A fiber-reinforced resin-based composite material and a method for producing and using the same

Abstract

The application provides a fiber reinforced resin-based composite material and a preparation method and application thereof, the fiber reinforced resin-based composite material comprises a phenolic resin composite material layer and a polyimide composite material layer; the phenolic resin composite material layer comprises one or at least two layers of a phenolic resin / fiber composite material layer; the polyimide composite material layer comprises one or at least two layers of a polyimide / fiber composite material layer; raw materials for preparing the polyimide comprise a diamine compound, a dianhydride compound and a catalyst; the application regulates the polyimide resin forming temperature by a method of doping the catalyst, and the fiber reinforced resin-based composite material is prepared by a layer arrangement process and hot-pressing solidification integrated forming, and has the characteristics of anti-ablation, good mechanical properties, fast preparation, batch production and low cost.

Description

Technical Field

[0001] This invention belongs to the field of composite material technology, specifically relating to a fiber-reinforced resin-based composite material, its preparation method, and its application. Background Technology

[0002] Phenolic resins are a class of high-molecular polymers formed by the condensation reaction of phenolic and aldehyde compounds. When impregnated with carbon fibers, phenolic resin-based composites are prepared. Due to their high char content and relatively stable char layer, phenolic resin-based composites are widely used as ablation materials for spacecraft and provide thermal protection for many space missions. However, compared with other advanced carbon materials, the amorphous carbon produced by carbonization of the phenolic matrix leads to stronger oxidation, corrosion, and thermomechanical susceptibility. These disadvantages make it difficult to meet the higher thermal protection requirements of aerospace materials.

[0003] Currently, methods to improve the ablation resistance of phenolic resins include adding inorganic fillers, such as ceramic particles (e.g., zirconium carbide, zirconium disilicide, or zirconium diboride). CN115636967A discloses an environmentally friendly ablation-resistant phenolic resin prepreg, a composite material, and a preparation method. The preparation method includes the following steps: S1. Heating hot-melt phenolic resin to melt it; S2. Mixing the molten hot-melt phenolic resin with an ablation-resistant additive, wherein the ablation-resistant additive is one or a combination of several of zirconium diboride, silicon carbide, hafnium carbide, boron nitride, glass powder, and kaolin; S3. Forming a film from the mixture of the hot-melt phenolic resin and the ablation-resistant additive; S4. Laminating the film with a reinforcing material, and then heating to composite it, thereby obtaining an environmentally friendly ablation-resistant phenolic resin prepreg. This technical solution involves adding an anti-ablation agent to a hot-melt phenolic resin matrix. The anti-ablation agent undergoes a chemical reaction during heating, resisting ablation. However, due to the significant temperature difference between the granulation temperature of the ceramic particles (approximately 1000℃) and the thermal degradation temperature of the phenolic resin (300-800℃), the phenolic resin may completely decompose before the ceramic particles participate in the reaction, leading to the failure of the coke layer structure. Furthermore, excessive inorganic filler content increases the brittleness of the phenolic resin, while the improvement in heat resistance and ablation resistance is relatively limited.

[0004] CN115746496A discloses a high-heat-resistant and high-toughness thermoplastic polyimide-modified phenolic molding compound and its preparation method. The high-heat-resistant and high-toughness thermoplastic polyimide-modified phenolic molding compound comprises the following components by weight: 50 parts linear phenolic resin, 10-20 parts thermoplastic polyimide, 20 parts reinforcing fiber, 10-15 parts inorganic filler, 5 parts curing agent, 1 part curing accelerator, 0.5-1 part plasticizer, and 0.5-1 part lubricant. This technical solution, through the addition of a small amount of thermoplastic polyimide, can significantly improve the heat resistance and toughness of the molding compound; however, its mechanical properties, heat resistance, and ablation resistance still need further improvement.

[0005] Therefore, there is a need to develop a fiber-reinforced resin matrix composite material that is resistant to ablation and has good mechanical properties. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a fiber-reinforced resin matrix composite material, its preparation method, and its applications. The fiber-reinforced resin matrix composite material exhibits ablation resistance, good mechanical properties, and can be prepared rapidly, in large quantities, and at low cost.

[0007] To achieve this objective, the present invention adopts the following technical solution:

[0008] In a first aspect, the present invention provides a fiber-reinforced resin-based composite material, the fiber-reinforced resin-based composite material comprising a phenolic resin composite material layer and a polyimide composite material layer;

[0009] The phenolic resin composite material layer includes one or at least two layers of phenolic resin / fiber composite material;

[0010] The polyimide composite material layer includes one or at least two layers of polyimide / fiber composite material layer;

[0011] The fiber-reinforced resin-based composite material includes phenolic resin, polyimide, and fibers;

[0012] The raw materials for preparing the polyimide include diamine compounds, dianhydride compounds, and catalysts.

[0013] In this invention, the polyimide is a polymer containing an imide ring structure in its main chain. Due to the conjugation effect between the aromatic heterocycles and CN on the chain, polyimides possess excellent properties such as heat resistance, heat oxidation resistance, and good mechanical properties. Compared to thermoplastic polyimides, thermosetting polyimides have better heat resistance and higher tensile strength, but their high curing temperature and poor processability severely limit their applications. The significant difference in molding temperatures between phenolic resin and polyimide resin makes the controllable composite of phenolic resin, polyimide, and fibers a challenging problem to be solved. The fiber-reinforced resin-based composite material of this invention controls the molding temperature of polyimide resin by doping with a catalyst. Then, it is compounded by a phenolic resin composite material layer and a polyimide composite material layer, and then cured by compression molding. During the molding process, the phenolic resin and polyimide react further, increasing the crosslinking density and significantly improving the heat resistance. The resulting fiber-reinforced resin-based composite material has both the high char residue of phenolic resin and the high-temperature oxidation resistance of polyimide, forming a domained composite material of phenolic resin and polyimide, which is resistant to ablation and has good mechanical properties.

[0014] Preferably, the raw materials for preparing the phenolic resin include phenolic compounds and aldehyde compounds.

[0015] Preferably, the phenolic compound includes any one or a combination of at least two of phenol, cresol, or xylenol.

[0016] Preferably, the aldehyde compound includes formaldehyde.

[0017] Preferably, the diamine compound includes 4,4-diaminodiphenyl ether.

[0018] Preferably, the dianhydride compounds include pyromellitic dianhydride and / or 3,3',4,4'-biphenyltetracarboxylic dianhydride.

[0019] Preferably, the catalyst comprises any one or a combination of at least two of benzimidazole, quinoline, or p-hydroxybenzoic acid.

[0020] Preferably, the fiber comprises a fiber cloth.

[0021] Preferably, the fiber cloth includes any one or a combination of at least two of basalt fiber cloth, carbon fiber cloth, quartz fiber cloth or polyimide fiber cloth.

[0022] Preferably, the fiber-reinforced resin-based composite material comprises the following components by weight: 20-35 parts of phenolic resin (e.g., 22, 24, 26, 28, 30, 32, or 34 parts, etc.), 20-35 parts of polyimide (e.g., 22, 24, 26, 28, 30, 32, or 34 parts, etc.), and 30-60 parts of fiber (e.g., 32, 35, 38, 40, 42, 45, 48, 50, 55, or 58 parts, etc.).

[0023] In this invention, the fiber weight fraction of the fiber in the fiber-reinforced resin matrix composite material is 30 to 60 parts. If the fiber weight fraction is too large, the resin cannot completely coat the fiber, resulting in poor ablation performance of the prepared fiber-reinforced resin matrix composite material. If the fiber weight fraction is too small, the fiber content in the fiber-reinforced resin matrix composite material is low, leading to reduced mechanical properties.

[0024] Preferably, the number of phenolic resin / fiber composite material layers in the phenolic resin composite material layer is 7 to 14, such as 8, 9, 10, 11, 12, 13 or 14 layers.

[0025] Preferably, the number of polyimide / fiber composite material layers in the polyimide composite material layer is 7 to 14, such as 8, 9, 10, 11, 12, 13 or 14 layers.

[0026] Preferably, the fiber-reinforced resin matrix composite material is laid up in a unidirectional layup or a multidirectional layup.

[0027] Preferably, the fiber-reinforced resin matrix composite material is laid up in a multi-directional manner along the fiber at a 45° angle and / or in a multi-directional manner perpendicular to the fiber direction.

[0028] In this invention, the unidirectional layup refers to a unidirectional layup in the 0° direction, and the layup along the direction perpendicular to the fiber direction refers to a multidirectional layup at 90° intersections.

[0029] In this invention, the layup method of the fiber-reinforced resin matrix composite material has an impact on its mechanical properties and ablation resistance. The mechanical properties of the fiber-reinforced resin matrix composite material can be adjusted by adjusting the fiber layup orientation. Laying the fiber along the fiber direction or laying it perpendicular to the fiber direction both help to improve the mechanical properties and ablation resistance. Among them, laying the fiber perpendicular to the fiber direction has a significant improvement on the mechanical properties. Therefore, fiber-reinforced resin matrix composite materials with different functions can be obtained by adjusting the layup arrangement.

[0030] In a second aspect, the present invention provides a method for preparing a fiber-reinforced resin-based composite material as described in the first aspect, the method comprising the following steps: sequentially laying prepreg of a phenolic resin / fiber composite material layer and prepreg of a polyimide / fiber composite material layer, and hot-pressing to obtain the fiber-reinforced resin-based composite material.

[0031] Preferably, the prepreg of the phenolic resin / fiber composite material layer is prepared as follows: the impregnation solution of fiber and phenolic resin is mixed, and vacuum is applied for 1-4 hours (e.g., 1.2h, 1.5h, 1.8h, 2h, 2.5h, 3h, 3.5h, 3.6h or 3.8h, etc.). Then, the fiber loaded with impregnation solution is laid flat on a glass plate with release paper attached, and the prepreg on the fiber surface is coated evenly with a coater. The fiber is then dried at 45-65℃ (e.g., 46℃, 48℃, 50℃, 52℃, 55℃, 58℃, 60℃, 62℃ or 64℃, etc.) for 1-5 hours (e.g., 1.2h, 1.5h, 1.8h, 2h, 2.5h, 3h, 3.5h, 4h or 4.5h, etc.) to obtain the prepreg of the phenolic resin / fiber composite material layer.

[0032] Preferably, the prepreg of the polyimide / fiber composite layer is prepared as follows: the impregnation liquid of the fiber and the polyimide is mixed, and the mixture is vacuumed for 1-4 hours (e.g., 1.2 hours, 1.5 hours, 1.8 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 3.6 hours, or 3.8 hours, etc.). Then, the fiber loaded with the impregnation liquid is laid flat on a glass plate with release paper attached, and the impregnation liquid on the surface of the fiber is coated evenly with a coater. The fiber is then dried at 45-65°C (e.g., 46°C, 48°C, 50°C, 52°C, 55°C, 58°C, 60°C, 62°C, or 64°C, etc.) for 1-5 hours (e.g., 1.2 hours, 1.5 hours, 1.8 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, or 4.5 hours, etc.) to obtain the prepreg of the polyimide / fiber composite layer.

[0033] In this invention, based on a prepreg process, fibers are first impregnated in a resin impregnation solution, and then dried to obtain prepregs for phenolic resin / fiber composite layers and polyimide / fiber composite layers. Finally, these are cured and molded under hot pressing in a mold, achieving integrated molding of phenolic and polyimide functional composite materials, thus obtaining the fiber-reinforced resin-based composite material. The preparation process of the fiber-reinforced resin-based composite material is as follows: Figure 1 As shown, the preparation method solves the problems of low efficiency, interface delamination and debonding in the integrated molding process of functional materials, and realizes rapid, batch and low-cost preparation.

[0034] In this invention, during the preparation of the prepreg of the polyimide / fiber composite layer, the drying process is used to partially evaporate the solvent while maintaining the flexibility of the fiber.

[0035] Preferably, the impregnation solution of the phenolic resin includes phenolic compounds and aldehyde compounds.

[0036] Preferably, the solid content of the impregnation solution of the phenolic resin is 50%-80%, such as 52%, 55%, 60%, 62%, 65%, 68%, 70%, 72%, 75%, or 78%.

[0037] Preferably, the impregnation solution of the polyimide includes a diamine compound, a dianhydride compound, and a catalyst.

[0038] Preferably, the solid content of the impregnation solution of the polyimide is 10%-30%, such as 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, or 28%.

[0039] Preferably, the hot pressing includes hot pressing at a pressure of 1-5 MPa (e.g., 1.2 MPa, 1.5 MPa, 1.8 MPa, 2 MPa, 2.2 MPa, 2.5 MPa, 3.0 MPa, 3.2 MPa, 3.5 MPa, 4 MPa, or 4.5 MPa, etc.) and a heat preservation temperature of 150℃-170℃ (e.g., 152℃, 154℃, 156℃, 158℃, 160℃, 162℃, 164℃, 166℃, or 168℃, etc.) for 1-3 hours. Heat-press at 250℃-270℃ (e.g., 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.6h, or 2.8h) for 1-3 hours (e.g., 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.6h, or 2.8h) for 1 hour ...

[0040] Thirdly, the present invention provides an application of the fiber-reinforced resin matrix composite material as described in the first aspect in aerospace structural materials.

[0041] Compared with the prior art, the present invention has the following beneficial effects:

[0042] In this invention, the molding temperature of the polyimide resin is controlled by doping with a catalyst. Then, a phenolic resin composite layer and a polyimide composite layer are compounded and molded, allowing the phenolic resin and polyimide to react further, increasing the crosslinking density and significantly improving heat resistance. The resulting fiber-reinforced resin composite exhibits ablation resistance and good mechanical properties. This method for preparing the fiber-reinforced resin composite solves the problems of low efficiency, interface delamination, and debonding in the integrated molding process of functional materials, achieving rapid, batch, and low-cost preparation. The tensile strength of the fiber-reinforced resin composite is 359-422 MPa, and the mass ablation rate is 0.82-0.99 mg / s². -1 . Attached Figure Description

[0043] Figure 1 This is a flowchart illustrating the preparation process of the fiber-reinforced resin-based composite material. Detailed Implementation

[0044] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0045] Example 1

[0046] This embodiment provides a fiber-reinforced resin-based composite material and its preparation method, wherein the fiber-reinforced resin-based composite material includes a phenolic resin composite material layer and a polyimide composite material layer;

[0047] The phenolic resin composite material layer comprises a 7-layer phenolic resin / fiber composite material layer;

[0048] The polyimide composite layer comprises a 7-layer polyimide / fiber composite layer.

[0049] The fiber-reinforced resin-based composite material comprises the following components by weight: 30 parts phenolic resin, 30 parts polyimide, and 40 parts fiber (carbon fiber cloth).

[0050] The preparation method of the above-mentioned fiber-reinforced resin matrix composite material is as follows.

[0051] Preparation of prepreg for phenolic resin / fiber composite layers:

[0052] The carbon fiber cloth and the phenolic resin impregnation solution (composed of phenol, formaldehyde and anhydrous ethanol solvent in a mass ratio of 2:2:1.7, with a solid content of 70%) were mixed and vacuumed for 2 hours. Then, the carbon fiber cloth loaded with the impregnation solution was laid flat on a glass plate with release paper attached, and the impregnation solution on the surface of the carbon fiber cloth was coated evenly with a coater. The mixture was dried at 65°C for 1 hour to obtain the prepreg of the phenolic resin / fiber composite material layer.

[0053] Preparation of prepreg for polyimide / fiber composite layers:

[0054] The carbon fiber cloth and the impregnation solution of polyimide (composed of 4,4-diaminodiphenyl ether, pyromellitic dianhydride, benzimidazole and N,N-dimethylacetamide solvent in a mass ratio of 100:100:1:600, with a solid content of 25%) were mixed and vacuumed for 2 hours. Then, the carbon fiber cloth loaded with the impregnation solution was laid flat on a glass plate with release paper attached, and the impregnation solution was coated evenly on the surface of the carbon fiber cloth with a coater. The mixture was dried at 65°C for 1 hour to obtain the prepreg of the polyimide / fiber composite material layer.

[0055] Preparation of fiber-reinforced resin-based composite materials:

[0056] Seven layers of the aforementioned phenolic resin / fiber composite prepreg and seven layers of the aforementioned polyimide / fiber composite prepreg were sequentially layered in a unidirectional layup manner and placed into a mold. After being secured, the mold was placed on a high-temperature flat vulcanizing machine. The heating program was set as follows: 25°C to 150°C, heating time 50 min, holding time 50 h, then heating from 150°C to 250°C, heating time 100 min, holding time 3 h, maintaining a pressure of 2 MPa throughout the process. After thermosetting, the mold was allowed to cool naturally to room temperature, and the sample was demolded to obtain the fiber-reinforced resin matrix composite material. The dimensions of the thermo-cured sample were 100 × 10 × 5 mm. 3 .

[0057] Example 2

[0058] This embodiment provides a fiber-reinforced resin-based composite material and its preparation method, wherein the fiber-reinforced resin-based composite material includes a phenolic resin composite material layer and a polyimide composite material layer;

[0059] The phenolic resin composite material layer comprises a 7-layer phenolic resin / fiber composite material layer;

[0060] The polyimide composite layer comprises a 7-layer polyimide / fiber composite layer.

[0061] The fiber-reinforced resin-based composite material comprises the following components by weight: 35 parts phenolic resin, 35 parts polyimide, and 30 parts fiber (basalt fiber cloth).

[0062] The preparation method of the above-mentioned fiber-reinforced resin matrix composite material is as follows.

[0063] Preparation of prepreg for phenolic resin / fiber composite layers:

[0064] Basalt fiber cloth and phenolic resin impregnation solution (composed of phenol, formaldehyde and anhydrous ethanol solvent in a mass ratio of 2:2:1, with a solid content of 80%) were mixed and vacuumed for 1 hour. Then, the carbon fiber cloth loaded with impregnation solution was laid flat on a glass plate with release paper attached, and the impregnation solution was coated evenly on the surface of the carbon fiber cloth with a coating tool. The mixture was dried at 55°C for 3 hours to obtain the prepreg of the phenolic resin / fiber composite material layer.

[0065] Preparation of prepreg for polyimide / fiber composite layers:

[0066] Basalt fiber cloth and polyimide impregnation solution (composed of 4,4-diaminodiphenyl ether, pyromellitic dianhydride, quinoline and N,N-dimethylacetamide solvent in a mass ratio of 100:100:1:500, with a solid content of 28.5%) were mixed and vacuumed for 1 hour. Then, the carbon fiber cloth loaded with impregnation solution was laid flat on a glass plate with release paper attached, and the impregnation solution was coated evenly on the surface of the carbon fiber cloth using a coater. The mixture was dried at 55°C for 3 hours to obtain the prepreg of the polyimide / fiber composite material layer.

[0067] Preparation of fiber-reinforced resin-based composite materials:

[0068] Seven layers of the aforementioned phenolic resin / fiber composite prepreg and seven layers of the aforementioned polyimide / fiber composite prepreg were sequentially layered in a unidirectional layup manner and placed into a mold. After being secured, the mold was placed on a high-temperature flat vulcanizing machine. The heating program was set as follows: 25°C to 150°C, heating time 80 min, holding time 2 h, then heating from 150°C to 250°C, heating time 50 min, holding time 1 h, maintaining a pressure of 5 MPa throughout the process. After heat curing, the mold was allowed to cool naturally to room temperature, and the sample was demolded to obtain the fiber-reinforced resin matrix composite material. The dimensions of the sample after hot-press curing were 200 × 50 × 10 mm. 3 .

[0069] Example 3

[0070] This embodiment provides a fiber-reinforced resin-based composite material and its preparation method, wherein the fiber-reinforced resin-based composite material includes a phenolic resin composite material layer and a polyimide composite material layer;

[0071] The phenolic resin composite material layer comprises a 7-layer phenolic resin / fiber composite material layer;

[0072] The polyimide composite layer comprises a 7-layer polyimide / fiber composite layer.

[0073] The fiber-reinforced resin-based composite material comprises the following components by weight: 20 parts phenolic resin, 20 parts polyimide, and 60 parts fiber (quartz fiber cloth).

[0074] The preparation method of the above-mentioned fiber-reinforced resin matrix composite material is as follows.

[0075] Preparation of prepreg for phenolic resin / fiber composite layers:

[0076] The impregnation solution of quartz fiber cloth and phenolic resin (composed of phenol, formaldehyde and anhydrous ethanol solvent in a mass ratio of 2:2:4, with a solid content of 50%) was mixed and vacuumed for 4 hours. Then, the carbon fiber cloth loaded with the impregnation solution was laid flat on a glass plate with release paper attached, and the impregnation solution was coated evenly on the surface of the carbon fiber cloth with a coating tool. It was dried at 45°C for 5 hours to obtain the prepreg of the phenolic resin / fiber composite material layer.

[0077] Preparation of prepreg for polyimide / fiber composite layers:

[0078] A prepreg of the polyimide composite layer was prepared by mixing quartz fiber cloth and polyimide impregnation solution (composed of 4,4-diaminodiphenyl ether, pyromellitic dianhydride, benzimidazole and N,N-dimethylacetamide solvent in a mass ratio of 100:100:1:1000, with a solid content of 16.7%) and evacuating the mixture for 4 hours. The carbon fiber cloth loaded with the impregnation solution was then laid flat on a glass plate covered with release paper, and the impregnation solution was coated evenly on the surface of the carbon fiber cloth using a coater. The mixture was then dried at 45°C for 5 hours to obtain the prepreg of the polyimide / fiber composite layer.

[0079] Preparation of fiber-reinforced resin-based composite materials:

[0080] Seven layers of the aforementioned phenolic resin / fiber composite prepreg and seven layers of the aforementioned polyimide / fiber composite prepreg were sequentially layered in a unidirectional layup manner and placed into a mold. After being secured, the mold was placed on a high-temperature flat vulcanizing machine. The heating program was set as follows: 25°C to 150°C, heating time 100 min, holding time 1 h, then heating from 150°C to 250°C, heating time 40 min, holding time 3 h, maintaining a pressure of 1 MPa throughout the process. After heat curing, the mold was allowed to cool naturally to room temperature, and the sample was demolded to obtain the fiber-reinforced resin matrix composite material. The dimensions of the sample after hot-press curing were 150 × 25 × 8 mm. 3 .

[0081] Example 4

[0082] This embodiment provides a fiber-reinforced resin-based composite material and its preparation method. The only difference between this embodiment and Embodiment 1 is that the phenolic resin composite material layer includes a 9-layer phenolic resin / fiber composite material layer; and the polyimide composite material layer includes a 9-layer polyimide / fiber composite material layer.

[0083] In the preparation of the fiber-reinforced resin-based composite material, the 9-layer prepreg of the above-mentioned phenolic resin / fiber composite material and the 9-layer prepreg of the above-mentioned polyimide / fiber composite material are sequentially stacked in a unidirectional layup manner and placed into a mold, otherwise the same as in Example 1.

[0084] Example 5

[0085] This embodiment provides a fiber-reinforced resin-based composite material and its preparation method. The only difference between this embodiment and Embodiment 1 is that the phenolic resin composite material layer includes 11 layers of phenolic resin / fiber composite material; and the polyimide composite material layer includes 11 layers of polyimide / fiber composite material.

[0086] In the preparation of the fiber-reinforced resin-based composite material, 11 layers of the above-mentioned phenolic resin / fiber composite material prepreg and 11 layers of the above-mentioned polyimide / fiber composite material prepreg are sequentially stacked in a unidirectional layup manner and placed into a mold, otherwise the same as in Example 1.

[0087] Example 6

[0088] This embodiment provides a fiber-reinforced resin-based composite material and its preparation method. The only difference between this embodiment and Embodiment 1 is that the phenolic resin composite material layer includes 14 layers of phenolic resin / fiber composite material; and the polyimide composite material layer includes 14 layers of polyimide / fiber composite material.

[0089] In the preparation of the fiber-reinforced resin-based composite material, 14 layers of the above-mentioned phenolic resin / fiber composite material prepreg and 14 layers of the above-mentioned polyimide / fiber composite material prepreg are sequentially stacked in a unidirectional layup manner and placed into a mold, otherwise the same as in Example 1.

[0090] Example 7

[0091] This embodiment provides a fiber-reinforced resin-based composite material and its preparation method. The only difference between this embodiment and Embodiment 1 is that the phenolic resin composite material layer includes a 5-layer phenolic resin / fiber composite material layer; and the polyimide composite material layer includes a 5-layer polyimide / fiber composite material layer.

[0092] In the preparation of the fiber-reinforced resin-based composite material, five layers of the above-mentioned phenolic resin / fiber composite material prepreg and five layers of the above-mentioned polyimide / fiber composite material prepreg are sequentially stacked in a unidirectional layup manner and placed into a mold, otherwise the same as in Example 1.

[0093] Example 8

[0094] This embodiment provides a fiber-reinforced resin matrix composite material and its preparation method. The only difference between this embodiment and Embodiment 1 is that, in the preparation of the fiber-reinforced resin matrix composite material, 7 layers of the above-mentioned phenolic resin / fiber composite material prepreg and 7 layers of the above-mentioned polyimide / fiber composite material prepreg are sequentially stacked in a multi-directional layup manner along the fiber oblique 45° direction and placed into a mold. The rest is the same as in Embodiment 1.

[0095] Example 9

[0096] This embodiment provides a fiber-reinforced resin-based composite material and its preparation method. The only difference between this embodiment and Embodiment 1 is that, in the preparation of the fiber-reinforced resin-based composite material, 7 layers of the above-mentioned phenolic resin / fiber composite material prepreg and 7 layers of the above-mentioned polyimide / fiber composite material prepreg are sequentially stacked in a multi-directional layup manner perpendicular to the fiber direction and placed into a mold. The rest is the same as in Embodiment 1.

[0097] Example 10

[0098] This embodiment provides a fiber-reinforced resin matrix composite material and its preparation method. The only difference between this embodiment and Embodiment 1 is that the fiber-reinforced resin matrix composite material includes the following components by weight: 30 parts of phenolic resin, 30 parts of polyimide, and 20 parts of fiber (carbon fiber cloth).

[0099] In the preparation method of the fiber-reinforced resin matrix composite material, the composition of the impregnation solution of the phenolic resin is adjusted to phenol, formaldehyde and anhydrous ethanol solvent in a mass ratio of 2:2:0.98, and the solid content of the impregnation solution of the phenolic resin is 90%; the composition of the impregnation solution of the polyimide is adjusted to 4,4-diaminodiphenyl ether, pyromellitic dianhydride, benzimidazole and N,N-dimethylacetamide solvent in a mass ratio of 100:100:1:370, and the solid content of the impregnation solution of the polyimide is 35%.

[0100] Everything else is the same as in Example 1.

[0101] Example 11

[0102] This embodiment provides a fiber-reinforced resin matrix composite material and its preparation method. The only difference between this embodiment and Embodiment 1 is that the fiber-reinforced resin matrix composite material includes the following components by weight: 30 parts of phenolic resin, 30 parts of polyimide, and 70 parts of fiber (carbon fiber cloth).

[0103] In the preparation method of the fiber-reinforced resin matrix composite material, the composition of the impregnation solution of the phenolic resin is adjusted to phenol, formaldehyde and anhydrous ethanol solvent in a mass ratio of 2:2:5, and the solid content of the impregnation solution of the phenolic resin is 44%; the composition of the impregnation solution of the polyimide is adjusted to 4,4-diaminodiphenyl ether, pyromellitic dianhydride, benzimidazole and N,N-dimethylacetamide solvent in a mass ratio of 100:100:1:1200, and the solid content of the impregnation solution of the polyimide is 14%.

[0104] Everything else is the same as in Example 1.

[0105] Comparative Example 1

[0106] This comparative example provides a fiber-reinforced resin-based composite material and its preparation method. The only difference between this example and Example 1 is that the fiber-reinforced resin-based composite material does not include a polyimide composite material layer, and the phenolic resin composite material layer includes a 14-layer phenolic resin / fiber composite material layer.

[0107] The fiber-reinforced resin-based composite material comprises the following components by weight: 60 parts phenolic resin and 40 parts fiber (carbon fiber cloth).

[0108] In the preparation of the fiber-reinforced resin matrix composite material, the 14 layers of the above-mentioned phenolic resin / fiber composite material prepreg are stacked in a unidirectional layup manner and placed into the mold, and the rest is the same as in Example 1.

[0109] Comparative Example 2

[0110] This comparative example provides a fiber-reinforced resin-based composite material and its preparation method. The only difference between this example and Example 1 is that the fiber-reinforced resin-based composite material does not include a phenolic resin composite material layer, and the phenolic resin composite material layer includes a 14-layer polyimide / fiber composite material layer.

[0111] The fiber-reinforced resin-based composite material comprises the following components by weight: 60 parts polyimide and 40 parts fiber (carbon fiber cloth).

[0112] In the preparation of the fiber-reinforced resin matrix composite material, the 14 layers of the above-mentioned polyimide / fiber composite material prepreg are stacked in a unidirectional layup manner and placed into the mold, and the rest is the same as in Example 1.

[0113] The fiber-reinforced resin matrix composites provided in the examples and comparative examples were subjected to the following performance tests:

[0114] (1) Tensile strength: Tested according to GB / T 1040.1-2018, with test conditions referring to GB / T1040.2-2006. The test direction of tensile strength is perpendicular to the direction of the fibers in the outermost phenolic resin / fiber composite material layer.

[0115] (2) Ablation resistance: The mass ablation rate was tested using a self-made thermal protection material ablation test platform. The parameters of the self-made thermal protection material ablation test platform are shown in Table 1.

[0116] Table 1

[0117] Equipment Information Relevant parameters Equipment Information Relevant parameters ablative gases butane Central flame temperature >1500℃ Nozzle diameter 2.0mm Gas working pressure 0.4MPa ablation distance 60mm gas flow rate 558L / h ablation angle 90° Heat flux density <![CDATA[1038±103.8KW / m 2 ]]> Temperature measurement optris CT 3M ablation time 120s

[0118] The test results are shown in Table 2.

[0119] Table 2

[0120]

[0121]

[0122] According to the test results in Table 2, the tensile strength of the fiber-reinforced resin matrix composites provided in Examples 1-11 is 359-422 MPa, and the mass ablation rate is 0.82-0.99 mg / s. -1 .

[0123] A comparison of Examples 1 and 4-6 shows that the tensile properties of the composite material gradually improve with the increase of the layup thickness, reaching a maximum of 422 MPa, while the ablation properties do not change significantly.

[0124] Compared with Example 1, it can be seen that if the number of phenolic resin / fiber composite layers in the phenolic resin composite layer and the number of polyimide / fiber composite layers in the polyimide composite layer are too low (Example 7), the tensile properties of the fiber-reinforced resin matrix composite material will decrease. This proves that the number of phenolic resin / fiber composite layers in the phenolic resin composite layer and the number of polyimide / fiber composite layers in the polyimide composite layer are both within a specific range, and the prepared fiber-reinforced resin matrix composite material has better performance.

[0125] Compared with Example 1, it can be seen that if the fibers are laid in a multi-directional layup along a 45° angle (Example 8), the tensile strength is increased and the mass ablation rate is decreased; if the fibers are laid in a multi-directional layup perpendicular to the fiber direction (Example 9), the tensile strength is increased and the mass ablation rate is decreased. Different mechanical properties can be obtained by adjusting the fiber layup orientation. Both the fiber-angled 45° direction and the fiber-perpendicular direction have an effect on improving mechanical properties, with the effect being more significant along the fiber-perpendicular direction, resulting in a slight improvement in ablation performance. This demonstrates that fiber-reinforced resin matrix composites prepared by multi-directional layups along a 45° angle and / or along the fiber-perpendicular direction have better performance.

[0126] Compared with Example 1, it can be seen that if the weight fraction of the fiber is too low (Example 10), the tensile strength of the fiber-reinforced resin matrix composite material decreases and the mechanical properties are reduced; if the weight fraction of the fiber is too high (Example 11), the ablation resistance of the fiber-reinforced resin matrix composite material is reduced. This proves that the fiber-reinforced resin matrix composite material prepared with a specific weight fraction of fiber has better performance.

[0127] Compared with Example 1, it can be seen that if the fiber-reinforced resin matrix composite material does not include the polyimide composite material layer (Comparative Example 1), the tensile strength decreases, the mass ablation rate increases, and the ablation performance decreases; if the fiber-reinforced resin matrix composite material does not include the phenolic resin composite material layer (Comparative Example 2), the tensile strength decreases, proving that the fiber-reinforced resin matrix composite material prepared using the polyimide composite material layer and the phenolic resin composite material layer has better performance.

[0128] The applicant declares that the present invention is illustrated by the above embodiments, but the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials used in the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A fiber-reinforced resin-based composite material, characterized in that, The fiber-reinforced resin-based composite material includes a phenolic resin composite layer and a polyimide composite layer; The phenolic resin composite material layer includes one or at least two layers of phenolic resin / fiber composite material; The polyimide composite material layer includes one or at least two layers of polyimide / fiber composite material layer; The fiber-reinforced resin-based composite material comprises the following components in parts by weight: 20-35 parts phenolic resin, 20-35 parts polyimide, and 30-60 parts fiber; The fiber-reinforced resin matrix composite material is laid up in a multi-directional manner along the fiber at a 45° angle and / or in a multi-directional manner perpendicular to the fiber direction. The preparation method of the fiber-reinforced resin-based composite material includes the following steps: sequentially laying prepreg of phenolic resin / fiber composite material layer and prepreg of polyimide / fiber composite material layer, and hot pressing to obtain the fiber-reinforced resin-based composite material; The preparation method of the prepreg of the phenolic resin / fiber composite material layer is as follows: the impregnation liquid of fiber and phenolic resin is mixed, vacuumed for 1-4 h, then the fiber loaded with impregnation liquid is laid flat on a glass plate with release paper attached, and the prepreg on the surface of the fiber is coated smoothly with a coater, and dried at 45-65℃ for 1-5 h to obtain the prepreg of the phenolic resin / fiber composite material layer. The prepreg of the polyimide / fiber composite material layer is prepared as follows: the impregnation liquid of fiber and polyimide is mixed, vacuumed for 1-4 h, then the fiber loaded with impregnation liquid is laid flat on a glass plate with release paper attached, and the impregnation liquid on the surface of the fiber is coated evenly with a coater, and dried at 45-65℃ for 1-5 h to obtain the prepreg of the polyimide / fiber composite material layer. The impregnation solution of the phenolic resin includes phenolic compounds and aldehyde compounds; The impregnation solution for the polyimide includes diamine compounds, dianhydride compounds, and a catalyst; The hot pressing includes hot pressing at 150℃-170℃ for 1-3 hours under a pressure of 1-5 MPa, and hot pressing at 250℃-270℃ for 1-3 hours.

2. The fiber-reinforced resin-based composite material according to claim 1, characterized in that, The phenolic compounds include any one or a combination of at least two of phenol, cresol, or xylenol.

3. The fiber-reinforced resin-based composite material according to claim 1, characterized in that, The aldehyde compounds include formaldehyde.

4. The fiber-reinforced resin-based composite material according to claim 1, characterized in that, The diamine compounds include 4,4-diaminodiphenyl ether.

5. The fiber-reinforced resin-based composite material according to claim 1, characterized in that, The dianhydride compounds include pyromellitic dianhydride and / or 3,3',4,4'-biphenyltetracarboxylic dianhydride.

6. The fiber-reinforced resin-based composite material according to claim 1, characterized in that, The catalyst includes any one or a combination of at least two of benzimidazole, quinoline, or p-hydroxybenzoic acid.

7. The fiber-reinforced resin-based composite material according to claim 1, characterized in that, The fibers include fiber cloth.

8. The fiber-reinforced resin-based composite material according to claim 7, characterized in that, The fiber cloth includes any one or a combination of at least two of basalt fiber cloth, carbon fiber cloth, quartz fiber cloth or polyimide fiber cloth.

9. The fiber-reinforced resin-based composite material according to claim 1, characterized in that, The number of phenolic resin / fiber composite material layers in the phenolic resin composite material layer is 7 to 14.

10. The fiber-reinforced resin-based composite material according to claim 1, characterized in that, The polyimide composite material layer has 7 to 14 layers of polyimide / fiber composite material.

11. A method for preparing a fiber-reinforced resin-based composite material as described in any one of claims 1-10, characterized in that, The preparation method includes the following steps: sequentially laying up the prepreg of the phenolic resin / fiber composite material layer and the prepreg of the polyimide / fiber composite material layer, and hot pressing them to obtain the fiber-reinforced resin-based composite material. The preparation method of the prepreg of the phenolic resin / fiber composite material layer is as follows: the impregnation liquid of fiber and phenolic resin is mixed, vacuumed for 1-4 h, then the fiber loaded with impregnation liquid is laid flat on a glass plate with release paper attached, and the prepreg on the surface of the fiber is coated smoothly with a coater, and dried at 45-65℃ for 1-5 h to obtain the prepreg of the phenolic resin / fiber composite material layer. The prepreg of the polyimide / fiber composite material layer is prepared as follows: the impregnation liquid of fiber and polyimide is mixed, vacuumed for 1-4 h, then the fiber loaded with impregnation liquid is laid flat on a glass plate with release paper attached, and the impregnation liquid on the surface of the fiber is coated evenly with a coater, and dried at 45-65℃ for 1-5 h to obtain the prepreg of the polyimide / fiber composite material layer. The impregnation solution of the phenolic resin includes phenolic compounds and aldehyde compounds; The impregnation solution for the polyimide includes diamine compounds, dianhydride compounds, and a catalyst; The hot pressing includes hot pressing at 150℃-170℃ for 1-3 hours under a pressure of 1-5 MPa, and hot pressing at 250℃-270℃ for 1-3 hours.

12. The preparation method according to claim 11, characterized in that, The solid content of the impregnation solution of the phenolic resin is 50%-80%.

13. The preparation method according to claim 11, characterized in that, The solid content of the impregnation solution for the polyimide is 10%-30%.

14. The application of fiber-reinforced resin matrix composites according to any one of claims 1-10 in aerospace structural materials.

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