CN115678426B - Super-temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating coating and preparation method thereof - Google Patents
Super-temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating coating and preparation method thereof Download PDFInfo
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- 238000000576 coating method Methods 0.000 title claims abstract description 71
- 239000011248 coating agent Substances 0.000 title claims abstract description 68
- 238000002679 ablation Methods 0.000 title claims abstract description 53
- 238000007665 sagging Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 167
- 239000002245 particle Substances 0.000 claims abstract description 105
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 101
- 239000000919 ceramic Substances 0.000 claims abstract description 100
- 229910000077 silane Inorganic materials 0.000 claims abstract description 95
- 239000000843 powder Substances 0.000 claims abstract description 62
- 229920005989 resin Polymers 0.000 claims abstract description 62
- 239000011347 resin Substances 0.000 claims abstract description 62
- -1 phenolic aldehyde Chemical class 0.000 claims abstract description 59
- 150000004645 aluminates Chemical class 0.000 claims abstract description 57
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000007788 liquid Substances 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 32
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052796 boron Inorganic materials 0.000 claims abstract description 32
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 32
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 32
- 239000005011 phenolic resin Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 30
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 22
- 239000004917 carbon fiber Substances 0.000 claims abstract description 22
- 239000010445 mica Substances 0.000 claims abstract description 20
- 229910052618 mica group Inorganic materials 0.000 claims abstract description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003973 paint Substances 0.000 claims abstract description 15
- 239000000853 adhesive Substances 0.000 claims abstract description 5
- 230000001070 adhesive effect Effects 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims description 86
- 238000003756 stirring Methods 0.000 claims description 81
- 239000000243 solution Substances 0.000 claims description 69
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 68
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 63
- 229910052710 silicon Inorganic materials 0.000 claims description 63
- 239000010703 silicon Substances 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 54
- 239000000413 hydrolysate Substances 0.000 claims description 54
- 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 38
- 239000007864 aqueous solution Substances 0.000 claims description 34
- 235000012239 silicon dioxide Nutrition 0.000 claims description 33
- 239000011259 mixed solution Substances 0.000 claims description 32
- 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
- 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
- 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 24
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 21
- 230000008569 process Effects 0.000 claims description 21
- 239000006260 foam Substances 0.000 claims description 20
- 239000003054 catalyst Substances 0.000 claims description 19
- 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
- 239000004005 microsphere Substances 0.000 claims description 17
- 238000000498 ball milling Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 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
- 229910021485 fumed silica Inorganic materials 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
- 239000000203 mixture Substances 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
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 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
- 239000000047 product Substances 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
- 239000006185 dispersion Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 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
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 239000011152 fibreglass Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 125000003944 tolyl group Chemical group 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 description 28
- 238000009413 insulation Methods 0.000 description 13
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- 229920001296 polysiloxane Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920002050 silicone resin Polymers 0.000 description 5
- 239000000945 filler Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000012774 insulation 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
- 229920002379 silicone rubber Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- 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 organosilicon ablation-resistant sagging-resistant heat-insulating coating and a preparation method thereof, wherein the coating consists of nano silicon dioxide dispersion liquid, phenolic aldehyde modified alcohol-soluble organosilicon resin, mica powder, silane modified carbon fiber, foamed ceramic particles coated by aluminate, absolute ethyl alcohol and the like; the super temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating coating adopts the alcohol-soluble organosilicon resin modified by the boron phenolic resin and with a specific methylphenyl 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 a rocket shell; according to the super temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating coating, the foamed ceramic particles are coated by aluminate, and the binding force and affinity of the foamed ceramic particles and resin are improved through bonding; 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 coating, in particular to an ultra-temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating coating and a preparation method thereof.
Background
Ablation-resistant heat-insulating paint is widely applied in the fields of metallurgy, power generation and the like, the ablation-resistant heat-insulating paint needs to achieve the heat-proof purpose by utilizing self-phase-change heat absorption and mass exchange, and is widely applied to rocket shell body heat protection in the aerospace field, because the flying speed of a rocket is very high, 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 more than 1000 ℃, and therefore, the ablation-resistant heat-insulating paint is required to carry out heat protection on the rocket, and the flight failure of the rocket is avoided.
The ablation-resistant heat-insulating coating has good anti-corrosion and heat-insulating effects on coated equipment, and can provide reliable guarantee for normal operation of the equipment, and the lower the density is, the better the special use and use environment are. The lower the density is, the lower the gravity burden on the using equipment is, and the use environment is changeable, so that the requirement on the high-low temperature alternating environment is higher, and the cracking is avoided under the high-low temperature alternating environment.
The ablation-resistant heat insulation material can be divided into epoxy resin, silicone rubber light and organic silicone resin; the ablation-resistant heat insulation material with the epoxy resin as a 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; the silicon rubber light heat-insulating coating has small density and small gravity burden on equipment in aerospace, but is easy to crack in a high-low temperature alternating environment and cannot meet complex and changeable use environments; in addition, the existing organosilicon high-temperature-resistant heat-insulating coating is generally at the temperature below 700 ℃, the high-temperature ablation cannot meet the requirements of the aerospace field, the coating needs multiple construction, 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 sagging-resistant heat-insulating coating and the preparation method thereof, wherein the super-temperature-resistant organic silicon ablation-resistant sagging-resistant coating adopts a special organic silicon production process, is added with high-temperature sintering filler, forms a ceramic coating in a high-temperature state, and has good temperature resistance, ablation resistance and good heat insulation effect.
The invention aims to achieve the aim, and the aim is achieved by the following technical scheme:
the super temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating 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 foamed ceramic particles coated by aluminate, 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 ethyl orthosilicate and ethanol into a reaction kettle, adding a hydrochloric acid aqueous solution into a high-level tank under stirring, dripping 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 ethyl orthosilicate hydrolysate; mixing tetraethoxysilane hydrolysate and morpholine according to a volume ratio of 9:1, detecting gel time after mixing, and stopping dripping the aqueous solution of hydrochloric acid when the gel time is 4-6 minutes, so as to obtain the ethyl orthosilicate hydrolysate for later use;
The mass ratio of the ethyl orthosilicate to the ethanol is 30: 60-70 parts; the content of silicon dioxide in the tetraethoxysilane is 35-40%;
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 material mixing 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 material mixing tank in sequence, and controlling the temperature of the material mixing tank to be below 5 ℃ in the adding process, and dispersing for 30-40 minutes to obtain silane mixed solution;
adding 60-65 parts of ethanol water solution with the mass concentration of 30-35% into a reaction kettle, dropwise adding silane mixed solution into the reaction kettle under stirring, controlling the dropwise adding speed to be 2-2.5L/min, and controlling the temperature of the reaction kettle to be 10-15 ℃ during 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 into the solution, adding 20-25 parts of absolute ethyl alcohol into the solution, stirring and mixing uniformly, and cooling to 20-30 ℃ to obtain the alcohol-soluble organic silicon resin;
The catalyst mixed solution is prepared from n-butyl titanate, zinc naphthenate and absolute ethyl alcohol according to the mass ratio of 2-3: 1-2: 7, mixing to obtain the product;
(4) the alcohol-soluble organic silicon resin and the boron phenolic resin ethanol solution obtained in the step (3) are mixed according to the 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%, stirring and mixing uniformly, drying for 2-3 hours at 140-150 ℃, ball milling, and sieving through a 120-mesh screen 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 fiber to the silane coupling agent-ethanol solution is 1:1 to 3;
the aluminate coated foam ceramic particles 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 ℃, then adding the foamed ceramic particles into a mixer, starting stirring, adding aluminate into a dry powder mixer in batches, heating to 75-80 ℃ for dispersing for 1-2 hours, cooling to below 40 ℃, stopping stirring, placing the foamed ceramic particles to 20-30 ℃, and discharging to obtain the foamed ceramic particles coated with aluminate; the adding times of the aluminate can be adjusted according to actual needs, and the aluminate is generally divided into 3 to 5 times, so that the aluminate can be distributed more uniformly in the foamed ceramic particles by adding the aluminate in the steps of times, the dispersing speed is increased, and otherwise, the aluminate is easy to agglomerate;
Wherein the mass ratio of the foam ceramic particles to the aluminate is 100:2 to 4.
Preferably, the nano silicon dioxide dispersion liquid is prepared by the following steps:
the preparation method comprises the steps of drying silicon dioxide with the particle size of 15-20 nm, adding the silicon dioxide into a silane-ethanol solution with the temperature of 55-60 ℃, and performing ultrasonic dispersion for 1-1.5 hours to obtain a dispersion liquid for later use;
the silane-ethanol solution is prepared by mixing gamma-methacryloxypropyl trimethoxy silane and ethanol according to the mass ratio of 1-1.2: 100 to obtain;
adding absolute ethyl alcohol into a dispersing kettle, starting stirring, adding citric acid into the dispersing kettle, adding the dispersing liquid obtained in the first step, dispersing for 1-2 hours, adding triethanolamine into the dispersing kettle, adjusting the pH value to 6-7, and filtering by a 360-mesh vibrating screen to obtain nano silicon dioxide dispersing liquid;
wherein the mass volume ratio of the silicon dioxide to the silane-ethanol solution to the absolute ethyl alcohol to the citric acid is 1kg:2 to 2.1L:2 to 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 temperature-resistant organic silicon ablation-resistant sagging-resistant heat-insulating coating, which comprises the steps of sequentially adding 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 foamed ceramic particles coated by aluminate, 5-8 parts of ceramic powder, 3.2-5 parts of glass powder and 10-20 parts of absolute ethyl alcohol into a ball mill according to parts by weight, grinding to 30-40 micrometers, adding 10-15 parts of nano silicon dioxide dispersion liquid, 0.5-0.8 part of expanded microspheres, 0.2-0.6 part of fumed silica and 0.1-0.4 part of organic bentonite, and stirring and dispersing for 25-30 minutes to obtain the super temperature-resistant organic silicon ablation-resistant sagging-resistant heat-insulating coating;
The phenolic aldehyde modified alcohol-soluble organic silicon resin is prepared by the following steps:
(1) adding ethyl orthosilicate and ethanol into a reaction kettle, adding a hydrochloric acid aqueous solution into a high-level tank under stirring, dripping 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 ethyl orthosilicate hydrolysate; mixing tetraethoxysilane hydrolysate and morpholine according to a volume ratio of 9:1, detecting gel time after mixing, and stopping dripping the aqueous solution of hydrochloric acid when the gel time is 4-6 minutes, so as to obtain the ethyl orthosilicate hydrolysate for later use;
the mass ratio of the ethyl orthosilicate to the ethanol is 30: 60-70 parts; the content of silicon dioxide in the tetraethoxysilane is 35-40%;
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 material mixing 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 material mixing tank in sequence, and controlling the temperature of the material mixing tank to be below 5 ℃ in the adding process, and dispersing for 30-40 minutes to obtain silane mixed solution;
adding 60-65 parts of ethanol water solution with the mass concentration of 30-35% into a reaction kettle, dropwise adding silane mixed solution into the reaction kettle under stirring, controlling the dropwise adding speed to be 2-2.5L/min, and controlling the temperature of the reaction kettle to be 10-15 ℃ during 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 into the solution, adding 20-25 parts of absolute ethyl alcohol into the solution, stirring and mixing uniformly, and cooling to 20-30 ℃ to obtain the alcohol-soluble organic silicon resin;
the catalyst mixed solution is prepared from n-butyl titanate, zinc naphthenate and absolute ethyl alcohol according to the mass ratio of 2-3: 1-2: 7, mixing to obtain the product;
(4) the alcohol-soluble organic silicon resin and the boron phenolic resin ethanol solution obtained in the step (3) are mixed according to the 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%, stirring and mixing uniformly, drying for 2-3 hours at 140-150 ℃, ball milling, and sieving through a 120-mesh screen 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 fiber to the silane coupling agent-ethanol solution is 1:1 to 3;
the aluminate coated foam ceramic particles 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 ℃, then adding the foamed ceramic particles into a mixer, starting stirring, adding aluminate into a dry powder mixer in batches, heating to 75-80 ℃ for dispersing for 1-2 hours, cooling to below 40 ℃, stopping stirring, placing the foamed ceramic particles to 20-30 ℃, and discharging to obtain the foamed ceramic particles coated with aluminate;
wherein the mass ratio of the foam 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 organosilicon ablation-resistant sagging-resistant heat-insulating coating adopts the alcohol-soluble organosilicon resin modified by the boron phenolic resin and with a specific methylphenyl 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 dispersion is easier, and the viscosity of the coating is reduced, so that the thickness of a paint film is reduced during coating, and the effect of reducing the weight of the coating on a rocket shell is achieved;
The super temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating coating provided by the invention is prepared by preprocessing nano silicon dioxide with gamma-methacryloxypropyl trimethoxy silane, so that the wetting property of the nano silicon dioxide is improved, the nano silicon dioxide is easy to disperse in ethanol, and the binding force between the nano silicon dioxide and organosilicon resin in the film forming process is improved, so that the temperature resistance of the resin is improved. And in the second step, citric acid is used as a dispersing agent, and steric hindrance is formed due to charge repulsion, so that the dispersion stability of nano silicon dioxide can be maintained, and triethanolamine is used for regulating the pH value, so that a certain thickening effect is achieved, and the system stability is improved.
According to the super temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating coating, the foamed ceramic particles are coated by aluminate, and the binding force and affinity of the foamed ceramic particles and resin are improved through bonding; the viscosity of the system is obviously reduced, the manufacturability of paint production is improved, in addition, the use amount of the heat insulation filler is increased from 8-10 parts when not coated to 10-13 parts after coating due to the reduction of the viscosity, 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 expansion microsphere, the expansion microsphere is expanded 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 modified by boron phenolic resin and containing methyl and phenyl, wherein the molar ratio of the methyl to the phenyl is 4-4.5: the gel time at the temperature of 1, 200 ℃ is 200-260 seconds, and the hardness of the swing rod is more than or equal to 0.7.
The nano silicon dioxide dispersion liquid of the invention is available outsourced and is obtained by dispersing nano silicon dioxide in ethanol, wherein the silicon dioxide content 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 plastics composite material Co.
The invention is further described below in connection with specific embodiments.
Example 1
An ultra-temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating coating is prepared from the following raw materials: 10kg of nano silicon dioxide dispersion liquid, 20kg of phenolic modified alcohol-soluble organic silicon resin, 30kg of mica powder, 8kg of silane modified carbon fiber, 5kg of ceramic powder, 10kg of foamed ceramic particles coated by aluminate, 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 ethyl orthosilicate and 6kg of ethanol into a reaction kettle, adding a hydrochloric acid aqueous solution into a head tank under stirring, dripping the hydrochloric acid aqueous solution into the reaction kettle at a speed of 60ml/min, and controlling the reaction temperature to 35 ℃ to obtain ethyl orthosilicate hydrolysate; mixing tetraethoxysilane hydrolysate and morpholine according to a volume ratio of 9:1, detecting gel time after mixing, and stopping dripping the aqueous solution of hydrochloric acid when the gel time is 4 minutes, so as to obtain the hydrolysate of the tetraethoxysilane for later use;
the content of silicon dioxide in the tetraethoxysilane is 35%;
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 material mixing tank, cooling to-5 ℃, sequentially adding 5kg of toluene and 4kg of butanone into the material mixing tank, controlling the temperature of the material mixing tank to be below 5 ℃ in the adding process, and dispersing for 30 minutes to obtain silane mixed solution;
adding 30kg of ethanol water solution with the mass concentration of 30% into a reaction kettle, dropwise adding a silane mixed solution into the reaction kettle under stirring, controlling the dropwise adding speed to be 2L/min, and controlling the temperature of the reaction kettle to be 10 ℃ during the dropwise adding process to obtain a 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 into the solution, adding 10kg of absolute ethyl alcohol into the solution, stirring and mixing uniformly, and cooling to 20 ℃ to obtain the 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 the product;
(4) mixing 20kg of the alcohol-soluble organic silicon resin obtained in the step (3) with 5kg of the boron phenolic resin ethanol solution, heating to 60 ℃, and stirring and dispersing to obtain phenolic modified alcohol-soluble organic silicon resin;
the mass concentration of the boron phenolic resin in the boron phenolic resin ethanol solution is 45%;
the aluminate coated foam ceramic particles are prepared according to the following steps:
baking 10kg of foamed ceramic particles in a baking oven at 115 ℃ for 1.5 hours, placing the foamed ceramic particles to 20 ℃, then adding the foamed ceramic particles into a mixer, starting stirring, adding 0.2kg of aluminate into a dry powder mixer in batches, heating to 75 ℃ for dispersing for 1 hour, cooling to below 40 ℃, stopping stirring, placing the foamed ceramic particles to 20 ℃, and discharging to obtain the foamed ceramic particles coated with the aluminate;
the silane modified carbon fiber is prepared by the following steps:
adding 8kg of chopped carbon fiber with the length of 8-10 mm into 8kg of silane coupling agent-ethanol solution with the mass concentration of 5%, stirring and mixing uniformly, drying at 140 ℃ for 2 hours, ball-milling, and sieving by a 120-mesh screen to obtain silane modified carbon fiber; the silane coupling agent is vinyl triethoxysilane.
Example 2
An ultra-temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating coating is prepared from 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 foamed ceramic particles coated by aluminate, 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 according to the following steps:
(1) adding 6kg of ethyl orthosilicate and 14kg of ethanol into a reaction kettle, adding a hydrochloric acid aqueous solution into a head tank under stirring, dripping the hydrochloric acid aqueous solution into the reaction kettle at a speed of 70ml/min, and controlling the reaction temperature to 45 ℃ to obtain ethyl orthosilicate hydrolysate; mixing tetraethoxysilane hydrolysate and morpholine according to a volume ratio of 9:1, detecting gel time after mixing, and stopping dripping the aqueous solution of hydrochloric acid when the gel time is 6 minutes, so as to obtain the hydrolysate of the tetraethoxysilane for later use;
the content of silicon dioxide in the tetraethoxysilane is 40%; 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 material mixing tank, cooling to 0 ℃, sequentially adding 7.5kg of toluene and 5kg of butanone into the material mixing tank, controlling the temperature of the material mixing tank to be 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, controlling the dropwise adding speed to be 2.5L/min, and controlling the temperature of the reaction kettle to be 15 ℃ during 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 liquor into the solution, adding 12.5kg of absolute ethyl alcohol into the solution, stirring and mixing uniformly, and cooling to 30 ℃ to obtain the 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 the product;
(4) mixing 24kg of the alcohol-soluble organic silicon resin obtained in the step (3) with 4kg of the boron phenolic resin ethanol solution, heating to 65 ℃, and stirring and dispersing to obtain phenolic modified alcohol-soluble organic silicon resin;
the mass concentration of the boron phenolic resin in the boron phenolic resin ethanol solution is 55%;
the aluminate coated foam ceramic particles 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 ℃, then adding the foamed ceramic particles into a mixer, starting stirring, adding 0.8kg of aluminate into a dry powder mixer in batches, heating to 80 ℃ for dispersing for 2 hours, cooling to below 40 ℃, stopping stirring, placing the foamed ceramic particles to 30 ℃, and discharging to obtain the foamed ceramic particles coated by the aluminate;
The silane modified carbon fiber is prepared by the following steps:
adding 10kg of chopped carbon fiber with the length of 8-10 mm into 30kg of silane coupling agent-ethanol solution with the mass concentration of 10%, stirring and mixing uniformly, drying at 150 ℃ for 3 hours, ball-milling, and sieving by a 120-mesh screen to obtain silane modified carbon fiber; the silane coupling agent is a silane coupling agent KH550.
Example 3
An ultra-temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating coating is prepared from the following raw materials: 12kg of nano silicon dioxide dispersion liquid, 22kg of phenolic modified alcohol-soluble organic silicon resin, 32kg of mica powder, 8.5kg of silane modified carbon fiber, 6kg of ceramic powder, 11kg of foamed ceramic particles coated by aluminate, 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 particle size 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 by the following steps:
drying 10kg of silicon dioxide with the particle size of 15-18 nm, adding the dried silicon dioxide into 20L of silane-ethanol solution with the temperature of 55 ℃ and performing ultrasonic dispersion for 1 hour to obtain dispersion liquid for later use;
The silane-ethanol solution is prepared by mixing gamma-methacryloxypropyl trimethoxy silane and ethanol according to a mass ratio of 1:100 to obtain;
adding 20L of absolute ethyl alcohol into a dispersing kettle, starting stirring, adding 0.2kg of citric acid into the dispersing kettle, adding the dispersing liquid obtained through the first step, dispersing for 1 hour, adding triethanolamine into the dispersing kettle, adjusting the pH value to 6, and filtering through a 360-mesh vibrating screen to obtain nano silicon dioxide dispersing liquid;
the phenolic aldehyde modified alcohol-soluble organic silicon resin is prepared according to the following steps:
(1) adding 6kg of ethyl orthosilicate and 13.6kg of ethanol into a reaction kettle, adding a hydrochloric acid aqueous solution into a high-level 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 38 ℃ to obtain ethyl orthosilicate hydrolysate; mixing tetraethoxysilane hydrolysate and morpholine according to a volume ratio of 9:1, detecting gel time after mixing, and stopping dripping the aqueous solution of hydrochloric acid when the gel time is 4.5 minutes, so as to obtain the ethyl orthosilicate hydrolysate for later use;
the content of silicon dioxide in the tetraethoxysilane is 38%; 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 material mixing tank, cooling to-2 ℃, sequentially adding 7kg of toluene and 4.25kg of butanone into the material mixing tank, controlling the temperature of the material mixing tank to be below 5 ℃ in the adding process, and dispersing for 32 minutes to obtain a silane mixed solution;
Adding 31kg of an ethanol water solution with the mass concentration of 32% into a reaction kettle, dropwise adding a silane mixed solution into the reaction kettle under stirring, controlling the dropwise adding speed to be 2.2L/min, and controlling the temperature of the reaction kettle to be 14 ℃ in the dropwise adding process to obtain a 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, adding 12kg of absolute ethyl alcohol into the catalyst mixed liquor, stirring and uniformly mixing, and cooling to 22 ℃ to obtain the 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 the product;
(4) mixing 22.5kg of the alcohol-soluble organic silicon resin obtained in the step (3) with 5kg of the boron phenolic resin ethanol solution, heating to 62 ℃, and stirring and dispersing to obtain phenolic modified alcohol-soluble organic silicon resin;
the mass concentration of the boron phenolic resin in the boron phenolic resin ethanol solution is 48%;
the aluminate coated foam ceramic particles are prepared according to the following steps:
baking 12kg of foamed ceramic particles in a baking oven at 116 ℃ for 1.8 hours, placing the foamed ceramic particles to 24 ℃, then adding the foamed ceramic particles into a mixer, starting stirring, adding 0.3kg of aluminate into a dry powder mixer in batches, heating to 76 ℃ for dispersing for 1.5 hours, cooling to below 40 ℃, stopping stirring, placing the foamed ceramic particles to 22 ℃, and discharging to obtain the foamed ceramic particles coated with the aluminate;
The silane modified carbon fiber is prepared by the following steps:
adding 9kg of chopped carbon fiber with the length of 8-10 mm into 18kg of silane coupling agent-ethanol solution with the mass concentration of 6%, stirring and mixing uniformly, drying at 142 ℃ for 2.5 hours, ball-milling, and sieving with a 120-mesh screen to obtain silane modified carbon fiber; the silane coupling agent is a silane coupling agent KH560.
Example 4
An ultra-temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating coating is prepared from the following raw materials: 14kg of nano silicon dioxide dispersion liquid, 24kg of phenolic modified alcohol-soluble organic silicon resin, 33kg of mica powder, 8.5kg of silane modified carbon fiber, 7kg of ceramic powder, 12kg of foamed ceramic particles coated by aluminate, 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 particle 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 by the following steps:
drying 15kg of silicon dioxide with the particle size of 18-20 nm, adding the silicon dioxide into 31.5L of 60 ℃ silane-ethanol solution, and performing ultrasonic dispersion for 1.5 hours to obtain a dispersion liquid for later use;
The silane-ethanol solution is prepared by mixing gamma-methacryloxypropyl trimethoxy silane and ethanol according to a mass ratio of 1.2:100 to obtain;
adding 33L of absolute ethyl alcohol into a dispersing kettle, starting stirring, adding 0.45kg of citric acid into the dispersing kettle, adding the dispersing liquid obtained through the technical scheme, dispersing for 1-2 hours, adding triethanolamine into the dispersing kettle, adjusting the pH value to 7, and filtering through a 360-mesh vibrating screen to obtain nano silicon dioxide dispersing liquid;
the phenolic aldehyde modified alcohol-soluble organic silicon resin is prepared according to the following steps:
(1) adding 6kg of ethyl orthosilicate and 13.6kg of ethanol into a reaction kettle, adding a hydrochloric acid aqueous solution into a high-level tank under stirring, dropwise adding the mixture into the reaction kettle at a speed of 62ml/min, and controlling the reaction temperature to 40 ℃ to obtain ethyl orthosilicate hydrolysate; mixing tetraethoxysilane hydrolysate and morpholine according to a volume ratio of 9:1, detecting gel time after mixing, and stopping dripping the aqueous solution of hydrochloric acid when the gel time is 5 minutes, so as to obtain the hydrolysate of the tetraethoxysilane for later use;
the content of silicon dioxide in the tetraethoxysilane is 38%; 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 material mixing tank, cooling to-2 ℃, sequentially adding 6kg of toluene and 4.80kg of butanone into the material mixing tank, controlling the temperature of the material mixing tank to be below 5 ℃ in the adding process, and dispersing for 32 minutes to obtain a silane mixed solution;
Adding 32kg of ethanol water solution with the mass concentration of 30% into a reaction kettle, dropwise adding a silane mixed solution into the reaction kettle under stirring, controlling the dropwise adding speed to be 2.2L/min, and controlling the temperature of the reaction kettle to be 12 ℃ during the dropwise adding process to obtain a 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 liquor into the solution, adding 11kg of absolute ethyl alcohol into the solution, stirring and mixing uniformly, and cooling to 25 ℃ to obtain the 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 the product;
(4) mixing 22kg of the alcohol-soluble organic silicon resin obtained in the step (3) with 4kg of the boron phenolic resin ethanol solution, heating to 62 ℃, and stirring and dispersing to obtain phenolic modified alcohol-soluble organic silicon resin;
the mass concentration of the boron phenolic resin in the boron phenolic resin ethanol solution is 50%;
the aluminate coated foam ceramic particles 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 ℃, then adding the foamed ceramic particles into a mixer, starting stirring, adding 0.36kg of aluminate into a dry powder mixer in batches, heating to 78 ℃ for dispersing for 1.5 hours, cooling to below 40 ℃, stopping stirring, placing the foamed ceramic particles to 25 ℃, and discharging to obtain the foamed ceramic particles coated with the aluminate;
The silane modified carbon fiber is prepared by the following steps:
adding 9kg of chopped carbon fiber with the length of 8-10 mm into 13.5kg of silane coupling agent-ethanol solution with the mass concentration of 8%, stirring and mixing uniformly, drying at 148 ℃ for 2.5 hours, ball-milling, and sieving with a 120-mesh screen to obtain silane modified carbon fiber; the silane coupling agent is vinyl triethoxysilane.
Example 5
An ultra-temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating coating is prepared from the following raw materials: 13kg of nano silicon dioxide dispersion liquid, 24kg of phenolic modified alcohol-soluble organic silicon resin, 32kg of mica powder, 9.5kg of silane modified carbon fiber, 6kg of ceramic powder, 12kg of foamed ceramic particles coated by aluminate, 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 particle 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 by the following steps:
drying 10kg of silicon dioxide with the particle size of 15-16 nm, adding the dried silicon dioxide into 20L of silane-ethanol solution with the temperature of 58 ℃, and performing ultrasonic dispersion for 1.2 hours to obtain a dispersion liquid for later use;
The silane-ethanol solution is prepared by mixing gamma-methacryloxypropyl trimethoxy silane and ethanol according to a mass ratio of 1.1:100 to obtain;
adding 21L of absolute ethyl alcohol into a dispersing kettle, stirring, adding 0.25kg of citric acid into the dispersing kettle, adding the dispersing liquid obtained through the step, dispersing for 1.5 hours, adding triethanolamine into the dispersing kettle, adjusting the pH value to 6.5, filtering through a 360-mesh vibrating screen, and drying at 95 ℃ for 1.5 hours to obtain nano silicon dioxide dispersing liquid;
the phenolic aldehyde modified alcohol-soluble organic silicon resin is prepared according to the following steps:
(1) adding 3kg of ethyl orthosilicate and 6.6kg of ethanol into a reaction kettle, adding a hydrochloric acid aqueous solution into a high-level tank under stirring, dropwise adding the mixture into the reaction kettle at a speed of 68ml/min, and controlling the reaction temperature to 40 ℃ to obtain ethyl orthosilicate hydrolysate; mixing tetraethoxysilane hydrolysate and morpholine according to a volume ratio of 9:1, detecting gel time after mixing, and stopping dripping the aqueous solution of hydrochloric acid when the gel time is 5 minutes, so as to obtain the hydrolysate of the tetraethoxysilane for later use;
the content of silicon dioxide in the tetraethoxysilane is 38%; 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 material mixing tank, cooling to-4 ℃, sequentially adding 7kg of toluene and 4.5kg of butanone into the material mixing tank, controlling the temperature of the material mixing tank to be below 5 ℃ in the adding process, and dispersing for 35 minutes to obtain silane mixed solution;
Adding 32kg of 34% ethanol water solution into a reaction kettle, dropwise adding a silane mixed solution into the reaction kettle under stirring, controlling the dropwise adding speed to be 2.4L/min, and controlling the temperature of the reaction kettle to be 14 ℃ during the dropwise adding process to obtain a 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 liquor into the solution, adding 12kg of absolute ethyl alcohol into the solution, stirring and mixing the solution uniformly, and cooling to 25 ℃ to obtain the 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 the product;
(4) mixing 25kg of the alcohol-soluble organic silicon resin obtained in the step (3) with 5kg of the boron phenolic resin ethanol solution, heating to 64 ℃, and stirring and dispersing to obtain phenolic modified alcohol-soluble organic silicon resin;
the mass concentration of the boron phenolic resin in the boron phenolic resin ethanol solution is 50%;
the aluminate coated foam ceramic particles 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 ℃, then adding the foamed ceramic particles into a mixer, starting stirring, adding 0.36kg of aluminate into a dry powder mixer in batches, heating to 78 ℃ for dispersing for 1.5 hours, cooling to below 40 ℃, stopping stirring, placing the foamed ceramic particles to 25 ℃, and discharging to obtain the foamed ceramic particles coated with the aluminate;
The silane modified carbon fiber is prepared by the following steps:
adding 10kg of chopped carbon fiber with the length of 8-10 mm into 20kg of 8% silane coupling agent-ethanol solution, stirring and mixing uniformly, drying at 145 ℃ for 2.5 hours, ball milling, sieving with a 120-mesh screen, and obtaining silane modified carbon fiber; the silane coupling agent is a silane coupling agent KH560.
Example 6
The preparation method of the super temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating coating of 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 foamed ceramic particles coated by aluminate, 5kg of ceramic powder, 3.2kg of glass powder and 10kg of absolute ethyl alcohol are sequentially added into a ball mill, ball milling and stirring are carried out to obtain a mixture, grinding is carried out until the thickness is 30 microns, 10kg of nano silicon dioxide dispersion liquid, 0.5kg of expanded microspheres, 0.2kg of fumed silica and 0.1kg of organic bentonite are added into the mixture, stirring and dispersing are carried out for 25 minutes, and the super-temperature-resistant organic silicon ablation-resistant anti-sagging heat insulation coating is obtained.
Example 7
The preparation method of the super temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating coating of 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 foamed ceramic particles coated by aluminate, 8kg of ceramic powder, 5kg of glass powder and 20kg of absolute ethyl alcohol into a ball mill in sequence, ball milling and stirring to obtain a mixture, grinding to 40 micrometers, adding 15kg of nano silicon dioxide dispersion liquid, 0.8kg of expanded microspheres, 0.6kg of fumed silica and 0.4kg of organic bentonite, stirring and dispersing for 30 minutes, and obtaining the super-temperature-resistant organic silicon ablation-resistant sagging-resistant heat insulation coating.
Example 8
The preparation method of the super temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating coating of the embodiment 3 comprises the following steps: adding 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 foamed ceramic particles coated by aluminate, 6kg of ceramic powder, 3.5kg of glass powder and 12kg of absolute ethyl alcohol into a ball mill in sequence, ball-milling and stirring to obtain a mixture, grinding to 32 micrometers, adding 12kg of nano silicon dioxide dispersion liquid, 0.6kg of expanded microspheres, 0.3kg of fumed silica and 0.2kg of organic bentonite, stirring and dispersing for 26 minutes, and obtaining the super-temperature-resistant organic silicon ablation-resistant anti-sagging heat-insulating coating.
Example 9
The preparation method of the super temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating coating of the embodiment 4 comprises the following steps: 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 foamed ceramic particles coated by aluminate, 7kg of ceramic powder, 4.5kg of glass powder and 18kg of absolute ethyl alcohol are sequentially added into a ball mill, ball milling and stirring are carried out to obtain a mixture, grinding is carried out until the mixture is 35 microns, 14kg of nano silicon dioxide dispersion liquid, 0.7kg of expanded microspheres, 0.5kg of fumed silica and 0.3kg of organic bentonite are added into the mixture, stirring and dispersing are carried out for 28 minutes, and the super-temperature-resistant organic silicon ablation-resistant anti-sagging heat insulation coating is obtained.
Example 10
The preparation method of the super temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating coating of the embodiment 5 comprises the following steps: 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 foamed ceramic particles coated by aluminate, 6kg of ceramic powder, 4kg of glass powder and 15kg of absolute ethyl alcohol are sequentially added into a ball mill, ball milling and stirring are carried out to obtain a mixture, grinding is carried out until 35 microns, 13kg of nano silicon dioxide dispersion liquid, 0.7kg of expanded microspheres, 0.5kg of fumed silica and 0.2kg of organic bentonite are added into the mixture, stirring and dispersing are carried out for 28 minutes, and thus the super-temperature-resistant organic silicon ablation-resistant sagging-resistant heat insulation coating is obtained.
The properties of the phenolic-modified alcohol-soluble silicone resins obtained in examples 1 to 5 were measured, and the results are shown in Table 1.
Table 1 table of properties of the phenolic modified alcohol-soluble silicone resins of examples 1 to 5
The super heat-resistant organosilicon ablation-resistant sagging-resistant heat-insulating coating obtained in examples 1 to 5 was subjected to performance test, and the results are shown in Table 2. The viscosity is detected by using a GB/T9751.1 rotational viscometer, the solid content is specified by GB/T1725, the baking temperature is 105+/-2 ℃, the baking time is 2 hours, the sample quantity is about 2g, the high temperature resistance is detected by using GB1735, the hardness is detected by using a pendulum rod durometer according to GB/T1730, the adhesive force is detected by using a GB/T5210 pull-out method, the impact resistance is detected by using GB1732, the thermal stability is 5 hours at 1300+/-20 ℃, and the paint film performance is observed; the paint film performance is observed in three periods (1 hour per period) by adopting (1000+/-20) DEG C and (-40+/-5) DEG C in high-low temperature alternation, and the sagging resistance is detected according to the GB/T9264 rule.
Table 2 table of the results of the performance test of the super heat-resistant silicone ablation-resistant sagging-resistant heat-insulating coatings obtained in examples 1 to 5
The super temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating coating has low viscosity, good sagging resistance and easy coating; the high temperature resistant temperature of the modified resin coating can reach 1300 ℃, the heat resistance, the adhesive force and the impact resistance 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 attractive force, increased repulsive force, easier dispersion, reduced viscosity of the coating, increased addition of the heat insulation filler, improved heat insulation effect, and the raw materials contain the expansion microspheres, the expansion is carried out in the film forming process, and the coating density is only 0.3-0.35 g/cm when the thickness of the coating is 1.5-2 mm 3 Far smaller than the existing 0.4-0.6 g/cm 3 Coating density of (c) is provided.
Since the super heat-resistant silicone ablation-resistant sagging-resistant heat-insulating coating obtained in example 5 had the best performance, a comparison experiment was performed based on example 5 as follows.
Comparative example 1
The silicone ablation-resistant thermal insulation coating was identical to example 5 except that the phenolic aldehyde modified alcohol-soluble silicone resin component was a commercially available alcohol-soluble silicone resin.
Comparative example 2
The silicone ablation-resistant thermal insulation coating was identical to example 5 except that the silane-modified carbon fiber component was not modified with silane, and the carbon fiber was directly used.
Comparative example 3
The silicone ablation-resistant heat-insulating coating was identical to example 5 except that the aluminate-coated ceramic foam particle component was directly treated with ceramic foam particles without aluminate coating.
The properties of the silicone ablation-resistant heat-insulating coatings obtained in comparative examples 1 to 3 were measured, and the results are shown in Table 3.
Table 3 shows the results of testing the properties of the heat-insulating coating materials for ablation resistance of the silicones obtained in comparative examples 1 to 3
As can be seen from the results in Table 3, the heat resistance of the organosilicon ablation-resistant heat-insulating coating obtained by adopting the commercially available alcohol-soluble organosilicon resin is obviously reduced, and the paint film has serious cracks and falling after being observed at the temperature of 1300+/-20 ℃ for 5 hours at 780 ℃ and has poor heat stability, poor high-low temperature alternation and poor sagging property; the mutual attraction force among carbon fiber particles is reduced after the silane coupling agent is treated, and the repulsive force is increased to be easier to disperse, so that the viscosity and sagging resistance of a paint film can be influenced.
The aluminate coated ceramic foam particles increase the binding force and affinity of the ceramic foam particles with the resin through bonding. Obviously reduces the viscosity of the system and improves the manufacturability of the paint production. The use amount of the foam ceramic particles can be increased by 5-7% due to the reduction of the viscosity in the production process, so that the heat insulation performance is improved, and compared with untreated foam ceramic particles, the heat conductivity coefficient of the foam ceramic particles is reduced from 0.05-0.08W/(m.K) to 0.03-0.06W/(m.K).
Claims (4)
1. An ultra-temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating coating is characterized in that: the adhesive consists of 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 foamed ceramic particles coated by aluminate, 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 ethyl orthosilicate and ethanol into a reaction kettle, adding a hydrochloric acid aqueous solution into a high-level tank under stirring, dripping 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 ethyl orthosilicate hydrolysate; mixing tetraethoxysilane hydrolysate and morpholine according to a volume ratio of 9:1, detecting gel time after mixing, and stopping dripping the aqueous solution of hydrochloric acid when the gel time is 4-6 minutes, so as to obtain the ethyl orthosilicate hydrolysate for later use;
the mass ratio of the ethyl orthosilicate to the ethanol is 30: 60-70 parts; the content of silicon dioxide in the tetraethoxysilane is 35-40%;
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 material mixing 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 material mixing tank in sequence, and controlling the temperature of the material mixing tank to be below 5 ℃ in the adding process, and dispersing for 30-40 minutes to obtain silane mixed solution;
adding 60-65 parts of ethanol water solution with the mass concentration of 30-35% into a reaction kettle, dropwise adding silane mixed solution into the reaction kettle under stirring, controlling the dropwise adding speed to be 2-2.5L/min, and controlling the temperature of the reaction kettle to be 10-15 ℃ during 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 into the solution, adding 20-25 parts of absolute ethyl alcohol into the solution, stirring and mixing uniformly, and cooling to 20-30 ℃ to obtain the alcohol-soluble organic silicon resin;
the catalyst mixed solution is prepared from n-butyl titanate, zinc naphthenate and absolute ethyl alcohol according to the mass ratio of 2-3: 1-2: 7, mixing to obtain the product;
(4) The alcohol-soluble organic silicon resin and the boron phenolic resin ethanol solution obtained in the step (3) are mixed according to the 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 boron phenolic resin is produced by Beijing glass fiber reinforced plastic institute composite material Co., ltd;
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%, stirring and mixing uniformly, drying for 2-3 hours at 140-150 ℃, ball milling, and sieving through a 120-mesh screen 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 fiber to the silane coupling agent-ethanol solution is 1:1 to 3;
the aluminate coated foam ceramic particles 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 ℃, then adding the foamed ceramic particles into a mixer, starting stirring, adding aluminate into a dry powder mixer in batches, heating to 75-80 ℃ for dispersing for 1-2 hours, cooling to below 40 ℃, stopping stirring, placing the foamed ceramic particles to 20-30 ℃, and discharging to obtain the foamed ceramic particles coated with aluminate;
Wherein the mass ratio of the foam ceramic particles to the aluminate is 100:2 to 4;
the nano silicon dioxide dispersion liquid is prepared by the following steps:
the preparation method comprises the steps of drying silicon dioxide with the particle size of 15-20 nm, adding the silicon dioxide into a silane-ethanol solution with the temperature of 55-60 ℃, and performing ultrasonic dispersion for 1-1.5 hours to obtain a dispersion liquid for later use;
the silane-ethanol solution is prepared by mixing gamma-methacryloxypropyl trimethoxy silane and ethanol according to the mass ratio of 1-1.2: 100 to obtain;
adding absolute ethyl alcohol into a dispersing kettle, starting stirring, adding citric acid into the dispersing kettle, adding the dispersing liquid obtained in the first step, dispersing for 1-2 hours, adding triethanolamine into the dispersing kettle, adjusting the pH value to 6-7, and filtering by a 360-mesh vibrating screen to obtain nano silicon dioxide dispersing liquid;
wherein the mass volume ratio of the silicon dioxide to the silane-ethanol solution to the absolute ethyl alcohol to the citric acid is 1kg:2 to 2.1L:2 to 2.2L: 0.02-0.03 kg.
2. The super temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating coating according to claim 1, wherein the heat-insulating coating is characterized by: the particle size of the mica powder is 300-400 meshes.
3. The super temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating coating according to claim 1, wherein the heat-insulating coating is characterized by: the particle size of the glass powder is 5000-8000 meshes.
4. The method for preparing the super temperature-resistant organosilicon ablation-resistant sagging-resistant heat-insulating paint is characterized in that: the method comprises the following steps:
sequentially adding 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 foamed ceramic particles coated by aluminate, 5-8 parts of ceramic powder, 3.2-5 parts of glass powder and 10-20 parts of absolute ethyl alcohol into a ball mill, ball-milling and stirring to obtain a mixture, grinding to 30-40 micrometers, adding 10-15 parts of nano silicon dioxide dispersion liquid, 0.5-0.8 part of expanded microspheres, 0.2-0.6 part of fumed silica and 0.1-0.4 part of organic bentonite, and stirring and dispersing for 25-30 minutes to obtain the super-temperature-resistant organic silicon ablation-resistant anti-sagging heat-insulating coating;
the phenolic aldehyde modified alcohol-soluble organic silicon resin is prepared by the following steps:
(1) adding ethyl orthosilicate and ethanol into a reaction kettle, adding a hydrochloric acid aqueous solution into a high-level tank under stirring, dripping 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 ethyl orthosilicate hydrolysate; mixing tetraethoxysilane hydrolysate and morpholine according to a volume ratio of 9:1, detecting gel time after mixing, and stopping dripping the aqueous solution of hydrochloric acid when the gel time is 4-6 minutes, so as to obtain the ethyl orthosilicate hydrolysate for later use;
The mass ratio of the ethyl orthosilicate to the ethanol is 30: 60-70 parts; the content of silicon dioxide in the tetraethoxysilane is 35-40%;
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 material mixing 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 material mixing tank in sequence, and controlling the temperature of the material mixing tank to be below 5 ℃ in the adding process, and dispersing for 30-40 minutes to obtain silane mixed solution;
adding 60-65 parts of ethanol water solution with the mass concentration of 30-35% into a reaction kettle, dropwise adding silane mixed solution into the reaction kettle under stirring, controlling the dropwise adding speed to be 2-2.5L/min, and controlling the temperature of the reaction kettle to be 10-15 ℃ during 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 into the solution, adding 20-25 parts of absolute ethyl alcohol into the solution, stirring and mixing uniformly, and cooling to 20-30 ℃ to obtain the alcohol-soluble organic silicon resin;
The catalyst mixed solution is prepared from n-butyl titanate, zinc naphthenate and absolute ethyl alcohol according to the mass ratio of 2-3: 1-2: 7, mixing to obtain the product;
(4) the alcohol-soluble organic silicon resin and the boron phenolic resin ethanol solution obtained in the step (3) are mixed according to the 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%, stirring and mixing uniformly, drying for 2-3 hours at 140-150 ℃, ball milling, and sieving through a 120-mesh screen 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 fiber to the silane coupling agent-ethanol solution is 1:1 to 3;
the aluminate coated foam ceramic particles 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 ℃, then adding the foamed ceramic particles into a mixer, starting stirring, adding aluminate into a dry powder mixer in batches, heating to 75-80 ℃ for dispersing for 1-2 hours, cooling to below 40 ℃, stopping stirring, placing the foamed ceramic particles to 20-30 ℃, and discharging to obtain the foamed ceramic particles coated with aluminate;
Wherein the mass ratio of the foam ceramic particles to the aluminate is 100:2 to 4.
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