Heat-insulating composite material, its preparation method and application

Abstract

The present invention discloses a heat-insulating composite material, its preparation method and application, relating to the field of phenolic resin-based composite materials. First, a modified phenolic resin composition for the heat-insulating composite material is provided, which includes phenolic resin, curing agent, phenolic modifier, coupling agent and organic solvent. Then, the fiber cloth is impregnated with the modified phenolic resin composition to obtain a prepreg, and the prepreg is laid and subjected to hot pressing and curing treatment with gradient temperature rise to obtain the heat-insulating composite material. This composite material has a small density, combines mechanical properties and high heat flux ablation resistance, and has reusable performance, and is suitable for application in a thermal protection system, especially for the thermal protection of the bottom of the large bottom of a reentry carrier rocket.

Description

Technical Field

[0001] The present invention relates to the field of phenolic resin-based composite materials, and specifically to a heat-insulating and heat-protecting composite material, its preparation method and application. Background Art

[0002] In the fields of modern science and technology and industry, higher and higher requirements are placed on the performance of materials. Especially in some specific application scenarios, such as the aerospace field, during the process of a spacecraft entering the atmosphere, the surface of the spacecraft will withstand extremely high temperatures and heat fluxes. Therefore, a material with heat-insulating and heat-protecting properties is needed to effectively block the heat flux transfer and protect the internal structure and equipment of the spacecraft.

[0003] In traditional spacecraft, phenolic resin-based composite materials are usually used as ablative materials. When the ablative material withstands high temperatures, an ablative reaction will occur, forming a heat-insulating carbonized layer to protect the internal structure of the aircraft. With the improvement of the scientific and technological level and the increasing demand for space exploration, the development of the aerospace field faces new opportunities and challenges. The use cost of disposable launch vehicles is extremely high, and reusable launch vehicles are the key means to reduce space transportation costs and an effective way to enhance the space rapid response ability. Their ultimate goal is to recover expensive rocket bodies, engines, and electrical equipment, representing the highest level in the current aerospace science and technology field.

[0004] The bottom structure of the rocket body tail and the side wall structure of the tail cabin during the flight of the launch vehicle are the key parts for heat protection of the launch vehicle. If specific materials are not used for heat protection, the structural metal materials will completely lose their load-bearing capacity in the thermal vibration environment, not only unable to be recovered, but also leading to catastrophic consequences. Currently, the most common launch vehicles use glass fiber / phenolic resin (fiberglass) laminates as hard structures (heat protection plates). However, the erosion heat flux at the bottom of the large bottom of the new reusable reentry launch vehicle has increased by an order of magnitude compared with that of the current launch vehicles. The heat protection performance of the currently used ablative materials cannot meet the usage requirements, such as the back temperature not exceeding 100°C, the unablated and carbonized thickness exceeding 3 mm, and the mechanical properties of light weight and high strength. Therefore, it is urgent to develop a new type of ablative heat-insulating and heat-protecting composite material to solve the problem that the heat protection ability of the ablative materials at the bottom of the current launch vehicles cannot meet the heat protection requirements of the new reusable rockets. Summary of the Invention

[0005] In view of this, the purpose of the present invention is to provide a heat-insulating and heat-protecting composite material, its preparation method and application.

[0006] The purpose of the present invention is achieved through the following technical solutions:

[0007] <First Aspect>

[0008] The present invention provides a preparation method of a heat-insulating and heat-protecting composite material, comprising the following steps:

[0009] S1. Uniformly impregnate the modified phenolic resin composition into the fiber cloth, and remove the solvent to obtain a prepreg. The modified phenolic resin composition is a mixture of liquid phenolic resin, curing agent, phenolic modifier, coupling agent and organic solvent;

[0010] S2. Lay and stack the prepreg, and after hot pressing and curing treatment, cool down and release the pressure to obtain the heat and insulation composite material.

[0011] As an embodiment, the mass ratio of the modified phenolic resin composition to the fiber cloth is (170 - 200) : (80 - 100).

[0012] As an embodiment, the modified phenolic resin composition is uniformly impregnated into the fiber cloth by using a flow injection impregnation method.

[0013] As an embodiment, the parameters of the flow injection impregnation method are: pressure 1 - 2 MPa, temperature 20 - 30 °C, and flow rate 15 - 25 mL / min.

[0014] In some embodiments, the parameters of the flow injection impregnation method are: pressure 1 MPa, temperature 25 °C, and flow rate 20 mL / min.

[0015] As an embodiment, the fiber cloth does not contain inorganic fillers.

[0016] As an embodiment, the fiber cloth is a fiber cloth woven from one or more of high silica fiber, quartz fiber, and glass fiber.

[0017] As an embodiment, the high silica fiber cloth is selected.

[0018] As an embodiment, the single-layer thickness of the high silica fiber cloth is 0.24 - 0.28 mm, and the unit area mass is 230 - 250 g / m 2 .

[0019] In some embodiments, the single-layer thickness of the high silica fiber cloth is 0.26 mm, and the unit area mass is 240 g / m 2 .

[0020] As an embodiment, the prepreg is alternately laid in a 0° / 90° manner.

[0021] As an embodiment, the hot pressing and curing treatment is carried out by heating in a gradient temperature rising manner.

[0022] As an embodiment, the parameters of the hot pressing and curing treatment are as follows: the pressure is 2 - 6 MPa, the temperature is raised to 140 - 170 °C by gradient heating, and the heat preservation time is 4 - 8 h.

[0023] In some embodiments, in the hot pressing and curing treatment, the pressure is 5 MPa.

[0024] As an embodiment, the method of gradient heating is as follows: first, the temperature is raised to 60 - 100 °C and kept warm for 2 - 6 h, then the temperature is raised to 110 - 130 °C and kept warm for 2 - 6 h, and then the temperature is raised to 140 - 170 °C and kept warm for 4 - 8 h.

[0025] As an embodiment, the method of gradient heating is as follows: first, the temperature is raised to 60 - 100 °C and kept warm for 4 - 5 h, then the temperature is raised to 110 - 130 °C and kept warm for 4 - 5 h, and then the temperature is raised to 140 - 170 °C and kept warm for 4 - 6 h.

[0026] In some embodiments, the method of gradient heating is as follows: first, the temperature is raised to 60 °C and kept warm for 5 h, then the temperature is raised to 110 °C and kept warm for 5 h, and then the temperature is raised to 140 °C and kept warm for 5 h.

[0027] As an embodiment, in S2, the cooling is carried out by furnace cooling.

[0028] As an embodiment, in S2, the pressure relief is carried out after the temperature is reduced to below 70 °C.

[0029] In some embodiments, in S2, the pressure relief is carried out after the temperature is reduced to 60 °C.

[0030] As an embodiment, in S1, the solvent is removed by air drying.

[0031] In some embodiments, in S1, the solvent is removed by air drying at room temperature, and the drying time is 24 - 48 h.

[0032] <Second aspect>

[0033] The present invention provides a modified phenolic resin composition for heat - insulating and heat - shielding composite materials, which is as follows by mass parts:

[0034] Liquid phenolic resin: 80 - 100 parts;

[0035] Curing agent: 10 - 20 parts;

[0036] Phenolic modifier: 1 - 20 parts;

[0037] Coupling agent: 1 - 10 parts;

[0038] Organic solvent: 50 - 80 parts.

[0039] As an embodiment, the liquid phenolic resin is liquid boron-modified phenolic resin.

[0040] As an embodiment, the curing agent is selected from one or more of hexamethylenetetramine, triethylenetetramine, and 4,4-diphenylsulfonediamine.

[0041] In some embodiments, the curing agent is hexamethylenetetramine.

[0042] As an embodiment, the phenolic modifier is selected from one or more of methyltrimethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane.

[0043] In some embodiments, the phenolic modifier is methyltrimethoxysilane.

[0044] As an embodiment, the coupling agent is selected from one or more of KH550 coupling agent, KH560 coupling agent, and KH570 coupling agent.

[0045] In some embodiments, the coupling agent is KH550 coupling agent.

[0046] As an embodiment, the organic solvent is selected from anhydrous ethanol and / or acetic acid.

[0047] In some embodiments, the organic solvent is anhydrous ethanol.

[0048] In some embodiments, the organic solvent is acetic acid.

[0049] As an embodiment, the modified phenolic resin composition is mixed uniformly by stirring.

[0050] As an embodiment, the stirring parameter of the modified phenolic resin composition is 200-400 r / min.

[0051] In some embodiments, the modified phenolic resin composition is stirred at a speed of 300 r / min.

[0052] As an embodiment, the modified phenolic resin composition is mixed uniformly at 20-80°C.

[0053] In some embodiments, the modified phenolic resin composition is mixed at 20°C until uniformly mixed.

[0054] As an embodiment, the modified phenolic resin composition comprises the following components in parts by mass:

[0055] Liquid phenolic resin: 80~100 parts;

[0056] Hexamethylenetetramine: 10-20 parts;

[0057] Methyltrimethoxysilane: 1-20 parts;

[0058] KH550: 1 to 10 servings;

[0059] Anhydrous ethanol: 50~80 parts.

[0060] In some embodiments, the modified phenolic resin composition comprises, in parts by mass:

[0061] Liquid phenolic resin: 80~100 parts;

[0062] Hexamethylenetetramine: 10 parts;

[0063] Methyltrimethoxysilane: 2-10 parts;

[0064] KH550: 1 to 10 servings;

[0065] Anhydrous ethanol: 60~80 parts.

[0066] Compared with the prior art, the present invention has the following beneficial effects:

[0067] The present invention provides a modified phenolic resin composition for heat-insulating composite materials. First, the resin matrix in the composition is a liquid boron-modified phenolic resin. Compared with a powdered phenolic resin matrix, the resin matrix has better bonding performance with fibers, and the overall performance of the prepared heat-insulating composite material is better. Second, the composition uses organic silane as a phenolic modifier to further improve the heat resistance and ablation resistance of the phenolic resin, thereby obtaining a modified phenolic resin with a cross-linked network and having good thermal stability at high temperatures. Third, the present invention does not use inorganic fillers, but instead uses silane to introduce silicon elements to improve the ablation performance. At the same time, silane can be better mixed and dispersed evenly with the phenolic resin, is low in price, and is better than inorganic fillers.

[0068] The present invention provides a method for preparing a heat-insulating composite material, in which a fiber braid is obtained by weaving a high-strength fiber material, and a modified phenolic resin is impregnated on the surface of the fiber braid to improve the interface bonding performance between the resin and the fiber. The preparation is carried out through a gradient temperature curing step. The prepared heat-insulating composite material has good mechanical properties and excellent ablation resistance, effectively solving the problem that the currently used heat-insulating materials cannot withstand large heat flow ablation and multiple ablation.

[0069] The present invention provides an application of the above-mentioned heat-insulating composite material, which is applied to spacecraft thermal protection, engine components, etc. in the aerospace field, and is particularly suitable for application in thermal protection of the bottom of a recoverable carrier rocket. DETAILED DESCRIPTION

[0070] The present invention will be described in detail below in conjunction with embodiments. The following embodiments will help those skilled in the art to further understand the present invention, but do not limit the present invention in any form. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several adjustments and improvements can still be made. These all fall within the protection scope of the present invention.

[0071] This specific embodiment provides a heat-insulating and heat-protecting composite material, a preparation method thereof, a use thereof, and a prepreg composition for this preparation method.

[0072] A preparation method of a heat-insulating and heat-protecting composite material includes the following steps:

[0073] S1. Prepare the prepreg

[0074] Mix phenolic resin, curing agent, phenolic modifier, coupling agent and organic solvent, and stir evenly to obtain a modified phenolic resin solution (hereinafter referred to as prepreg);

[0075] S2. Impregnate the fiber cloth and cure and crosslink

[0076] S21. Impregnate the fiber cloth: Evenly impregnate the prepreg into the fiber cloth, dry it, and remove most of the solvent to obtain a prepreg;

[0077] S22. Cure and crosslink: After laying the prepreg to a certain thickness, cure it by a hot pressing and curing process, release the pressure after cooling in the furnace, and demold to obtain a heat-insulating and heat-protecting composite material that can resist high heat flux ablation and be reused.

[0078] The preparation method of the above heat-insulating and heat-protecting composite material will be specifically introduced below through three embodiments.

[0079] Embodiment 1

[0080] In S1, the formula of the prepreg composition is as follows:

[0081] The phenolic resin selects a liquid boron-modified phenolic resin, and the dosage is 100 parts (parts by mass, and the following dosages, unless otherwise specified, all represent parts by mass);

[0082] The curing agent selects hexamethylenetetramine, and the dosage is 10 parts;

[0083] The phenolic modifier selects methyltrimethoxysilane, and the dosage is 10 parts;

[0084] The coupling agent selects KH550 coupling agent, and the dosage is 5 parts; [[ID=4 3]]

[0085] The organic solvent selects anhydrous ethanol, and the dosage is 60 parts.

[0086] In this embodiment, in S1, the parameters for uniform stirring are: stirring at 20 °C and 300 rpm for 20 min.

[0087] In S2, the prepreg solution is uniformly impregnated into the fiber cloth. After impregnation, the fiber cloth is dried in air and most of the solvent is removed to obtain the prepreg. The impregnation method is: the flow injection impregnation process. Using an RTM injection machine, the pressure is 1 MPa, the temperature is 25 °C, and the flow rate is 20 mL / min. After the prepreg solution is uniformly impregnated into the fiber cloth, the solvent is removed by drying at room temperature for 24 h.

[0088] In this embodiment, the fiber cloth selected is a high silica fiber cloth with a unit area mass of 240 g / m 2 and a thickness of 0.26 mm, and the dosage is 80 parts.

[0089] In this embodiment, most of the solvent is removed by air drying at room temperature.

[0090] In S2, the prepreg is alternately laminated in the 0° / 90° manner to obtain the impregnated fiber cloth layer.

[0091] In S2, the hot pressing and curing process is as follows: under a pressure of 5 MPa, first heat up to 60 °C at a heating rate of 5 °C / min, hold at 60 °C for 5 h, then heat up to 110 °C at a heating rate of 5 °C / min, hold at 110 °C for 5 h, then heat up to 140 °C at a heating rate of 5 °C / min, hold at 140 °C for 5 h. Finally, after curing is completed, slowly cool the furnace to 60 °C and then release the pressure to demold and obtain the thermal insulation and heat protection composite material with a thickness of 15 mm.

[0092] Example 2

[0093] In S1, the formula of each composition in the prepreg solution is as follows:

[0094] The phenolic resin selected is a liquid boron-modified phenolic resin, and the dosage is 100 parts;

[0095] The curing agent selected is hexamethylenetetramine, and the dosage is 10 parts;

[0096] The phenolic modifier selected is methyltrimethoxysilane, and the dosage is 2 parts;

[0097] The coupling agent selected is KH550 coupling agent, and the dosage is 1 part;

[0098] The organic solvent selected is anhydrous ethanol, and the dosage is 80 parts.

[0099] In this embodiment, in S1, the parameters for uniform stirring are: stirring at 20 °C and 300 rpm for 20 min.

[0100] In S2, the prepreg solution is evenly impregnated into the fiber cloth. After impregnation, the fiber cloth is air-dried to remove most of the solvent, obtaining a prepreg. The impregnation method is: the flow injection impregnation process, using an RTM injection machine, with a pressure of 1 MPa, a temperature of 25 °C, and a flow rate of 20 mL / min. After the prepreg solution is evenly impregnated into the fiber cloth, the solvent is removed by room temperature drying for 24 h.

[0101] In this embodiment, the fiber cloth selected is a high silica fiber cloth with a unit area mass of 240 g / m 2 , a thickness of 0.26 mm, and a dosage of 100 parts.

[0102] In this embodiment, most of the solvent is removed by air-drying at room temperature.

[0103] In S2, the prepregs are alternately laminated in a 0° / 90° manner to obtain an impregnated fiber cloth layer.

[0104] In S2, the hot pressing and curing process is as follows: under a pressure of 5 MPa, first heat up to 60 °C at a heating rate of 5 °C / min, hold at 60 °C for 5 h, then heat up to 110 °C at a heating rate of 5 °C / min, hold at 110 °C for 5 h, then heat up to 140 °C at a heating rate of 5 °C / min, hold at 140 °C for 5 h. Finally, after curing, slowly cool in the furnace to 60 °C and then remove the pressure to demold and obtain a heat-insulating and heat-resistant composite material with a thickness of 15 mm.

[0105] Example 3

[0106] In S1, the formulations of the respective compositions in the prepreg solution are as follows:

[0107] The phenolic resin selected is a liquid boron-modified phenolic resin, with a dosage of 80 parts;

[0108] The curing agent selected is hexamethylenetetramine, with a dosage of 10 parts;

[0109] The phenolic modifier selected is methyltrimethoxysilane, with a dosage of 5 parts;

[0110] The coupling agent selected is KH550 coupling agent, with a dosage of 10 parts;

[0111] The organic solvent selected is anhydrous ethanol, with a dosage of 70 parts.

[0112] In this embodiment, in S1, the parameters for uniform stirring are: stirring at 20 °C and 300 rpm for 20 min.

[0113] In S2, the prepreg solution is uniformly impregnated into the high silica fiber, and the impregnated fiber cloth is dried in air and most of the solvent is removed to obtain the prepreg. The impregnation method is: the flow injection impregnation process, using an RTM injection machine, with a pressure of 1 MPa, a temperature of 25 °C, and a flow rate of 20 mL / min. After the prepreg solution is uniformly impregnated into the fiber cloth, the solvent is removed by drying at room temperature for 24 h.

[0114] In this example, the fiber cloth selected is a high silica fiber cloth with a unit area mass of 240 g / m 2 and a thickness of 0.26 mm, and the dosage is 100 parts.

[0115] In this example, most of the solvent is removed by drying at room temperature.

[0116] In S2, the prepregs are alternately laminated in a 0° / 90° manner to obtain an impregnated fiber cloth layer.

[0117] In S2, the hot pressing and curing process is as follows: under a pressure of 5 MPa, first heat up to 60 °C at a heating rate of 5 °C / min, hold for 5 h at 60 °C, then heat up to 110 °C at a heating rate of 5 °C / min, hold for 5 h at 110 °C, then heat up to 140 °C at a heating rate of 5 °C / min, hold for 5 h at 140 °C, and finally, after curing, slowly cool in the furnace to 60 °C and then release the pressure to demold and obtain a heat-insulating and heat-resistant composite material with a thickness of 15 mm.

[0118] Example 4

[0119] In S1, the formulation of the prepreg solution is as follows:

[0120] The phenolic resin selected is a liquid boron-modified phenolic resin, and the dosage is 100 parts;

[0121] The curing agent selected is hexamethylenetetramine, and the dosage is 10 parts;

[0122] The phenolic modifier selected is methyltrimethoxysilane, and the dosage is 10 parts;

[0123] The coupling agent selected is KH550 coupling agent, and the dosage is 5 parts;

[0124] The organic solvent selected is acetic acid, and the dosage is 60 parts.

[0125] In this example, in S1, the parameters for uniform stirring are: stirring at 20 °C and 300 rpm for 20 min.

[0126] In S2, the prepreg solution is evenly impregnated into the fiber cloth. The impregnated fiber cloth is air-dried and most of the solvent is removed to obtain the prepreg. The impregnation method is: the flow injection impregnation process, using an RTM injection machine, with a pressure of 1 MPa, a temperature of 25 °C, and a flow rate of 20 mL / min. After the prepreg solution is evenly impregnated into the fiber cloth, the solvent is removed by air-drying at room temperature, and the drying time is 48 h.

[0127] In this example, the fiber cloth selected is a high-silica fiber cloth with a unit area mass of 240 g / m 2 , a thickness of 0.26 mm, and the dosage is 80 parts.

[0128] In this example, most of the solvent is removed by air-drying at room temperature.

[0129] In S2, the prepregs are alternately laminated in the 0° / 90° manner to obtain the impregnated fiber cloth layer.

[0130] In S2, the hot pressing and curing process is as follows: under a pressure of 5 MPa, first heat up to 60 °C at a heating rate of 5 °C / min, keep the temperature at 60 °C for 5 h, then heat up to 110 °C at a heating rate of 5 °C / min, keep the temperature at 110 °C for 5 h, then heat up to 140 °C at a heating rate of 5 °C / min, keep the temperature at 140 °C for 5 h, and finally, after the curing is completed, slowly cool the furnace to 60 °C and then remove the pressure to demold and obtain a heat-insulating and heat-resistant composite material with a thickness of 15 mm.

[0131] Example 5

[0132] In S1, the formulation of the prepreg solution is as follows:

[0133] The phenolic resin selected is a liquid boron-modified phenolic resin, and the dosage is 90 parts;

[0134] The curing agent selected is hexamethylenetetramine, and the dosage is 10 parts;

[0135] The phenolic modifier selected is methyltrimethoxysilane, and the dosage is 20 parts;

[0136] The coupling agent selected is KH550 coupling agent, and the dosage is 5 parts;

[0137] The organic solvent selected is anhydrous ethanol, and the dosage is 60 parts.

[0138] In this example, in S1, the parameters for uniform stirring are: stirring at 20 °C and a rotation speed of 300 rpm for 20 min.

[0139] In S2, the prepreg solution was evenly impregnated into the fiber cloth. After the impregnated fiber cloth was dried and most of the solvent was removed, prepreg was obtained. The impregnation method was: the flow injection impregnation process. Using an RTM injection machine, the pressure was 1 MPa, the temperature was 25 °C, and the flow rate was 20 mL / min. After the prepreg solution was evenly impregnated into the fiber cloth, the solvent was removed by drying at room temperature, and the drying time was 48 h.

[0140] In this example, the fiber cloth selected was a high-silica fiber cloth with a unit area mass of 240 g / m 2 , a thickness of 0.26 mm, and the dosage was 80 parts.

[0141] In this example, most of the solvent was removed by drying at room temperature.

[0142] In S2, the prepreg was alternately laminated in the 0°-90° manner to obtain an impregnated fiber cloth layer.

[0143] In S2, the hot pressing and curing process was as follows: under a pressure of 5 MPa, first heated to 60 °C at a heating rate of 5 °C / min, held at 60 °C for 5 h, then heated to 110 °C at a heating rate of 5 °C / min, held at 110 °C for 5 h, then heated to 140 °C at a heating rate of 5 °C / min, held at 140 °C for 5 h. Finally, after the curing was completed, it was slowly cooled in the furnace to 60 °C and then the pressure was removed, and a heat-insulating and heat-resistant composite material with a thickness of 15 mm was demolded.

[0144] Testing and analysis

[0145] The performance tests of the heat-insulating and heat-resistant composite materials prepared in the above Examples 1 to 5 are introduced below. The test results are shown in Table 1, and the test methods for each performance are as follows:

[0146] Density: Tested according to GB / T 1463-2005;

[0147] Tensile strength: Tested according to GB / T 1447-2005;

[0148] Flexural strength: Tested according to GB / T 1449-2005;

[0149] Thermal conductivity: Tested according to GB / T 3139-2005;

[0150] Ablation performance: Tested according to GJB 323A-96.

[0151]

[0152] As can be seen from the data in Table 1, the thermal conductivity of the thermal insulation composite materials prepared in Examples 1 to 5 is 0.082~0.157 W / (m·k), the tensile strength is about 170 MPa, and the flexural strength is about 280 MPa; through the oxyacetylene ablation test (the test conditions are 850 kW / m 2 heat flux density ablation for 91 s, 2522 kW / m 2 heat flux density ablation for 15 s, 850 kW / m 2 heat flux density ablation for 35 s), the temperature rise on the back is 60~80 °C, and the thickness of the non-carbonized composite material after ablation exceeds 9 mm (the thickness of the composite material is 15 mm). The ablated carbonized layer can block the heat of secondary ablation. That is to say, the thermal insulation composite material prepared by the present invention has the advantages of low density, excellent mechanical properties, excellent resistance to high heat flux ablation, and reusability.

[0153] The thermal insulation composite material prepared by the above method is suitable for applications in spacecraft thermal protection, engine components, etc. in the aerospace field, especially suitable for the thermal protection of the bottom of the return vehicle rocket.

[0154] Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, substitutions, and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended embodiments and their equivalents.

Claims

1. A preparation method of a heat-insulating composite material, characterized in that It includes the following steps: S1. The modified phenolic resin composition is uniformly impregnated into the high-silica fiber cloth by the flow injection impregnation method, and the solvent is removed to obtain a prepreg. The modified phenolic resin composition is as follows by mass fraction: liquid boron-modified phenolic resin: 80 - 100 parts, curing agent: 10 - 20 parts, phenolic modifier: 1 - 20 parts, coupling agent: 1 - 10 parts, organic solvent: 50 - 80 parts; S2. The prepreg is laid and stacked, and after hot pressing and curing treatment, it is cooled and depressurized to obtain the thermal insulation and heat protection composite material. The hot pressing and curing treatment is carried out by gradient heating; The phenolic modifier is selected from one or more of methyltrimethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane; the coupling agent is selected from one or more of KH550 coupling agent, KH560 coupling agent, and KH570 coupling agent.

2. The preparation method of the heat-insulating composite material according to claim 1, wherein The mass ratio of the modified phenolic resin composition to the high-silica fiber cloth is (170 - 200) : (80 - 100).

3. The preparation method of the heat-insulating composite material according to claim 1, characterized in that, The parameters of the hot pressing and curing treatment are: the pressure is 2 - 6 MPa, and it is heated to 140 - 170 °C by gradient heating, and the heat preservation time is 4 - 8 h.

4. The preparation method of the heat-insulating and heat-proof composite material according to claim 1, characterized in that, In S2, the cooling is carried out by furnace cooling, and the depressurization is carried out after the temperature drops below 70 °C.

5. The preparation method of the heat-insulating composite material according to claim 1, characterized in that, The parameters of the flow injection impregnation method are: the pressure is 1 - 2 MPa, the temperature is 20 - 30 °C, and the flow rate is 15 - 25 mL / min.

6. The preparation method of the heat-insulating composite material according to claim 5, characterized in that, It also includes one or more of the following technical features: A1. The curing agent is selected from one or more of hexamethylenetetramine, triethylenetetramine, and 4,4-diphenylsulfone diamine; B1. The organic solvent is selected from absolute ethanol and / or acetic acid.

7. The preparation method of the heat-insulating composite material according to claim 5, characterized in that, It also includes one or more of the following technical features: A2. The modified phenolic resin composition is mixed evenly by stirring, and the stirring parameters are 200 - 400 r / min; B2. The modified phenolic resin composition is mixed evenly at 20 - 80 °C.

8. A heat-insulating and heat-proof composite material, characterized in that: It is prepared by the preparation method of the thermal insulation and heat protection composite material according to any one of claims 1 to 7.

9. The application of the anti-heat-insulating composite material according to claim 8, characterized in that, The thermal insulation and heat protection composite material is used for a thermal protection system.

Images