Carbon fiber reinforced polyaryletherketone composite material and preparation method thereof

Abstract

The invention relates to the field of polyaryletherketone composite materials, in particular to a carbon fiber reinforced polyaryletherketone composite material and a preparation method thereof.The preparation method comprises the following steps that carbon fibers are subjected to surface oxidation treatment to obtain oxidized carbon fibers; immersing into the sizing liquid, taking out and drying to obtain modified carbon fibers; the sizing liquid contains 0.1 to 3 weight percent of sizing agent; the sizing agent is an in-situ graft of hydroxylated polyaryletherketone and a carbon nano tube; alternately laminating the modified carbon fiber and first polyaryletherketone resin for multiple layers, and performing hot pressing to obtain a carbon fiber reinforced polyaryletherketone composite material; according to the method, the interlaminar shear strength, the bending strength and the bending modulus of the composite material can be remarkably improved.

Description

Technical Field

[0001] This invention relates to the field of polyaryletherketone composite materials, and more specifically to a carbon fiber reinforced polyaryletherketone composite material and its preparation method. Background Technology

[0002] Carbon fiber (CF) reinforced polyaryletherketone (PAEK) composites have broad application prospects in the automotive, aerospace, and biomedical fields due to their excellent mechanical properties, corrosion resistance, ease of processing, and recyclability. PAEK, as a high-performance thermoplastic polymer, possesses excellent thermal stability, chemical inertness, flame retardancy, and mechanical strength, making it an ideal matrix material for composites. However, the interfacial adhesion between CF and PAEK is weak, mainly due to the non-polar structure of the carbon fiber surface and the inertness of the PAEK chains, resulting in low stress transfer efficiency and preventing the full realization of the composite's mechanical properties.

[0003] Currently, methods for improving the interfacial adhesion between carbon fiber (CF) and carbon fiber (PAEK) mainly include plasma treatment, acid oxidation, and ozone treatment. However, these methods may damage the surface of the carbon fiber, reduce its strength, and are unlikely to achieve a dual improvement in interfacial adhesion and fiber strength. Furthermore, traditional composite material preparation methods struggle to simultaneously meet the comprehensive requirements of high strength, high modulus, and excellent interfacial adhesion. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a carbon fiber reinforced polyaryletherketone composite material and its preparation method. The method of this invention can significantly improve the interlaminar shear strength, flexural strength, and flexural modulus of the composite material.

[0005] To achieve the above objectives, the present invention is implemented through the following technical solution:

[0006] A method for preparing a carbon fiber reinforced polyaryletherketone composite material includes the following steps:

[0007] S1. Oxidized carbon fiber is obtained by surface oxidation treatment of carbon fiber.

[0008] S2. Immerse the oxidized carbon fiber in the sizing solution, remove it and dry it to obtain modified carbon fiber;

[0009] The sizing solution contains 0.1-3 wt% of a sizing agent and a first good solvent; the sizing agent is an in-situ graft of hydroxylated polyarylether ketone and carbon nanotubes;

[0010] S3. After alternatingly stacking multiple layers of the modified carbon fiber and the first polyaryletherketone resin, hot pressing is performed to obtain a carbon fiber reinforced polyaryletherketone composite material.

[0011] Furthermore, the method for obtaining the in-situ graft of hydroxylated polyarylether ketone with carbon nanotubes includes the following steps:

[0012] (1) Hydroxylated polyarylether ketones were dissolved in a second good solvent and then mixed with carbon nanotubes to form a uniformly dispersed suspension;

[0013] (2) The suspension is mixed with a dicarboxydiimide compound and an alkyl-substituted aminopyridine compound. Under stirring, the hydroxyl groups in the hydroxylated polyarylether ketone undergo an esterification reaction with the surface carboxyl groups of the carbon nanotubes. The dicarboxydiimide compound is a dehydrating condensing agent and the alkyl-substituted aminopyridine compound is a catalyst. The precipitate is obtained by precipitating in unsuitable solvents (such as alcohols, water, etc.), washing (such as alcohols, water, etc.), and drying to obtain the in-situ graft of hydroxylated polyarylether ketone and carbon nanotubes.

[0014] Furthermore, the dicarbodiimide compound is selected from one or more of N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, N,N-di-tert-butylcarbodiimide, 1,3-di-p-tolylcarbodiimide, 1-phenyl-3-cycloalkylcarbodiimide, 1-phenyl-3-(cycloalkylmethylene)carbodiimide, 1-tert-butyl-3-n-hexylcarbodiimide, and bis(trimethylsilyl)carbodiimide; the alkyl-substituted aminopyridine compound is selected from one or more of 4-dimethylaminopyridine, 2-diethylaminopyridine, and 4-dibutylaminopyridine.

[0015] Furthermore, the mass ratio of the hydroxylated polyarylether ketone, carbon nanotubes, dicarbodiimide compounds, and alkyl-substituted aminopyridine compounds is 3-8:0.1-0.8:15-20:1.2-2; the concentration of all the former materials in the second good solvent is 50-90 g / L; the temperature of the esterification reaction is 30-80℃ and the reaction time is 24-72 h; the carbon nanotubes are multi-walled carbon nanotubes with a diameter of 6-13 nm and a length of 2.5-20 micrometers.

[0016] Furthermore, the method for obtaining the hydroxylated polyarylether ketone is as follows: under a protective atmosphere, the second polyarylether ketone resin and a reducing agent are subjected to a hydrogenation reduction reaction in DMSO, so that the carbonyl group in the second polyarylether ketone resin is reduced to a hydroxyl group. After the reaction is completed, the resin is filtered, washed, and dried to obtain the hydroxylated polyarylether ketone.

[0017] Furthermore, the first polyaryletherketone resin and the second polyaryletherketone resin are selected from one or more of PEEK, PEK, PEKK, PEEKK, and PEEKKK, respectively.

[0018] The first good solvent and the second good solvent are respectively selected from one or more of DMF, DMSO, DMAc, NMP, and halogenated hydrocarbons (such as chloroform);

[0019] The reducing agent is selected from one or more of NaBH4, LiAlH4, and hydrogen. When using the hydrogen, a noble metal catalyst is required for hydrogenation.

[0020] Furthermore, in the second polyaryletherketone resin, the ratio of the number of carbonyl groups in the repeating unit of the polyaryletherketone molecule to the number of reducing agents is 1:1.3-2.3. If the amount of reducing agent is lower than the lower limit, the hydroxylation rate is low, the surface modification is incomplete, and the subsequent grafting reaction is affected. If the amount of reducing agent is higher than the upper limit, the by-products (such as borate esters) increase, and the mechanical properties are severely reduced. Preferably, in the second polyaryletherketone resin, the ratio of the number of carbonyl groups in the repeating unit of the polyaryletherketone molecule to the number of reducing agents is 1:1.5-1.8.

[0021] The concentration of the second polyaryletherketone resin in the DMSO is 30-50 g / L;

[0022] The hydrogenation reduction reaction is carried out at a temperature of 110-130℃ for a reaction time of 6-36h. A reduction reaction temperature below 120℃ can reduce the hydrolysis of NaBH4, but excessively high temperatures will accelerate the reduction and increase the risk of side reactions. Furthermore, when the temperature is above 130℃, the decomposition of NaBH4 is accelerated, which may release hydrogen gas and cause the pressure to rise, thus placing higher demands on the reaction apparatus.

[0023] Furthermore, before the carbon fiber undergoes the surface oxidation treatment, it also needs to be desizing, such as high-temperature calcination at 300-800°C, or reflux reaction in acetone for at least 12 hours.

[0024] The specific method of the surface oxidation treatment is as follows: the desizing carbon fiber is immersed in a Meldrum acid solution at 30-80℃ for 1-2 hours, followed by water washing until neutral, and then dried to obtain oxidized carbon fiber; the concentration of the Meldrum acid solution is 5-10 wt%, and the solvent is one or more of water, ethanol, and isopropanol.

[0025] Furthermore, in S2, the immersion temperature of the oxidized carbon fiber in the slurry is 15-40℃ and the immersion time is 1-3h; the hot pressing temperature is 370-390℃, the pressure is 2-10MPa, and the hot pressing time is 20-50min.

[0026] Furthermore, the modified carbon fiber comprises, by weight percentage (100wt%), oxidized carbon fiber accounts for 90%-99.9% and sizing agent accounts for 0.1%-10%;

[0027] In the composite material, the modified carbon fiber accounts for 50%-70% and the PAEK resin accounts for 30%-50% by weight of 100 wt%.

[0028] In another aspect, the present invention provides a carbon fiber reinforced polyaryletherketone composite material obtained by the above preparation method.

[0029] Beneficial technical effects: This invention involves desizing, oxidizing, and resizing carbon fibers. Using an in-situ graft of hydroxylated polyaryletherketone and carbon nanotubes as the sizing agent for the oxidized carbon fibers, only a small amount of this sizing agent is needed to improve the adhesion between the fiber and the matrix, significantly enhancing the interlaminar shear strength, flexural strength, and flexural modulus of the composite material. The method of this invention does not damage the surface of the carbon fibers, maintaining their original high strength. The process is simple, low-cost, and suitable for large-scale industrial production. The modified composite material exhibits significantly improved interlaminar shear strength, flexural strength, and flexural modulus, meeting the application requirements of high-performance composite materials. Detailed Implementation

[0030] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit the present invention or its application or use. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0031] Unless otherwise specifically stated, the numerical values ​​set forth in these embodiments do not limit the scope of the invention. Techniques and methods known to those skilled in the art may not be discussed in detail, but where appropriate, such techniques and methods should be considered part of the specification. In all examples shown and discussed herein, any specific values ​​should be interpreted as merely exemplary and not as limitations. Therefore, other examples of exemplary embodiments may have different values. It should be noted that values ​​expressed, for example, as "within the range of ab" or "between the range of ab," do not include the endpoint values ​​a and b; values ​​expressed as "for ab," "is ab," or "ab" include the endpoint values ​​a and b.

[0032] Furthermore, it should be noted that the use of terms such as "first" and "second" to limit solvents, etc., is merely for the purpose of distinguishing materials. Unless otherwise stated, the above terms have no special meaning and therefore should not be construed as limiting the scope of protection of this invention.

[0033] Experimental methods not specified in the following examples are generally performed according to national standards; if there is no corresponding national standard, they are performed according to general standard requirements or general methods.

[0034] The following case uses PEEK as an example of polyaryletherketone.

[0035] Example 1

[0036] This case study describes the preparation of hydroxylated PEEK, which includes the following steps:

[0037] Under a nitrogen protective atmosphere and with continuous stirring, PEEK resin powder (model 3600P) was added to DMSO, and NaBH4 was added in three batches. The mixture was heated to carry out a hydrogenation reduction reaction to reduce the carbonyl group in PEEK to a hydroxyl group. After the reaction was completed, the mixture was filtered and washed successively with anhydrous ethanol, deionized water, 2 mol / L dilute hydrochloric acid, and deionized water (to remove residual borate and solvent). The mixture was then dried under vacuum at 60°C to obtain hydroxylated PEEK.

[0038] The specific dosage and reaction conditions are shown in Table 1 below.

[0039] Table 1 Preparation parameters of hydroxylated PEEK

[0040]

[0041] Example 2

[0042] This case study describes the preparation of an in-situ graft of hydroxylated polyaryletherketones and carbon nanotubes, including the following steps:

[0043] (1) 4.5g of hydroxylated PEEK-I was dissolved in 100mL of DMF and stirred for 24h. Then, 100mL of DMF solution containing 0.6g of multi-walled carbon nanotubes (diameter 6-13nm, length 2.5-20μm) (pre-dispersed evenly) was added and ultrasonically mixed for 1h to form a uniformly dispersed suspension.

[0044] (2) 18.5 g of N,N'-dicyclohexylcarbodiimide (DCC) and 1.36 g of 4-(dimethylamino)pyridine (DMAP) were uniformly dissolved in 200 mL of DMF, and then mixed with the suspension described above. The mixture was stirred at 50 °C for 50 h for esterification. After the reaction was completed, the product was precipitated with anhydrous ethanol. After the product was separated, it was washed with anhydrous ethanol and water several times, and then dried in a vacuum drying oven at 60 °C to constant weight. The in-situ graft of hydroxylated polyaryletherketone multi-walled carbon nanotubes was obtained, abbreviated as MWNT-g-PEEK①.

[0045] Example 3

[0046] This case study describes the preparation of an in-situ graft of hydroxylated polyaryletherketones and carbon nanotubes, including the following steps:

[0047] (1) 4.4g of hydroxylated PEEK-II was dissolved in 100mL of DMF and stirred for 24h. Then, 100mL of DMF solution containing 0.4g of multi-walled carbon nanotubes (diameter 6-13nm, length 2.5-20μm) (pre-dispersed evenly) was added and ultrasonically mixed for 1h to form a uniformly dispersed suspension.

[0048] (2) 18.5 g of N,N'-dicyclohexylcarbodiimide (DCC) and 1.36 g of 4-(dimethylamino)pyridine (DMAP) were uniformly dissolved in 200 mL of DMF, and then mixed with the suspension described above. The mixture was stirred at 40 °C for 68 h for esterification. After the reaction was completed, the product was precipitated with anhydrous ethanol. After the product was separated, it was washed with anhydrous ethanol and water several times, and then dried in a vacuum drying oven at 60 °C to constant weight. The in-situ graft of hydroxylated polyaryletherketone multi-walled carbon nanotubes was obtained, abbreviated as MWNT-g-PEEK②.

[0049] Example 4

[0050] This case study describes the preparation of an in-situ graft of hydroxylated polyaryletherketones and carbon nanotubes, including the following steps:

[0051] (1) Dissolve 6g of hydroxylated PEEK-II in 100mL of DMF and stir for 24h. Then add 100mL of DMF solution containing 0.8g of multi-walled carbon nanotubes (diameter 6-13nm, length 2.5-20μm) (pre-dispersed evenly) and ultrasonically mix for 1h to form a uniformly dispersed suspension.

[0052] (2) 20g of N,N'-dicyclohexylcarbodiimide (DCC) and 1.5g of 4-(dimethylamino)pyridine (DMAP) were uniformly dissolved in 200mL of DMF, and then mixed with the suspension described above. The mixture was stirred at 50℃ for 48h for esterification. After the reaction was completed, the product was precipitated with anhydrous ethanol. After the product was separated, it was washed with anhydrous ethanol and water several times, and then dried in a vacuum drying oven at 60℃ to constant weight. The in-situ graft of hydroxylated polyaryletherketone multi-walled carbon nanotubes was obtained, abbreviated as MWNT-g-PEEK③.

[0053] Example 5

[0054] This case study describes a method for preparing carbon fiber reinforced polyaryletherketone composite materials, including the following steps:

[0055] S1. 100g of commercial carbon fiber fabric (CCF, model SYT45-3K) was refluxed in a sufficient amount of acetone at 80℃ for 24 hours to remove the original coating agent on the surface, and 95g of desizing carbon fiber (denoted as DCF) was obtained.

[0056] 95g of DCF was placed in 500mL of McFurther acid solution (concentration 8wt%, solvent is anhydrous ethanol) and soaked at 30℃ for 2h. Then, it was washed with deionized water until neutral to remove residual McFurther acid and reaction byproducts. The product was then separated by centrifugation or filtration and dried in a vacuum drying oven at 60℃ for 12h to obtain 90g of oxidized carbon fiber (denoted as OCF).

[0057] S2. A DMF solution containing 0.1 wt% MWNT-g-PEEK② was prepared as the sizing agent using MWNT-g-PEEK②.

[0058] 90g of OCF was immersed in 200g of the above sizing solution for 2 hours, then dried at 80°C for 12 hours, then heated to 100°C for 6 hours, and finally heated to 120°C for 2 hours to obtain 90.2g of modified carbon fiber (of which OCF accounted for about 99.78% and sizing agent accounted for about 0.22%).

[0059] S3. 90.2g of the modified carbon fiber and 80g of PEEK resin powder (model 3600P) are evenly distributed and layered in multiple layers, and then hot-pressed at 380℃ and 5MPa for 30min to obtain carbon fiber reinforced polyaryletherketone composite material (the modified carbon fiber accounts for about 53.0% and the PEEK accounts for about 47.0% of the composite material).

[0060] Example 6

[0061] The preparation method of the carbon fiber reinforced polyaryletherketone composite material in this case is the same as that in Example 5, except that the content of MWNT-g-PEEK② in the slurry of S2 is 0.3wt%.

[0062] In this case, the modified carbon fiber contained approximately 99.34% OCF and approximately 0.66% sizing agent; the composite material contained approximately 53.11% modified carbon fiber and approximately 46.89% PEEK.

[0063] Example 7

[0064] The preparation method of the carbon fiber reinforced polyaryletherketone composite material in this case is the same as that in Example 5, except that the content of MWNT-g-PEEK② in the slurry of S2 is 0.5wt%.

[0065] In this case, the modified carbon fiber contained 98.90% OCF and approximately 1.10% sizing agent; the composite material contained approximately 53.22% modified carbon fiber and 46.78% PEEK.

[0066] Example 8

[0067] The preparation method of the carbon fiber reinforced polyaryletherketone composite material in this case is the same as that in Example 5, except that the content of MWNT-g-PEEK② in the slurry of S2 is 0.7wt%.

[0068] In this case, the modified carbon fiber contained approximately 98.47% OCF and approximately 1.53% sizing agent; the composite material contained approximately 53.32% modified carbon fiber and approximately 46.67% PEEK.

[0069] Example 9

[0070] The preparation method of the carbon fiber reinforced polyaryletherketone composite material in this case is the same as that in Example 5, except that the content of MWNT-g-PEEK② in the slurry of S2 is 1.0wt%.

[0071] In this case, the modified carbon fiber contained 97.83% OCF and approximately 2.17% sizing agent; the composite material contained approximately 53.49% modified carbon fiber and approximately 46.51% PEEK.

[0072] Example 10

[0073] The preparation method of the carbon fiber reinforced polyaryletherketone composite material in this case is the same as that in Example 8, except that MWNT-g-PEEK① is dissolved in DMF in the slurry of S2; and the amount of PEEK resin powder used in S3 is 90g.

[0074] In this case, the modified carbon fiber contained 97.83% OCF and approximately 2.17% sizing agent; the composite material contained approximately 50.39% modified carbon fiber and approximately 49.61% PEEK.

[0075] Example 11

[0076] The preparation method of the carbon fiber reinforced polyaryletherketone composite material in this case is the same as that in Example 8, except that MWNT-g-PEEK③ is dissolved in DMF in the slurry of S2; and the amount of PEEK resin powder used in S3 is 55g.

[0077] In this case, the modified carbon fiber contained 97.83% OCF and approximately 2.17% sizing agent; the composite material contained approximately 62.43% modified carbon fiber and approximately 37.57% PEEK.

[0078] Comparative Example 1

[0079] The composite material preparation method in this case is the same as S3 in Example 5. The difference is that commercial carbon fiber fabric (CCF, model SYT45-3K) and PEEK resin powder are directly hot-pressed together, and the proportion of CCF in the composite material is controlled to be 55wt% and the proportion of PEEK to be 45wt%.

[0080] Comparative Example 2

[0081] The composite preparation method in this case is the same as S3 in Example 5. The difference is that the desizing carbon fiber (DCF) and PEEK resin powder obtained in step S1 of Example 5 are directly hot-pressed together, and the proportion of DCF in the composite is controlled to be 55wt% and the proportion of PEEK to be 45wt%.

[0082] Comparative Example 3

[0083] The composite material preparation method in this case is the same as S3 in Example 5. The difference is that the oxidized carbon fiber (OCF) and PEEK resin powder from step S1 in Example 5 are directly hot-pressed together, and the OCF content in the composite material is controlled to be 55wt% and the PEEK content to be 45wt%.

[0084] Comparative Example 4

[0085] The composite material preparation method in this case is the same as S3 in Example 5, except that...

[0086] OCF is obtained by oxidizing DCF with concentrated sulfuric acid. The specific process is as follows: DCF is placed in 70% concentrated sulfuric acid and soaked at 50°C for 3 hours. Then it is washed with a large amount of deionized water until neutral and finally vacuum dried at 60°C for 12 hours to obtain OCF.

[0087] SPEEK (50% sulfonation, model SPV-50) was dissolved in DMF to form a sizing solution (containing 5 wt% SPEEK) to treat the OCF (obtained by treatment with concentrated sulfuric acid) from the previous step. The OCF was treated with the same method as in S2 of Example 5 to obtain modified carbon fiber (OCF content 90 wt%, sizing agent content 10 wt%). The composite material was prepared using the same method as in S3 of Example 5. The obtained composite material contained approximately 55.6% modified carbon fiber and approximately 44.4% PEEK.

[0088] The composite properties of Examples 5-11 and the comparative examples are shown in Table 2 below.

[0089] Table 2 Composite performance of each case

[0090]

[0091] Table 2 shows that modifying carbon fibers with MWNT-g-PEEK significantly improves the interlaminar shear strength, flexural strength, and flexural modulus of the composite material, while reducing porosity; in particular, using a 0.7 wt% MWNT-g-PEEK② sizing agent provides the best overall performance. This indicates that the modification method of this invention can effectively improve the interfacial adhesion between carbon fibers and the PEEK matrix.

[0092] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A method for preparing a carbon fiber reinforced polyaryletherketone composite material, characterized in that, Includes the following steps: S1. Oxidized carbon fiber is obtained by surface oxidation treatment of carbon fiber. S2. Immerse the oxidized carbon fiber in the sizing solution, remove it and dry it to obtain modified carbon fiber; The sizing solution contains 0.1-3 wt% sizing agent and a first good solvent; The sizing agent is an in-situ graft of hydroxylated polyaryletherketone and carbon nanotubes; S3. After alternatingly stacking multiple layers of the modified carbon fiber and the first polyaryletherketone resin, hot pressing is performed to obtain a carbon fiber reinforced polyaryletherketone composite material.

2. The method for preparing a carbon fiber reinforced polyaryletherketone composite material according to claim 1, characterized in that, The method for obtaining the in-situ graft of hydroxylated polyarylether ketone and carbon nanotube includes the following steps: (1) Hydroxylated polyarylether ketones were dissolved in a second good solvent and then mixed with carbon nanotubes to form a uniformly dispersed suspension; (2) The suspension is mixed with a dicarbodiimide compound and an alkyl-substituted aminopyridine compound. Under stirring, the hydroxyl groups in the hydroxylated polyarylether ketone undergo an esterification reaction with the surface carboxyl groups of the carbon nanotubes. The dicarbodiimide compound is a dehydrating condensing agent and the alkyl-substituted aminopyridine compound is a catalyst. The precipitate is obtained by precipitating out the undesirable solvent, washing, and drying to obtain the in-situ graft of hydroxylated polyarylether ketone and carbon nanotubes.

3. The method for preparing a carbon fiber reinforced polyaryletherketone composite material according to claim 2, characterized in that, The dicarbodiimide compounds are selected from one or more of N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, N,N-di-tert-butylcarbodiimide, 1,3-di-p-tolylcarbodiimide, 1-phenyl-3-cycloalkylcarbodiimide, 1-phenyl-3-(cycloalkylmethylene)carbodiimide, 1-tert-butyl-3-n-hexylcarbodiimide, and bis(trimethylsilyl)carbodiimide; The alkyl-substituted aminopyridine compound is selected from one or more of 4-dimethylaminopyridine, 2-diethylaminopyridine, and 4-dibutylaminopyridine.

4. The method for preparing a carbon fiber reinforced polyaryletherketone composite material according to claim 3, characterized in that, The mass ratio of the hydroxylated polyarylether ketone, carbon nanotubes, dicarbodiimide compound, and alkyl-substituted aminopyridine compound is 3-8:0.1-0.8:15-20:1.2-2; the total amount of the hydroxylated polyarylether ketone, carbon nanotubes, dicarbodiimide compound, and alkyl-substituted aminopyridine compound in the second good solvent is 50-90 g / L. The esterification reaction is carried out at a temperature of 30-80℃ for a reaction time of 24-72 hours. The carbon nanotubes are multi-walled carbon nanotubes with a diameter of 6-13 nm and a length of 2.5-20 μm.

5. The method for preparing a carbon fiber reinforced polyaryletherketone composite material according to claim 2, characterized in that, The method for obtaining the hydroxylated polyarylether ketone is as follows: under a protective atmosphere, a second polyarylether ketone resin and a reducing agent are subjected to a hydrogenation reduction reaction in DMSO, so that the carbonyl group in the second polyarylether ketone resin is reduced to a hydroxyl group. After the reaction is completed, the resin is filtered, washed, and dried to obtain the hydroxylated polyarylether ketone.

6. The method for preparing a carbon fiber reinforced polyaryletherketone composite material according to claim 5, characterized in that, The first polyaryletherketone resin and the second polyaryletherketone resin are respectively selected from one or more of PEEK, PEK, PEKK, PEEKK and PEKEKK; The first good solvent and the second good solvent are respectively selected from one or more of DMF, DMSO, DMAc, NMP, and haloalkanes; The reducing agent is selected from one or more of NaBH4, LiAlH4, and hydrogen. When using the hydrogen, a noble metal catalyst is required for hydrogenation. In the second polyaryletherketone resin, the ratio of the number of carbonyl groups in the repeating unit of the polyaryletherketone molecule to the number of reducing agents is 1:1.3-2.3; The concentration of the second polyaryletherketone resin in the DMSO is 30-50 g / L; The hydrogenation reduction reaction is carried out at a temperature of 110-130℃ for a reaction time of 6-36 hours.

7. A method for preparing a carbon fiber reinforced polyaryletherketone composite material according to any one of claims 1-6, characterized in that, In S1, the carbon fiber needs to undergo a desizing treatment before the surface oxidation treatment is performed; The specific method of the surface oxidation treatment is as follows: the desizing carbon fiber is immersed in the McFarland acid solution at 30-80℃ for 1-2 hours, then washed with water until neutral, and dried to obtain oxidized carbon fiber; the concentration of the McFarland acid solution is 5-10wt%, and the solvent is one or more of water, ethanol, and isopropanol.

8. A method for preparing a carbon fiber reinforced polyaryletherketone composite material according to any one of claims 1-6, characterized in that, The oxidized carbon fiber described in S2 is immersed in the slurry at a temperature of 15-40℃ for 1-3 hours; the hot pressing temperature is 370-390℃, the pressure is 2-10 MPa, and the hot pressing time is 20-50 minutes.

9. A method for preparing a carbon fiber reinforced polyaryletherketone composite material according to any one of claims 1-6, characterized in that, In the composite material, the modified carbon fiber accounts for 50%-70% and the PAEK resin accounts for 30%-50% by weight of 100 wt%. The modified carbon fiber comprises, by weight percentage (100wt%), 90%-99.9% oxidized carbon fiber and 0.1%-10% sizing agent.

10. A carbon fiber reinforced polyaryletherketone composite material, characterized in that, It is prepared using the preparation method according to any one of claims 1-9.

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