CN102409528B - A kind of preparation method of graphene oxide grafted carbon fiber reinforced body - Google Patents

Abstract

A preparation method of a carbon fiber reinforcement grafted by graphene oxide relates to a preparation method of a carbon fiber reinforcement grafted by graphene oxide. The invention solves the problems of harsh process conditions, long process period, toxic process, and difficult industrial production for current carbon fiber surface modification methods. The invention adopts a 'grafting' method, and grafts graphene oxide on acidified carbon fiber surfaces through an acylation reaction by using polyamide-amine with a lot of amido active groups; the invention has low cost, is simple, practical, environment-friendly, and nontoxic, and can be completed within a short period. The method particularly comprises the following steps: mixing acidified carbon fibers and a polyamide-amine methanolsolution, reacting to prepare carbon fibers modified by polyamide-amine, adding the prepared carbon fibers in a graphene oxide acetone suspension, mixing, reacting, filtering, drying the precipitatestill the weight is constant. The obtained carbon fiber reinforcement has interfacial shear strength with epoxy resin of up to 79.77-105.50 MPa which is improved.

Description

A kind of preparation method of graphene oxide grafted carbon fiber reinforced body

technical field

The invention relates to a preparation method of a graphene oxide grafted carbon fiber reinforced body.

Background technique

Carbon fiber (CF) is an important reinforcement material developed after the 1950s. The mechanical properties of its composites are closely related to the interfacial bond strength between carbon fiber and matrix. Good interfacial bonding can effectively transfer loads, thereby improving the mechanical properties of materials. However, the surface of untreated carbon fiber is inert and the interface with the resin matrix is weak, which affects the full play of the excellent performance of carbon fiber composite materials. Therefore, it is usually necessary to carry out surface treatment on carbon fiber to improve the interfacial bonding quality of its composite material, thereby improving the interfacial mechanical properties of the material. Commonly used carbon fiber surface modification methods mainly include chemical vapor deposition, chemical oxidation, and chemical grafting. These methods can increase the surface polarity or specific surface area of carbon fibers to varying degrees, and improve the interfacial properties between them and resins. However, the traditional carbon fiber surface modification method also has problems such as demanding process conditions and technical equipment, long process time, toxic process, and difficulty in industrialized mass production. Graphene oxide has good mechanical properties, simple preparation, good dispersion, and rich functional groups on the surface, but there are few reports on its modification of carbon fiber surface.

Contents of the invention

The purpose of the present invention is to solve the problems that the existing carbon fiber surface modification method has harsh process conditions, long process time, toxic process and difficult industrial production. The present invention provides a preparation method of graphene oxide grafted carbon fiber reinforcement .

The preparation method of the graphene oxide grafted carbon fiber reinforced body of the present invention is realized through the following steps: one, carbon fiber is carried out acidification treatment, obtains acidification carbon fiber; (PAMAM) methanol solution is mixed to obtain a mixed solution, then the mixed solution is heated to 20°C-50°C, and then reacted at a constant temperature for 4-12 hours, then the acidified carbon fiber is taken out and washed with methanol for 2-5 times and water for 2-5 times , and then vacuum-dried at 40-60°C to constant weight to obtain polyamide-amine-modified carbon fibers, wherein the mass ratio of acidified carbon fiber to polyamide-amine is 0.1-4:1; 3. Add graphene oxide to acetone solution , ultrasonic treatment for 20 to 60 minutes to obtain a graphene oxide acetone suspension with a graphene oxide concentration of 0.01 to 1 g/L; 4. Add the polyamide-amine-modified carbon fiber prepared in step 2 to the oxidized carbon fiber prepared in step 3. The mixed solution is obtained from the graphene acetone suspension, and then the mixed solution is heated to 60-100°C, then reacted at a constant temperature for 6-12 hours, and then filtered, and the filtered precipitate is alternately washed with acetone and deionized water for 3-6 hours. Once again, the precipitate after washing is vacuum-dried to constant weight at 40-60°C to obtain a graphene oxide grafted carbon fiber reinforcement; wherein the mass ratio of graphene oxide to polyamide-amine-modified carbon fiber is controlled in step 4 It is 1:1.5～9.

In step 1 of the present invention, the existing disclosed method may be used to acidify the carbon fiber. For example, the present invention can adopt the following method to carry out acidification treatment to carbon fiber: according to the ratio of carbon fiber and concentrated nitric acid is 1g: 350ml, carbon fiber is added in concentrated nitric acid, and then under the constant temperature condition of 70 ℃～90 ℃, after reacting for 1～3h, Take out the carbon fiber, wash until the pH value of the washing solution is about 7, and then dry it at 80°C and -0.1MPa for 2 to 6 hours to obtain the acidified carbon fiber.

The graphene oxide used in the third step of the present invention is prepared by using the existing disclosed method. For example, the present invention can adopt the following method to prepare graphene oxide: a. Add concentrated sulfuric acid to the reactor, and then, under stirring, Add graphite powder and sodium nitrate into the reactor to obtain mixture A, then stir mixture A at 0°C for 20-40 minutes, and then add potassium permanganate to the reactor to obtain mixture B, wherein the volume of concentrated sulfuric acid The mass ratio of graphite powder and sodium nitrate is 18～24mL: 1g, the mass ratio of graphite powder and sodium nitrate is 2:1, and the mass ratio of potassium permanganate and sodium nitrate is 6:1; b, mixture B is mixed at 30～40 Stir and react at a constant temperature at ℃ for 20-40 minutes to obtain a mixture C, then add dropwise warm water at 30-40°C to the mixture C to dilute to a volume 2.8-3.5 times that of the mixture C, then raise the temperature to 90-100°C, and then react at a constant temperature 50 to 90 minutes to obtain mixture D; c. Dilute the mixture D with warm water at 30 to 40°C until the volume is 5.8 to 8 times the volume of concentrated sulfuric acid in step a, and then add H ₂ O ₂ with a concentration of 30% by mass, Stir evenly to obtain mixture E, then suction filter mixture E and wash with deionized water until the filtrate is neutral, then dry the precipitate at 40-60°C under vacuum for 5-8 hours to obtain graphite oxide, wherein 30% of The ratio of the volume of _H2O2 to the mass of sodium _nitrate in step a is 4mL: 1g; d, the graphite oxide obtained in step c is placed in an ethanol solution, and ultrasonically dispersed for 50-90min to obtain a sol of graphene oxide, and then Graphene oxide can be obtained by drying the graphene oxide sol at 40-60° C. under vacuum for 5 hours. Wherein step a will control the adding speed of potassium permanganate when adding potassium permanganate, do not make the temperature in the reactor rise too fast.

The graphene oxide grafted carbon fiber reinforced body of the present invention is obtained by grafting graphene oxide onto polyamide-amine modified carbon fibers.

The "grafting-to" method ("Grafting-to" method) used in the present invention utilizes acylation reaction to graft graphene oxide with abundant functional groups on the surface by means of polyamide-amine (PAMAM) with a large number of amine active groups. Branching to the carbon fiber surface after acid oxidation treatment has the characteristics of low cost, no need for long-term high-temperature heating, simple and easy, environmentally friendly and non-toxic, and the main process can be completed in a relatively short period of time.

In addition, in the carbon fiber/epoxy resin composite material prepared by using the new graphene oxide grafted carbon fiber reinforcement obtained by the method of the present invention as a reinforcement, the graphene oxide grafted carbon fiber new reinforcement not only has a mechanical engagement with the matrix, but also The surface has a large number of active functional groups, which are easy to form chemical bonds with the matrix, which improves the surface energy and wetting performance of carbon fibers, and makes the interface shear strength of carbon fibers and epoxy resin reach 79.77-105.50MPa, which is higher than that of ordinary carbon fibers and epoxy resin. Strength (37.68MPa) increased by 110% to 180%.

Description of drawings

Fig. 1 is a scanning electron micrograph of the graphene oxide grafted carbon fiber reinforcement prepared in Embodiment 18.

Detailed ways

The technical solution of the present invention is not limited to the specific embodiments listed below, but also includes any combination of the specific embodiments.

Specific Embodiment 1: This embodiment is a preparation method of graphene oxide grafted carbon fiber reinforcement, which is achieved through the following steps: 1. Carbon fiber is subjected to acidification treatment to obtain acidified carbon fiber; 2. The acidified carbon fiber and mass percentage concentration Mix 1% polyamide-amine (PAMAM) methanol solution to obtain a mixed solution, then raise the temperature of the mixed solution to 20°C-50°C, and then react at a constant temperature for 4-12 hours, then take out the acidified carbon fiber and wash it with methanol for 2-5 wash with water for 2-5 times, and then vacuum-dry at 40-60°C to constant weight to obtain polyamide-amine-modified carbon fibers, wherein the mass ratio of acidified carbon fibers to polyamide-amine is 0.1-4:1; three 1. Add graphene oxide into the acetone solution, and ultrasonically treat it for 20-60 minutes to obtain a graphene oxide acetone suspension with a graphene oxide concentration of 0.01-1 g/L; Carbon fibers are added to the graphene oxide acetone suspension prepared in step 3 to obtain a mixed solution, then the mixed solution is heated to 60-100°C, and then reacted at a constant temperature for 6-12 hours, and then filtered, and the filtered precipitate is sequentially washed with acetone and Alternate washing with deionized water for 3 to 6 times, and then vacuum-drying the washed precipitate to constant weight at 40 to 60°C to obtain a graphene oxide grafted carbon fiber reinforcement; in step 4, control graphene oxide and polyamide - The mass ratio of the amine-modified carbon fibers is 1:1.5-9.

In Step 1 of this embodiment, the existing disclosed method may be used to acidify the carbon fiber. The graphene oxide used in the third step is prepared by the existing disclosed method. The polyamide-amine (PAMAM) used in step 2 of this embodiment is a commercially available product.

The "grafting-to" method adopted in this embodiment utilizes acylation reaction, with the help of polyamide-amine (PAMAM) with a large number of amine-based active groups, the graphene oxide with abundant functional groups on the surface Grafting to the carbon fiber surface after acid oxidation treatment has the characteristics of low cost, no need for long-term high-temperature heating, simple and easy, environmentally friendly and non-toxic, and the main process can be completed in a relatively short period of time.

In addition, in the carbon fiber/epoxy resin composite material prepared by using the new graphene oxide grafted carbon fiber reinforcement obtained by the method of this embodiment as a reinforcement, the graphene oxide grafted carbon fiber new reinforcement not only has mechanical engagement with the matrix , and the surface has a large number of active functional groups, which are easy to form chemical bonds with the matrix, improve the surface energy and wettability of carbon fibers, and make the interface shear strength of carbon fibers and epoxy resin grafted in this embodiment reach 79.77-105.50MPa, which is higher than ordinary The interfacial shear strength (37.68MPa) of carbon fiber and epoxy resin increased by 110%-180%.

Specific embodiment two: the difference between this embodiment and specific embodiment one is that the carbon fiber is acidified by the following method in the step one: the ratio of carbon fiber and concentrated nitric acid is 1g: 350ml, the carbon fiber is added in the concentrated nitric acid, and then at 70 After reacting at a constant temperature of ℃-90℃ for 1-3h, take out the carbon fiber, wash until the pH of the washing solution is about 7, and then dry it at 80℃ and -0.1MPa for 2-6h to obtain acidified carbon fiber. Other steps and parameters are the same as those in Embodiment 1.

In this embodiment, before the carbon fiber is acidified, the carbon fiber is subjected to conventional desizing treatment. The specific desizing treatment can be carried out as follows: put the carbon fiber into an analytically pure acetone solution, reflux at a constant temperature for 24-48 hours at 70-80° C., and perform desizing treatment.

Specific embodiment 3: The difference between this embodiment and specific embodiment 1 or 2 is that in step 2, the temperature of the mixed solution is raised to 25° C. to 40° C., and then reacted at a constant temperature for 6 to 10 hours. Other steps and parameters are the same as those in Embodiment 1 or Embodiment 2.

Embodiment 4: The difference between this embodiment and Embodiment 1 or 2 is that in Step 2, the temperature of the mixed solution is raised to 30° C., and then reacted at constant temperature for 8 hours. Other steps and parameters are the same as those in Embodiment 1 or Embodiment 2.

Embodiment 5: The difference between this embodiment and one of Embodiments 1 to 4 is that in step 2, vacuum drying is carried out at 50° C. to constant weight. Other steps and parameters are the same as in one of the specific embodiments 1 to 4.

Embodiment 6: This embodiment differs from Embodiment 1 to Embodiment 5 in that the mass ratio of acidified carbon fiber to polyamide-amine in step 2 is 0.5-2:1. Other steps and parameters are the same as one of the specific embodiments 1 to 5.

Embodiment 7: The difference between this embodiment and one of Embodiments 1 to 5 is that the mass ratio of acidified carbon fiber to polyamide-amine in step 2 is 1:1. Other steps and parameters are the same as one of the specific embodiments 1 to 5.

Specific embodiment eight: the difference between this embodiment and one of specific embodiments one to seven is that the graphene oxide adopted in step 3 is prepared by the following method: a, adding concentrated sulfuric acid to the reactor, and then under stirring, Add graphite powder and sodium nitrate to the reactor to obtain mixture A, then stir mixture A at 0°C for 20-40 minutes, and then add potassium permanganate to the reactor to obtain mixture B, in which concentrated sulfuric acid The ratio of volume and sodium nitrate quality is 18～24mL: 1g, the mass ratio of graphite powder and sodium nitrate is 2: 1, the mass ratio of potassium permanganate and sodium nitrate is 6: 1; b, mix B at 30～ Stir and react at 40°C for 20-40 minutes to obtain mixture C, then add 30-40°C warm water dropwise to mixture C to dilute to a volume 2.8-3.5 times that of mixture C, then raise the temperature to 90-100°C, and then keep the temperature constant React for 50-90 minutes to obtain mixture D; c. Dilute the mixture D with warm water at 30-40°C until the volume is 5.8-8 times the volume of concentrated sulfuric acid in step a, and then add H ₂ O ₂ with a concentration of 30% by mass , stirred evenly to obtain a mixture E, then the mixture E was suction-filtered and washed with deionized water until the filtrate was neutral, and then the precipitate was dried under vacuum at 40-60°C for 5-8 hours to obtain graphite oxide, wherein the added 30 The ratio of the volume of % H ₂ O ₂ to the mass of sodium nitrate in step a is 4mL: 1g; d, the graphite oxide obtained in step c is placed in an ethanol solution, and ultrasonically dispersed for 50-90min to obtain a sol of graphene oxide, The graphene oxide sol can be obtained by drying the graphene oxide sol at 40-60° C. under vacuum for 5 hours. Other steps and parameters are the same as one of the specific embodiments 1 to 7.

In this embodiment, when adding potassium permanganate in step a, the adding speed of potassium permanganate should be controlled, so as not to make the temperature in the reactor rise too fast.

The preparation method of this embodiment is simple and easy, and the prepared graphene oxide has the advantages of good dispersibility, and the surface is convenient for grafting due to its abundant functional groups.

Embodiment 9: The difference between this embodiment and Embodiment 1 to Embodiment 8 is that the graphene oxide acetone suspension with a graphene oxide concentration of 0.05-0.8 g/L is obtained in step 3. Other steps and parameters are the same as those in Embodiments 1 to 8.

Embodiment 10: This embodiment differs from Embodiments 1 to 8 in that the graphene oxide acetone suspension with a graphene oxide concentration of 0.1-0.6 g/L is obtained in step 3. Other steps and parameters are the same as those in Embodiments 1 to 8.

Embodiment 11: The difference between this embodiment and Embodiment 1 to Embodiment 8 is that in Step 3, a suspension of graphene oxide in acetone with a graphene oxide concentration of 0.2-0.4 g/L is obtained. Other steps and parameters are the same as those in Embodiments 1 to 8.

Embodiment 12: This embodiment is different from Embodiment 1 to Embodiment 8 in that the graphene oxide acetone suspension with a graphene oxide concentration of 0.3 g/L is obtained in step 3. Other steps and parameters are the same as those in Embodiments 1 to 8.

Embodiment 13: This embodiment differs from Embodiments 1 to 12 in that in step 4, the temperature of the mixed solution is raised to 100° C., and then reacted at a constant temperature for 6 to 12 hours. Other steps and parameters are the same as those in Embodiments 1 to 12.

Embodiment 14: The difference between this embodiment and Embodiment 1 to 12 is that in step 4, the temperature of the mixed solution is raised to 100° C., and then reacted at constant temperature for 10 h. Other steps and parameters are the same as those in Embodiments 1 to 12.

Embodiment 15: This embodiment differs from Embodiments 1 to 14 in that the mass ratio of graphene oxide to carbon fiber modified with polyamide-amine is controlled to be 1:1.8-5 in step 4. Other steps and parameters are the same as those in Embodiments 1 to 14.

Embodiment 16: This embodiment differs from Embodiment 1 to Embodiment 14 in that the mass ratio of graphene oxide to carbon fiber modified with polyamide-amine is controlled to be 1:2 in step 4. Other steps and parameters are the same as those in Embodiments 1 to 14.

Embodiment 17: This embodiment is the graphene oxide grafted carbon fiber reinforced body of one of the embodiments 1 to 16. The graphene oxide used in step 3 is prepared by the following method: a. Add 90mL~120mL concentrated sulfuric acid into the reactor, and then add 10g of graphite powder and 5g of sodium nitrate into the reactor under stirring to obtain a mixture A, then stir the mixture A at 0°C for 20~40min, then Then add 30g of potassium permanganate to the reactor to obtain mixture B; b. Stir the mixture B at 35°C for 30 minutes to obtain mixture C, then add 225mL of warm water at 30-40°C to the mixture C to dilute , then raised the temperature to 98°C, and then reacted at a constant temperature for 60 minutes to obtain a mixture D; c. Dilute the mixture D with warm water at 30-40°C to a volume of 700mL, and then add 20mL of H ₂ O ₂ with a concentration of 30% by mass, Stir evenly to obtain mixture E, then suction filter mixture E and wash with deionized water until the filtrate is neutral, then dry the precipitate at 50°C under vacuum for 5 hours to obtain graphite oxide; d, place the graphite oxide obtained in step c In an ethanol solution, ultrasonically disperse for 60 minutes to obtain a sol of graphene oxide, and then dry the sol of graphene oxide at 50° C. under vacuum for 5 hours to obtain graphene oxide.

In step c of this embodiment, the mixture E is then suction-filtered and washed with deionized water until the filtrate is neutral. The specific operation is as follows: first wash twice with 5% (mass) HCl, and then wash three times with water until the filtrate is neutral.

In step d of this embodiment, ultrasonic dispersion is carried out for 60 minutes under the conditions of 150 W and 75 KHz.

The preparation method of this embodiment is simple and easy, and the prepared graphene oxide has the advantages of good dispersibility, and the surface is convenient for grafting due to its abundant functional groups.

Embodiment 18: This embodiment is a method for preparing a graphene oxide grafted carbon fiber reinforcement, which is achieved through the following steps: 1. Acidify the carbon fiber to obtain an acidified carbon fiber; 2. Mix the acidified carbon fiber with the mass percentage Mix the polyamide-amine (PAMAM) methanol solution with a concentration of 1% to obtain a mixed solution, then raise the temperature of the mixed solution to 30°C, and then react at a constant temperature for 8 hours, then take out the acidified carbon fiber and wash it with methanol for 3 times and water for 3 times , and then vacuum-dried at 50°C to constant weight to obtain polyamide-amine-modified carbon fibers, wherein the mass ratio of acidified carbon fibers to polyamide-amine was 1:1; 3. Add graphene oxide into acetone solution and ultrasonically treat 60min, get the graphene oxide acetone suspension that graphene oxide concentration is 0.3g/L; Four, the carbon fiber that the polyamide-amine modification that step 2 prepares is added in the graphene oxide acetone suspension that step 3 prepares The mixed solution was obtained, and then the mixed solution was heated to 100° C., then reacted at a constant temperature for 10 h, and then filtered, and the filtered precipitate was washed alternately with acetone and deionized water for 5 times, and then the washed precipitate was heated at 50° C. Vacuum drying to constant weight to obtain a graphene oxide grafted carbon fiber reinforcement; wherein in step 4, the mass ratio of graphene oxide and polyamide-amine modified carbon fiber is controlled to be 1:2.

In Step 1 of this embodiment, the method described in Embodiment 2 is used to acidify the carbon fibers.

In Step 3 of this embodiment, the graphene oxide is prepared by the method described in Embodiment 17.

The carbon fibers used in this embodiment are domestic fibers produced and provided by Jilin Shenzhou Carbon Fiber Co., Ltd. (carbon fiber specification: 12K).

The scanning electron micrograph of the graphene oxide grafted carbon fiber reinforcement prepared in this embodiment is shown in FIG. 1 . It can be seen that a large amount of graphene oxide has been successfully grafted on the surface of the carbon fiber.

In this embodiment, the prepared graphene oxide grafted carbon fiber reinforcement is tested for its interface shear strength with epoxy resin. The test method is as follows: 1. Mix epoxy resin E-51 and curing agent 3,3'- Ethyl 4,4'-diaminodiphenylmethane (referred to as H-256) is formulated into a glue solution at a mass ratio of 100:32, and the glue solution is dropped on the single graphene oxide grafted carbon fiber prepared in this embodiment , so that the glue droplets wrap the carbon fibers, and expose the two ends of the carbon fibers outside the glue droplets to obtain a prefabricated body; 2. Put the prefabricated body under the conditions of 90°C/1h+120°C/2h+150°C/2h Curing to obtain a single fiber/epoxy resin droplet composite material sample; 3. Using the FA-620 tester of Japan Toei Co., Ltd., the interfacial shear strength of the sample was tested by the micro-debonding method.

It is measured that the interface shear strength between the graphene oxide grafted carbon fiber reinforcement prepared in this embodiment and the epoxy resin reaches 105.50 MPa. Compared with the interfacial shear strength of unmodified domestic carbon fiber and epoxy resin (recorded in the twenty-first specific embodiment), it has increased by 180%.

Embodiment 19: This embodiment is different from Embodiment 18 in that the mass ratio of graphene oxide and carbon fiber modified with polyamide-amine is controlled to be 1:3 in step 4. Other steps and parameters are the same as those in Embodiment 18.

The carbon fibers used in this embodiment are domestic fibers produced and provided by Jilin Shenzhou Carbon Fiber Co., Ltd. (carbon fiber specification: 12K).

The graphene oxide grafted carbon fiber reinforcement prepared in this embodiment is used to prepare a test sample, and the specific method for preparing the test sample is the same as that described in Embodiment 18. The interfacial shear strength of the graphene oxide grafted carbon fiber reinforcement prepared in this embodiment and the epoxy resin was tested to reach 95.08 MPa. Compared with the interfacial shear strength of unmodified domestic carbon fiber and epoxy resin (recorded in the twenty-first specific embodiment), it has increased by 152%.

Embodiment 20: This embodiment is different from Embodiment 18 in that the mass ratio of graphene oxide and polyamide-amine modified carbon fiber is controlled to be 1:5 in step 4. Other steps and parameters are the same as those in Embodiment 18.

The carbon fibers used in this embodiment are domestic fibers produced and provided by Jilin Shenzhou Carbon Fiber Co., Ltd. (carbon fiber specification: 12K).

The graphene oxide grafted carbon fiber reinforcement prepared in this embodiment is used to prepare a test sample, and the specific method for preparing the test sample is the same as that described in Embodiment 18. The interfacial shear strength of the graphene oxide grafted carbon fiber reinforcement prepared in this embodiment and the epoxy resin obtained by the test is 79.77 MPa. Compared with the interfacial shear strength of unmodified domestic carbon fiber and epoxy resin (recorded in the twenty-first specific embodiment), it has increased by 112%.

Specific Embodiment Twenty-one: This embodiment is a comparative experiment: test the interface shear strength of domestic carbon fiber and epoxy resin, the test method is as follows: 1. Mix epoxy resin E-51 and curing agent 3,3'-diethyl The base 4,4'-diaminodiphenylmethane (referred to as H-256) is formulated into a glue solution at a mass ratio of 100:32, and the glue solution is dropped on a single domestic carbon fiber, so that the glue solution droplet wraps the carbon fiber, and The two ends of the carbon fiber are exposed outside the glue droplet to obtain a preform; 2. The preform is cured under the conditions of 90°C/1h+120°C/2h+150°C/2h to obtain a single fiber/epoxy resin droplet Composite material sample; 3. Use the FA-620 tester of Japan Toei Co., Ltd. to test the interfacial shear strength of the sample by micro-debonding method.

The measured interfacial shear strength of domestic carbon fiber and epoxy resin is 37.68MPa.

The domestic fiber used in this embodiment is the carbon fiber (specification: 12K) produced by Jilin Shenzhou Carbon Fiber Co., Ltd.

Claims (10)

1. the preparation method of a carbon fiber reinforcement grafted by graphene oxide, is characterized in that the preparation method of carbon fiber reinforcement grafted by graphene oxide, and it is realized by following steps: one, carbon fiber is carried out to acidification, obtain the acidifying carbon fiber; Two, the polyamide-amide methanol solution that is 1% by acidifying carbon fiber and mass percent concentration is mixed to get mixed liquor, then mixed liquor is warming up to 20 ℃～50 ℃, isothermal reaction 4～12h again, then use successively methanol wash 2～5 times and water washing 2～5 times after the acidifying carbon fiber being taken out, again 40～60 ℃ of lower vacuumizes to constant weight, obtain the carbon fiber that polyamide-amide is modified, wherein the mass ratio of acidifying carbon fiber and polyamide-amide is 0.1～4: 1; Three, graphene oxide is added in acetone soln to ultrasonic processing 20～60min, the graphite oxide allydione turbid liquid that to obtain graphene oxide concentration be 0.01～1g/L; Four, obtain mixed liquor in the graphite oxide allydione turbid liquid that the carbon fiber that polyamide-amide step 2 prepared is modified adds step 3 to prepare, then mixed liquor is warming up to 60～100 ℃, isothermal reaction 6～12h again, then filter, by filter sediment with acetone and deionized water, alternately wash 3～6 times successively, sediment after washing again to constant weight, obtains carbon fiber reinforcement grafted by graphene oxide 40～60 ℃ of lower vacuumizes; The mass ratio of wherein in step 4, controlling the carbon fiber of graphene oxide and polyamide-amide modification is 1: 1.5～9.

2. the preparation method of a kind of carbon fiber reinforcement grafted by graphene oxide according to claim 1, is characterized in that in step 2, the mass ratio of acidifying carbon fiber and polyamide-amide is 0.5～2: 1.

3. the preparation method of a kind of carbon fiber reinforcement grafted by graphene oxide according to claim 1, is characterized in that in step 2, the mass ratio of acidifying carbon fiber and polyamide-amide is 1: 1.

4. according to claim 1, the preparation method of 2 or 3 described a kind of carbon fiber reinforcement grafted by graphene oxides, it is characterized in that prepared by the graphene oxide adopted in step 3: a by the following method, the concentrated sulfuric acid is added in reactor, then under stirring, again graphite powder and sodium nitrate are added in reactor to obtain to mixture A, then by mixture A stirring reaction 20～40min under the condition of 0 ℃, and then add potassium permanganate to obtain mixture B in reactor, wherein, the ratio of concentrated sulfuric acid volume and sodium nitrate quality is 18～24mL: 1g, the mass ratio of graphite powder and sodium nitrate is 2: 1, the mass ratio of potassium permanganate and sodium nitrate is 6: 1, b, by mixture B after 30～40 ℃ of lower constant temperature stirring reaction 20～40min mixture C, and then to be diluted to volume to the warm water that drips 30～40 ℃ in mixture C be 2.8～3.5 times of mixture C, then be warming up to 90～100 ℃, then isothermal reaction 50～90min, obtain mixture D, c, mixture D is diluted to volume with the warm water of 30～40 ℃ is 5.8～8 times of concentrated sulfuric acid volume in step a, then adds the H that mass percent concentration is 30% ₂o ₂, the mixture E that stirs to obtain, then wash to filtrate and be neutral by the mixture E suction filtration and with deionized water, then, by sediment dry 5～8h under 40～60 ℃ of vacuum conditions, obtain graphite oxide, wherein, and 30% the H added ₂o ₂volume and step a in the ratio of sodium nitrate quality be 4mL: 1g, d, the graphite oxide that step c is obtained are placed in ethanolic solution, and ultrasonic dispersion 50～90min obtains the colloidal sol of graphene oxide, then the colloidal sol of graphene oxide after dry 5h, is obtained to graphene oxide under 40～60 ℃ of vacuum conditions.

5. according to the preparation method of claim 1,2 or 3 described a kind of carbon fiber reinforcement grafted by graphene oxides, it is characterized in that in step 3 obtaining the graphite oxide allydione turbid liquid that graphene oxide concentration is 0.05～0.8g/L.

6. according to the preparation method of claim 1,2 or 3 described a kind of carbon fiber reinforcement grafted by graphene oxides, it is characterized in that in step 3 obtaining the graphite oxide allydione turbid liquid that graphene oxide concentration is 0.1～0.6g/L.

7. according to the preparation method of claim 1,2 or 3 described a kind of carbon fiber reinforcement grafted by graphene oxides, it is characterized in that in step 3 obtaining the graphite oxide allydione turbid liquid that graphene oxide concentration is 0.2～0.4g/L.

8. according to the preparation method of claim 1,2 or 3 described a kind of carbon fiber reinforcement grafted by graphene oxides, it is characterized in that in step 3 obtaining the graphite oxide allydione turbid liquid that graphene oxide concentration is 0.3g/L.

9. according to the preparation method of claim 1,2 or 3 described a kind of carbon fiber reinforcement grafted by graphene oxides, it is characterized in that in step 4 controlling graphene oxide is 1: 1.8～5 with the mass ratio of the carbon fiber of polyamide-amide modification.

10. according to the preparation method of claim 1,2 or 3 described a kind of carbon fiber reinforcement grafted by graphene oxides, it is characterized in that in step 4 controlling graphene oxide is 1: 2 with the mass ratio of the carbon fiber of polyamide-amide modification.

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