CN113845692B - Polycarbosilane/phenolic aldehyde dual-system network structure aerogel and composite material and preparation method thereof - Google Patents
Polycarbosilane/phenolic aldehyde dual-system network structure aerogel and composite material and preparation method thereof Download PDFInfo
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- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/16—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
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- C08J2461/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2461/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2461/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/16—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
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- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
Abstract
The invention relates to polycarbosilane/phenolic aldehyde dual-system network structure aerogel, a composite material thereof and a preparation method thereof. The method comprises the steps of taking phenolic resin and polycarbosilane as reaction raw materials, dissolving and mixing the raw materials, carrying out sol-gel reaction under a heating condition to obtain wet gel, and drying the wet gel to obtain the polycarbosilane/phenolic aldehyde binary system network structure aerogel. The invention can be compounded with fiber products in situ according to requirements to further improve the mechanical property of the fiber products. The invention also relates to the phenolic aerogel or the composite material thereof prepared by the method, which has the characteristics of low density, good heat resistance, low heat conductivity coefficient, good mechanical property, low line ablation rate, good scour resistance and the like, can be used for low-density heat-proof and heat-insulating materials of a thermal protection system of an aerospace craft, and has important application value.
Description
Technical Field
The invention relates to polycarbosilane/phenolic aldehyde dual-system network structure aerogel, a composite material and a preparation method thereof, which are mainly used as low-density heat-proof and heat-insulating materials of a heat protection system of an aerospace craft.
Background
The aerospace craft generates serious pneumatic heating when reentering/entering the atmosphere, and a thermal protection system is an essential part for ensuring the normal operation of internal equipment and electronic devices of the aerospace craft. The thermal protection/insulation material is a key component of the thermal protection system, and the effectiveness of the thermal protection/insulation material is concerned with the success or even life safety of the flight.
The mesoporous size (1-100 nm) of the aerogel can restrict the movement of gas molecules to a certain extent and reduce the heat transfer generated by gas molecule collision, so that the macroscopic thermal conductivity of the aerogel is extremely low, the aerogel is a super thermal insulation material with excellent performance, and the aerogel shows a great application prospect in the field of aerospace vehicle thermal protection systems.
The phenolic aerogel is an organic aerogel which is researched more, and has excellent performances of low density, high specific surface area, low thermal conductivity and the like. However, under high temperature conditions, methylene in the phenolic aerogel is easy to break to generate severe degradation, so that the phenolic aerogel has low mass retention rate at high temperature, severe volume shrinkage, easy fragmentation and very limited temperature resistance, and the defects limit the application of the phenolic aerogel in the aerospace field. Therefore, how to improve the temperature resistance of the phenolic aerogel becomes a focus of attention in the field.
CN105838022A is a hybrid aerogel obtained by dispersing linear phenolic aldehyde, barium phenolic aldehyde or high-carbon phenolic aldehyde resin in an ethanol solvent, then compounding with silica sol and drying, and has the characteristics of high porosity and low density, and simultaneously overcomes the defects of brittle silica aerogel and easy slag falling. As the service temperature of the aerospace craft is above 1000 ℃, the high-temperature stability of the silicon dioxide aerogel is poor, sintering and phase change are easy to occur in a high-temperature environment, and the heat insulation performance is rapidly reduced. CN111234299A and CN112175230A improve the temperature resistance of the phenolic aerogel by a boron modification means, the former synthesizes boron modified phenolic resin by reacting phenol, formaldehyde and boric acid, and then the boron modified phenolic resin is prepared into the phenolic aerogel, so that the phenolic aerogel has the advantages of high heat resistance, high skeleton strength and the like; the boron modified phenolic aerogel is prepared by adding organic boric acid such as tributyl borate and the like into linear phenolic resin, reacting under the action of a curing agent to obtain boron composite phenolic wet gel, and drying under normal pressure to obtain the boron modified phenolic aerogel. Since boric acid is easy to precipitate at 100-300 ℃, the problem that the modified phenolic aerogel is unstable in the curing or aging process exists, and the precipitated boric acid can cause corrosion and pollution to molds and equipment and is not beneficial to large-scale preparation. CN110746637A discloses a ceramic modified ablation-resistant phenolic aerogel and a preparation method thereof, which is to dissolve linear phenolic resin and boric acid in ethanol solution, and then add an ablation-resistant ceramic powder filler to improve the ablation resistance of the ceramic modified ablation-resistant phenolic aerogel. The method has the defects of nonuniform dispersion of ablation-resistant filler, poor product quality controllability, precipitation of boric acid and the like. CN109200955B discloses an organic-inorganic dual-network structure phenolic aldehyde/alumina aerogel composite material, which is prepared by using resorcinol, formaldehyde and crystalline aluminum chloride as raw materials, growing an organic-inorganic dual-network structure composite gel in situ through hydrolysis and polycondensation, depositing an alumina atomic layer on the dual-network structure composite gel by adopting a chemical liquid phase method, and finally aging and drying. The alumina component in the aerogel can generate phase transformation in the high-temperature use process to influence the high-temperature use performance of the aerogel.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide polycarbosilane/phenolic aldehyde dual-system network structure aerogel with excellent temperature resistance, heat insulation performance and mechanical performance and a preparation method of a composite material thereof.
Specifically, the invention provides a preparation method of polycarbosilane/phenolic binary system network structure aerogel in a first aspect, which is characterized by comprising the following steps:
(1) Mixing and uniformly stirring phenolic resin, a first organic solvent and an optional curing agent to obtain a phenolic resin solution S1;
(2) Mixing and uniformly stirring polycarbosilane, a second organic solvent and a catalyst to obtain polycarbosilane solution S2;
(3) Mixing and uniformly stirring the phenolic resin solution S1 and the polycarbosilane solution S2 to obtain polycarbosilane/phenolic resin composite solution S3;
(4) Transferring the composite solution S3 into a closed container, and carrying out sol-gel reaction under a heating condition to obtain polycarbosilane/phenolic aldehyde binary system network structure wet gel;
(5) And drying the polycarbosilane/phenolic aldehyde binary system network structure wet gel to obtain the polycarbosilane/phenolic aldehyde binary system network structure aerogel.
The invention provides a preparation method of a polycarbosilane/phenolic aldehyde binary system network structure aerogel composite material in a second aspect, which is characterized by comprising the following steps:
(1) Mixing and uniformly stirring phenolic resin, a first organic solvent and an optional curing agent to obtain a phenolic resin solution S1;
(2) Mixing and uniformly stirring polycarbosilane, a second organic solvent and a catalyst to obtain polycarbosilane solution S2;
(3) Mixing and uniformly stirring the phenolic resin solution S1 and the polycarbosilane solution S2 to obtain polycarbosilane/phenolic resin composite solution S3;
(4') transferring the composite solution S3 into a closed container to be compounded with a fiber product in situ, and then carrying out sol-gel reaction under a heating condition to obtain the fiber-reinforced polycarbosilane/phenolic aldehyde binary system network structure composite material wet gel.
(5') drying the fiber-reinforced polycarbosilane/phenolic aldehyde binary system network structure composite material wet gel to obtain the fiber-reinforced polycarbosilane/phenolic aldehyde binary system network structure composite material aerogel.
In a third aspect, the invention provides the polycarbosilane/phenolic aldehyde binary system network structure aerogel prepared by the preparation method in the first aspect of the invention.
In a fourth aspect, the invention provides a fiber-reinforced polycarbosilane/phenolic binary system network structure composite aerogel prepared by the preparation method in the second aspect.
Compared with the prior art, the invention has the following technical advantages:
(1) According to the polycarbosilane/phenolic aldehyde dual-system network structure aerogel and the composite material thereof prepared by the invention, the high-temperature resistance characteristic of the silicon carbide ceramic aerogel obtained after the polycarbosilane aerogel is subjected to high-temperature cracking is utilized, so that the temperature resistance of the phenolic aldehyde aerogel is improved, the decomposition and carbonization temperature of the phenolic aldehyde aerogel is delayed, the high-temperature ablation resistance and the heat insulation performance are improved, and the mechanical property of a three-dimensional network framework is improved;
(2) The polycarbosilane/phenolic aldehyde binary network structure aerogel prepared by the invention can well coat fiber products, and the prepared composite material has excellent ablation resistance, heat insulation performance and mechanical performance.
(3) The polycarbosilane/phenolic aldehyde dual-system network structure aerogel and the composite material thereof prepared by the invention combine phenolic aldehyde aerogel and polycarbosilane aerogel together, and the mechanical property of the polycarbosilane aerogel is improved by utilizing the high strength of the phenolic aldehyde aerogel.
(4) The prepared phenolic aerogel is pyrolyzed at high temperature to obtain carbon aerogel, and the polycarbosilane aerogel is pyrolyzed at high temperature to obtain silicon carbide ceramic aerogel, so that the defects of high brittleness, poor mechanical property and the like of the silicon carbide ceramic aerogel are overcome by utilizing the high strength of the carbon aerogel;
(5) The invention can improve the high-temperature stability of the carbon aerogel by utilizing the high-temperature resistance of the silicon carbide ceramic aerogel.
(6) The polycarbosilane/phenolic aldehyde aerogel with a double-network structure and the composite material thereof have the characteristics of low density, good heat resistance, low heat conductivity, low ablation rate, good erosion resistance and the like, and are particularly suitable for the heat-proof and heat-insulating materials of a thermal protection system of an aerospace craft.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
As described above, the present invention provides, in a first aspect, a method for preparing a polycarbosilane/phenolic binary system network structure aerogel, wherein the method comprises the following steps:
(1) Mixing and uniformly stirring phenolic resin, a first organic solvent and an optional curing agent to obtain a phenolic resin solution S1;
(2) Mixing and uniformly stirring polycarbosilane, a second organic solvent and a catalyst to obtain polycarbosilane solution S2;
(3) Mixing and uniformly stirring the phenolic resin solution S1 and the polycarbosilane solution S2 to obtain polycarbosilane/phenolic resin composite solution S3;
(4) Transferring the composite solution S3 into a closed container, and carrying out sol-gel reaction under the heating condition to obtain polycarbosilane/phenolic aldehyde binary system network structure wet gel;
(5) And drying the polycarbosilane/phenolic aldehyde binary system network structure wet gel to obtain the polycarbosilane/phenolic aldehyde binary system network structure aerogel.
The polycarbosilane is an organic silicon compound which takes silicon carbon as a main chain and contains organic groups on side chains, and SiC ceramic is obtained after pyrolysis, and the SiC ceramic has the excellent properties of light weight, high strength, oxidation resistance, wear resistance, corrosion resistance and the like.
Preferably, in the step (1), the phenol resin is any one of a novolac type phenol resin and a Resole type phenol resin.
It is also preferred; when the phenol resin is a Novolak type phenol resin, the curing agent is any one of hexamethylenetetramine, paraformaldehyde, aniline, and a resol type phenol resin.
Alternatively, in the case where the phenolic resin is a Resole-type phenolic resin, the addition amount of the curing agent is zero (i.e., no curing agent needs to be added).
Preferably, in step (1), the first organic solvent is any one or more of methyl acetate, ethyl acetate, butyl acetate, dimethyl carbonate, acetone, butanone, methyl isobutyl ketone and cyclohexanone; more preferably any one or more of methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone and cyclohexanone.
It is also preferred or more preferred that in step (2), the second organic solvent is any one or a combination of more of diethyl ether, dibutyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, ethylene glycol dibutyl ether, cyclopentyl methyl ether, methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone; more preferably any one or more of butyl ether, tetrahydrofuran, cyclopentyl methyl ether, methyl acetate, ethyl acetate and butanone.
Further preferably or more preferably, in step (1), the mass ratio of the phenolic resin to the first organic solvent is from 1.
The amount of the curing agent used in the present invention is not particularly limited as long as the intended curing purpose can be achieved.
However, where a curing agent is used, the mass ratio of the curing agent to the phenolic resin may be 1.
Preferably, in step (2), the polycarbosilane is any one or more of solid polycarbosilane, polymethylsilane, vinyl polycarbosilane, allyl polycarbosilane and ethynyl polycarbosilane.
It is also preferable that, in the step (2), the catalyst is any one of a platinum catalyst, dicumyl peroxide, azobisisobutyronitrile and dibenzoyl oxide.
Preferably, in step (2), the mass ratio of the polycarbosilane to the second organic solvent is 1.
The amount of the catalyst used in the present invention is not particularly limited as long as the intended catalytic reaction can be achieved, that is, only a catalytic amount of the catalyst is required. For example, in some preferred embodiments, the catalyst concentration may be 0.01wt% to 3wt% (e.g., 0.05, 0.1, 1, 2, or 3 wt%).
Preferably, in the step (3), the mass ratio of the polycarbosilane to the phenolic resin in the polycarbosilane/phenolic resin composite solution S3 is 1.
Preferably, in step (4), the sol-gel reaction is carried out at a reaction temperature of 70 ℃ to 150 ℃ (e.g., 80, 100, 120, or 140 ℃) for 8 hours to 32 hours (e.g., 12, 16, 20, 24, or 28 hours).
Preferably, in the step (5), the drying treatment may be performed by atmospheric drying or supercritical drying; preferably, the atmospheric drying is performed by: the wet gel is removed, left to air for 24 to 48 hours (e.g., 36 hours), and then dried at 50 to 70 ℃ (e.g., 60 hours) for 12 to 24 hours (e.g., 18 hours) at atmospheric pressure.
The invention provides a preparation method of a polycarbosilane/phenolic aldehyde binary system network structure aerogel composite material in a second aspect, which is characterized by comprising the following steps:
(1) Mixing and uniformly stirring phenolic resin, a first organic solvent and an optional curing agent to obtain a phenolic resin solution S1;
(2) Mixing and uniformly stirring polycarbosilane, a second organic solvent and a catalyst to obtain polycarbosilane solution S2;
(3) Mixing and uniformly stirring the phenolic resin solution S1 and the polycarbosilane solution S2 to obtain polycarbosilane/phenolic resin composite solution S3;
(4') transferring the composite solution S3 into a closed container to be compounded with a fiber product in situ, and then carrying out sol-gel reaction under the heating condition to obtain the fiber-reinforced polycarbosilane/phenolic aldehyde binary system network structure composite material wet gel.
(5') drying the fiber-reinforced polycarbosilane/phenolic aldehyde binary system network structure composite material wet gel to obtain the fiber-reinforced polycarbosilane/phenolic aldehyde binary system network structure composite material aerogel.
Regarding the above steps (1) to (3), reference may be made to the corresponding contents described for the first aspect of the present invention, and details are not repeated herein.
Preferably, in step (4'), the fiber product is a fiber felt, a fiber blanket or a fiber board made of any one or more of quartz fiber, high silica fiber, glass fiber, carbon fiber and silicon carbide fiber.
Preferably, in step (4'), the sol-gel reaction is carried out at a reaction temperature of 70 ℃ to 150 ℃ (e.g., 80, 100, 120, or 140 ℃) for 8 hours to 32 hours (e.g., 12, 16, 20, 24, or 28 hours).
Preferably, in the step (5'), the drying treatment may be performed by atmospheric drying or supercritical drying; preferably, the atmospheric drying is performed by: the wet gel is removed, left to air for 24 to 48 hours (e.g., 36 hours), and then dried at 50 to 70 ℃ (e.g., 60 hours) under atmospheric pressure for 12 to 24 hours (e.g., 18 hours).
In a third aspect, the invention provides the polycarbosilane/phenolic binary system network structure aerogel prepared by the preparation method of the first aspect of the invention. Preferably, the density is less than 0.28g/cm 3 The linear shrinkage rate is less than 10%, the residual weight (900 ℃) is 70% or more, the room-temperature thermal conductivity is less than 0.042W/(m.K), and/or the compressive strength is 1.00MPa or more.
In a fourth aspect, the invention provides a fiber reinforced polycarbosilane/phenolic binary system network structure composite aerogel prepared by the preparation method of the second aspect of the invention. Preferably, the density is less than 0.69g/cm 3 The linear shrinkage is less than 10%, the residual weight (900 ℃) is more than 70%, the heat conductivity coefficient at room temperature is less than 0.051W/(m.K), and/or the compressive strength is more than 4.95 MPa.
Examples
The present invention will be described in further detail with reference to examples. It should be noted that these examples are provided for the purpose of further illustrating the present invention and are not intended to limit the scope of the present invention.
The main raw materials used in this example are shown in the following table:
example 1
Mixing 10g of Novolak type phenolic resin and 90g of cyclohexanone, stirring uniformly, adding 0.5g of hexamethylenetetramine, mixing and stirring uniformly to obtain S1; mixing 10g of solid polycarbosilane and 90g of butyl ether, stirring uniformly, adding 0.001g of platinum catalyst, and stirring uniformly to obtain S2; and (3) mixing and uniformly stirring the S1 and the S2, transferring the mixture into a hydrothermal kettle, reacting for 8 hours at 150 ℃, taking out wet gel, airing at room temperature for 24 hours, and then transferring the wet gel into a 70 ℃ oven for drying for 12 hours to obtain the polycarbosilane/phenolic aldehyde binary network structure aerogel, wherein the density, linear shrinkage rate, residual weight (900 ℃), thermal conductivity (room temperature) and compressive strength of the aerogel are shown in Table 1.
Example 2
Mixing 15g of resol type phenolic resin and 85g of ethyl acetate, and uniformly stirring to obtain S1; mixing 1.88g of polymethylsilane and 10.65g of tetrahydrofuran, stirring uniformly, adding 0.00094g of dicumyl peroxide, and stirring uniformly to obtain S2; and (3) mixing and uniformly stirring the S1 and the S2, transferring the mixture into a hydrothermal kettle, reacting for 10 hours at 80 ℃, taking out wet gel, airing at room temperature for 30 hours, and then transferring the wet gel into a 55 ℃ oven for drying for 18 hours to obtain the polycarbosilane/phenolic aldehyde binary network structure aerogel, wherein the density, linear shrinkage rate, residual weight (900 ℃), thermal conductivity (room temperature) and compressive strength of the aerogel are shown in Table 1.
Example 3
Mixing 20g of Novolak type phenolic resin and 80g of butyl acetate, stirring uniformly, adding 1.33g of paraformaldehyde, and stirring uniformly to obtain S1; mixing 3.33g of vinyl polycarbosilane and 13.32g of cyclopentyl methyl ether, stirring uniformly, adding 0.0033g of azobisisobutyronitrile, and stirring uniformly to obtain S2; and (3) mixing and uniformly stirring the S1 and the S2, transferring the mixture into a hydrothermal kettle, reacting for 12 hours at 130 ℃, taking out wet gel, airing at room temperature for 36 hours, and then transferring the wet gel into a 65 ℃ oven for drying for 20 hours to obtain the polycarbosilane/phenolic aldehyde binary network structure aerogel, wherein the density, linear shrinkage rate, residual weight (900 ℃), thermal conductivity (room temperature) and compressive strength of the aerogel are shown in Table 1.
Example 4
Mixing 25g of resol type phenolic resin and 75g of methyl acetate, and uniformly stirring to obtain S1; 5g of allyl polycarbosilane and 15g of methyl acetate are mixed and stirred evenly, 0.025g of dibenzoyl oxide is added and mixed and stirred evenly to obtain S2; and (3) mixing and uniformly stirring the S1 and the S2, transferring the mixture into a hydrothermal kettle, reacting at 70 ℃ for 24 hours, taking out the wet gel, airing at room temperature for 38 hours, and then drying by supercritical CO2 for 24 hours to obtain the polycarbosilane/phenolic aldehyde binary system network structure aerogel, wherein the density, linear shrinkage rate, residual weight (900 ℃), thermal conductivity (room temperature) and compressive strength of the aerogel are shown in Table 1.
Example 5
Uniformly stirring 30g of Novolak type phenolic resin and 70g of mixed solvent of butyl acetate and butanone, adding 3g of aniline, and uniformly stirring to obtain S1; mixing 7.5g of ethynylpolycarbosilane and 17.5g of ethyl acetate, stirring uniformly, adding 0.075g of platinum catalyst, and stirring uniformly to obtain S2; and (3) mixing and uniformly stirring the S1 and the S2, transferring the mixture into a hydrothermal kettle, reacting at 80 ℃ for 18 hours, taking out the wet gel, airing at room temperature for 40 hours, and then transferring the wet gel into a 50 ℃ oven for drying for 12 hours to obtain the polycarbosilane/phenolic aldehyde binary system network structure aerogel, wherein the density, linear shrinkage rate, residual weight (900 ℃), thermal conductivity (room temperature) and compressive strength of the aerogel are shown in Table 1.
Example 6
Mixing and stirring 12g of resol type phenolic resin and 88g of butanone to obtain S1; mixing and stirring 4g of polymethylsilane and 29.3g of butanone uniformly, adding 0.06g of dicumyl peroxide, mixing and stirring uniformly to obtain S2; and (3) mixing and uniformly stirring the S1 and the S2, transferring the mixture into a hydrothermal kettle with a quartz fiber felt, reacting for 28 hours at 90 ℃, taking out the wet gel, airing for 42 hours at room temperature, and drying for 18 hours at 70 ℃ to obtain the quartz fiber reinforced polycarbosilane/phenolic aldehyde composite aerogel, wherein the density, linear shrinkage rate, residual weight (900 ℃), thermal conductivity (room temperature) and compressive strength of the quartz fiber reinforced polycarbosilane/phenolic aldehyde composite aerogel are shown in Table 1.
Example 7
After stirring a mixed solvent of 27g of Novolak type phenolic resin and 73g of methyl butanone uniformly, adding 5.4g of resin type phenolic resin, and stirring uniformly to obtain S1; mixing 13.5g of vinyl polycarbosilane, 36.5g of ethyl acetate and butanone, stirring uniformly, adding 0.27g of azobisisobutyronitrile, and stirring uniformly to obtain S2; and (3) mixing and uniformly stirring the S1 and the S2, transferring the mixture into a hydrothermal kettle with a carbon fiber felt, reacting for 30 hours at 100 ℃, taking out the wet gel, airing at room temperature for 48 hours, and then transferring the wet gel into a 65 ℃ oven for drying for 20 hours to obtain the carbon fiber reinforced polycarbosilane/phenolic aldehyde composite aerogel, wherein the density, linear shrinkage rate, residual weight (900 ℃), thermal conductivity (room temperature) and compressive strength of the carbon fiber reinforced polycarbosilane/phenolic aldehyde composite aerogel are shown in Table 1.
Example 8
Mixing 18g of resol type phenolic resin with 82g of ethyl acetate and methyl butanone, and uniformly stirring to obtain S1; mixing and stirring 2g of solid polycarbosilane, 6.35g of ethyl acetate and tetrahydrofuran uniformly, adding 0.06g of platinum catalyst, and mixing and stirring uniformly to obtain S2; and (3) mixing and uniformly stirring the S1 and the S2, transferring the mixture into a hydrothermal kettle with a high silica fiber and carbon fiber composite fiber plate, reacting for 32 hours at 80 ℃, taking out wet gel, airing for 28 hours at room temperature, and drying for 24 hours at 70 ℃ to obtain the polycarbosilane/phenolic aldehyde composite aerogel reinforced by the high silica fiber and carbon fiber composite fiber plate (carbon fibers account for 30 percent of the total fiber mass), wherein the density, linear shrinkage rate, residual weight (900 ℃), thermal conductivity (room temperature) and compressive strength of the polycarbosilane/phenolic aldehyde composite aerogel are shown in Table 1.
TABLE 1 Properties of the materials prepared in the examples.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (12)
1. The preparation method of the polycarbosilane/phenolic aldehyde binary system network structure aerogel is characterized by comprising the following steps:
(1) Mixing and uniformly stirring phenolic resin, a first organic solvent and an optional curing agent to obtain a phenolic resin solution S1;
(2) Mixing and uniformly stirring polycarbosilane, a second organic solvent and a catalyst to obtain polycarbosilane solution S2;
(3) Mixing and uniformly stirring the phenolic resin solution S1 and the polycarbosilane solution S2 to obtain polycarbosilane/phenolic resin composite solution S3;
(4) Transferring the composite solution S3 into a closed container, and carrying out sol-gel reaction under the heating condition to obtain polycarbosilane/phenolic aldehyde binary system network structure wet gel;
(5) Drying the polycarbosilane/phenolic aldehyde binary system network structure wet gel to obtain polycarbosilane/phenolic aldehyde binary system network structure aerogel;
wherein:
in the step (1), the first organic solvent is any one or a combination of methyl acetate, ethyl acetate, butyl acetate, dimethyl carbonate, acetone, butanone, methyl isobutyl ketone and cyclohexanone; and/or
In the step (2), the second organic solvent is any one or more of diethyl ether, butyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, ethylene glycol dibutyl ether, cyclopentyl methyl ether, methyl acetate, ethyl acetate, butyl acetate and butanone.
2. The preparation method of the polycarbosilane/phenolic aldehyde binary system network structure aerogel composite material is characterized by comprising the following steps:
(1) Mixing and uniformly stirring phenolic resin, a first organic solvent and an optional curing agent to obtain a phenolic resin solution S1;
(2) Mixing and uniformly stirring polycarbosilane, a second organic solvent and a catalyst to obtain polycarbosilane solution S2;
(3) Mixing and uniformly stirring the phenolic resin solution S1 and the polycarbosilane solution S2 to obtain polycarbosilane/phenolic resin composite solution S3;
(4') transferring the composite solution S3 into a closed container to be compounded with a fiber product in situ, and then carrying out sol-gel reaction under a heating condition to obtain fiber-reinforced polycarbosilane/phenolic aldehyde binary system network structure composite material wet gel;
(5') drying the fiber-reinforced polycarbosilane/phenolic aldehyde binary system network structure composite material wet gel to obtain fiber-reinforced polycarbosilane/phenolic aldehyde binary system network structure composite material aerogel;
wherein:
the first organic solvent is any one or combination of methyl acetate, ethyl acetate, butyl acetate, dimethyl carbonate, acetone, butanone, methyl isobutyl ketone and cyclohexanone; and/or
The second organic solvent is any one or a combination of more of diethyl ether, butyl ether, tetrahydrofuran, diethylene glycol dimethyl ether, ethylene glycol dibutyl ether, cyclopentyl methyl ether, methyl acetate, ethyl acetate, butyl acetate and butanone.
3. The production method according to claim 1 or 2, characterized in that:
the phenolic resin is any one of Novolak type phenolic resin and resol type phenolic resin.
4. The production method according to claim 1 or 2, characterized in that:
the phenolic resin is any one of thermoplastic phenolic resin and thermosetting phenolic resin.
5. The production method according to claim 1 or 2, characterized in that:
when the phenolic resin is Novolak type phenolic resin, the curing agent is any one of hexamethylenetetramine, paraformaldehyde, aniline and resol type phenolic resin; when the phenolic resin is a Resole-type phenolic resin, the addition amount of the curing agent is zero.
6. The production method according to claim 1 or 2, characterized in that:
the mass ratio of the phenolic resin to the first organic solvent is 1; and/or
The mass ratio of the curing agent to the phenolic resin, when present, is from 1.
7. The production method according to claim 1 or 2, characterized in that:
the polycarbosilane is any one or combination of more of solid polycarbosilane, polymethylsilane, vinyl polycarbosilane, allyl polycarbosilane and ethynyl polycarbosilane; and/or
The catalyst is any one of platinum catalyst, dicumyl peroxide, azodiisobutyronitrile and dibenzoyl oxide.
8. The production method according to claim 1 or 2, characterized in that:
the mass ratio of the polycarbosilane to the second organic solvent is 1; and/or
The mass ratio of the polycarbosilane to the phenolic resin in the polycarbosilane/phenolic resin composite solution S3 is 1.
9. The method according to claim 2, wherein the fiber product is a fiber mat, a fiber blanket or a fiber board made of any one or more of quartz fiber, high silica fiber, glass fiber, carbon fiber and silicon carbide fiber.
10. The production method according to claim 1 or 2, characterized in that:
the reaction temperature of the sol-gel reaction is 70 ℃ to 150 ℃, and the reaction time is 8 hours to 32 hours;
the drying treatment may be performed by atmospheric drying or supercritical drying.
11. The method of manufacturing according to claim 10, wherein:
the normal pressure drying is carried out in the following way: taking out the wet gel, naturally airing for 24 to 48 hours, and then drying at 50 to 70 ℃ for 12 to 24 hours under normal pressure.
12. Polycarbosilane/phenolic two-system network structure aerogel or fiber-reinforced polycarbosilane/phenolic two-system network structure composite aerogel prepared by the preparation method according to any one of claims 1 to 11.
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