is 100:2 to 4.
Compared with the prior art, the invention has the following advantages:
the super-temperature-resistant organic silicon ablation-resistant anti-sagging heat-insulating coating adopts the boron phenolic resin modified alcohol-soluble organic silicon resin with a specific methyl phenyl ratio as a base material, and the heat resistance, the adhesive force and the impact resistance of the heat-insulating coating are obviously superior to those of the prior art; the carbon fiber pretreated by silane has the advantages that the mutual attractive force among particles is reduced, the repulsive force is increased, the carbon fiber is easier to disperse, and the viscosity of the coating is reduced, so that the thickness of a paint film is reduced during coating, and the function of reducing the weight of the coating on a rocket shell is achieved;
according to the super-temperature-resistant organic silicon ablation-resistant anti-sagging heat-insulation coating, the gamma-methacryloxypropyltrimethoxysilane is adopted to pretreat the nano-silica, so that the wettability of the nano-silica is improved, the nano-silica is easy to disperse in ethanol, the binding force between the nano-silica and organic silicon resin in a film forming process is improved, and the temperature resistance of the resin is improved. And in the second step, citric acid is used as a dispersing agent, steric hindrance is formed under the charge repulsion action, so that the dispersion stability of the nano silicon dioxide can be maintained, and triethanolamine is used for adjusting the pH value, so that a certain thickening effect is achieved, and the system stability is improved.
According to the super-temperature-resistant organic silicon ablation-resistant anti-sagging heat-insulation coating, the foamed ceramic particles are coated by the aluminate, and the binding force and affinity between the foamed ceramic particles and resin are improved through the bonding effect; the viscosity of the system is obviously reduced, the manufacturability of the paint production is improved, in addition, the reduction of the viscosity is favorable for improving the using amount of the heat insulation filler, the using amount is increased from 8-10 parts when the heat insulation filler is not coated to 10-13 parts after coating, so that the heat insulation performance of the paint is improved, and the heat conductivity coefficient of a paint film is reduced by 0.03-0.06W/(m.K) from 0.05-0.08W/(m.K); and because the raw materials contain the expanded microspheres, the expanded microspheres expand in the film forming process, the thickness of the coating is 1.5-2 mm, and the density of the coating is only 0.3-0.35 g/cm 3 。
Detailed Description
The phenolic aldehyde modified alcohol-soluble organic silicon resin is organic silicon resin which is modified by boron phenolic resin and contains methyl and phenyl, wherein the molar ratio of the methyl to the phenyl is 4-4.5: the gel time is 200-260 seconds at 1,200 ℃, and the hardness of the swing rod is more than or equal to 0.7.
The nano silicon dioxide dispersion liquid can be purchased from outsourcing and is obtained by dispersing nano silicon dioxide in ethanol, wherein the content of the silicon dioxide is 15-20%, and the particle size is 15-20 nm.
The boron phenolic resin adopted in the invention is produced by Beijing glass fiber reinforced plastic institute composite material Co.
The invention is further described with reference to specific examples.
Example 1
The super-temperature-resistant organic silicon anti-ablation anti-sagging heat-insulation coating is composed of the following raw materials: 10kg of nano silicon dioxide dispersion liquid, 20kg of phenolic aldehyde modified alcohol-soluble organic silicon resin, 30kg of mica powder, 8kg of silane modified carbon fiber, 5kg of ceramic powder, 10kg of aluminate coated foamed ceramic particles, 3.5kg of zinc oxide, 3.5kg of silicon carbide, 0.5kg of expanded microspheres, 3.2kg of glass powder, 0.2kg of fumed silica, 0.1kg of organic bentonite and 10kg of absolute ethyl alcohol;
the phenolic aldehyde modified alcohol-soluble organic silicon resin is prepared by the following steps:
(1) adding 3kg of tetraethoxysilane and 6kg of ethanol into a reaction kettle, adding a hydrochloric acid aqueous solution into an overhead tank under stirring, dropwise adding the hydrochloric acid aqueous solution into the reaction kettle at a speed of 60ml/min, and controlling the reaction temperature to be 35 ℃ to obtain tetraethoxysilane hydrolysate; mixing tetraethoxysilane hydrolysate and morpholine according to a volume ratio of 9:1, detecting the gel time after mixing, and stopping dripping the hydrochloric acid aqueous solution when the gel time is 4 minutes to obtain tetraethoxysilane hydrolysate for later use;
the content of silicon dioxide in the tetraethoxysilane is 35 percent;
the mass concentration of the hydrochloric acid aqueous solution is 0.8%;
(2) sequentially adding 17kg of methyltriethoxysilane, 2.5kg of dimethyldiethoxysilane and 5kg of diphenyldiethoxysilane into a batching tank, cooling to-5 ℃, sequentially adding 5kg of toluene and 4kg of butanone into the batching tank, controlling the temperature of the batching tank below 5 ℃ in the adding process, and dispersing for 30 minutes to obtain a silane mixed solution;
adding 30kg of ethanol aqueous solution with the mass concentration of 30% into a reaction kettle, dropwise adding silane mixed solution into the reaction kettle while stirring, wherein the dropwise adding speed is 2L/min, and the temperature of the reaction kettle is controlled to be 10 ℃ in the dropwise adding process to obtain silane hydrolysate;
(3) adding the silane hydrolysate obtained in the step (2) into 10kg of the n-silane ethyl ester hydrolysate obtained in the step (1), distilling under reduced pressure to remove the solvent, heating to 110 ℃, dropwise adding 0.02kg of catalyst mixed solution, adding 10kg of absolute ethyl alcohol, stirring, uniformly mixing, and cooling to 20 ℃ to obtain alcohol-soluble organic silicon resin;
the catalyst mixed solution is prepared from n-butyl titanate, zinc naphthenate and absolute ethyl alcohol according to a mass ratio of 2:1:7, mixing to obtain;
(4) mixing 20kg of the alcohol-soluble organic silicon resin obtained in the step (3) with 5kg of boron phenolic resin ethanol solution, heating to 60 ℃, and stirring for dispersion to obtain phenolic aldehyde modified alcohol-soluble organic silicon resin;
the mass concentration of the boron phenolic resin in the boron phenolic resin ethanol solution is 45%;
the foamed ceramic particles coated with the aluminate are prepared according to the following steps:
baking 10kg of foamed ceramic particles in an oven at 115 ℃ for 1.5 hours, placing the foamed ceramic particles to 20 ℃, adding the foamed ceramic particles into a mixer, starting stirring, adding 0.2kg of aluminate into a dry powder mixer in batches, heating the mixture to 75 ℃, dispersing the mixture for 1 hour, cooling the mixture to below 40 ℃, stopping stirring, placing the mixture to 20 ℃, and discharging the mixture to obtain aluminate-coated foamed ceramic particles;
the silane modified carbon fiber is prepared by the following steps:
adding 8kg of chopped carbon fibers with the length of 8-10 mm into 8kg of silane coupling agent-ethanol solution with the mass concentration of 5%, uniformly stirring, drying for 2 hours at 140 ℃, and sieving by a 120-mesh sieve after ball milling to obtain silane modified carbon fibers; the silane coupling agent is vinyl triethoxysilane.
Example 2
The super-temperature-resistant organic silicon anti-ablation anti-sagging heat-insulation coating is composed of the following raw materials: 15kg of nano silicon dioxide dispersion liquid, 25kg of phenolic aldehyde modified alcohol-soluble organic silicon resin, 35kg of mica powder, 10kg of silane modified carbon fiber, 8kg of ceramic powder, 13kg of aluminate coated foamed ceramic particles, 5kg of zinc oxide, 5kg of silicon carbide, 0.8kg of expanded microspheres, 5kg of glass powder, 0.6kg of fumed silica, 0.4kg of organic bentonite and 20kg of absolute ethyl alcohol;
the phenolic aldehyde modified alcohol-soluble organic silicon resin is prepared by the following steps:
(1) adding 6kg of tetraethoxysilane and 14kg of ethanol into a reaction kettle, adding a hydrochloric acid aqueous solution into an overhead tank under stirring, dropwise adding the hydrochloric acid aqueous solution into the reaction kettle at a speed of 70ml/min, and controlling the reaction temperature to be 45 ℃ to obtain tetraethoxysilane hydrolysate; mixing tetraethoxysilane hydrolysate and morpholine according to a volume ratio of 9:1, detecting the gel time after mixing, and stopping dripping the hydrochloric acid aqueous solution when the gel time is 6 minutes to obtain tetraethoxysilane hydrolysate for later use;
the content of silicon dioxide in the tetraethoxysilane is 40 percent; the mass concentration of the hydrochloric acid aqueous solution is 1.2%;
(2) sequentially adding 18kg of methyltriethoxysilane, 3kg of dimethyldiethoxysilane and 7.5kg of diphenyldiethoxysilane into a batching tank, cooling to 0 ℃, sequentially adding 7.5kg of toluene and 5kg of butanone into the batching tank, controlling the temperature of the batching tank below 5 ℃ in the adding process, and dispersing for 40 minutes to obtain a silane mixed solution;
adding 32.5kg of ethanol water solution with the mass concentration of 35% into a reaction kettle, dropwise adding silane mixed solution into the reaction kettle under stirring, wherein the dropwise adding speed is 2.5L/min, and the temperature of the reaction kettle is controlled to be 15 ℃ in the dropwise adding process to obtain silane hydrolysate;
(3) adding the silane hydrolysate obtained in the step (2) into 12.5kg of the n-silane ethyl ester hydrolysate obtained in the step (1), distilling under reduced pressure to remove the solvent, heating to 110 ℃, dropwise adding 0.015kg of catalyst mixed solution, adding 12.5kg of absolute ethyl alcohol, stirring, uniformly mixing, and cooling to 30 ℃ to obtain alcohol-soluble organic silicon resin;
the catalyst mixed solution is prepared from n-butyl titanate, zinc naphthenate and absolute ethyl alcohol according to a mass ratio of 3:2:7 mixing to obtain;
(4) mixing 24kg of the alcohol-soluble organic silicon resin obtained in the step (3) with 4kg of boron phenolic resin ethanol solution, heating to 65 ℃, and stirring for dispersion to obtain phenolic aldehyde modified alcohol-soluble organic silicon resin;
the mass concentration of the boron phenolic resin in the boron phenolic resin ethanol solution is 55 percent;
the foamed ceramic particles coated with the aluminate are prepared according to the following steps:
baking 20kg of foamed ceramic particles in an oven at 120 ℃ for 2 hours, placing the foamed ceramic particles to 30 ℃, adding the foamed ceramic particles into a mixer, starting stirring, adding 0.8kg of aluminate into a dry powder mixer in batches, heating the mixture to 80 ℃, dispersing the mixture for 2 hours, cooling the mixture to below 40 ℃, stopping stirring, placing the mixture to 30 ℃, and discharging the mixture to obtain aluminate-coated foamed ceramic particles;
the silane modified carbon fiber is prepared by the following steps:
adding 10kg of chopped carbon fibers with the length of 8-10 mm into 30kg of silane coupling agent-ethanol solution with the mass concentration of 10%, uniformly stirring, drying for 3 hours at 150 ℃, and sieving by a 120-mesh sieve after ball milling to obtain silane modified carbon fibers; the silane coupling agent is a silane coupling agent KH550.
Example 3
The super-temperature-resistant organic silicon anti-ablation anti-sagging heat-insulation coating is composed of the following raw materials: 12kg of nano silicon dioxide dispersion liquid, 22kg of phenolic aldehyde modified alcohol-soluble organic silicon resin, 32kg of mica powder, 8.5kg of silane modified carbon fiber, 6kg of ceramic powder, 11kg of aluminate coated foamed ceramic particles, 4kg of zinc oxide, 4kg of silicon carbide, 0.6kg of expanded microspheres, 3.5kg of glass powder, 0.3kg of fumed silica, 0.2kg of organic bentonite and 12kg of absolute ethyl alcohol;
the grain diameter of the glass powder is 5000-6000 meshes; the particle size of the mica powder is 300-350 meshes;
the nano silicon dioxide dispersion liquid is prepared according to the following steps:
drying 10kg of silicon dioxide with the particle size of 15-18 nm, adding the silicon dioxide into a silane-ethanol solution 20L at 55 ℃, and ultrasonically dispersing for 1 hour to obtain a dispersion liquid for later use;
the silane-ethanol solution is prepared by mixing gamma-methacryloxypropyltrimethoxysilane and ethanol according to a mass ratio of 1:100, obtaining;
adding 20L of anhydrous ethanol into a dispersion kettle, starting stirring, adding 0.2kg of citric acid into the dispersion kettle, then adding the dispersion liquid obtained in the step, adding triethanolamine into the dispersion kettle after dispersing for 1 hour, adjusting the pH value to 6, and filtering by using a vibrating screen with 360 meshes to obtain the nano-silica dispersion liquid;
the phenolic aldehyde modified alcohol-soluble organic silicon resin is prepared by the following steps:
(1) adding 6kg of tetraethoxysilane and 13.6kg of ethanol into a reaction kettle, adding a hydrochloric acid aqueous solution into an overhead tank under stirring, dropwise adding the hydrochloric acid aqueous solution into the reaction kettle at a speed of 65ml/min, and controlling the reaction temperature to be 38 ℃ to obtain tetraethoxysilane hydrolysate; mixing tetraethoxysilane hydrolysate and morpholine according to a volume ratio of 9:1, detecting the gel time after mixing, and stopping dripping the hydrochloric acid aqueous solution when the gel time is 4.5 minutes to obtain tetraethoxysilane hydrolysate for later use;
the content of silicon dioxide in the tetraethoxysilane is 38 percent; the mass concentration of the hydrochloric acid aqueous solution is 0.9%;
(2) sequentially adding 17.5kg of methyltriethoxysilane, 2.75kg of dimethyldiethoxysilane and 7kg of diphenyldiethoxysilane into a batching tank, cooling to-2 ℃, sequentially adding 7kg of toluene and 4.25kg of butanone into the batching tank, controlling the temperature of the batching tank below 5 ℃ in the adding process, and dispersing for 32 minutes to obtain a silane mixed solution;
adding 31kg of 32% ethanol aqueous solution into a reaction kettle, dropwise adding silane mixed solution into the reaction kettle while stirring, wherein the dropwise adding speed is 2.2L/min, and the temperature of the reaction kettle is controlled to be 14 ℃ in the dropwise adding process to obtain silane hydrolysate;
(3) adding the silane hydrolysate obtained in the step (2) into 11kg of the n-silane ethyl ester hydrolysate obtained in the step (1), distilling under reduced pressure to remove the solvent, heating to 110 ℃, dropwise adding 0.013kg of catalyst mixed liquor into the hydrolysate, adding 12kg of absolute ethyl alcohol into the catalyst mixed liquor, stirring and uniformly mixing, and cooling to 22 ℃ to obtain alcohol-soluble organic silicon resin;
the catalyst mixed solution is prepared from n-butyl titanate, zinc naphthenate and absolute ethyl alcohol according to a mass ratio of 2.5:1.5:7, mixing to obtain;
(4) mixing 22.5kg of the alcohol-soluble organic silicon resin obtained in the step (3) with 5kg of boron phenolic resin ethanol solution, heating to 62 ℃, and stirring for dispersion to obtain phenolic aldehyde modified alcohol-soluble organic silicon resin;
the mass concentration of the boron phenolic resin in the boron phenolic resin ethanol solution is 48 percent;
the foamed ceramic particles coated with the aluminate are prepared according to the following steps:
baking 12kg of foamed ceramic particles in an oven at 116 ℃ for 1.8 hours, placing the foamed ceramic particles to 24 ℃, adding the foamed ceramic particles into a mixer, starting stirring, adding 0.3kg of aluminate into a dry powder mixer in batches, heating the mixture to 76 ℃, dispersing the mixture for 1.5 hours, cooling the mixture to below 40 ℃, stopping stirring, placing the mixture to 22 ℃, and discharging the mixture to obtain aluminate-coated foamed ceramic particles;
the silane modified carbon fiber is prepared by the following steps:
adding 9kg of chopped carbon fibers with the length of 8-10 mm into 18kg of silane coupling agent-ethanol solution with the mass concentration of 6%, uniformly stirring, drying at 142 ℃ for 2.5 hours, and sieving by a 120-mesh sieve after ball milling to obtain silane modified carbon fibers; the silane coupling agent is a silane coupling agent KH560.
Example 4
The super-temperature-resistant organic silicon anti-ablation anti-sagging heat-insulation coating is composed of the following raw materials: 14kg of nano silicon dioxide dispersion liquid, 24kg of phenolic aldehyde modified alcohol-soluble organic silicon resin, 33kg of mica powder, 8.5kg of silane modified carbon fiber, 7kg of ceramic powder, 12kg of aluminate coated foamed ceramic particles, 4.5kg of zinc oxide, 4.5kg of silicon carbide, 0.7kg of expanded microspheres, 4.5kg of glass powder, 0.5kg of fumed silica, 0.3kg of organic bentonite and 18kg of absolute ethyl alcohol;
the grain size of the glass powder is 6000-7000 meshes; the particle size of the mica powder is 350-380 meshes;
the nano silicon dioxide dispersion liquid is prepared according to the following steps:
drying 15kg of silicon dioxide with the particle size of 18-20 nm, adding the silicon dioxide into 31.5L of silane-ethanol solution at 60 ℃, and ultrasonically dispersing for 1.5 hours to obtain dispersion liquid for later use;
the silane-ethanol solution is prepared by mixing gamma-methacryloxypropyltrimethoxysilane and ethanol according to a mass ratio of 1.2:100, obtaining;
adding 33L of anhydrous ethanol into a dispersion kettle, starting stirring, adding 0.45kg of citric acid into the dispersion kettle, then adding the dispersion liquid obtained in the step, after dispersing for 1-2 hours, adding triethanolamine into the dispersion liquid, adjusting the pH value to 7, and filtering by using a vibrating screen of 360 meshes to obtain the nano-silica dispersion liquid;
the phenolic aldehyde modified alcohol-soluble organic silicon resin is prepared by the following steps:
(1) adding 6kg of tetraethoxysilane and 13.6kg of ethanol into a reaction kettle, adding a hydrochloric acid aqueous solution into an overhead tank under stirring, dropwise adding the hydrochloric acid aqueous solution into the reaction kettle at a speed of 62ml/min, and controlling the reaction temperature to be 40 ℃ to obtain tetraethoxysilane hydrolysate; mixing tetraethoxysilane hydrolysate and morpholine according to a volume ratio of 9:1, detecting the gel time after mixing, and stopping dripping the hydrochloric acid aqueous solution when the gel time is 5 minutes to obtain tetraethoxysilane hydrolysate for later use;
the content of silicon dioxide in the tetraethoxysilane is 38 percent; the mass concentration of the hydrochloric acid aqueous solution is 0.9%;
(2) sequentially adding 17.2kg of methyltriethoxysilane, 2.80kg of dimethyldiethoxysilane and 6.5kg of diphenyldiethoxysilane into a batching tank, cooling to-2 ℃, sequentially adding 6kg of toluene and 4.80kg of butanone into the batching tank, controlling the temperature of the batching tank below 5 ℃ in the adding process, and dispersing for 32 minutes to obtain a silane mixed solution;
adding 32kg of ethanol aqueous solution with the mass concentration of 30% into a reaction kettle, dropwise adding silane mixed solution into the reaction kettle while stirring, wherein the dropwise adding speed is 2.2L/min, and the temperature of the reaction kettle is controlled to be 12 ℃ in the dropwise adding process to obtain silane hydrolysate;
(3) adding the silane hydrolysate obtained in the step (2) into 11kg of the n-silane ethyl ester hydrolysate obtained in the step (1), distilling under reduced pressure to remove the solvent, heating to 110 ℃, dropwise adding 0.012kg of catalyst mixed solution into the silane hydrolysate, adding 11kg of absolute ethyl alcohol into the catalyst mixed solution, stirring and uniformly mixing, and cooling to 25 ℃ to obtain alcohol-soluble organic silicon resin;
the catalyst mixed solution is prepared from n-butyl titanate, zinc naphthenate and absolute ethyl alcohol according to a mass ratio of 3:1:7, mixing to obtain;
(4) mixing 22kg of the alcohol-soluble organic silicon resin obtained in the step (3) with 4kg of boron phenolic resin ethanol solution, heating to 62 ℃, and stirring for dispersion to obtain phenolic aldehyde modified alcohol-soluble organic silicon resin;
the mass concentration of the boron phenolic resin in the boron phenolic resin ethanol solution is 50 percent;
the foamed ceramic particles coated with the aluminate are prepared according to the following steps:
baking 12kg of foamed ceramic particles in an oven at 118 ℃ for 1.8 hours, placing the foamed ceramic particles to 25 ℃, adding the foamed ceramic particles into a mixer, starting stirring, adding 0.36kg of aluminate into a dry powder mixer in batches, heating the mixture to 78 ℃, dispersing the mixture for 1.5 hours, cooling the mixture to below 40 ℃, stopping stirring, placing the mixture to 25 ℃, and discharging the mixture to obtain aluminate-coated foamed ceramic particles;
the silane modified carbon fiber is prepared by the following steps:
adding 9kg of chopped carbon fibers with the length of 8-10 mm into 13.5kg of silane coupling agent-ethanol solution with the mass concentration of 8%, uniformly stirring, drying at 148 ℃ for 2.5 hours, and sieving by a 120-mesh sieve after ball milling to obtain silane modified carbon fibers; the silane coupling agent is vinyl triethoxysilane.
Example 5
The super-temperature-resistant organic silicon anti-ablation anti-sagging heat-insulation coating is composed of the following raw materials: 13kg of nano silicon dioxide dispersion liquid, 24kg of phenolic aldehyde modified alcohol-soluble organic silicon resin, 32kg of mica powder, 9.5kg of silane modified carbon fiber, 6kg of ceramic powder, 12kg of aluminate coated foamed ceramic particles, 4kg of zinc oxide, 4kg of silicon carbide, 0.7kg of expanded microspheres, 4kg of glass powder, 0.5kg of fumed silica, 0.2kg of organic bentonite and 15kg of absolute ethyl alcohol;
the grain size of the glass powder is 7000-8000 meshes; the particle size of the mica powder is 380-400 meshes;
the nano silicon dioxide dispersion liquid is prepared according to the following steps:
drying 10kg of silicon dioxide with the particle size of 15-16 nm, adding the silicon dioxide into a silane-ethanol solution 20L at 58 ℃, and ultrasonically dispersing for 1.2 hours to obtain a dispersion liquid for later use;
the silane-ethanol solution is prepared by mixing gamma-methacryloxypropyltrimethoxysilane and ethanol according to a mass ratio of 1.1:100, obtaining;
adding 21L of anhydrous ethanol into a dispersion kettle, starting stirring, adding 0.25kg of citric acid into the dispersion kettle, then adding the dispersion liquid obtained in the step, after dispersing for 1.5 hours, adding triethanolamine into the dispersion kettle, adjusting the pH value to 6.5, filtering by using a 360-mesh vibrating screen, and drying for 1.5 hours at 95 ℃ to obtain the nano-silica dispersion liquid;
the phenolic aldehyde modified alcohol-soluble organic silicon resin is prepared by the following steps:
(1) adding 3kg of tetraethoxysilane and 6.6kg of ethanol into a reaction kettle, adding a hydrochloric acid aqueous solution into an overhead tank under stirring, dropwise adding the hydrochloric acid aqueous solution into the reaction kettle at a speed of 68ml/min, and controlling the reaction temperature to be 40 ℃ to obtain tetraethoxysilane hydrolysate; mixing tetraethoxysilane hydrolysate and morpholine according to a volume ratio of 9:1, detecting the gel time after mixing, and stopping dripping the hydrochloric acid aqueous solution when the gel time is 5 minutes to obtain tetraethoxysilane hydrolysate for later use;
the content of silicon dioxide in the tetraethoxysilane is 38 percent; the mass concentration of the hydrochloric acid aqueous solution is 1%;
(2) sequentially adding 17.5kg of methyltriethoxysilane, 2.7kg of dimethyldiethoxysilane and 6kg of diphenyldiethoxysilane into a batching tank, cooling to-4 ℃, sequentially adding 7kg of toluene and 4.5kg of butanone into the batching tank, controlling the temperature of the batching tank below 5 ℃ in the adding process, and dispersing for 35 minutes to obtain a silane mixed solution;
adding 32kg of ethanol aqueous solution with the mass concentration of 34% into a reaction kettle, dropwise adding silane mixed solution into the reaction kettle while stirring, wherein the dropwise adding speed is 2.4L/min, and the temperature of the reaction kettle is controlled to be 14 ℃ in the dropwise adding process to obtain silane hydrolysate;
(3) adding the silane hydrolysate obtained in the step (2) into 12kg of the n-silane ethyl ester hydrolysate obtained in the step (1), distilling under reduced pressure to remove the solvent, heating to 110 ℃, dropwise adding 0.015kg of catalyst mixed solution into the silane hydrolysate, adding 12kg of absolute ethyl alcohol into the catalyst mixed solution, stirring and uniformly mixing, and cooling to 25 ℃ to obtain alcohol-soluble organic silicon resin;
the catalyst mixed solution is prepared from n-butyl titanate, zinc naphthenate and absolute ethyl alcohol according to a mass ratio of 2:2:7, mixing to obtain;
(4) mixing 25kg of the alcohol-soluble organic silicon resin obtained in the step (3) with 5kg of boron phenolic resin ethanol solution, heating to 64 ℃, and stirring for dispersion to obtain phenolic aldehyde modified alcohol-soluble organic silicon resin;
the mass concentration of the boron phenolic resin in the boron phenolic resin ethanol solution is 50 percent;
the foamed ceramic particles coated with the aluminate are prepared according to the following steps:
baking 12kg of foamed ceramic particles in an oven at 118 ℃ for 2 hours, placing the foamed ceramic particles to 30 ℃, adding the foamed ceramic particles into a mixer, starting stirring, adding 0.36kg of aluminate into a dry powder mixer in a grading manner, heating the mixture to 78 ℃, dispersing the mixture for 1.5 hours, cooling the mixture to below 40 ℃, stopping stirring, placing the mixture to 25 ℃, and discharging the mixture to obtain aluminate-coated foamed ceramic particles;
the silane modified carbon fiber is prepared by the following steps:
adding 10kg of chopped carbon fibers with the length of 8-10 mm into 20kg of silane coupling agent-ethanol solution with the mass concentration of 8%, uniformly stirring, drying at 145 ℃ for 2.5 hours, and sieving by a 120-mesh sieve after ball milling to obtain silane modified carbon fibers; the silane coupling agent is a silane coupling agent KH560.
Example 6
The preparation method of the super-temperature-resistant silicone ablation-resistant anti-sagging heat-insulation coating in the embodiment 1 comprises the following steps:
20kg of phenolic aldehyde modified alcohol-soluble organic silicon resin, 30kg of mica powder, 8kg of silane modified carbon fiber, 3.5kg of zinc oxide, 3.5kg of silicon carbide, 10kg of aluminate coated foamed ceramic particles, 5kg of ceramic powder, 3.2kg of glass powder and 10kg of absolute ethyl alcohol are sequentially added into a ball mill for ball milling and stirring to obtain a mixture, the mixture is ground to 30 microns, 10kg of nano silicon dioxide dispersion liquid, 0.5kg of expanded microspheres, 0.2kg of gas phase silicon dioxide and 0.1kg of organic bentonite are added into the mixture, and the mixture is stirred and dispersed for 25 minutes to obtain the super temperature-resistant organic silicon anti-burning hanging anti-heat-insulation coating.
Example 7
The preparation method of the super-temperature-resistant, anti-ablation, anti-sagging and heat-insulating silicone coating in the embodiment 2 comprises the following steps: adding 25kg of phenolic aldehyde modified alcohol-soluble organic silicon resin, 35kg of mica powder, 10kg of silane modified carbon fiber, 5kg of zinc oxide, 5kg of silicon carbide, 13kg of aluminate coated foamed ceramic particles, 8kg of ceramic powder, 5kg of glass powder and 20kg of absolute ethyl alcohol into a ball mill in sequence, carrying out ball milling and stirring to obtain a mixture, grinding the mixture to 40 micrometers, adding 15kg of nano-silica dispersion liquid, 0.8kg of expanded microspheres, 0.6kg of fumed silica and 0.4kg of organic bentonite into the mixture, and stirring and dispersing the mixture for 30 minutes to obtain the super-temperature-resistant organic silicon anti-burning anti-sagging heat-insulating coating.
Example 8
The preparation method of the super-temperature-resistant silicone ablation-resistant anti-sagging heat-insulating coating in the embodiment 3 comprises the following steps: 22kg of phenolic aldehyde modified alcohol-soluble organic silicon resin, 32kg of mica powder, 8.5kg of silane modified carbon fiber, 4kg of zinc oxide, 4kg of silicon carbide, 11kg of aluminate coated foamed ceramic particles, 6kg of ceramic powder, 3.5kg of glass powder and 12kg of absolute ethyl alcohol are sequentially added into a ball mill for ball milling and stirring to obtain a mixture, the mixture is ground to 32 microns, 12kg of nano silicon dioxide dispersion liquid, 0.6kg of expanded microspheres, 0.3kg of fumed silica and 0.2kg of organic bentonite are added into the mixture, and the mixture is stirred and dispersed for 26 minutes to obtain the super-temperature-resistant organic silicon anti-burning anti-sagging heat-insulation coating.
Example 9
The preparation method of the super-temperature-resistant silicone ablation-resistant anti-sagging heat-insulation coating of embodiment 4 comprises the following steps: adding 24kg of phenolic aldehyde modified alcohol-soluble organic silicon resin, 33kg of mica powder, 8.5kg of silane modified carbon fiber, 4.5kg of zinc oxide, 4.5kg of silicon carbide, 12kg of aluminate coated foamed ceramic particles, 7kg of ceramic powder, 4.5kg of glass powder and 18kg of absolute ethyl alcohol into a ball mill in sequence, carrying out ball milling and stirring to obtain a mixture, grinding the mixture to 35 microns, adding 14kg of nano-silica dispersion liquid, 0.7kg of expanded microspheres, 0.5kg of fumed silica and 0.3kg of organic bentonite into the mixture, and stirring and dispersing for 28 minutes to obtain the super-temperature-resistant organic silicon anti-burning-corrosion heat-insulation coating.
Example 10
The preparation method of the super-temperature-resistant, anti-ablation, anti-sagging and heat-insulating silicone coating of embodiment 5 comprises the following steps: adding 24kg of phenolic aldehyde modified alcohol-soluble organic silicon resin, 32kg of mica powder, 9.5kg of silane modified carbon fiber, 4kg of zinc oxide, 4kg of silicon carbide, 12kg of aluminate coated foamed ceramic particles, 6kg of ceramic powder, 4kg of glass powder and 15kg of absolute ethyl alcohol into a ball mill in sequence, carrying out ball milling and stirring to obtain a mixture, grinding the mixture to 35 microns, adding 13kg of nano silicon dioxide dispersion liquid, 0.7kg of expanded microspheres, 0.5kg of fumed silica and 0.2kg of organic bentonite into the mixture, and stirring and dispersing for 28 minutes to obtain the super temperature-resistant organic silicon anti-ablation anti-sagging heat-insulation coating.
The performance of the phenol-modified alcohol-soluble silicone resins obtained in examples 1 to 5 was examined, and the results are shown in table 1.
TABLE 1 Properties of phenolic-modified alcohol-soluble Silicone resins of examples 1-5
The performance of the super-temperature-resistant silicone ablation-resistant anti-sagging heat-insulating coating obtained in examples 1 to 5 was tested, and the results are shown in table 2. The viscosity is detected by a GB/T9751.1 rotational viscometer, the solid content GB/T1725 is regulated, the baking temperature is 105 +/-2 ℃, the baking time is 2 hours, the sample amount is about 2g, the high temperature resistance is detected by GB1735, the hardness is detected by a pendulum rod hardometer according to GB/T1730, the adhesion force GB/T5210 pull-open method is detected, the impact resistance is detected by GB1732, the thermal stability is 5 hours at 1300 +/-20 ℃, and the performance of a paint film is observed; the high and low temperature alternation adopts (1000 plus or minus 20) DEG C and (-40 plus or minus 5) DEG C, the paint film performance is observed in three cycles (1 hour per cycle), and the anti-sagging property is detected according to GB/T9264.
TABLE 2 Performance test results of the super-heat-resistant organosilicon ablation-resistant anti-sagging heat-insulating coating obtained in examples 1 to 5
The super-temperature-resistant, ablation-resistant, anti-sagging and heat-insulating organosilicon coating disclosed by the invention is low in viscosity, good in sagging resistance and easy to coat; the high temperature resistance of the modified resin coating can reach 1300 ℃, the heat resistance, the adhesive force and the impact resistance of the product of the heat insulation coating are obviously superior to those of the prior art, the carbon fiber and the foamed ceramic particles coated by the aluminate after silane pretreatment have the advantages of reduced inter-particle attraction, increased repulsive force and easier dispersion, and the viscosity of the coating is reduced, thereby reducing the viscosity of the coating, increasing the addition amount of the heat insulation filler and improving the heat insulation effect, and because the raw material contains the expanded microspheres, the expansion is realized in the film forming process, when the thickness of the coating is 1.5-2 mm, the density of the coating is only 0.3-0.35 g/cm 3 Is far less than the prior 0.4-0.6 g/cm 3 The coating density of (2).
Since the performance of the super-temperature-resistant silicone ablation-resistant anti-sagging heat-insulating coating obtained in example 5 is optimal, a comparative experiment is performed based on example 5.
Comparative example 1
An organic silicon ablation-resistant heat-insulating coating is completely the same as in example 5 except that a commercial alcohol-soluble organic silicon resin is used as the phenolic-modified alcohol-soluble organic silicon resin component.
Comparative example 2
An organosilicon ablation-resistant heat-insulating coating is completely the same as example 5 except that silane-modified carbon fiber components are not subjected to silane modification and carbon fibers are directly adopted.
Comparative example 3
An organosilicon ablation-resistant heat-insulating coating is completely the same as that of example 5, except that the components of the foamed ceramic particles coated with the aluminate are not subjected to aluminate coating treatment, and the foamed ceramic particles are directly adopted.
The performance of the silicone ablation-resistant heat-insulating coating obtained in comparative examples 1 to 3 was examined, and the results are shown in table 3.
Table 3 table of performance test results of the organosilicon anti-ablation heat-insulating coating obtained in comparative examples 1 to 3
The results in table 3 show that the heat resistance of the organic silicon ablation-resistant heat-insulating coating obtained by using the commercially available alcohol-soluble organic silicon resin is obviously reduced, only 780 ℃, the heat stability is 5 hours at 1300 +/-20 ℃, the cracks and the falling of a paint film are observed seriously, the heat stability of the paint film is poor, the high-low temperature alternation is poor, and the sagging property is poor; after the silane coupling agent is treated, the mutual attraction among carbon fiber particles is reduced, and the repulsion force is increased, so that the carbon fiber particles are easier to disperse, and the viscosity and the anti-sagging performance of a paint film are influenced.
The aluminate coated ceramic foam particles improve the binding force and affinity with resin through bonding. Obviously reduces the viscosity of the system and improves the manufacturability of the paint production. The dosage of the foamed ceramic particles can be increased by 5-7 percent due to the reduction of viscosity in the production, thereby improving the heat insulation performance, and compared with untreated foamed ceramic particles, the heat conductivity coefficient is reduced from 0.05-0.08W/(m.K) to 0.03-0.06W/(m.K).
Claims (5)
1. The super-temperature-resistant organic silicon anti-ablation anti-sagging heat-insulation coating is characterized by comprising the following components in parts by weight: the composite material comprises the following raw materials in parts by weight: 10-15 parts of nano silicon dioxide dispersion liquid, 20-25 parts of phenolic aldehyde modified alcohol soluble organic silicon resin, 30-35 parts of mica powder, 8-10 parts of silane modified carbon fiber, 5-8 parts of ceramic powder, 10-13 parts of aluminate coated foamed ceramic particles, 3.5-5 parts of zinc oxide, 3.5-5 parts of silicon carbide, 0.5-0.8 part of expanded microspheres, 3.2-5 parts of glass powder, 0.2-0.6 part of fumed silica, 0.1-0.4 part of organic bentonite and 10-20 parts of absolute ethyl alcohol;
the phenolic aldehyde modified alcohol-soluble organic silicon resin is prepared by the following steps:
(1) adding tetraethoxysilane and ethanol into a reaction kettle, adding a hydrochloric acid aqueous solution into an overhead tank under stirring, dropwise adding the hydrochloric acid aqueous solution into the reaction kettle at a speed of 60-70 ml/min, and controlling the reaction temperature to be 35-45 ℃ to obtain tetraethoxysilane hydrolysate; mixing tetraethoxysilane hydrolysate and morpholine according to a volume ratio of 9:1, detecting the gel time after mixing, and stopping dripping the hydrochloric acid aqueous solution when the gel time is 4-6 minutes to obtain tetraethoxysilane hydrolysate for later use;
the mass ratio of the ethyl orthosilicate to the ethanol is 30:60 to 70 percent; the content of silicon dioxide in the tetraethoxysilane is 35 to 40 percent;
the mass concentration of the hydrochloric acid aqueous solution is 0.8-1.2%;
(2) adding 34-36 parts by weight of methyltriethoxysilane, 5-6 parts by weight of dimethyldiethoxysilane and 10-15 parts by weight of diphenyldiethoxysilane into a batching tank in sequence, cooling to-5-0 ℃, adding 10-15 parts by weight of toluene and 8-10 parts by weight of butanone into the batching tank in sequence, controlling the temperature of the batching tank below 5 ℃ in the adding process, and dispersing for 30-40 minutes to obtain a silane mixed solution;
adding 60-65 parts of ethanol aqueous solution with the mass concentration of 30-35% into a reaction kettle, dropwise adding silane mixed solution into the reaction kettle while stirring, wherein the dropwise adding speed is 2-2.5L/min, and the temperature of the reaction kettle is controlled to be 10-15 ℃ in the dropwise adding process to obtain silane hydrolysate;
(3) adding the silane hydrolysate obtained in the step (2) into 20-25 parts of the n-silane ethyl ester hydrolysate obtained in the step (1), distilling under reduced pressure to remove the solvent, heating to 110 ℃, dropwise adding 0.02-0.03 part of catalyst mixed solution, adding 20-25 parts of absolute ethyl alcohol, stirring, uniformly mixing, and cooling to 20-30 ℃ to obtain alcohol-soluble organic silicon resin;
the catalyst mixed liquid is prepared from n-butyl titanate, zinc naphthenate and absolute ethyl alcohol according to the mass ratio of 2-3: 1 to 2:7, mixing to obtain;
(4) and (3) mixing the alcohol-soluble organic silicon resin obtained in the step (3) with the boron phenolic resin ethanol solution according to a mass ratio of 4-6: 1, mixing, heating to 60-65 ℃, stirring and dispersing to obtain phenolic aldehyde modified alcohol-soluble organic silicon resin;
the mass concentration of the boron phenolic resin in the boron phenolic resin ethanol solution is 45-55%;
the silane modified carbon fiber is prepared by the following steps:
adding chopped carbon fibers with the length of 8-10 mm into a silane coupling agent-ethanol solution with the mass concentration of 5-10%, uniformly stirring, drying at the temperature of 140-150 ℃ for 2-3 hours, and sieving by a 120-mesh sieve after ball milling to obtain silane modified carbon fibers; the silane coupling agent is vinyl triethoxysilane, a silane coupling agent KH550 or a silane coupling agent KH560;
the mass ratio of the chopped carbon fibers to the silane coupling agent-ethanol solution is 1:1 to 3;
the aluminate-coated foamed ceramic particles are prepared by the following steps:
baking the foamed ceramic particles in an oven at 115-120 ℃ for 1.5-2 hours, placing the foamed ceramic particles to 20-30 ℃, adding the foamed ceramic particles into a mixer, starting stirring, adding aluminate ester into a dry powder mixer in batches, heating the mixture to 75-80 ℃, dispersing the mixture for 1-2 hours, cooling the mixture to below 40 ℃, stopping stirring, placing the mixture to 20-30 ℃, and discharging the materials to obtain the foamed ceramic particles coated with the aluminate ester;
wherein the mass ratio of the foamed ceramic particles to the aluminate is 100:2 to 4.
2. The super-temperature-resistant silicone ablation-resistant anti-sagging heat-insulation coating as claimed in claim 1, wherein: the nano silicon dioxide dispersion liquid is prepared according to the following steps:
drying silicon dioxide with the particle size of 15-20 nm, adding the silicon dioxide into a silane-ethanol solution at the temperature of 55-60 ℃, and ultrasonically dispersing for 1-1.5 hours to obtain a dispersion liquid for later use;
the silane-ethanol solution is prepared by mixing gamma-methacryloxypropyltrimethoxysilane and ethanol according to the mass ratio of 1-1.2: 100, obtaining the product;
adding anhydrous ethanol into a dispersion kettle, starting stirring, adding citric acid into the dispersion, then adding the dispersion obtained in the step, after dispersing for 1-2 hours, adding triethanolamine into the dispersion, adjusting the pH value to 6-7, and filtering by using a vibrating screen of 360 meshes to obtain the nano-silica dispersion;
wherein the mass volume ratio of the silicon dioxide, the silane-ethanol solution, the absolute ethyl alcohol and the citric acid is 1kg: 2-2.1L: 2-2.2L: 0.02-0.03 kg.
3. The super-temperature-resistant silicone ablation-resistant anti-sagging heat-insulation coating as claimed in claim 1, wherein: the particle size of the mica powder is 300-400 meshes.
4. The super-temperature-resistant silicone ablation-resistant anti-sagging heat-insulation coating as claimed in claim 1, wherein: the grain size of the glass powder is 5000-8000 meshes.
5. The preparation method of the super-temperature-resistant organosilicon ablation-resistant anti-sagging heat-insulation coating as claimed in claim 1, is characterized in that: the method comprises the following steps:
according to parts by weight, 20-25 parts of phenolic aldehyde modified alcohol soluble organic silicon resin, 30-35 parts of mica powder, 8-10 parts of silane modified carbon fiber, 3.5-5 parts of zinc oxide, 3.5-5 parts of silicon carbide, 10-13 parts of aluminate coated foamed ceramic particles, 5-8 parts of ceramic powder, 3.2-5 parts of glass powder and 10-20 parts of absolute ethyl alcohol are sequentially added into a ball mill and stirred to obtain a mixture, the mixture is ground to 30-40 micrometers, 10-15 parts of nano silicon dioxide dispersion liquid, 0.5-0.8 part of expanded microspheres, 0.2-0.6 part of gas phase silicon dioxide and 0.1-0.4 part of organic bentonite are added into the mixture, and the mixture is stirred and dispersed for 25-30 minutes to obtain the super temperature-resistant organic silicon anti-burning anti-sagging heat insulation coating;
the phenolic aldehyde modified alcohol-soluble organic silicon resin is prepared by the following steps:
(1) adding tetraethoxysilane and ethanol into a reaction kettle, adding a hydrochloric acid aqueous solution into an overhead tank under stirring, dropwise adding the hydrochloric acid aqueous solution into the reaction kettle at a speed of 60-70 ml/min, and controlling the reaction temperature to be 35-45 ℃ to obtain tetraethoxysilane hydrolysate; mixing tetraethoxysilane hydrolysate and morpholine according to a volume ratio of 9:1, detecting the gel time after mixing, and stopping dripping the hydrochloric acid aqueous solution when the gel time is 4-6 minutes to obtain tetraethoxysilane hydrolysate for later use;
the mass ratio of the ethyl orthosilicate to the ethanol is 30:60 to 70 percent; the content of silicon dioxide in the tetraethoxysilane is 35 to 40 percent;
the mass concentration of the hydrochloric acid aqueous solution is 0.8-1.2%;
(2) adding 34-36 parts by weight of methyltriethoxysilane, 5-6 parts by weight of dimethyldiethoxysilane and 10-15 parts by weight of diphenyldiethoxysilane into a batching tank in sequence, cooling to-5-0 ℃, adding 10-15 parts by weight of toluene and 8-10 parts by weight of butanone into the batching tank in sequence, controlling the temperature of the batching tank below 5 ℃ in the adding process, and dispersing for 30-40 minutes to obtain a silane mixed solution;
adding 60-65 parts of ethanol aqueous solution with the mass concentration of 30-35% into a reaction kettle, dropwise adding silane mixed solution into the reaction kettle while stirring, wherein the dropwise adding speed is 2-2.5L/min, and the temperature of the reaction kettle is controlled to be 10-15 ℃ in the dropwise adding process to obtain silane hydrolysate;
(3) adding the silane hydrolysate obtained in the step (2) into 20-25 parts of the n-silane ethyl ester hydrolysate obtained in the step (1), distilling under reduced pressure to remove the solvent, heating to 110 ℃, dropwise adding 0.02-0.03 part of catalyst mixed solution, adding 20-25 parts of absolute ethyl alcohol, stirring, uniformly mixing, and cooling to 20-30 ℃ to obtain alcohol-soluble organic silicon resin;
the catalyst mixed liquid is prepared from n-butyl titanate, zinc naphthenate and absolute ethyl alcohol according to the mass ratio of 2-3: 1 to 2:7, mixing to obtain;
(4) and (3) mixing the alcohol-soluble organic silicon resin obtained in the step (3) with the boron phenolic resin ethanol solution according to a mass ratio of 4-6: 1, mixing, heating to 60-65 ℃, stirring and dispersing to obtain phenolic aldehyde modified alcohol-soluble organic silicon resin;
the mass concentration of the boron phenolic resin in the boron phenolic resin ethanol solution is 45-55%;
the silane modified carbon fiber is prepared by the following steps:
adding chopped carbon fibers with the length of 8-10 mm into a silane coupling agent-ethanol solution with the mass concentration of 5-10%, uniformly stirring, drying at the temperature of 140-150 ℃ for 2-3 hours, and sieving by a 120-mesh sieve after ball milling to obtain silane modified carbon fibers; the silane coupling agent is vinyl triethoxysilane, a silane coupling agent KH550 or a silane coupling agent KH560;
the mass ratio of the chopped carbon fibers to the silane coupling agent-ethanol solution is 1:1 to 3;
the foamed ceramic particles coated with the aluminate are prepared according to the following steps:
baking the foamed ceramic particles in an oven at 115-120 ℃ for 1.5-2 hours, placing the foamed ceramic particles to 20-30 ℃, adding the foamed ceramic particles into a mixer, starting stirring, adding aluminate ester into a dry powder mixer in batches, heating the mixture to 75-80 ℃, dispersing the mixture for 1-2 hours, cooling the mixture to below 40 ℃, stopping stirring, placing the mixture to 20-30 ℃, and discharging the materials to obtain the foamed ceramic particles coated with the aluminate ester;
wherein the mass ratio of the foamed ceramic particles to the aluminate is 100:2 to 4.
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