CN113290997B - Surface-compounded thermal protection material and preparation method thereof - Google Patents

Surface-compounded thermal protection material and preparation method thereof Download PDF

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CN113290997B
CN113290997B CN202110587898.7A CN202110587898A CN113290997B CN 113290997 B CN113290997 B CN 113290997B CN 202110587898 A CN202110587898 A CN 202110587898A CN 113290997 B CN113290997 B CN 113290997B
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flame retardant
compounded
glass beads
temperature resistant
mercapto
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CN113290997A (en
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李向梅
陈勃
何吉宇
杨荣杰
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Beijing Institute of Technology BIT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/06—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/10—Layered products comprising a layer of natural or synthetic rubber next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
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    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
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Abstract

The invention relates to a surface composite thermal protection material which is of a sandwich structure, wherein a middle layer is a thermal insulation material base body, and protective layers are covered on the upper surface and the lower surface of the thermal insulation material base body; the heat-insulating material matrix comprises the following raw materials: ethylene propylene diene monomer, fiber, a heat insulating agent, polymer resin and a composite flame retardant, wherein the protective layer is high-temperature-resistant mica paper or high-temperature-resistant fabric. The EPDM heat insulation material is prepared by compounding the fiber fabric or the mica paper on the surface of the EPDM heat insulation material matrix and vulcanizing and compacting, and the obtained surface composite heat protection material is thin, has excellent heat insulation effect and mechanical property, and can be kept without burning through or burning for a long time under high-temperature flame.

Description

Surface-compounded thermal protection material and preparation method thereof
Technical Field
The invention belongs to the field of thermal protection composite materials, and particularly relates to a surface-compounded thermal protection material and a preparation method thereof.
Background
With the development of modern science and technology, various novel aerospace vehicles emerge endlessly, the heat insulation technology is listed as a key technology by developed countries such as Europe and America as the core of thermal protection engineering, and in recent years, heat insulation materials developed by developed countries of various military mainly comprise three types: fibrous thermal insulation materials, multilayer reflective thermal control materials and granular thermal insulation materials.
The fibrous thermal insulation material is prepared into the forms of fiber felt, fiber cloth, fiber and the like by using inorganic fibers or organic high-temperature resistant fibers by utilizing the characteristics of light weight, low heat conduction and high temperature resistance of the fibrous thermal insulation material, and then is compounded into the flexible thermal insulation material. The multilayer reflective thermal control material is made of multilayer reflective fibers and metal fragments scattered, and is widely applied to various satellites developed at home and abroad. The granular heat insulating material has hollow structure, low density and high heat conductivity, and may be used as heat insulating stuffing or prepared into porous heat insulating material through mixing hollow ceramic bead, ceramic microsphere and fiber, adhering and hot pressing.
A great deal of research and application has been conducted in various countries and regions with respect to these three main kinds of heat insulating materials. The flexible multi-layer composite material containing metal foil and foam heat insulation layer is developed in America, and the composite material is composed of at least one layer of surfactant, a microstructure surfactant, a filler and a binder; the second layer is composed of a metal component and also has a base fabric layer bonded to the first layer. The composite material is useful for preparing building materials and fabrics, the adhesive can be acrylic rubber, the filler can be silicon dioxide, the composite material has small blockage, good heat reflectivity, flame retardance and no weight loss, the disintegration of the material is reduced in open fire, the weight of the product is easily increased by calcium carbide and mica, the weight can be reduced and the fire resistance can be improved by glass fiber and ceramic microspheres, and the highest temperature born by the composite material is 1100 ℃. The base cloth can be made of any temperature-resistant reinforcing material, the strength of the composite material is improved, and the material has excellent thermal insulation and fireproof performance.
There are also known ceramic fillers which are produced by melting relatively low melting point inorganic materials (e.g. glass, silicates) at high temperature to form a solid network of carbon layers and other solid particles, similar to the sintering process of ceramics, and are therefore referred to as ceramic fillers. But tends to result in a decrease in the toughness of the insulation material.
Ethylene Propylene Diene Monomer (EPDM) has low density, high thermal decomposition temperature, good thermal-oxidative aging resistance, large filling coefficient and good compatibility with various propellants and shell composite materials, and is a common rubber of the prior ablation-resistant materials. However, when the EPDM heat insulation material is used in some fields, the rubber base material and the organic filler are likely to be cracked into small molecules at high temperature, the ablation resistance is limited, the use conditions of high temperature, high pressure and high-speed airflow cannot be met, and in order to meet the ablation resistance and the scouring resistance, inorganic filler, organic resin and the like are required to be added to increase the ablation resistance; the added inorganic filler, such as silica, is fused and then bonded with a carbon layer formed at high temperature, so that the formed carbon layer is not easy to peel off and fall off, and the ablation resistance of the EPDM heat insulation material is improved; the addition of polymer fibers improves the ablation resistance of the EPDM material, but the addition of fibers may result in a decrease in elongation at break, the occurrence of thermal strain due to the various temperature-alternating environments encountered by the engine during transportation and storage, and the lack of compatibility between the expansion coefficients of the housing and the thermal insulation layer, which requires the thermal insulation layer to have a sufficiently large elongation, due to the large difference between the expansion coefficients of the housing and the thermal insulation layer.
CN107915906A, CN104448576A, CN102120849A, CN112225998A, CN112397829A, CN112225998A, CN111409208A each disclose some EPDM based insulation materials. However, the comprehensive performance is not ideal enough, the mechanical property cannot meet the requirement, or the heat insulation performance cannot meet the requirement, particularly in the field of heat insulation in a specific space, the thickness of the heat insulation material is required, and the thickness of the heat insulation layer needs to be increased to meet the required heat insulation performance at high temperature for most EPDM heat insulation materials, so that the application of the materials is limited. In addition, although the ethylene propylene diene monomer matrix is added with the flame retardant, the addition amount of the flame retardant cannot be too large in consideration of the mechanical property. Therefore, under high-temperature flame, the surface of the ethylene propylene diene monomer rubber-based heat-insulating material can be ignited and burnt, and if the burning temperature is too high, the flame can further spread to the whole surface of the material, so that the heat insulation of the material is failed.
Disclosure of Invention
In order to solve the problems that the EPDM thermal insulation material in the prior art is possibly subjected to thermal insulation failure under high-temperature flame, even burns through and burns, the thickness of the EPDM thermal insulation material needs to be increased to increase the thermal insulation performance of the EPDM thermal insulation material, so that the application of the EPDM thermal insulation material in certain fields is limited. According to the invention, the surface of the EPDM material is adhered with the protective layer which is high temperature resistant and not easy to burn, so that the material is not directly contacted with flame, and the surface of the material can be effectively prevented from being heated and ignited.
The invention provides a surface-compounded thermal protection material which is of a sandwich structure, wherein a middle layer is a thermal insulation material base body, and protective layers are covered on the upper surface and the lower surface of the thermal insulation material base body; the heat-insulating material matrix comprises the following raw materials: ethylene propylene diene monomer, fiber, a heat insulating agent, polymer resin and a composite flame retardant, wherein the protective layer is high-temperature-resistant mica paper or high-temperature-resistant fabric.
The thickness of the heat insulation material matrix is 2-10mm, and the thickness of the protective layer is 0.1-0.5 mm; preferably, the thickness of the heat insulation material matrix is 3-5mm, and the thickness of the protective layer is 0.15-0.3 mm.
The heat insulating agent comprises at least one of silica aerogel and mercapto-modified glass beads. Preferably a mixture of silica aerogel and mercapto-modified glass microspheres. The silica aerogel and the sulfydryl modified glass beads can play a synergistic role, and simultaneously, the mechanical property, the heat insulation property and the burning resistance of the thermal protection material are optimized. More preferably, the mass ratio of the silica aerogel to the mercapto-modified glass microspheres is 1-2: 1-2; the particle size of the sulfhydryl modified glass bead is 50-100 μm.
The mercapto-modified glass bead is prepared by the following preparation method: the glass beads are firstly hydroxylated by alkali liquor and then treated by a silane coupling agent containing sulfhydryl groups.
Specifically, the preparation method of the sulfhydryl modified glass bead comprises the following steps: treating the glass beads with alkali liquor under the conditions of heating, refluxing and stirring, washing the glass beads to be neutral, and drying the glass beads to obtain glass beads with surface hydroxylation treatment; and then adding a silane coupling agent containing sulfydryl into the alcohol-water mixed solution, reacting under the heating and stirring conditions, washing with alcohol, and drying to obtain the sulfydryl modified glass beads. Further, the alkali liquor is 0.2-0.5M alkaline solution of sodium hydroxide and/or potassium hydroxide, and the heating and stirring are carried out at 70-100 ℃ and the stirring speed is 200-500 rpm; the proportion of glass beads, alkali liquor and silane coupling agent containing sulfydryl is 5-10 g: 30-60 mL: 0.5 to 1; the alcohol-water solution is a mixed solvent of alcohol and water according to a ratio of 3-5:1, and the alcohol in the alcohol-water solution and the alcohol cleaning is methanol and/or ethanol.
The mercapto silane coupling agent is at least one selected from KH-590, KH591, KH-580, KH-581 and KH-582.
Further, the heat-insulating material matrix comprises the following raw materials in parts by mass: 100 parts of ethylene propylene diene monomer, 4-10 parts of fiber, 20-50 parts of heat insulating agent, 10-40 parts of polymer resin and 10-40 parts of composite flame retardant.
Further, the heat insulation material matrix comprises the following raw materials in parts by mass: 100 parts of ethylene propylene diene monomer, 5-8 parts of fiber, 20-30 parts of heat insulating agent, 20-30 parts of polymer resin and 20-30 parts of composite flame retardant.
The ethylene propylene diene monomer is blocky, and the ethylene monomer content of the ethylene propylene diene monomer is 45-50%.
The fiber comprises at least one of poly-p-phenylene benzobisoxazole fiber (PBO), polybenzimidazole fiber (PBI), aramid fiber, poly-p-phenylene terephthalamide fiber (PAN), polyacrylonitrile fiber (PAN) and polyphenylene sulfide fiber (PPS). Preferably, the fibers are poly (p-Phenylene Benzobisoxazole) (PBO) fibers and polyphenylene sulfide (PPS) fibers according to a mass ratio of 2-3: 1, compounding.
The poly-p-Phenylene Benzobisoxazole (PBO) belongs to polyaryl heterocyclic fibers, has excellent physical and mechanical properties, high exercise strength and tensile modulus and high heat-resistant and flame-retardant properties, but when the PBO is used as a composite material, a PBO rigid molecular main chain forms a high-oriented ordered structure, is beneficial to thermal stability, and has poor compatibility with EPDM. Compounding PBO fiber and PPS fiber according to a certain mass ratio,
the polymer resin is at least one of boron phenolic resin, molybdenum phenolic resin, terpene resin and organic silicon resin.
The composite flame retardant is a phosphorus flame retardant, and the silicon flame retardant and the nitrogen flame retardant are compounded according to the mass ratio of 3-8: 1-2: 1-2. The phosphorus flame retardant is selected from at least one of diethyl aluminum hypophosphite (ADP) and ammonium polyphosphate, the silicon flame retardant is selected from at least one of cage octaphenyl silsesquioxane (OPS) and polyphenyl silsesquioxane, and the nitrogen flame retardant is selected from at least one of Melamine Cyanurate (MCA), melamine and melamine phosphate.
Preferably, the composite flame retardant is ADP, OPS and MCA according to the mass ratio of 3-5: 1-2: 1-2.
More preferably, nylon 6 is also added into the composite flame retardant, and the nylon 6 accounts for 5-15wt% of the composite flame retardant.
Optionally, the heat insulating material matrix of the present invention further comprises other auxiliary materials, such as plasticizers, activators, accelerators, vulcanizing agents, crosslinking agents, and the like. The plasticizer comprises liquid paraffin; the activating agent comprises nano zinc oxide and/or stearic acid; the accelerator comprises N-cyclohexyl-2-benzothiazole sulfonamide and/or diphenyl guanidine; the vulcanizer comprises bis (tert-butylperoxyisopropyl) benzene (BIPB).
Preferably, the protective layer is high-temperature-resistant mica paper or high-temperature-resistant fabric, and the high-temperature-resistant fabric comprises poly-p-phenylene benzobisoxazole fabric, polybenzimidazole fabric and aramid fabric.
More preferably, the high temperature resistant mica paper or the high temperature resistant fabric is subjected to surface sulfhydrylation treatment.
The surface sulfydryl treatment of the high-temperature resistant mica paper or the high-temperature resistant fabric is to wash the high-temperature resistant mica paper or the high-temperature resistant fabric to remove impurities on the surface, dry the high-temperature resistant mica paper or the high-temperature resistant fabric, then soak the high-temperature resistant mica paper or the high-temperature resistant fabric in an alcohol-water solution containing a sulfydryl silane coupling agent, take out the high-temperature resistant mica paper or the high-temperature resistant fabric after full reaction, dry the high-temperature resistant mica paper or the high-temperature resistant fabric to obtain the surface sulfydryl modified high-temperature resistant mica paper/fabric after washing and drying.
Further, the cleaning is to soak in an alcohol aqueous solution for 1-2h, then ultrasonically clean for 10-30min, and clean the used alcohol aqueous solution and an alcohol aqueous solution of a silane coupling agent containing a mercapto group, wherein the volume ratio of alcohol to water is 1: 1-3, wherein the alcohol is at least one of methanol, ethanol and isopropanol; the dipping time in the alcohol-water solution of the silane coupling agent containing the sulfydryl is 5-10 h.
The invention also provides a preparation method of the surface composite thermal protection material, which comprises the following steps:
s1, weighing ethylene propylene diene monomer, fiber, a heat insulating agent, polymer resin and a composite flame retardant, and mixing to obtain a heat insulating material matrix;
s2, preparing the heat insulation material substrate into a certain size, adhering a protective layer on each of the two surfaces of the substrate, placing the substrate in a mould, standing and vulcanizing to obtain the surface composite thermal protection material.
Further, in step S1, mixing is performed in a two-roll mixer at a mixing temperature of 15 to 30 ℃, a two-roll ratio of 3 to 5:1, adjusting the distance between two rollers within 0.1-3 mm; in the step S2, the standing time is 5-15h, the vulcanization temperature is 150-170 ℃, the pressure is 10-20MPa, and the vulcanization time is 20-30 mi. The vulcanization is carried out under a press vulcanizer.
The invention has the beneficial technical effects that:
the invention provides a surface-compounded thermal protection material and a preparation method thereof, the composite material is prepared by taking ethylene propylene diene monomer rubber, a compound flame retardant, silica aerogel and surface mercapto-modified glass beads as a heat insulating agent, taking polymer resin as a raw material to prepare a heat insulating material matrix, compounding fiber fabric or mica paper on the surface of the heat insulating material matrix, and vulcanizing and compacting, and the obtained surface-compounded thermal protection material has excellent heat insulating effect and mechanical property.
Drawings
FIG. 1 is a pictorial view of a flame combustion high temperature test system.
FIG. 2 is a schematic view of a flame combustion high temperature testing system.
FIG. 3 is an SEM photograph of mercapto-modified glass beads obtained in preparation example 1.
FIG. 4 shows the front and back side ablation of the material after the thermal insulation test of example 1.
FIG. 5 shows the front and back side ablation of the material after the thermal insulation test of example 12.
Detailed Description
The invention provides a surface-compounded thermal protection material and a preparation method thereof, and the invention is further explained in detail by combining the drawings and specific embodiments.
Ethylene Propylene Diene Monomer (EPDM) was purchased from Nippon Sumitomo and was model 505A. The boron phenolic resin is purchased from Tianyu high-temperature resin materials Limited of Anhui, and is named as FB high-temperature resistant resin. Glass beads were purchased from 3M company under model number S32. The compressive strength was 13.78MPa, the density was 0.32g/cc, and the average particle diameter was 75 μm. The main component is Si; the silica aerogel is purchased from Doudu Elizable science and technology Limited company, has heat conductivity coefficient of 0.013, hydrophobicity and loose packing density of 40-80kg/m3Specific surface area of 532m2/g。
The high-temperature resistant mica paper is purchased from E-commerce, the model is HB-YMP, the thickness is 0.3mm, and the high-temperature resistant aramid fabric is purchased from Dalian Ling Tao Yuan science and technology development Limited company, the model is 308/2, and the thickness is 0.3 mm;
the performance of the prepared thermal protection material is tested, and the method specifically comprises the following steps:
the EPDM heat insulating material obtained by the invention is subjected to the following performance tests:
1. and (3) testing mechanical properties:the EPDM insulation materials prepared in the examples were tested for Tensile Strength (Tensile Strength) and Elongation at break (Elongation at break) according to the specific requirements of GB/T528-2009 using a Universal electronic testing machine CMT4104, MTS USA, with sample size of 100mm x 3mm, and cut into corresponding 2 model dumbbell test pieces with 2 model cutting knife, each group of test pieces is not less than 5, Tensile rate is set to 500mm/min, and testing environment temperature is 20 ℃.
2. And (3) testing the heat conductivity coefficient:and (3) carrying out a heat conductivity test on the thermal protection material prepared in the steps 1, 2 and 3 by using a German Nachi company NETZSCH LFA467 type laser flash method heat conductivity measuring instrument and taking GB/T22588-2008 as a test basis. The sample size was 25mm × 25mm × 3mm, and the test temperature was 25 ℃.
3. Testing the heat insulation performance:the back temperature test of the surface-compounded thermal protection material prepared by the invention is carried out at 800 ℃ by adopting a flame combustion high-temperature test system self-made by Beijing university of Phytology. The liquefied petroleum gas is used as an ignition source, flame is vertical to the front surface of a sample, the temperature of the flame is monitored in real time by 1 thermocouple in contact with the surface of the sample, and the temperature of the back surface is monitored in real time by 2 thermocouples in direct contact with the back surface of the sample; the temperature acquisition time interval is 1s, and the data is recorded by the test software. Experimental results were averaged from data collected from 2 thermocouples on the back of the sample. The sample size was 100mm × 100mm × 3 mm.
In the prior art, the heat insulation performance is basically tested by testing the heat conductivity coefficient and the line ablation rate, the actual heat insulation performance is rarely detected under specific high-temperature flame, the heat conductivity coefficient can reflect the heat insulation performance of the material in theory, but the specific implementation effect is different, and the actual heat insulation data of the material may be different from the heat conductivity according to the influence of the using environment, specific problems, air flow and other conditions. Specifically, in the temperature range of 500-.
Preparation example 1
Preparing the mercapto-modified glass beads:
(1) carrying out hydroxylation treatment on the surfaces of the hollow glass beads: putting 50g of hollow glass microspheres into a 2L three-neck flask, adding 500ml of sodium hydroxide solution with the concentration of 0.3mol/L, refluxing and stirring for 1.5h at 80 ℃, then cleaning with clear water until the pH value is 7, removing water by adopting reduced pressure filtration, and drying in an oven at 100 ℃ for 12h to obtain the hollow glass microspheres with hydroxylation treatment on the surfaces.
(2) Modifying the mercapto group of the hollow glass bead: placing 50g of hollow glass microspheres subjected to surface hydroxylation treatment in a 2L three-neck flask, and then mixing the hollow glass microspheres in a volume ratio of 1: 3 to the flask was added 500ml of a mixed solution of ethanol and water, 5g of silane coupling agent KH591 was added, and the mixture was magnetically stirred for 3 hours under a heating condition of 80 ℃. And after the reaction is finished, washing the microspheres with ethanol, performing vacuum filtration, and drying the hollow glass microspheres subjected to vacuum filtration in an oven at 100 ℃ for 12 hours to obtain the mercapto-modified glass microspheres 1, wherein an electron microscope photograph of the mercapto-modified glass microspheres is shown in FIG. 5.
Preparation example 2
The other conditions and operations were the same as in preparation example 1 except that the silane coupling agent KH591 was used in an amount of 2.5g in step (2), to give mercapto-modified glass microspheres 2.
Preparation example 3
The other conditions and operations were the same as in preparation example 1 except that the amount of the silane coupling agent KH591 in step (2) was 10g, to give mercapto-modified glass microspheres 3.
Preparation example 4
Taking 5g of high-temperature-resistant mica paper, and putting the paper into a container with the volume ratio of 100mL being 1: 3, slowly stirring and soaking the mixture in a deionized water solution for 1-2 hours, then cleaning the mixture by ultrasonic waves for 10mm, soaking the mixture in deionized water for 30min, and then drying the soaked mixture in an electric heating constant-temperature blast drying oven for 2 hours at the temperature of 90 ℃ to completely volatilize water.
Taking 10g of silane coupling agent KH591, adding 90ml of ethanol and water according to the volume ratio of 1: 1, and injecting the mica paper into a culture dish of 150mm, horizontally soaking the cleaned and dried mica paper in the culture dish of 150mm for 6 hours, slowly washing the soaked sample with deionized water for 2-3 times, and then drying the sample in an electric heating constant-temperature air blast drying oven at 90 ℃ for 2 hours to obtain the mica paper with the surface modified by sulfydryl.
Preparation example 5
The other conditions and operations are the same as those in preparation example 4, except that the high-temperature-resistant mica paper is replaced by the high-temperature-resistant aramid fabric, and finally the surface mercapto-modified high-temperature-resistant aramid fabric is obtained.
Example 1
S1, firstly plasticating 100g of ethylene propylene diene monomer on a double-roll mixing mill, adding 6g of PBO fiber, 2g of PPS fiber, feeding the mixture for 20 times, adding 15g of diethyl aluminum hypophosphite, 5g of cage octaphenyl silsesquioxane, 5g of melamine cyanurate and 3g of nylon 6 after the fibers are uniformly dispersed in the EPDM, plasticating for 20 times, adding 10g of the mercapto-modified glass microspheres 1, 10g of silicon dioxide aerogel, 20g of boron phenolic resin, 2g of BIPB and 0.5g of diphenylguanidine obtained in preparation example 1 after the fillers are uniformly dispersed, and feeding the mixture for 20 times to uniformly disperse the fillers to obtain the matrix. Wherein the mixing temperature of the double-roller mixing mill is 25 ℃, the speed ratio of the double rollers is 3: 1, the distance between the double rollers is adjusted within 0.1 mm-3 mm.
S2, adjusting the distance between two rollers, preparing the uniformly mixed substrate into 100mm multiplied by 3mm, adhering a layer of 100mm multiplied by 0.3mm modified aramid fabric obtained in the preparation example 5 on the surface of the substrate, placing the substrate in a mold with the same size, standing for 8 hours, and vulcanizing in a flat vulcanizing machine, wherein the vulcanizing temperature is controlled at 160 ℃, the pressure is set at 12MPa, and the vulcanizing time is 1680S, so that the surface composite thermal protection material is obtained.
Example 2
The other steps and conditions were the same as in example 1 except that in step S1, the amount of the mercapto-modified glass beads 1 was changed to 20g, and the amount of the silica aerogel was changed to 20 g.
Example 3
The other steps and conditions were the same as in example 1 except that in step S1, the amount of the mercapto-modified glass beads 1 was changed to 30g, and the amount of the silica aerogel was changed to 30 g.
Example 4
The other steps and conditions were the same as in example 3, except that in step S1, the amount of the mercapto-modified glass beads 1 was changed to 40g, and the amount of the silica aerogel was changed to 20 g.
Example 5
The other steps and conditions were the same as in example 1, except that in step S1, the amount of the mercapto-modified glass beads 1 was changed to 20g, and the amount of the silica aerogel was changed to 40 g.
Example 6
The other steps and conditions were the same as in example 3, except that in step S1, the mercapto-modified glass beads obtained in production example 1 were replaced with the same mass of mercapto-modified glass beads 2 obtained in production example 2.
Example 7
The other steps and conditions were the same as in example 3, except that in step S1, the mercapto-modified glass beads obtained in production example 1 were replaced with the same quality of mercapto-modified glass beads 3 obtained in production example 3.
Example 8
The other steps and conditions were the same as in example 3 except that in step S1, the fibers were 5.3g of PBO fibers and 2.7g of PPS fibers.
Example 9
The other steps and conditions were the same as in example 3 except that in step S1, the fiber was 8g of PBO fiber.
Example 10
The other steps and conditions were the same as in example 3 except that in step S1, the fiber was 8g of PPS fiber.
Example 11
The other steps and conditions were the same as in example 3 except that in step S1, the fibers were 6g of PBI fibers and 2g of PPS fibers.
Example 12
The other steps and conditions were the same as in example 3 except that in step S2, the 100mm × 100mm × 0.3mm modified aramid fabric was replaced with the modified high temperature resistant insulating mica paper obtained in preparation example 6 in the same size.
Example 13
The other steps and conditions were the same as in example 3, except that in step S2, the aramid fabric used was not surface-mercapto-modified, and a commercially available high-temperature resistant aramid fabric was used as it is.
Example 14
The present embodiment is different from embodiment 1 in that, in step S1, the silica aerogel is replaced with equal mass of the specific surface area of 230m2The same as in example 1 except for the same white carbon black/g.
Example 15
This example is different from example 1 in that, in step S1, the glass beads were not surface-modified with mercapto groups, and commercially available glass beads were used as they are.
Example 16
The present example is different from example 1 in that, in step S1, the mercapto-modified glass beads 1 were not added, and the amount of silica aerogel used was 20 g.
Example 17
The present example is different from example 1 in that, in step S1, no silica aerogel is added, and the amount of the mercapto-modified glass beads 1 is 20 g.
Comparative example 1
This comparative example is different from example 1 in that the mechanical and thermal insulation performance of the thermal insulation material substrate obtained in step S2 was tested without compounding in step S2.
Application example
The following performance tests were performed on the surface-compounded thermal protection material obtained in the present invention, and the results are shown in table 1 below:
TABLE 1
Figure BDA0003088355800000111
Figure BDA0003088355800000121
Note: in which example 16 and comparative example 1 burned through before the stable back temperature was reached, and thus a stable back temperature could not be obtained.
As can be found from Table 1, the mechanical property and burning resistance of the thermal protection material are greatly improved by the surface composite thermal protection material with the sandwich structure obtained after the thermal insulation material matrix based on the EPDM is bonded and protected by adopting the high-temperature-resistant mica paper or the high-temperature-resistant fabric. Although the heat conductivity coefficient of the high-temperature resistant aramid fiber fabric is relatively large. However, in terms of actual heat insulation and burning resistance, after the surface of the heat insulation material matrix is protected by the aramid fiber fabric, the heat insulation effect and the burning resistance are better in the actual high-temperature flame of 800 ℃.
The high-temperature-resistant fabric is more preferably used for protecting, such as the high-temperature-resistant aramid fabric, and compared with high-temperature-resistant mica paper as a protective layer substance, the high-temperature-resistant fabric can remarkably improve the mechanical property and the actual heat insulation effect of the heat insulation material.

Claims (13)

1. A surface composite thermal protection material is of a sandwich structure, an intermediate layer is a heat insulation material matrix, and protective layers are covered on the upper surface and the lower surface of the heat insulation material matrix; the heat-insulating material matrix comprises the following raw materials: 100 parts of ethylene propylene diene monomer, 4-10 parts of fiber, 20-50 parts of heat insulating agent, 10-40 parts of polymer resin and 10-40 parts of composite flame retardant, wherein the protective layer is high-temperature-resistant mica paper or high-temperature-resistant fabric;
the heat insulating agent comprises a mixture of silicon dioxide aerogel and sulfydryl modified glass beads, and the particle size of the sulfydryl modified glass beads is 50-100 mu m; the mass ratio of the silica aerogel to the mercapto-modified glass beads is 1-2: 1-2;
the mercapto-modified glass bead is prepared by the following preparation method: hydroxylating glass beads by using alkali liquor, and then treating the glass beads by using a silane coupling agent containing sulfydryl;
the thickness of the heat insulation material matrix is 2-10mm, and the thickness of the protective layer is 0.1-0.5 mm.
2. The surface-compounded thermal protective material of claim 1, wherein the thickness of the thermal insulating material base is 3-5mm and the thickness of the protective layer is 0.15-0.3 mm.
3. The surface-compounded thermal protective material according to claim 1, wherein the preparation method of the mercapto-modified glass bead comprises the following steps: treating the glass beads with alkali liquor under the conditions of heating, refluxing and stirring, washing the glass beads to be neutral, and drying the glass beads to obtain glass beads with surface hydroxylation treatment; and then adding a silane coupling agent containing sulfydryl into the alcohol-water mixed solution, reacting under the heating and stirring conditions, washing with alcohol, and drying to obtain the sulfydryl modified glass beads.
4. The surface-compounded thermal protective material according to claim 3, wherein the ratio of the glass beads, the alkali solution and the mercapto silane coupling agent is 5-10 g: 30-60 mL: 0.5-1.
5. The surface-compounded thermal protective material of claim 4, wherein said mercapto-containing silane coupling agent is at least one member selected from the group consisting of KH-590, KH591, KH-580, KH-581, KH-582.
6. The surface-compounded thermal protective material according to claim 1, wherein the thermal insulating material matrix comprises the following raw materials in parts by mass: 100 parts of ethylene propylene diene monomer, 5-8 parts of fiber, 20-30 parts of heat insulating agent, 20-30 parts of polymer resin and 20-30 parts of composite flame retardant.
7. The surface-compounded thermal protective material of claim 1, wherein the fibers comprise at least one of poly-p-Phenylene Benzobisoxazole (PBO), Polybenzimidazole (PBI), aramid, poly-p-phenylene terephthalamide (PAN), Polyacrylonitrile (PAN), polyphenylene sulfide (PPS).
8. The surface-compounded thermal protective material according to claim 7, wherein the fibers are poly-p-phenylene benzobisoxazole fibers (PBO) and polyphenylene sulfide fibers (PPS) in a mass ratio of 2-3: 1, compounding.
9. The surface-compounded thermal protective material according to claim 1, wherein the ethylene propylene diene monomer is in a block shape, and the ethylene monomer content is 45-50%; and/or
The polymer resin is selected from at least one of boron phenolic resin, molybdenum phenolic resin, terpene resin and organic silicon resin; and/or
The composite flame retardant is a phosphorus flame retardant, and the silicon flame retardant and the nitrogen flame retardant are compounded according to the mass ratio of 3-8: 1-2: 1-2; the phosphorus flame retardant is selected from at least one of diethyl aluminum hypophosphite (ADP) and ammonium polyphosphate, the silicon flame retardant is selected from at least one of cage octaphenyl silsesquioxane (OPS) and polyphenyl silsesquioxane, and the nitrogen flame retardant is selected from at least one of Melamine Cyanurate (MCA), melamine and melamine phosphate; and/or
The high-temperature-resistant fabric comprises a poly (p-phenylene benzobisoxazole) fabric, a polybenzimidazole fabric and an aramid fabric.
10. The surface-compounded thermal protective material of claim 9, wherein nylon 6 is further added to the compounded flame retardant, and the nylon 6 accounts for 5-15wt% of the compounded flame retardant.
11. The surface-compounded thermal protective material of claim 1, wherein the high temperature resistant mica paper or high temperature resistant fabric is surface-sulfhydrylated.
12. The surface-compounded thermal protection material of claim 11, wherein the surface mercapto treatment of the high temperature resistant mica paper or the high temperature resistant fabric is to wash the high temperature resistant mica paper or the high temperature resistant fabric to remove surface impurities, dry the mica paper or the high temperature resistant fabric, then soak the mica paper or the high temperature resistant fabric in an alcohol-water solution containing a mercapto silane coupling agent, take out the mica paper or the high temperature resistant fabric after sufficient reaction, dry the mica paper or the high temperature resistant fabric after sufficient reaction, wash the mica paper or the high temperature resistant fabric with surface mercapto modification, and dry the mica paper or the high temperature resistant fabric with surface mercapto modification.
13. A method of preparing the surface-compounded thermal protective material of any one of claims 1 to 12, comprising the steps of:
s1, weighing ethylene propylene diene monomer, fiber, a heat insulating agent, polymer resin and a composite flame retardant, and mixing to obtain a heat insulating material matrix;
s2, preparing the heat insulation material substrate into a certain size, adhering a protective layer on each of the two surfaces of the substrate, standing in a mold for vulcanization to obtain the surface composite heat protection material.
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