CN102409528B - Preparation method of carbon fiber reinforcement grafted by graphene oxide - Google Patents
Preparation method of carbon fiber reinforcement grafted by graphene oxide Download PDFInfo
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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
Technical field
The present invention relates to a kind of preparation method of carbon fiber reinforcement grafted by graphene oxide.
Background technology
Carbon fiber (CF) is a kind of important reinforcing material grown up after the 1950's.The interface binding intensity of the mechanical property of its composite and carbon fiber and matrix is closely related.Good interface combination is transmitted load effectively, thereby improves the mechanical property of material.But undressed carbon fiber surface inertia is large, a little less than the interface of resin matrix is combined, thereby affected giving full play to of carbon fibre composite excellent properties.Therefore, usually to carry out surface treatment to carbon fiber, improve the interface bond quality of its composite, thereby improve the interface mechanical characteristic of material.Carbon fiber surface modification method commonly used mainly contains chemical vapour deposition technique, chemical oxidation and chemical graft etc., and these methods can increase surface polarity or the specific area of carbon fiber to some extent, improves the interface performance between itself and resin.But traditional carbon fiber surface modification method also exists process conditions, technical equipment requires harshness, the process time is long, and process is toxic, is difficult to the problems such as industrialized mass production.Graphene oxide has good mechanical property, and its preparation is simple, good dispersion, and surface has abundant functional group, but its study on the modification to carbon fiber surface rarely has report.
Summary of the invention
The objective of the invention is in order to solve existing carbon fiber surface modification method process conditions harshness, the process time is long, and technical process is toxic, is difficult to the problem of suitability for industrialized production, the invention provides a kind of preparation method of carbon fiber reinforcement grafted by graphene oxide.
The preparation method of carbon fiber reinforcement grafted by graphene oxide of the present invention realizes by following steps: one, carbon fiber is carried out to acidification, obtain the acidifying carbon fiber; Two, polyamide-amide (PAMAM) 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.
In step 1 of the present invention, adopting existing open method to carry out acidification to carbon fiber gets final product.For example, the present invention can adopt following method to carry out acidification to carbon fiber: the ratio in carbon fiber and red fuming nitric acid (RFNA) is 1g: 350ml, carbon fiber is added in red fuming nitric acid (RFNA), then after reacting 1～3h under the constant temperature of 70 ℃～90 ℃, take out carbon fiber, wash to cleaning solution pH value be 7 left and right, then in 80 ℃ ,-the 0.1MPa condition under dry 2～6h, obtain the carbon fiber of acidifying.
The graphene oxide adopted in step 3 of the present invention utilizes existing open method to prepare, for example, the present invention can be prepared as follows graphene oxide: a, 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, can be obtained to graphene oxide under 40～60 ℃ of vacuum conditions.To control the speed that adds of potassium permanganate while wherein in step a, adding potassium permanganate, not make the temperature in reactor rise too fast.
Carbon fiber reinforcement grafted by graphene oxide of the present invention is that graphene oxide is grafted on the carbon fiber that polyamide-amide modifies and obtains.
" being grafted to " method (" Grafting-to " method) that the present invention adopts is utilized acylation reaction; by the polyamide-amide with a large amount of amido active groups (PAMAM); surface is had to the graphene oxide that enriches functional group and be grafted to the carbon fiber surface after acid oxidase is processed; there is cost low; without long-time high-temperature heating; simple, environment-protecting asepsis, but main technique such as completes within a short period of time at the characteristics.
In addition, the graphene oxide grafting carbon fiber novel enhanced body that the inventive method of take obtains is in the carbon fiber/epoxy resin composite material that reinforcement prepares, not only there is the mechanical engagement effect in graphene oxide grafting carbon fiber novel enhanced body with matrix, and surface has a large amount of active function groups, easy and matrix forms chemical bond, surface energy and the wetting property of carbon fiber have been improved, make the interface shear strength of carbon fiber and epoxy resin reach 79.77～105.50MPa, improved 110%～180% than the interface shear strength of common carbon fibers and epoxy resin (37.68MPa).
The accompanying drawing explanation
Fig. 1 is the electron scanning micrograph of the carbon fiber reinforcement grafted by graphene oxide for preparing of the specific embodiment 18.
The specific embodiment
Technical solution of the present invention is not limited to the following cited specific embodiment, also comprises any combination between each specific embodiment.
The specific embodiment one: the preparation method that present embodiment is carbon fiber reinforcement grafted by graphene oxide, it is realized by following steps: one, carbon fiber is carried out to acidification, obtain the acidifying carbon fiber; Two, polyamide-amide (PAMAM) 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.
In the present embodiment step 1, adopting existing open method to carry out acidification to carbon fiber gets final product.The graphene oxide adopted in step 3 utilizes existing open method to prepare.The polyamide-amide adopted in the present embodiment step 2 (PAMAM) is commercially available prod.
" being grafted to " method (" Grafting-to " method) that present embodiment adopts is utilized acylation reaction; by the polyamide-amide with a large amount of amido active groups (PAMAM); surface is had to the graphene oxide that enriches functional group and be grafted to the carbon fiber surface after acid oxidase is processed; there is cost low; without long-time high-temperature heating; simple, environment-protecting asepsis, but main technique such as completes within a short period of time at the characteristics.
In addition, the graphene oxide grafting carbon fiber novel enhanced body that the method for present embodiment of take obtains is in the carbon fiber/epoxy resin composite material that reinforcement prepares, not only there is the mechanical engagement effect in graphene oxide grafting carbon fiber novel enhanced body with matrix, and surface has a large amount of active function groups, easy and matrix forms chemical bond, surface energy and the wetting property of carbon fiber have been improved, make carbon fiber after the present embodiment grafting and the interface shear strength of epoxy resin reach 79.77～105.50MPa, improved 110%～180% than the interface shear strength of common carbon fibers and epoxy resin (37.68MPa).
The specific embodiment two: what present embodiment was different from the specific embodiment one is in step 1, to adopt following method to carry out acidification to carbon fiber: the ratio in carbon fiber and red fuming nitric acid (RFNA) is 1g: 350ml, carbon fiber is added in red fuming nitric acid (RFNA), then after reacting 1～3h under the constant temperature of 70 ℃～90 ℃, take out carbon fiber, wash to cleaning solution pH value be 7 left and right, again in 80 ℃ ,-the 0.1MPa condition under dry 2～6h, obtain the carbon fiber of acidifying.Other step and parameter are identical with the specific embodiment one.
Before carbon fiber is carried out to acidification, first carbon fiber is carried out to conventional destarch processing in present embodiment.Concrete destarch is processed and can be carried out as follows: carbon fiber is put into to analytically pure acetone soln, and under 70～80 ℃, constant temperature backflow 24～48h, carry out the destarch processing.
The specific embodiment three: what present embodiment was different from the specific embodiment one or two is then mixed liquor to be warming up to 25 ℃～40 ℃ in step 2, then isothermal reaction 6～10h.Other step and parameter are identical with the specific embodiment one or two.
The specific embodiment four: what present embodiment was different from the specific embodiment one or two is then mixed liquor to be warming up to 30 ℃ in step 2, then isothermal reaction 8h.Other step and parameter are identical with the specific embodiment one or two.
The specific embodiment five: present embodiment is different from one of specific embodiment one to four be in step 2 again 50 ℃ of lower vacuumizes to constant weight.Other step and parameter are identical with one of specific embodiment one to four.
The specific embodiment six: present embodiment is different from one of specific embodiment one to five is that in step 2, the mass ratio of acidifying carbon fiber and polyamide-amide is 0.5～2: 1.Other step and parameter are identical with one of specific embodiment one to five.
The specific embodiment seven: present embodiment is different from one of specific embodiment one to five is that in step 2, the mass ratio of acidifying carbon fiber and polyamide-amide is 1: 1.Other step and parameter are identical with one of specific embodiment one to five.
The specific embodiment eight: what present embodiment was different from one of specific embodiment one to seven is 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, can be obtained to graphene oxide under 40～60 ℃ of vacuum conditions.Other step and parameter are identical with one of specific embodiment one to seven.
To control the speed that adds of potassium permanganate while in present embodiment, in step a, adding potassium permanganate, not make the temperature in reactor rise too fast.
The preparation method of present embodiment is simple, and the graphene oxide prepared has good dispersion, and the advantages such as grafting are convenient to owing to having abundant functional group in surface.
The specific embodiment nine: what present embodiment was different from one of specific embodiment one to eight is to obtain the graphite oxide allydione turbid liquid that graphene oxide concentration is 0.05～0.8g/L in step 3.Other step and parameter are identical with one of specific embodiment one to eight.
The specific embodiment ten: what present embodiment was different from one of specific embodiment one to eight is to obtain the graphite oxide allydione turbid liquid that graphene oxide concentration is 0.1～0.6g/L in step 3.Other step and parameter are identical with one of specific embodiment one to eight.
The specific embodiment 11: what present embodiment was different from one of specific embodiment one to eight is to obtain the graphite oxide allydione turbid liquid that graphene oxide concentration is 0.2～0.4g/L in step 3.Other step and parameter are identical with one of specific embodiment one to eight.
The specific embodiment 12: what present embodiment was different from one of specific embodiment one to eight is to obtain the graphite oxide allydione turbid liquid that graphene oxide concentration is 0.3g/L in step 3.Other step and parameter are identical with one of specific embodiment one to eight.
The specific embodiment 13: what present embodiment was different from one of specific embodiment one to 12 is then mixed liquor to be warming up to 100 ℃ in step 4, then isothermal reaction 6～12h.Other step and parameter are identical with one of specific embodiment one to 12.
The specific embodiment 14: what present embodiment was different from one of specific embodiment one to 12 is then mixed liquor to be warming up to 100 ℃ in step 4, then isothermal reaction 10h.Other step and parameter are identical with one of specific embodiment one to 12.
The specific embodiment 15: present embodiment is different from one of specific embodiment one to 14 is that to control graphene oxide in step 4 be 1: 1.8～5 with the mass ratio of the carbon fiber of polyamide-amide modification.Other step and parameter are identical with one of specific embodiment one to 14.
The specific embodiment 16: present embodiment is different from one of specific embodiment one to 14 is that to control graphene oxide in step 4 be 1: 2 with the mass ratio of the carbon fiber of polyamide-amide modification.Other step and parameter are identical with one of specific embodiment one to 14.
The specific embodiment 17: prepared by the graphene oxide adopted in the step 3 in the preparation method of the carbon fiber reinforcement grafted by graphene oxide that present embodiment is one of specific embodiment one to 16 by the following method: a, 90mL～120mL concentrated sulfuric acid is added in reactor, then under stirring, again 10g graphite powder and 5g 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 30g potassium permanganate to obtain mixture B in reactor; B, by mixture B after 35 ℃ of lower constant temperature stirring reaction 30min mixture C, and then, to the warm water dilution of 30～40 ℃ that drips 225mL in mixture C, then be warming up to 98 ℃, then isothermal reaction 60min, obtain mixture D; C, mixture D is diluted to volume with the warm water of 30～40 ℃ is 700mL, then adds the H that the mass percent concentration of 20mL 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 5h under 50 ℃ of vacuum conditions, obtain graphite oxide; D, the graphite oxide that step c is obtained are placed in ethanolic solution, and ultrasonic dispersion 60min obtains the colloidal sol of graphene oxide, then the colloidal sol of graphene oxide after dry 5h, can be obtained to graphene oxide under 50 ℃ of vacuum conditions.
Then wash to filtrate and be neutral by the mixture E suction filtration and with deionized water in present embodiment step c, concrete operations are as follows: first use 5% (quality) HCl to wash twice, after washing 3 times, until filtrate is neutral.
Carry out ultrasonic dispersion 60min in the present embodiment steps d under 150W, 75KHz condition.
The preparation method of present embodiment is simple, and the graphene oxide prepared has good dispersion, and the advantages such as grafting are convenient to owing to having abundant functional group in surface.
The specific embodiment 18: the preparation method that present embodiment is carbon fiber reinforcement grafted by graphene oxide, it is realized by following steps: one, carbon fiber is carried out to acidification, obtain the acidifying carbon fiber; Two, polyamide-amide (PAMAM) 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 30 ℃, isothermal reaction 8h again, then the taking-up of acidifying carbon fiber is used successively again to methanol wash 3 times and water washing 3 times, again 50 ℃ 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 1: 1; Three, graphene oxide is added in acetone soln to ultrasonic processing 60min, the graphite oxide allydione turbid liquid that to obtain graphene oxide concentration be 0.3g/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 100 ℃, isothermal reaction 10h again, then filter, by filter sediment with acetone and deionized water, alternately wash 5 times successively, sediment after washing again to constant weight, obtains carbon fiber reinforcement grafted by graphene oxide 50 ℃ of lower vacuumizes; The mass ratio of wherein in step 4, controlling the carbon fiber of graphene oxide and polyamide-amide modification is 1: 2.
In the present embodiment step 1, adopt the method for record in the specific embodiment two to carry out acidification to carbon fiber.
The graphene oxide that the method that adopts the specific embodiment 17 to put down in writing in the present embodiment step 3 prepares.
The carbon fiber that present embodiment adopts is domestic fiber, by carbon fiber Co., Ltd of Jilin divine boat, is produced (carbon fiber specification: 12K) is provided.
The electron scanning micrograph of the carbon fiber reinforcement grafted by graphene oxide that present embodiment prepares, as shown in Figure 1, visible, in carbon fiber surface success grafting a large amount of graphene oxides.
Present embodiment is carried out the interface shear strength test of itself and epoxy resin to the carbon fiber reinforcement grafted by graphene oxide prepared, method of testing is as follows: one, by epoxy resin E-51 and curing agent 3,3 '-diethyl 4,4 '-diaminodiphenyl-methane (being called for short H-256) is made into glue in mass ratio at 100: 32, glue is dropped on the single graphene oxide grafting carbon fiber that present embodiment prepares, make the glue drop wrap carbon fiber, and the two ends that make carbon fiber are exposed outside the glue drop, obtain precast body; Two, precast body is solidified under 90 ℃/1h+120 ℃/2h+150 ℃/2h condition, obtain filament/epoxy resin droplet composite sample; Three, utilize the eastern flourish FA-620 of Co., Ltd. type tester of Japan, adopt the interface shear strength of micro-unsticking method test sample.
Record, the carbon fiber reinforcement grafted by graphene oxide that present embodiment prepares and the interface shear strength of epoxy resin reach 105.50MPa.Do not improved 180% than carrying out the domestic carbon fibre of modification and the interface shear strength of epoxy resin (specific embodiment 21 records).
The specific embodiment 19: present embodiment is different from the specific embodiment 18 is that to control graphene oxide in step 4 be 1: 3 with the mass ratio of the carbon fiber of polyamide-amide modification.Other step and parameter are identical with the specific embodiment 18.
The carbon fiber that present embodiment adopts is domestic fiber, by carbon fiber Co., Ltd of Jilin divine boat, is produced (carbon fiber specification: 12K) is provided.
The carbon fiber reinforcement grafted by graphene oxide that present embodiment is prepared prepares test sample, test sample prepare concrete grammar with in the specific embodiment 18 record method identical.The carbon fiber reinforcement grafted by graphene oxide that the present embodiment that test obtains prepares and the interface shear strength of epoxy resin reach 95.08MPa.Do not improved 152% than carrying out the domestic carbon fibre of modification and the interface shear strength of epoxy resin (specific embodiment 21 records).
The specific embodiment 20: present embodiment is different from the specific embodiment 18 is that to control graphene oxide in step 4 be 1: 5 with the mass ratio of the carbon fiber of polyamide-amide modification.Other step and parameter are identical with the specific embodiment 18.
The carbon fiber that present embodiment adopts is domestic fiber, by carbon fiber Co., Ltd of Jilin divine boat, is produced (carbon fiber specification: 12K) is provided.
The carbon fiber reinforcement grafted by graphene oxide that present embodiment is prepared prepares test sample, test sample prepare concrete grammar with in the specific embodiment 18 record method identical.The carbon fiber reinforcement grafted by graphene oxide that the present embodiment that test obtains prepares and the interface shear strength of epoxy resin reach 79.77MPa.Do not improved 112% than carrying out the domestic carbon fibre of modification and the interface shear strength of epoxy resin (specific embodiment 21 records).
The specific embodiment 21: present embodiment is the contrast experiment: the interface shear strength of test domestic carbon fibre and epoxy resin, method of testing is as follows: one, by epoxy resin E-51 and curing agent 3,3 '-diethyl 4,4 '-diaminodiphenyl-methane (being called for short H-256) is made into glue in mass ratio at 100: 32, glue is dropped on single domestic carbon fibre, make the glue drop wrap carbon fiber, and make the two ends of carbon fiber exposed outside the glue drop, obtain precast body; Two, precast body is solidified under 90 ℃/1h+120 ℃/2h+150 ℃/2h condition, obtain filament/epoxy resin droplet composite sample; Three, utilize the eastern flourish FA-620 of Co., Ltd. type tester of Japan, adopt the interface shear strength of micro-unsticking method test sample.
Record, the interface shear strength of domestic carbon fibre and epoxy resin is 37.68MPa.
The domestic fiber adopted in present embodiment is the carbon fiber (specification: 12K) that carbon fiber Co., Ltd of Jilin divine boat produces.
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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