Fluorine-containing carbon fiber composite material and preparation method thereof

Abstract

The invention discloses a fluorine-containing carbon fiber composite material and a preparation method thereof, and belongs to the field of carbon fiber composite materials. The method comprises the following steps: carrying out modification treatment on a carbon fiber material by using fluorinated nanoparticles and fluorine-containing epoxy resin to obtain a modified carbon fiber material; and winding the modified carbon fiber material, dipping in a common epoxy resin system, and curing to form a modified coating consisting of fluorinated nanoparticles, fluorine-containing epoxy resin and epoxy resin on the surface of the carbon fiber material, thereby obtaining the fluorine-containing carbon fiber composite material. The strength and toughness of the carbon fiber composite material are improved through comprehensive multi-scale combined action of the fluorinated nanoparticles, the fluorine-containing epoxy resin and the common epoxy resin, so that the problem that an existing carbon fiber composite material is poor in interface performance and toughness is solved.

Description

Technical Field

[0001] The present invention relates to the field of carbon fiber composite materials, and particularly to a fluorine-containing carbon fiber composite material and a preparation method thereof. Background Art

[0002] Carbon fiber composite material (CFRP) is a composite material formed by using carbon fiber or carbon fiber fabric as the reinforcement and combining with matrices such as resin, ceramic, and metal. This material has a series of excellent properties such as high specific strength, high specific modulus, high temperature resistance, corrosion resistance, fatigue resistance, and creep resistance, and has been widely used in the fields of aerospace, automotive, shipbuilding, construction, and sports equipment.

[0003] However, although carbon fiber composite materials perform well in many fields, there are still some challenges in their practical applications. One of the most significant problems is the poor interfacial performance between carbon fiber and the matrix. The surface of carbon fiber is smooth and has few active functional groups, resulting in difficulty in forming an effective bond with the polymer matrix, thus affecting the mechanical properties of the overall composite material.

[0004] In addition, the surface treatment method of carbon fiber also has an important impact on the interfacial bonding force of the composite material. For example, by oxidation methods such as ozonation treatment, nitric acid treatment, etc., the surface roughness of carbon fiber can be increased, but at the same time as the roughness is increased, the toughness of the carbon fiber composite material will be greatly reduced, resulting in brittle fracture of the composite material under impact. Summary of the Invention

[0005] The purpose of the present invention is to provide a fluorine-containing carbon fiber composite material and a preparation method thereof. The present invention solves the technical problems of poor interfacial performance and toughness of existing carbon fiber composite materials.

[0006] To achieve the above object, the present invention adopts the following technical solutions:

[0007] A preparation method of a fluorine-containing carbon fiber composite material, comprising the following steps:

[0008] a. Prepare fluorinated nanoparticles;

[0009] Add nanoparticles and fluorine-containing silane coupling agent into a solvent, and carry out a reaction to obtain fluorinated nanoparticles;

[0010] b. Impregnation modification of carbon fiber material;

[0011] Disperse the fluorinated nanoparticles and fluorine-containing epoxy resin in water together to form a mixed modification liquid;

[0012] First, place the carbon fiber material in the mixed modification liquid for impregnation treatment, and then place it in a common epoxy resin system for impregnation treatment to obtain a fluorine-containing carbon fiber composite material;

[0013] Alternatively, prepare a fluorinated nanoparticle dispersion using fluorinated nanoparticles; prepare a mixed resin system by mixing a fluorinated epoxy resin and a common epoxy resin;

[0014] First, impregnate the carbon fiber material in the fluorinated nanoparticle dispersion, and then impregnate it in the mixed resin system to obtain a fluorinated carbon fiber composite.

[0015] The above-mentioned fluorinated carbon fiber composite forms a modified coating composed of fluorinated nanoparticles, fluorinated epoxy resin, and common epoxy on the surface of the carbon fiber material.

[0016] Preferably, in step a: the nanoparticles are any one of nano-silica, carbon nanotubes, and nano-titanium dioxide; the fluorinated silane coupling agent is any one of 1H,1H,2H,2H-perfluorooctyltriethoxysilane, 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, and 1H,1H,2H,2H-perfluorohexyltriethoxysilane; the addition amount of the fluorinated silane coupling agent is 0.1% - 5% of the amount of the nanoparticles.

[0017] Preferably, in step a: the solvent is ethanol; control the reaction time to be 1 - 6h; after the reaction is completed, put the obtained fluorinated nanoparticles into an oven at 50 - 100°C for drying for 0.5 - 4h.

[0018] Preferably, in step b: the carbon fiber material is any one of polyacrylonitrile-based carbon fiber, pitch-based carbon fiber, and phenolic-based carbon fiber;

[0019] The fluorinated epoxy resin is any one of bisphenol A hexafluoropropane diglycidyl ether, 1,4-bis(hydroxyhexafluoroisopropyl)benzene diglycidyl ether, and 4,4'-dihydroxyoctafluorobiphenyl diglycidyl ether;

[0020] The common epoxy resin in the common epoxy resin system and the mixed resin system is any one of bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol P epoxy resin, and phenolic epoxy resin. Of course, the resin system also contains a curing agent and additives in appropriate proportions.

[0021] Preferably, in step b: in the mixed modification liquid, the content of the fluorinated nanoparticles is 0.1% - 40%, and the content of the fluorinated epoxy resin is 0.1% - 80% by weight fraction.

[0022] When preparing the mixed modification liquid, it is further preferably by ultrasonic treatment. That is, after drying the fluorinated nanoparticles, ultrasonic treatment is carried out with the fluorinated epoxy resin to disperse them in water in the form of a microemulsion to form a mixed modification liquid.

[0023] Preferably, in step b: the concentration of the fluorinated nanoparticle dispersion is 1 mg / mL to 40 mg / mL; the content of the ordinary epoxy resin in the mixed resin system is 50% to 99.9%, and the content of the fluorinated epoxy resin is 0.1% to 50%.

[0024] Preferably, in step b: control the time of each impregnation treatment to be 1 h to 12 h, and after impregnation, place it at 25°C to 120°C for drying for 0.5 h to 24 h;

[0025] Before the carbon fiber material is impregnated with the ordinary epoxy resin system or the mixed resin system, first place it in an oven at 30 to 120°C and heat it for 10 min to 15 min to increase the fluidity of the adhesive.

[0026] Preferably, in step b: before the carbon fiber material is impregnated with the ordinary epoxy resin system or the mixed resin system, first perform a winding treatment; specifically, wind the carbon fiber around a frame and remove it after shaping.

[0027] Preferably, in step b: the mass ratio of the carbon fiber material in the obtained fluorinated carbon fiber composite material is 60% to 70%.

[0028] The present invention also provides a fluorinated carbon fiber composite material prepared by the method as described above.

[0029] Compared with the prior art, the beneficial technical effects of the present invention are as follows:

[0030] The present invention synchronously realizes the surface / interface enhancement of carbon fibers by designing and synthesizing a fluorinated epoxy-ordinary epoxy-fluorinated nanoparticle coating material and applying it to carbon fiber materials. On the one hand, the fluorinated epoxy resin component is rich in a large number of F-C bonds, which is beneficial to enhancing the interaction between carbon fibers and the resin. Moreover, the fluorinated epoxy resin has good flexibility. The introduction of the polymer chain segment on the surface of the carbon fiber can bring a flexible layer to the interface, which can consume the external energy by virtue of its own plastic deformation under external force, facilitating the uniform transmission of the load and relaxing the interfacial thermal stress. Therefore, it helps to improve the interfacial toughness of the composite material and ensure the structural integrity of the composite material under external impact. At the same time, the doping of ordinary epoxy can ensure the bonding between carbon fibers and the matrix, ensure the effective transmission of stress, adjust the overall curing rate of the system, reduce the defect problems in production, and also reduce the production cost. On the other hand, the fluorinated nanoparticles are also rich in a large number of F-C bonds, which can react with the oxygen-containing groups on the surface of the carbon fiber to enhance the interfacial chemical bond. At the same time, its surface energy is extremely low, which can optimize the wettability of the resin on the surface of the carbon fiber and reduce interfacial defects.

[0031] Therefore, the present invention combines the co - action of fluorinated nanoparticles, fluorinated epoxy resins and ordinary epoxy in multiple scales to improve the strength and toughness of carbon fiber composites, thereby solving the technical problems of poor interfacial properties and toughness of existing carbon fiber composites. Brief Description of the Drawings

[0032] Figure 1 It is a SEM image of a 25K polyacrylonitrile - based carbon fiber; among them, a) is the image at a scale of 10 microns, and b) is the image at a scale of 4 microns.

[0033] Figure 2 It is a SEM image of the modified fluorinated carbon fiber composites prepared in Examples 1 - 4 of the present invention; among them, a1) - d1) are the images at a scale of 10 microns, and a2) - d2) are the images at a scale of 4 microns.

[0034] Figure 3 It is a SEM image of the interface of the carbon fiber composites prepared in Examples 1 - 4 and Comparative Example 1 of the present invention; among them, (a) is the SEM image of the interface of the carbon fiber composite prepared in Comparative Example 1, and (b) - (e) are the SEM images of the interfaces of the fluorinated carbon fiber composites prepared in Examples 1 - 4 respectively.

[0035] Figure 4 [[ID=—18]]It is a comparative chart of the inter - laminar shear strength test of the carbon fiber composites prepared in Examples 1 - 4 and Comparative Example 1 of the present invention.

[0036] Figure 5 It is a comparative chart of the impact toughness test of the carbon fiber composites prepared in Examples 1 - 4 and Comparative Example 1 of the present invention. Detailed Embodiments

[0037] By introducing fluorine - containing groups into carbon fibers, the wettability and chemical bonding ability of the system are enhanced, and the interfacial shear strength is greatly improved in the single - fiber pull - out experiment; at the same time, by controlling the fluorine content of the system, the surface energy of the system can be controlled. Mild fluorination can retain moderate hydrophilicity, and high - degree fluorination can achieve super - hydrophobicity; the bond energy of the C - F bond is high, which can endow the fiber surface with resistance to acids, alkalis, oxidants and high - temperature environments, significantly extending the service life of the material; finally, the influence of fluorination on the mechanical properties of carbon fibers is extremely small, and even slightly improves them.

[0038] Based on this, the present invention proposes a carbon fiber composite and its preparation method. The technical solutions and embodiments of the present invention will be described in detail with reference to the accompanying drawings.

[0039] The present invention can be realized through the following two technical solutions:

[0040] In Technical Solution 1, fluorinated nanoparticles are first prepared using nanoparticles and a fluorosilane coupling agent, then carbon fibers are treated with a dispersion of the fluorinated nanoparticles, and finally a fluorinated carbon fiber composite is constructed using a mixed resin system of fluorinated epoxy and ordinary epoxy and the carbon fibers.

[0041] In Technical Solution 2, fluorinated nanoparticles are first prepared using nanoparticles and a fluorosilane coupling agent, then carbon fibers are treated with a mixed solution of the fluorinated nanoparticles and fluorinated epoxy, and finally a fluorinated carbon fiber composite is constructed using ordinary epoxy.

[0042] Specifically, Technical Solution 1 includes the following steps:

[0043] (1) Preparation of fluorinated nanoparticles;

[0044] The nanoparticles and the fluorosilane coupling agent are ultrasonically treated and then reacted in ethanol to obtain fluorinated nanoparticles, which are then dried.

[0045] For example, 20 g to 80 g of nanoparticles are dispersed in ethanol, and then 0.1% to 5% of the fluorosilane coupling agent is added. After reacting for 1 to 6 h, the obtained fluorinated nanoparticles are placed in an oven at 50 to 100 °C and dried for 0.5 to 4 h.

[0046] (2) Modification of carbon fibers with fluorinated nanoparticles;

[0047] The carbon fibers are impregnated with dispersions of fluorinated nanoparticles with different contents for surface coating modification. The addition of the fluorinated nanoparticles, due to their special surface effect and a large number of C-F bonds, can effectively modify the carbon fibers, thereby improving their interfacial properties with the resin matrix.

[0048] For example, a dispersion of fluorinated nanoparticles with a concentration of 1 mg / mL to 40 mg / mL is prepared, and the carbon fibers are immersed therein for 1 to 12 h and then placed in an oven at 25 to 100 °C and dried for 0.5 to 24 h to obtain carbon fibers modified with fluorinated nanoparticles.

[0049] (3) Preparation of a fluorinated nanoparticle-fluorinated epoxy-ordinary epoxy coating / carbon fiber composite;

[0050] 50 to 99.9 wt% of an ordinary epoxy resin system (including a curing agent and additives with appropriate ratios) and 0.1 to 50 wt% of fluorinated epoxy are weighed respectively to prepare a mixed epoxy resin system, which is placed in an oven at 30 to 120 °C and heated for 10 min to increase the fluidity of the glue solution. The mixed carbon fiber filaments modified with fluorinated nanoparticles are wound around an appropriate number of turns so that the content of carbon fibers in the cured carbon fiber composite is controlled at 60% to 70%. After fully infiltrating the resin system, it is cured according to the curing process of the ordinary epoxy resin.

[0051] The second technical solution includes the following steps:

[0052] (1) Preparation of fluorinated nanoparticles;

[0053] After ultrasonic treatment of the nanoparticles and the fluorosilane coupling agent, they are reacted in ethanol to obtain fluorinated nanoparticles, and then dried.

[0054] For example, take 20 g to 80 g of nanoparticles and disperse them in ethanol, then add 0.1% to 5% of the fluorosilane coupling agent, react for 1 to 6 h, and then put the obtained fluorinated nanoparticles into an oven at 50 to 100 °C for drying for 0.5 to 4 h.

[0055] (2) Fluorinated nanoparticle - fluorinated epoxy modified carbon fiber;

[0056] Prepare a dispersion of fluorinated nanoparticles and fluorinated epoxy, where the content of fluorinated nanoparticles is 0.1 wt% to 40 wt%, and the content of fluorinated epoxy resin is 0.1 wt% to 80 wt%. Immerse the carbon fiber in it for 1 to 12 h and then place it in an oven at 25 to 120 °C for drying for 0.5 to 24 h to obtain the carbon fiber modified by nano - silica - fluorinated epoxy.

[0057] (3) Preparation of fluorinated nanoparticle - fluorinated epoxy resin - ordinary epoxy coating / carbon fiber composite;

[0058] Weigh the ordinary epoxy resin system (including the curing agent and additives with appropriate ratios), and place it in an oven at 30 to 120 °C for heating for 10 min to increase the fluidity of the glue. Wind the carbon fiber tow modified by the mixed fluorinated nanoparticles for an appropriate number of turns so that the content of carbon fiber in the cured carbon fiber composite is controlled at 60% to 70%. After fully infiltrating the resin, cure it according to the curing process of the ordinary epoxy resin.

[0059] Among them, the ordinary epoxy resin has a higher surface energy compared with the fluorinated epoxy resin, which is beneficial to the bonding between the carbon fiber and the matrix. At the same time, the cost is lower, and reasonable doping can reduce the cost while maintaining the performance.

[0060] Appropriate winding can form a predetermined structural morphology or compactness, helping to maintain the required geometric dimensions and shape before curing, and preventing local stress concentration or defects caused by fiber loosening during curing. If the number of winding turns is too small and the carbon fiber content is too low, it will affect the strength of the material. However, there is a "saturation point" for the increase in carbon fiber content; if the number of turns is too large, it will lead to a decrease in performance due to stress transfer problems.

[0061] Preferably, the number of winding turns should be confirmed according to the following principle: (number of turns * 2 * length * fiber density) divided by the total weight of the molded spline is equal to 65% - 70%. Empirically, 12K carbon fiber is wound 14 turns, 25K carbon fiber is wound 6 turns, and 3K carbon fiber is wound 50 turns.

[0062] The present invention will be described in detail below through specific embodiments. The embodiments are exemplary and are intended to explain the present invention, but should not be construed as limiting the present invention.

[0063] Example 1

[0064] (1) Add 30 g of nano-silica and 0.15 g of FOTS (1H,1H,2H,2H-perfluorooctyltriethoxysilane) to 500 mL of ethanol, and disperse them fully by ultrasonic treatment. Then react for 4 h, place the reacted fluorinated silica in an oven at 80 °C for drying for 0.5 h, and then take it out and bottle it for subsequent use.

[0065] (2) Add 2 g of fluorinated silica to 400 mL of deionized water, and disperse it fully by ultrasonic treatment to form a dispersion. Subsequently, immerse 25K polyacrylonitrile-based carbon fiber into the dispersion, seal it with plastic wrap and let it stand for 2 hours to ensure that the modifier is evenly adsorbed on the fiber surface. Then, hang it in an oven at 100 °C for drying for 2 h to obtain carbon fiber modified with surface fluorinated silica respectively.

[0066] (3) Weigh 50 g of TECHSTORM 5245A epoxy resin, 48 g of TECHSTORM 5247B curing agent, and 2 g of TECHSTORM 5201C auxiliary agent to prepare a solution. After preparation, add 10 g of 4,4'-dihydroxyoctafluorobiphenyl diglycidyl ether and mix it evenly. Place it in an oven at 70 °C for heating for 10 min to increase the fluidity of the glue. Wind the carbon fiber tow modified with the above nano-silica around a 21 cm long frame for 6 turns, then remove the wound carbon fiber tow and fully immerse it in the above resin system. Subsequently, place it in a mold preheated to 70 °C and cool it to room temperature for waiting for molding.

[0067] (4) Subsequently, cure it according to the following process: Preheat the flat vulcanizer to 100 °C, place the mold on the flat plate and keep it at normal pressure for heat preservation, observe the state of the glue. When it reaches the gelation state, immediately pressurize it to 10 MPa. Press for 1 h at 100 °C, 140 °C, and 180 °C respectively. Then, turn off the flat vulcanizer and release the pressure. After the mold cools, open the mold and take out the spline, which is the prepared composite part.

[0068] Example 2

[0069] (1) 6 g of fluorinated silica was added to 500 mL of deionized water and fully dispersed by ultrasonic treatment. 12K polyacrylonitrile-based carbon fibers were then immersed in the dispersion, sealed with plastic wrap, and allowed to stand for 2 hours to ensure uniform adsorption of the modifier on the fiber surface. The fibers were then hung and dried in an oven at 80°C for 3 hours to obtain carbon fibers modified with surface fluorinated silica.

[0070] (2) Weigh 50g of E51 epoxy resin and 16g of H256 curing agent to prepare the solution. After the preparation is completed, add 15g of 1,4-bis(hydroxyhexafluoroisopropyl)benzene diglycidyl ether and mix them evenly. Place them in a 70℃ oven and heat for 10 minutes to increase the fluidity of the glue. Wrap the above-mentioned fluorinated silica-modified carbon fiber tow around a 21cm long frame for 12 turns. Then remove the wrapped carbon fiber tow and fully soak it in the resin system. Then, place it in a mold preheated to 70℃ and cool it to room temperature for molding.

[0071] (3) Subsequently, the curing process was carried out according to the following process: the flat plate vulcanizer was preheated to 90°C, the mold was placed on a flat plate and kept warm at normal pressure, the state of the glue was observed, and when it reached the gel state, the pressure was immediately increased to 10 MPa, the temperature was raised to 120°C, and maintained for 2 hours, and then the temperature was raised to 150°C and maintained for 4 hours. Subsequently, the flat plate vulcanizer was closed and the pressure was released. After the mold was cooled, it was opened and the sample strip was taken out to obtain the composite material part.

[0072] Example 3

[0073] (1) Add 2 g of fluorinated silica to 400 mL of deionized water and disperse it thoroughly by ultrasound. Then slowly add 80 g of diphenol hexafluoropropane diglycidyl ether and continue stirring until it is evenly dispersed in the aqueous phase to form a stable mixed system. Then put it into 12K polyacrylonitrile carbon fiber, seal it with plastic wrap and immerse it for 1 hour. After that, hang it in an 80 ° C oven and dry it for 3 hours to obtain surface fluorinated silica-fluorinated epoxy modified carbon fiber.

[0074] (2) Weigh 50g of TECHSTORM 190 epoxy resin and 14g of TECHSTORM 195 curing agent respectively and heat them in a 35℃ oven for 10min to increase the fluidity of the adhesive. Wrap the modified carbon fiber tow around a 21cm long frame for 12 turns. Then remove the wrapped carbon fiber tow and fully soak it in the resin system. Then, place it in a mold preheated to 40℃ and cool it to room temperature before molding.

[0075] (3) Subsequently, cure according to the following process: Preheat the flat vulcanizer to 50 °C, place the mold on the flat plate and keep it warm under normal pressure. Observe the state of the glue solution. When it reaches the gelation state, immediately apply pressure to 15 MPa. Press-mold at 60 °C, 70 °C, and 80 °C for 1 h respectively. Then, turn off the flat vulcanizer and release the pressure. After the mold cools down, open the mold and take out the sample bar, which is the prepared composite part.

[0076] Example 4

[0077] (1) Add 6 g of fluorinated silica to 500 mL of deionized water. After ultrasonic dispersion, slowly add 40 g of 1,4-bis(hydroxyhexafluoroisopropyl) benzene diglycidyl ether and continuously stir until it is completely dissolved to obtain a homogeneous mixed system. Then put it into 3K polyacrylonitrile-based carbon fiber, seal it with plastic wrap and impregnate for 3 h. After that, hang it in an oven at 70 °C and dry for 4 h to obtain carbon fibers modified with surface fluorinated silica-fluorinated epoxy respectively.

[0078] (2) Weigh 50 g of the solution prepared with TECHSTORM 5245A epoxy resin, 48 g of TECHSTORM 5247B curing agent, and 2 g of TECHSTORM 5201C additive respectively. Place it in an oven at 65 °C and heat for 10 min to increase the fluidity of the glue solution. Wind the above modified carbon fiber tow around a 21-cm-long frame for 50 turns, then take down the wound carbon fiber tow and fully immerse it in the resin system. Subsequently, place it in a mold preheated to 70 °C and cool it to room temperature for press-molding.

[0079] [[ID=]](3) Subsequently, cure according to the following process: Preheat the flat vulcanizer to 100 °C, place the mold on the flat plate and keep it warm under normal pressure. Observe the state of the glue solution. When it reaches the gelation state, immediately apply pressure to 18 MPa. Press-mold at 100 °C, 140 °C, and 180 °C for 1 h respectively. Then, turn off the flat vulcanizer and release the pressure. After the mold cools down, open the mold and take out the sample bar, which is the prepared composite part.

[0080] In the above Examples 2 - 4, the preparation method of fluorinated silica is the same as that in Example 1.

[0081] Comparative Example 1

[0082] (1) Weigh 50 g of TECHSTORM 5245A epoxy resin, 48 g of TECHSTORM 5247B curing agent, and 2 g of TECHSTORM 5201C additive to prepare a solution, obtaining a resin system. Place it in an oven at 70 °C and heat for 10 min to increase the fluidity of the adhesive. Wind 25K polyacrylonitrile-based carbon fiber tows around a 21-cm-long frame for 6 turns, then remove the wound carbon fiber tows and fully immerse them in the resin system. Subsequently, place the carbon fiber infiltrated with resin into a mold preheated to 70 °C and cool it to room temperature for waiting for molding.

[0083] (2) Subsequently, cure according to the following process: Preheat the flat vulcanizer to 100 °C, place the mold on the flat plate and keep it at normal pressure, observe the state of the adhesive, and immediately apply pressure to 10 MPa when it reaches the gelation state. Press for 1 h at temperatures of 100 °C, 140 °C, and 180 °C respectively. Subsequently, turn off the flat vulcanizer and release the pressure. After the mold cools, open the mold and take out the specimen bar, which is the prepared composite part.

[0084] Figure 1 It is the SEM image of 25K fiber unmodified carbon fiber, and it can be clearly observed that the fiber surface is smooth.

[0085] Through Figure 2 it can be observed that there are grooves on the surface of the modified fiber, which is beneficial to enhancing the performance of the composite material.

[0086] As Figure 3 shown, it can be found that the comparative example is not modified, and obvious holes appear at the interface, indicating poor interface performance, while in Examples 1-4 with interface modification, there are basically no holes at the interface, indicating good interface performance between the fiber and the resin.

[0087] Figure 4 It is the interlaminar shear strength (ILSS) of the composite material. It can be found that compared with Comparative Example 1, the interlaminar shear strengths of Examples 1-4 have all increased.

[0088] Figure 5 It is the impact toughness of the carbon fiber composite material. It can be found that compared with Comparative Example 1, the impact toughnesses of Examples 1-4 have all increased.

[0089] The above-described are only the preferred embodiments of the present invention, and the above specific embodiments are not limitations on the present invention. Within the scope of the technical idea of the present invention, various deformations and modifications can occur. Any retouching, modification, or equivalent replacement made by those of ordinary skill in the art according to the above description belongs to the scope protected by the present invention.

Claims

1. A preparation method of a fluorine-containing carbon fiber composite material, characterized in that, It includes the following steps: a. Prepare fluorinated nanoparticles; Add the nanoparticles and fluorosilane coupling agent into a solvent and react to obtain fluorinated nanoparticles; b. Impregnate and modify the carbon fiber material; Disperse the fluorinated nanoparticles and fluorinated epoxy resin in water together to form a mixed modification liquid; First, immerse the carbon fiber material in the mixed modification liquid, and then immerse it in a common epoxy resin system to obtain a fluorinated carbon fiber composite material; Alternatively, prepare a fluorinated nanoparticle dispersion with fluorinated nanoparticles; prepare a mixed resin system with fluorinated epoxy resin and common epoxy resin; First, immerse the carbon fiber material in the fluorinated nanoparticle dispersion, and then immerse it in the mixed resin system to obtain a fluorinated carbon fiber composite material.

2. The preparation method of a fluorine-containing carbon fiber composite material according to claim 1, characterized in that, In step a: The nanoparticles are any one of nano-silica, carbon nanotubes, and nano-titanium dioxide; the fluorosilane coupling agent is any one of 1H,1H,2H,2H-perfluorooctyltriethoxysilane, 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, and 1H,1H,2H,2H-perfluorohexyltriethoxysilane; the addition amount of the fluorosilane coupling agent is 0.1% - 5% of the amount of the nanoparticles.

3. The preparation method of a fluorine-containing carbon fiber composite material according to claim 1, characterized in that, In step a: The solvent is ethanol; control the reaction time to be 1 - 6 h; after the reaction is completed, put the obtained fluorinated nanoparticles into an oven at 50 - 100 °C for drying for 0.5 - 4 h.

4. The preparation method of a fluorine-containing carbon fiber composite material according to claim 1, characterized in that, In step b: The carbon fiber material is any one of polyacrylonitrile-based carbon fiber, pitch-based carbon fiber, and phenolic-based carbon fiber; The fluorinated epoxy resin is any one of bisphenol hexafluoropropane diglycidyl ether, 1,4-bis(hydroxyhexafluoroisopropyl)benzene diglycidyl ether, and 4,4'-dihydroxyoctafluorobiphenyl diglycidyl ether; The common epoxy resin in the common epoxy resin system and the mixed resin system is any one of bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol P epoxy resin, and phenolic epoxy resin.

5. The preparation method of a fluorine-containing carbon fiber composite material according to claim 1, characterized in that, In step b: In the mixed modification liquid, the content of the fluorinated nanoparticles is 0.1% - 40%, and the content of the fluorinated epoxy resin is 0.1% - 80% by weight fraction.

6. The preparation method of a fluorine-containing carbon fiber composite material according to claim 1, characterized in that, In step b: The concentration of the fluorinated nanoparticle dispersion is 1 mg / mL - 40 mg / mL; the content of the common epoxy resin in the mixed resin system is 50% - 99.9%, and the content of the fluorinated epoxy resin is 0.1% - 50%.

7. The preparation method of a fluorine-containing carbon fiber composite material according to claim 1, characterized in that, In step b: Control the time of each impregnation treatment to be 1 h - 12 h, and after impregnation, place it at 25 °C - 120 °C for drying for 0.5 h - 24 h; Before impregnating the carbon fiber material with the common epoxy resin system or the mixed resin system, first place it in an oven at 30 - 120 °C for heating for 10 min - 15 min to increase the fluidity of the adhesive liquid.

8. The preparation method of a fluorine-containing carbon fiber composite material according to claim 1, wherein, In step b: Before impregnating the carbon fiber material with the common epoxy resin system or the mixed resin system, first perform a winding treatment; specifically, wind the carbon fiber around a frame and remove it after shaping.

9. The preparation method of a fluorine-containing carbon fiber composite material according to claim 1, wherein, In step b: the mass ratio of the carbon fiber material in the obtained fluorine-containing carbon fiber composite material is 60% to 70%.

10. A fluorine-containing carbon fiber composite material, characterized in that: It is prepared by the method according to any one of claims 1 to 9.

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