CN102140230A - Preparation method of composite material consisting of carbon nanotube and functional carbon fiber-reinforced epoxy resin - Google Patents
Preparation method of composite material consisting of carbon nanotube and functional carbon fiber-reinforced epoxy resin Download PDFInfo
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Abstract
The invention relates to a preparation method of a composite material consisting of a carbon nanotube and functional carbon fiber-reinforced epoxy resin. The preparation method comprises the following steps of: performing carboxylation functionalization on the carbon nanotube and introducing diamine or polyamine onto the carbon nanotube to obtain a surface-aminated carbon nanotube; reaction the aminated carbon nanotube with surface-carboxylated carbon fibers to obtain an aminated carbon fiber surface on which the carbon nanotube is grafted, introducing diamine or polyamine onto the carbon fiber surface, fully aminating carboxyl which does not fully react with the aminated carbon nanotube on the carbon fiber surface and undergoing a prepolymerization reaction on the carbon fibers and epoxy resin to obtain a functionalized reinforced body of which the carbon fiber surface is grafted with the epoxy resin; reacting the aminated carbon nanotube with the epoxy resin to obtain a substrate of the epoxy resin toughened by the carbon nanotube; and compounding the obtained reinforced body of which the functionalized carbon fiber surface is grafted with the epoxy resin, with the substrate of the epoxy resin toughened by the carbon nanotube to obtain a needed product. The preparation method has simple reaction steps. The carbon fibers and substrate resin are toughened by means of the intensity and the toughness of the carbon nanotube, the bonding performance between the carbon fibers and the resin substrate is improved, and the interface bonding intensity of the composite material is enhanced, so that the overall performance of the composite material is enhanced.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to the preparation method of a kind of carbon nanotube and functionalization carbon-fibre reinforced epoxy resin composite material.
Background technology
Resins, epoxy is one of three big general thermosetting resins, has excellent adhesiveproperties, wear resisting property, mechanical property, electrical insulation capability, chemical stability, high and low temperature resistance.Because low, easy machine-shaping of its shrinking percentage and advantage such as with low cost are used widely in fields such as tackiness agent, coating, electric insulating material, strongthener and advanced composite materials.Carbon fiber (CF) has very excellent mechanical property, have good high temperature resistant, corrosion-resistant, rub resistance, antifatigue, low thermal coefficient of expansion, electroconductibility, electromagnetic wave shielding etc. simultaneously, be widely used in aerospace, automobile, field such as electric.CF/EP and CF/ bismaleimides (BMI) resin composite materials are applied in positions such as opportunity of combat fuselage, main wing, the vertical fin wing, the horizontal tail wing and covering abroad, played significant loss of weight effect, antifatigue, performance such as corrosion-resistant have been improved greatly, more external aviettes and unmanned spacecraft have been realized the matrix materialization of structure.But because the carbon fiber surface inertia is big, surface energy is low, has chemically active functional group few, reactive behavior is low, with the bad adhesion of matrix, has more defective in the composite material interface, and interfacial adhesion strength is low, the defective of composite material interface poor performance.In addition, carbon-fibre composite makes that in the poor mechanical property of vertical fibers direction the carbon-fibre composite interlaminar strength is low, has influenced the performance of carbon-fibre composite overall performance, has limited the application of material at aerospace field.Since the Iijima of Japan in 1991 finds carbon nanotube (CNTs) first by high-resolution-ration transmission electric-lens, CNTs is with its particular structure and excellent physical chemical property, be described as " ultimate fortifying fibre ", cause many scientists' very big concern very soon, and rapidly by with the various composite functional materials of the compound preparation of polymkeric substance.Though carbon nanotube has the potential application prospect in preparation light weight, high strength composite, it really be come true, also have many problems to need to solve.The surface energy of carbon nanotube is higher, reunites easily, makes it be difficult to homodisperse in polymkeric substance.How the homodisperse carbon nanotube and strengthen carbon nanotube and the body material interface between keying action, be the key that improves the every performance of matrix material.
To utilize the excellent separately mechanical property modified epoxy of carbon fiber and carbon nanotube, prepare carbon nanotube and functionalization carbon-fibre reinforced epoxy resin composite material, it will be very wide can predicting its prospect.
Summary of the invention
The object of the present invention is to provide the firm a kind of carbon nanotube of a kind of interface bonding and the preparation method of functionalization carbon-fibre reinforced epoxy resin composite material.
The carbon nanotube that the present invention proposes and the preparation method of functionalization carbon-fibre reinforced epoxy resin composite material are with after the carboxylated functionalization of carbon nanotube process, introduce diamine or polyamine again on carbon nanotube, obtain the aminated carbon nanotube in surface; Aminated carbon nanotube and surface are reacted through carboxylated carbon fiber, obtain aminated carbon fiber surface and be grafted with carbon nanotube, introduce diamine or polyamine at carbon fiber surface again, make the carboxyl of the complete and not aminated carbon nanotube reaction of carbon fiber surface fully aminated, with carbon fiber and epoxy reaction, the carbon fiber surface that obtains functionalization is grafted with the enhancing body of Resins, epoxy again; With aminated carbon nanotube and Resins, epoxy reaction, obtain the matrix of the Resins, epoxy of carbon nanotube highly malleablized; At last will more than the functionalization carbon fiber surface that obtains to be grafted with the matrix of Resins, epoxy of the enhancing body of Resins, epoxy and carbon nanotube highly malleablized compound by certain way, obtain carbon nanotube and functionalization carbon-fibre reinforced epoxy resin composite material.
Its concrete steps are as follows:
(1) takes by weighing 0.1～1 * 10g exsiccant carbon nanotube and 10～1 * 10
4The mL organic acid mixes, in 1 ~ 120kHz ultrasonic wave or 10 r/min ~ 10
6The centrifugal speed of r/min stirs down and handled 1～24 hour, be heated to 20～150 ℃ then, reacted 1～48 hour, through deionized water dilution washing, the millipore filtration suction filtration, repetitive scrubbing is neutral to filtrate repeatedly, is 25～150 ℃ of following vacuum-dryings 1～48 hour in temperature, obtains the carbon nanotube of purifying;
(2) with 1～1 * 10
2G exsiccant carbon fiber and acid with strong oxidizing property 1～1 * 10
4ML mixes, under 1 ~ 120kHz ultrasonic wave, handled 0.1～12 hour, be heated to 25～120 ℃ then, stirring and back flow reaction 0.2～12 hour, through deionized water wash, filter paper suction filtration, repetitive scrubbing repeatedly are neutral to filtrate, vacuum-drying is 1～48 hour under 25～150 ℃ of temperature, obtains the acidifying carbon fiber;
(3) with purifying carbon nano-tube 0.1～1 * 10g and the acid with strong oxidizing property 1～1 * 10 that obtain in the step (1)
3ML mixes, under 1 ~ 120kHz ultrasonic wave, handled 0.1～80 hour, be heated to 25～120 ℃ then, stirring and back flow reaction 1～80 hour, through deionized water dilution washing, ultramicropore filter membrane suction filtration, repetitive scrubbing repeatedly are neutral to filtrate, vacuum-drying is 1～48 hour under 25～200 ℃ of temperature, obtains the acidifying carbon nanotube;
(4) with step (3) gained acidifying carbon nanotube 0.1～1 * 10g, diamine or polyamine 1～1 * 10
3G, organic solvent 1～1 * 10
3ML and condensing agent 0.1～1 * 10g mix, with 1 ~ 120kHz ultrasonication 0.1～96 hour, under 25～220 ℃ of temperature, reacted 1～96 hour, and suction filtration and repetitive scrubbing, vacuum-drying is 1～48 hour under 25 ~ 200 ℃ of temperature, obtains aminating carbon nanotube;
(5) carbon nanotube 0.1～1 * 10g that step (4) gained is aminated, the acidifying carbon fiber 1～1 * 10 of step (2) gained
2G, organic solvent 1～1 * 10
3ML and condensing agent 0.1～1 * 10g mix, and with 1 ~ 120kHz ultrasonication 0.1～12 hour, temperature of reaction was 25～220 ℃, react after 0.1～96 hour, past diamine or the polyamine 0.1～1 * 10 of wherein adding
2G and condensing agent 0～1 * 10g reacted 1～96 hour again, suction filtration and repetitive scrubbing, and vacuum-drying is 1～48 hour under 25 ~ 200 ℃ of temperature, and the carbon fiber surface that obtains is grafted with amido and carbon nanotube;
(6) carbon fiber surface with step (5) gained is grafted with amido and carbon nanotube 0.1～1 * 10g and Resins, epoxy 1～1 * 10
3G is compound, and reaction through organic solvent washing repeatedly, was removed unreacted Resins, epoxy after 0.1～24 hour under temperature is 25～150 ℃, obtained the enhancing body that the functionalization carbon fiber surface is grafted with Resins, epoxy;
(7) carbon nanotube 0.1～1 * 10g, Resins, epoxy 1～1 * 10 that step (4) gained is aminated
3G and solidifying agent 1～1 * 10
3G is compound under 5～150 ℃ in temperature, and magnetic force or mechanical stirring and froth in vacuum were reacted 0.1～24 hour, obtained the matrix of the Resins, epoxy of carbon nanotube highly malleablized;
(8) the functionalization carbon fiber surface that step (6) is obtained is grafted with the enhancing body 1～1 * 10 of Resins, epoxy
2The matrix 1～1 * 10 of the Resins, epoxy of the carbon nanotube highly malleablized that g and step (7) obtain
3G is 50～180 ℃ of following froth in vacuum reactions 0.5～48 hour through the mold pressing composite molding in temperature, obtains carbon nanotube and functionalization carbon-fibre reinforced epoxy resin composite material.
Among the present invention, carbon nanotube described in the step (1) is the single wall of any preparation in arc-over, chemical gaseous phase deposition, template, sun power method or the laser evaporation method or multi-walled carbon nano-tubes or with its arbitrary proportion blended mixture.
Among the present invention, organic acid described in the step (1) is any or its multiple mixed solution in the hydrochloric acid of the sulfuric acid of nitric acid, 1～55% weight acid concentration of 1～35% weight acid concentration or 1～50% weight acid concentration.
Among the present invention, carbon fiber described in the step (2) is any or its multiple combination in unidirectional macrofiber cloth, two-way textile sheet, three-phase textile sheet or the random staple fibre cloth.
Among the present invention, step (2), (3) acid with strong oxidizing property described in is 1～70% weight acid concentration nitric acid, 1～100% weight acid concentration sulfuric acid, 1 ∕, 100～100 ∕, 1 mol ratio potassium permanganate and sulfuric acid mixed solution, 1 ∕, 100～100 ∕, 1 mol ratio nitric acid and sulfuric acid mixed solution, 1 ∕ 100～100 ∕, 1 mol ratio potassium permanganate and nitric acid mixing solutions, 1 ∕, 100～100 ∕, 1 mol ratio hydrogen peroxide and sulfuric acid mixture liquid, 1 ∕, 100～100 ∕, 1 mol ratio hydrogen peroxide and hydrochloric acid mixed solution, any or its multiple combination in 1 ∕ 100～100 ∕, 1 mol ratio hydrogen peroxide and nitric acid mixed solution or 15～95% weight concentration superoxols.
Among the present invention, diamine described in step (4), (5) is quadrol, polyethyene diamine, 1,2-propylene diamine, 1,3-propylene diamine, 1,2-butanediamine, 1, in the 3-butanediamine, 1,6-hexanediamine, Ursol D, cyclohexanediamine, mphenylenediamine, m-xylene diamine, two amido ditans, the Meng alkane diamines, divinyl propylamine, two amido ditans, chlorination hexanediamine, chlorination nonamethylene diamine, chlorination decamethylene diamine, 12 carbon diamines or 13 carbon diamines any; Described polyamine is triethylamine, fourth triamine, N-amine ethyl piperazidine, Dyhard RU 100, adipic dihydrazide, N, N-dimethyl dipropyl triamine, pentamethyl-diethylenetriamine, N, N, N, N, any or its multiple combination in N-five methyl diethylentriamine, tetraethylene pentamine, diethylenetriamine, triethylene tetramine, five ethene hexamines or six ethene, seven amine.
Among the present invention, step (4), (5) organic solvent described in is a benzene, toluene, dimethylbenzene, vinylbenzene, butyl toluene, tetrachloroethylene, trieline, Vinyl toluene, ethylene glycol ether, methylene dichloride, dithiocarbonic anhydride, the tricresyl phosphate ortho-cresol, methyl alcohol, ethanol, Virahol, hexanaphthene, pimelinketone, the toluene pimelinketone, ether, propylene oxide, acetone, espeleton, mibk, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, chlorobenzene, dichlorobenzene, methylene dichloride, trichloromethane, tetracol phenixin, trieline, zellon, trichloropropane, ethylene dichloride, N, dinethylformamide, dimethyl sulfoxide (DMSO), any or its multiple combination in dioxane or the tetrahydrofuran (THF).
Among the present invention, condensing agent is N in the step (4), (5), N '-dicyclohexylcarbodiimide, N, any or its multiple combination in N '-DIC or 1-ethyl-3-dimethylamine propyl carbodiimide.
Among the present invention, the carbon fiber surface that obtains described in the step (5) is grafted with amido and carbon nanotube, is that the carbon fiber surface of functionalization is grafted with diamine or polyamine and carbon nanotube.
Among the present invention, the functionalization carbon fiber surface that obtains described in the step (6) is grafted with the enhancing body of Resins, epoxy, is that the carbon fiber that the carbon fiber surface of functionalization is grafted with diamine or polyamine, carbon nanotube and epoxy strengthens body.
Among the present invention, Resins, epoxy described in step (6), (7) is meant among arbitrary in all Resins, epoxy that comprise Racemic glycidol ethers, glycidyl ester class, Racemic glycidol amine, alicyclic, epoxidation of olefins class, imide ring epoxy resins or glycolylurea epoxide resin or its multiple combination.
Among the present invention, solidifying agent described in the step (7) is m-xylene diamine, mphenylenediamine, 4,4
'Affixture, the sulfobenzide-3,3 of affixture, benzophenone tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride and the caprolactone of-two amido ditanes, two amido sulfobenzides, pyromellitic acid anhydride (PDMA), pyromellitic acid anhydride and caprolactone
', 4,4
'-tetracarboxylic dianhydride (DSDA), sulfobenzide-3,3
', 4,4
'The affixture of-tetracarboxylic dianhydride, N, N
'Any or its multiple combination in-dicarboxylic anhydride ditan or mellitic acid three acid anhydrides; The matrix of the Resins, epoxy of the described carbon nanotube highly malleablized that obtains is the matrix of the epoxy block polymer of carbon nanotubes.
Preparation method provided by the invention is simple, and the matrix material that obtains by the present invention utilizes the excellent separately mechanical property modified epoxy of carbon fiber and carbon nanotube, makes matrix material have good interlaminar shear strength.Therefore, the present invention has important science and technology value and actual application value.
Description of drawings
Fig. 1 is the XPS figure of carbon nanotube carboxyl-content.
Fig. 2 has provided carbon nanotube and functionalization carbon-fibre reinforced epoxy resin composite material profile scanning Electronic Speculum figure.
Fig. 3 has provided the carbon nanotube transmission electron microscope picture that concentrated nitric acid is modified.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
EXAMPLE l: (OD＜8nm) and carbon fiber are initial raw material with the multi-walled carbon nano-tubes of arc discharge method preparation, the walled carbon nanotubes purifying, acidifying and aminated back and the reaction of acidifying carbon fiber, behind the reaction certain hour, in system, add decamethylene diamine again, make the carboxyl of the complete and not aminated carbon nanotube reaction of carbon fiber surface fully aminated, the carbon fiber surface that obtains is grafted with carbon nanotube and decamethylene diamine, with carbon fiber and bisphenol A type epoxy resin (E-44) prepolymerization reaction, the carbon fiber surface that obtains functionalization is grafted with the enhancing body of bisphenol A type epoxy resin again; With aminated carbon nanotube and bisphenol A type epoxy resin reaction, obtain the matrix of the bisphenol A type epoxy resin of carbon nanotube highly malleablized; At last will more than the functionalization carbon fiber surface that obtains to be grafted with the matrix of bisphenol A type epoxy resin of the enhancing body of bisphenol A type epoxy resin and carbon nanotube highly malleablized compound by certain way, obtain carbon nanotube and functionalization carbon fiber and strengthen the bisphenol A type epoxy resin matrix material.
Step (1): in the single neck round-bottomed flask of the 250mL that agitator is housed, the multi-walled carbon nano-tubes raw material of adding 1.1g drying and 100mL, 20% salpeter solution, under the 1kHz ultrasonic wave, handled 24 hours, be heated to 20 ℃ then, reacted 48 hours, with the poly-inclined to one side tetrafluoroethylene millipore filtration suction filtration of ψ 0.45 μ m, with deionized water wash 3-10 time to neutrality, 65 ℃ of following vacuum-dryings obtained the multi-walled carbon nano-tubes of purifying after 24 hours;
Step (2): in the single neck round-bottomed flask of the 250mL that agitator is housed, the carbon fiber 20g of adding drying and 100mL, 60% weight concentration concentrated nitric acid, through 0.1 hour post-heating to 25 of 120kHz ultrasonication ℃, the stirring and the reaction down 12 hours that refluxes, through the filter paper suction filtration, to neutral, 100 ℃ of following vacuum-dryings obtained the acidifying carbon fiber after 48 hours with deionized water repetitive scrubbing 3-10 time;
Step (3): in the single neck round-bottomed flask of the 250mL that agitator is housed, the multi-walled carbon nano-tubes raw material 1g of the purifying that obtains in the adding step (1) and 100mL, 60% weight concentration concentrated nitric acid, through 1 hour post-heating to 25 of 120kHz ultrasonication ℃, the stirring and the reaction down 48 hours that refluxes, with the poly-inclined to one side tetrafluoroethylene millipore filtration suction filtration of ψ 0.22 μ m, to neutral, 80 ℃ of vacuum-dryings obtained the acidifying multi-walled carbon nano-tubes after 48 hours with deionized water repetitive scrubbing 3-10 time;
Step (4): in the 250mL three neck round-bottomed flasks that agitator is housed, add step (3) gained acidifying carbon nanotube 1g, decamethylene diamine 10g,, acetone 100mL and N, N-dicyclohexylcarbodiimide 10g is with the 100kHz ultrasonication after 24 hours, 50 ℃ of following stirring reactions 1 hour, suction filtration is removed unreacted reactant and byproduct of reaction, after using deionized water wash 3-10 time repeatedly, 80 ℃ of vacuum-drying 48 hours obtains the multi-walled carbon nano-tubes that the surface has amido;
Step (5): in the 500mL three neck round-bottomed flasks that agitator is housed, add aminated carbon nanotube 0.3g, step (2) acidifying carbon fiber 20g, acetone 100mL and the N of step (4), N-dicyclohexylcarbodiimide 10g, heating is also stirred, with the 60kHz ultrasonication after 0.1 hour, after reacting 96 hours under 25 ℃, in flask, add decamethylene diamine 2g and N, N-dicyclohexylcarbodiimide 1g reacted 48 hours again, suction filtration and repetitive scrubbing, 70 ℃ of following vacuum-dryings 24 hours, the carbon fiber surface that obtains was grafted with carbon nanotube and decamethylene diamine;
Step (6): have the carbon fiber 20g of amido and carbon nanotube and bisphenol A type epoxy resin 50g compound the surface grafting of step (5) gained, in temperature is under 100 ℃, react after 1 hour, through washing with acetone repeatedly, remove unreacted bisphenol A type epoxy resin, obtain the enhancing body that the functionalization carbon fiber surface is grafted with bisphenol A type epoxy resin;
Step (7): carbon nanotube 0.7g, bisphenol A type epoxy resin 70g and solidifying agent 4,4 that step (4) gained is aminated
'-two amido ditane 30g are compound under 100 ℃ in temperature, and magnetic force or mechanical stirring are disperseed and froth in vacuum was reacted 0.5 hour, obtain the matrix of the bisphenol A type epoxy resin of carbon nanotube highly malleablized;
Step (8): the functionalization carbon fiber surface that step (6) is obtained is grafted with the matrix 50g of bisphenol A type epoxy resin of the enhancing body 15g of bisphenol A type epoxy resin and the carbon nanotube highly malleablized that step (7) obtains through the mold pressing composite molding, 150 ℃ of following froth in vacuum reactions of temperature 5 hours, obtain carbon nanotube and functionalization carbon fiber and strengthen the bisphenol A type epoxy resin matrix material.
It is 6.8% that the XPS data that Fig. 1 provides can draw multi-wall carbon nano-tube tube-surface carboxyl-content.
Embodiment 2: (OD＜8nm) is an initial raw material with the Single Walled Carbon Nanotube of chemical Vapor deposition process preparation, Single Walled Carbon Nanotube is through purifying, acidifying and aminated back and the reaction of acidifying carbon fiber, behind the reaction certain hour, in system, add hexanediamine again, make the carboxyl of the complete and not aminated carbon nanotube reaction of carbon fiber surface fully aminated, the carbon fiber surface that obtains is grafted with carbon nanotube and hexanediamine, with carbon fiber and bisphenol A type epoxy resin (E-51) prepolymerization reaction, the carbon fiber surface that obtains functionalization is grafted with the enhancing body of bisphenol A type epoxy resin again; With aminated carbon nanotube and bisphenol A type epoxy resin reaction, obtain the matrix of the bisphenol A type epoxy resin of carbon nanotube highly malleablized; At last will more than the functionalization carbon fiber surface that obtains to be grafted with the matrix of bisphenol A type epoxy resin of the enhancing body of bisphenol A type epoxy resin and carbon nanotube highly malleablized compound by certain way, obtain carbon nanotube and functionalization carbon fiber and strengthen the bisphenol A type epoxy resin matrix material.
Step (1): in the single neck round-bottomed flask of the 500mL that the magnetic agitation rotor is housed, the Single Walled Carbon Nanotube raw material that adds the 3.1g drying, the sulfuric acid of 250mL, 20% weight concentration, with 120kHz ultrasonication 12 hours, be heated to 180 ℃ then, reacted 48 hours, with the poly-inclined to one side tetrafluoroethylene microfiltration membrane suction filtration of ψ 0.8 μ m, to neutral, 80 ℃ of vacuum-dryings obtained the carbon nanotube of purifying after 24 hours with the deionized water repetitive scrubbing;
Step (2): in the single neck round-bottomed flask of the 500mL that agitator is housed, the carbon fiber 30g of adding drying and 300mL, 60% weight concentration concentrated nitric acid, through 0.1 hour post-heating to 120 of 120kHz ultrasonication ℃, the stirring and the reaction down 3 hours that refluxes, through the filter paper suction filtration, to neutral, 90 ℃ of following vacuum-dryings obtained the acidifying carbon fiber after 48 hours with deionized water repetitive scrubbing 3-10 time;
Step (3): in the single neck round-bottomed flask of the 500mL that the magnetic agitation rotor is housed, the Single Walled Carbon Nanotube raw material 3g of the purifying that obtains in the adding step (1) and 200mL, 98% concentrated sulfuric acid solution, through 2 hours post-heating to 80 of 70kHz ultrasonication ℃, the stirring and the reaction down 80 hours that refluxes, with the poly-inclined to one side tetrafluoroethylene ultra-filtration membrane suction filtration of ψ 1.2 μ m, to neutral, 100 ℃ of vacuum-dryings obtained the acidifying Single Walled Carbon Nanotube after 24 hours with deionized water repetitive scrubbing 3-10 time;
Step (4): in the 500mL three neck round-bottomed flasks that the magnetic agitation rotor is housed, add step (3) gained acidifying Single Walled Carbon Nanotube 3g, hexanediamine 20g, N, dinethylformamide 20g and and N, N-dicyclohexylcarbodiimide 2g, reacted 12 hours down at 120 ℃ after 96 hours through the 1kHz ultrasonication, suction filtration is removed unreacted reactant and byproduct of reaction, repeatedly with behind the deionized water wash, 200 ℃ of vacuum-drying 1 hour obtains the Single Walled Carbon Nanotube that the surface has amido;
Step (5): in the 500mL three neck round-bottomed flasks that the magnetic agitation rotor is housed, add the aminated Single Walled Carbon Nanotube 1g of step (4), step (2) acidifying carbon fiber 30g, N, dinethylformamide 20g and N, N-dicyclohexylcarbodiimide 3g, heating is also stirred, with the 100kHz ultrasonication after 1 hour, after reacting 12 hours under 120 ℃, in beaker, add hexanediamine 5g and N, N-dicyclohexylcarbodiimide 2g reacted 24 hours again, suction filtration and repetitive scrubbing repeatedly, in 70 ℃ of following vacuum 36 hours, the carbon fiber surface that obtains was grafted with carbon nanotube and hexanediamine.
Step (6): it is compound that the carbon fiber surface of step (5) gained is grafted with amido and carbon nanotube 30g and bisphenol A type epoxy resin 300g, in temperature is under 50 ℃, react after 4 hours, through N, the dinethylformamide washing repeatedly, remove unreacted bisphenol A type epoxy resin, obtain the enhancing body that the functionalization carbon fiber surface is grafted with bisphenol A type epoxy resin;
Step (7): carbon nanotube 2g, bisphenol A type epoxy resin 200g and solidifying agent 4 that step (4) gained is aminated, 4 '-two amido ditane 50g, in temperature is compound under 5 ℃, magnetic force or mechanical stirring are disperseed and froth in vacuum was reacted 24 hours, obtain the matrix of the bisphenol A type epoxy resin of carbon nanotube highly malleablized;
Step (8): the functionalization carbon fiber surface that step (6) is obtained is grafted with the matrix 150g of bisphenol A type epoxy resin of the enhancing body 30g of bisphenol A type epoxy resin and the carbon nanotube highly malleablized that step (7) obtains through the mold pressing composite molding, in temperature is 160 ℃ of following froth in vacuum reactions 4 hours, obtains carbon nanotube and functionalization carbon fiber and strengthens the bisphenol A type epoxy resin matrix material.
XPS result shows that Single Walled Carbon Nanotube surface amido content is 6.4%.
Embodiment 3: (OD＜8nm) is an initial raw material with the Single Walled Carbon Nanotube of laser evaporation method preparation, Single Walled Carbon Nanotube is through purifying, acidifying and aminated back and the reaction of acidifying carbon fiber, behind the reaction certain hour, in system, add quadrol again, make the carboxyl of the complete and not aminated carbon nanotube reaction of carbon fiber surface fully aminated, the carbon fiber surface that obtains is grafted with carbon nanotube and quadrol, with carbon fiber and bisphenol A type epoxy resin (E-54) prepolymerization reaction, the carbon fiber surface that obtains functionalization is grafted with the enhancing body of bisphenol A type epoxy resin (E-54) again; With aminated carbon nanotube and bisphenol A type epoxy resin (E-54) reaction, obtain the matrix of the bisphenol A type epoxy resin (E-54) of carbon nanotube highly malleablized; At last will more than the functionalization carbon fiber surface that obtains to be grafted with the matrix of bisphenol A type epoxy resin (E-54) of the enhancing body of bisphenol A type epoxy resin (E-54) and carbon nanotube highly malleablized compound by certain way, obtain carbon nanotube and functionalization carbon fiber and strengthen bisphenol A type epoxy resin (E-54) matrix material.
Step (1): in the single neck round-bottomed flask of the 1000mL that the magnetic agitation rotor is housed, add 10g Single Walled Carbon Nanotube raw material and 250mL, 20% weight concentration sulphuric acid soln, with 120kHz ultrasonication 80 hours, heating and stirring and backflow under 150 ℃ then, reacted 48 hours, with the poly-inclined to one side tetrafluoroethylene millipore filtration suction filtration of ψ 0.8 μ m, to neutrality, 120 ℃ of vacuum-dryings obtain the Single Walled Carbon Nanotube of purifying after 48 hours with deionized water repetitive scrubbing 2-10 time;
Step (2): in the single neck round-bottomed flask of the 1000mL that agitator is housed, the carbon fiber 100g of adding drying and 300mL, 60% weight concentration concentrated nitric acid, adding is through 0.5 hour post-heating to 35 of 120kHz ultrasonication ℃, the stirring and the reaction down 12 hours that refluxes, through the filter paper suction filtration, to neutral, 70 ℃ of following vacuum-dryings obtained the acidifying carbon fiber after 48 hours with deionized water repetitive scrubbing 3-10 time;
Step (3): in the single neck round-bottomed flask of the 1000mL that the magnetic agitation rotor is housed, add the Single Walled Carbon Nanotube 9.8g of step (1) purifying and concentrated nitric acid and the vitriol oil mixed solution that 250mL, volume ratio are 3:1, through 0.1 hour post-heating to 55 of 120kHz ultrasonication ℃, the stirring and the reaction down 1 hour that refluxes, with the poly-inclined to one side tetrafluoroethylene ultra-filtration membrane suction filtration of ψ 1.2 μ m, to neutral, 65 ℃ of vacuum-dryings obtained the acidifying Single Walled Carbon Nanotube after 24 hours with the deionized water repetitive scrubbing;
Step (4): in the 1000mL three neck round-bottomed flasks that the magnetic agitation rotor is housed, add step (3) gained acidifying carbon nanotube 9.7g, quadrol 100g, acetone 600mL and N, N '-DIC 10g, through the 120Hz ultrasonication after 10 hours, be heated to 55 ℃, the reaction down 96 hours of stirring and reflux is after suction filtration and repetitive scrubbing remove repeatedly, 100 ℃ of vacuum-drying 50 hours obtains aminated Single Walled Carbon Nanotube;
Step (5): in the 1000mL three neck round-bottomed flasks that agitator is housed, the aminated Single Walled Carbon Nanotube 4g that adds step (4) gained, step (2) acidifying carbon fiber 100g, acetone 600mL and N, N '-DIC 5g, heating is also stirred, with the 60kHz ultrasonication after 0.2 hour, after reacting 8 hours under 55 ℃, in flask, add quadrol 5g and N again, N '-DIC 5g reacted 72 hours again, suction filtration and repetitive scrubbing, 70 ℃ of following vacuum-dryings 48 hours, the carbon fiber surface that obtains was grafted with carbon nanotube and quadrol.
Step (6): it is compound that the carbon fiber surface of step (5) gained is grafted with amido and carbon nanotube 100g and bisphenol A type epoxy resin (E-54) 100g, in temperature is under 80 ℃, react after 8 hours, through washing with acetone repeatedly, remove unreacted bisphenol A type epoxy resin (E-54), obtain the enhancing body that the functionalization carbon fiber surface is grafted with bisphenol A type epoxy resin (E-54);
Step (7): the carbon nanotube 5g that step (4) gained is aminated, bisphenol A type epoxy resin (E-54) 100g and solidifying agent mphenylenediamine 25g, in temperature is compound under 150 ℃, magnetic force or mechanical stirring are disperseed and froth in vacuum was reacted 0.1 hour, obtain the matrix of the bisphenol A type epoxy resin (E-54) of carbon nanotube highly malleablized;
Step (8): the functionalization carbon fiber surface that step (6) is obtained is grafted with the matrix 100g of bisphenol A type epoxy resin (E-54) of the enhancing body 100g of bisphenol A type epoxy resin (E-42) and the carbon nanotube highly malleablized that step (7) obtains through the mold pressing composite molding, in temperature is 160 ℃ of following froth in vacuum reactions 12 hours, obtains carbon nanotube and functionalization carbon fiber and strengthens bisphenol A type epoxy resin (E-54) matrix material.
XPS analysis result shows that Single Walled Carbon Nanotube surface amido content is 6.9%.
Fig. 2 has provided the section Electronic Speculum figure of carbon nanotube and functionalization carbon fiber enhancing bisphenol A type epoxy resin (E-42) matrix material.
Embodiment 4: (OD＜8nm) is an initial raw material with the Single Walled Carbon Nanotube of laser evaporation method preparation, Single Walled Carbon Nanotube is through purifying, acidifying and aminated back and the reaction of acidifying carbon fiber, behind the reaction certain hour, in system, add tetraethylene pentamine again, make the carboxyl of the complete and not aminated carbon nanotube reaction of carbon fiber surface fully aminated, the carbon fiber surface that obtains is connected to Single Walled Carbon Nanotube and tetraethylene pentamine, with carbon fiber and bisphenol A type epoxy resin (E-42) prepolymerization reaction, the carbon fiber surface that obtains functionalization is grafted with the enhancing body of bisphenol A type epoxy resin (E-42) again; With aminated carbon nanotube and bisphenol A type epoxy resin (E-42) reaction, obtain the matrix of the bisphenol A type epoxy resin (E-42) of carbon nanotube highly malleablized; At last will more than the functionalization carbon fiber surface that obtains to be grafted with the matrix of bisphenol A type epoxy resin (E-42) of the enhancing body of bisphenol A type epoxy resin (E-42) and carbon nanotube highly malleablized compound by certain way, obtain carbon nanotube and functionalization carbon fiber and strengthen bisphenol A type epoxy resin (E-42) matrix material.
Step (1): in the single neck round-bottomed flask of the 500mL that the magnetic agitation rotor is housed, add 2.1g Single Walled Carbon Nanotube raw material, the sulfuric acid of 200mL, 20% weight concentration, with 120kHz ultrasonication 10 hours, be heated to 100 ℃ then, reacted 48 hours, with the poly-inclined to one side tetrafluoroethylene microfiltration membrane suction filtration of ψ 0.8 μ m, to neutral, 100 ℃ of vacuum-dryings obtained the carbon nanotube of purifying after 24 hours with the deionized water repetitive scrubbing;
Step (2): in the single neck round-bottomed flask of the 500mL that the magnetic agitation rotor is housed, the carbon fiber 50g of adding drying and 100mL, 60% weight concentration concentrated nitric acid, through 0.1 hour post-heating to 45 of 120kHz ultrasonication ℃, the stirring and the reaction down 12 hours that refluxes, through the filter paper suction filtration, to neutral, 150 ℃ of following vacuum-dryings obtained the acidifying carbon fiber after 48 hours with deionized water repetitive scrubbing 3-10 time;
Step (3): in the single neck round-bottomed flask of the 500mL that the magnetic agitation rotor is housed, add step (1) gained acidifying carbon nanotube 2g and 100mL, 60% weight concentration concentrated nitric acid, through 1 hour post-heating to 65 of 120kHz ultrasonication ℃, the stirring and the reaction down 24 hours that refluxes, with the poly-inclined to one side tetrafluoroethylene ultra-filtration membrane suction filtration of ψ 1.2 μ m, to neutral, 70 ℃ of vacuum-dryings obtained the acidifying Single Walled Carbon Nanotube after 48 hours with deionized water repetitive scrubbing 3-10 time;
Step (4): in the 500mL three neck round-bottomed flasks that the magnetic agitation rotor is housed, add step (3) gained acidifying carbon nanotube 2g and tetraethylene pentamine 10g, acetone 100mL and N, N-dicyclohexylcarbodiimide 2g, with the 1kHz ultrasonication after 96 hours, reacted 12 hours down at 55 ℃, suction filtration is removed unreacted reactant and byproduct of reaction, repeatedly with behind the deionized water wash, 200 ℃ of vacuum-drying 1 hour obtains the Single Walled Carbon Nanotube that the surface has amido;
Step (5): in the 500mL three neck round-bottomed flasks that the magnetic agitation rotor is housed, add aminated carbon nanotube 0.5g, step (2) acidifying carbon fiber 40g, acetone 300mL, the N of step (4), N-dicyclohexylcarbodiimide 2g heating is also stirred, after 100kHz ultrasonication reaction 0.3 hour, add tetraethylene pentamine 2g again, reacted 64 hours down at 40 ℃, suction filtration and repetitive scrubbing, 70 ℃ of following vacuum-dryings 24 hours, the carbon fiber surface that obtains was grafted with carbon nanotube and tetraethylene pentamine.
Step (6): it is compound that the carbon fiber surface of step (5) gained is grafted with amido and carbon nanotube 40g and bisphenol A type epoxy resin (E-42) 100g, in temperature is under 90 ℃, react after 0.5 hour, through washing with acetone repeatedly, remove unreacted bisphenol A type epoxy resin (E-42), obtain the enhancing body that the functionalization carbon fiber surface is grafted with bisphenol A type epoxy resin (E-42);
Step (7): the carbon nanotube 1.5g that step (4) gained is aminated, bisphenol A type epoxy resin (E-42) 100g and solidifying agent 4,4 '-two amido ditane 25g, in temperature is compound under 60 ℃, magnetic force or mechanical stirring are disperseed and froth in vacuum was reacted 0.5 hour, obtain the matrix of the bisphenol A type epoxy resin (E-42) of carbon nanotube highly malleablized;
Step (8): the functionalization carbon fiber surface that step (6) is obtained is grafted with the matrix 100g of bisphenol A type epoxy resin (E-42) of the enhancing body 40g of bisphenol A type epoxy resin (E-42) and the carbon nanotube highly malleablized that step (7) obtains through the mold pressing composite molding, in temperature is 160 ℃ of following froth in vacuum reactions 12 hours, obtains carbon nanotube and functionalization carbon fiber and strengthens bisphenol A type epoxy resin (E-42) matrix material.
XPS result shows that Single Walled Carbon Nanotube surface amido content is 7.4%.
Embodiment 5: (OD＜8nm) and carbon fiber are initial raw material with the multi-walled carbon nano-tubes of arc discharge method preparation, the walled carbon nanotubes purifying, acidifying and aminated back and the reaction of acidifying carbon fiber, behind the reaction certain hour, in system, add triethylene tetramine again, make the carboxyl of the complete and not aminated carbon nanotube reaction of carbon fiber surface fully aminated, the carbon fiber surface that obtains is connected to multi-walled carbon nano-tubes and triethylene tetramine, with carbon fiber and bisphenol A type epoxy resin (E-42) prepolymerization reaction, the carbon fiber surface that obtains functionalization is grafted with the enhancing body of bisphenol A type epoxy resin (E-42) again; With aminated carbon nanotube and bisphenol A type epoxy resin (E-42) reaction, obtain the matrix of the bisphenol A type epoxy resin (E-42) of carbon nanotube highly malleablized; At last will more than the functionalization carbon fiber surface that obtains to be grafted with the matrix of bisphenol A type epoxy resin (E-42) of the enhancing body of bisphenol A type epoxy resin (E-42) and carbon nanotube highly malleablized compound by certain way, obtain carbon nanotube and functionalization carbon fiber and strengthen bisphenol A type epoxy resin (E-42) matrix material.
Step (1): in the single neck round-bottomed flask of the 250mL that agitator is housed, the multi-walled carbon nano-tubes raw material of adding 1.1g drying and 100mL, 20% salpeter solution, under the 120kHz ultrasonic wave, handled 12 hours, be heated to 60 ℃ then, reacted 48 hours, with the poly-inclined to one side tetrafluoroethylene microfiltration membrane suction filtration of ψ 0.8 μ m, with deionized water wash 3-10 time to neutrality, 85 ℃ of following vacuum-dryings obtained the multi-walled carbon nano-tubes of purifying after 24 hours;
Step (2): in the single neck round-bottomed flask of the 250mL that agitator is housed, the carbon fiber 25g of adding drying and 120mL, 60% weight concentration concentrated nitric acid, adding is through 12 hours post-heating to 25 of 120kHz ultrasonication ℃, the stirring and the reaction down 1 hour that refluxes, through the filter paper suction filtration, to neutral, 150 ℃ of following vacuum-dryings obtained the acidifying carbon fiber after 48 hours with deionized water repetitive scrubbing 3-10 time;
Step (3): in the single neck round-bottomed flask of the 250mL that agitator is housed, the multi-walled carbon nano-tubes 1g of the purifying that obtains in the adding step (1) and 120mL, 98% concentrated sulfuric acid solution, through 1 hour post-heating to 65 of 60kHz ultrasonication ℃, the stirring and the reaction down 24 hours that refluxes, with the poly-inclined to one side tetrafluoroethylene ultra-filtration membrane suction filtration of ψ 1.2 μ m, to neutral, 80 ℃ of vacuum-dryings obtained the acidifying multi-walled carbon nano-tubes after 48 hours with deionized water repetitive scrubbing 3-10 time;
Step (4): in the 250mL three neck round-bottomed flasks that agitator is housed, add step (3) gained acidifying carbon nanotube 1g, triethylene tetramine 10g, acetone 100mL and N, N '-DIC 1g, through the 100kHz ultrasonication after 1 hour, 50 ℃ of following stirring reactions 0.5 hour, suction filtration was removed unreacted reactant and byproduct of reaction, use deionized water wash 3-10 time repeatedly after, 80 ℃ of vacuum-drying 24 hours obtains the multi-walled carbon nano-tubes that the surface has amido;
Step (5): in the 500mL three neck round-bottomed flasks that agitator is housed, add the aminated multi-walled carbon nano-tubes 0.3g of step (4), step (2) acidifying carbon fiber 25g, acetone 100mL and N, N '-DIC 2g, heating is also stirred, with the 1kHz ultrasonication after 0.5 hour, after reacting 12 hours under 50 ℃, in flask, add triethylene tetramine 2g and N again, N '-DIC 1g reacted 48 hours again, suction filtration and repetitive scrubbing, 70 ℃ of following vacuum-dryings 24 hours, the carbon fiber surface that obtains was grafted with carbon nanotube and triethylene tetramine.
Step (6): it is compound that the carbon fiber surface of step (5) gained is grafted with amido and carbon nanotube 20g and bisphenol A type epoxy resin (E-42) 50g, in temperature is under 130 ℃, react after 3 hours, through washing with acetone repeatedly, remove unreacted bisphenol A type epoxy resin (E-42), obtain the enhancing body that the functionalization carbon fiber surface is grafted with bisphenol A type epoxy resin (E-42);
Step (7): the carbon nanotube 0.7g that step (4) gained is aminated and bisphenol A type epoxy resin (E-42) 20g and solidifying agent 4,4 '-two amido ditane 5g, in temperature is compound under 50 ℃, magnetic force or mechanical stirring are disperseed and froth in vacuum was reacted 1 hour, obtain the matrix of the bisphenol A type epoxy resin (E-42) of carbon nanotube highly malleablized;
Step (8): the functionalization carbon fiber surface that step (6) is obtained is grafted with the matrix 20g of bisphenol A type epoxy resin (E-42) of the enhancing body 20g of bisphenol A type epoxy resin (E-42) and the carbon nanotube highly malleablized that step (7) obtains through the mold pressing composite molding, in temperature is 160 ℃ of following froth in vacuum reactions 2 hours, obtains carbon nanotube and functionalization carbon fiber and strengthens bisphenol A type epoxy resin (E-42) matrix material.
XPS result shows that multi-wall carbon nano-tube tube-surface amido content is 7.2%.
Fig. 3 has provided the carbon nanotube transmission electron microscope picture that concentrated nitric acid is modified.
Above-mentioned description to embodiment is to understand and apply the invention for the ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention to improvement and modification that the present invention makes according to announcement of the present invention.
Claims (10)
1. the preparation method of carbon nanotube and functionalization carbon-fibre reinforced epoxy resin composite material is characterized in that concrete steps are as follows:
(1) takes by weighing 0.1～1 * 10g exsiccant carbon nanotube and 10～1 * 10
4The mL organic acid mixes, in 1 ~ 120kHz ultrasonic wave or 10 r/min ~ 10
6The centrifugal speed of r/min stirs down and handled 1～24 hour, is heated to 20～150 ℃ then, reacts 1～48 hour, through deionized water dilution washing, the millipore filtration suction filtration, repetitive scrubbing to filtrate is neutral, in temperature is 25～150 ℃ of following vacuum-dryings 1～48 hour, obtains the carbon nanotube of purifying;
(2) with 1～1 * 10
2G exsiccant carbon fiber and acid with strong oxidizing property 1～1 * 10
4ML mixes, under 1 ~ 120kHz ultrasonic wave, handled 0.1～12 hour, be heated to 25～120 ℃ then, stirring and back flow reaction 0.2～12 hour, through deionized water wash, the filter paper suction filtration, it is neutral that repetitive scrubbing to filtrate is, vacuum-drying is 1～48 hour under 25～150 ℃ of temperature, obtains the acidifying carbon fiber;
(3) with purifying carbon nano-tube 0.1～1 * 10g and the acid with strong oxidizing property 1～1 * 10 that obtain in the step (1)
3ML mixes, under 1 ~ 120kHz ultrasonic wave, handled 0.1～80 hour, be heated to 25～120 ℃ then, stirring and back flow reaction 1～80 hour, through deionized water dilution washing, ultramicropore filter membrane suction filtration, it is neutral that repetitive scrubbing to filtrate is, vacuum-drying is 1～48 hour under 25～200 ℃ of temperature, obtains the acidifying carbon nanotube;
(4) with step (3) gained acidifying carbon nanotube 0.1～1 * 10g, diamine or polyamine 1～1 * 10
3G, organic solvent 1～1 * 10
3ML and condensing agent 0.1～1 * 10g mix, with 1 ~ 120kHz ultrasonication 0.1～96 hour, after reacting 1～96 hour under 25～220 ℃ of temperature, suction filtration and repetitive scrubbing, vacuum-drying is 1～48 hour under 25 ~ 200 ℃ of temperature, obtains aminating carbon nanotube;
(5) carbon nanotube 0.1～1 * 10g that step (4) gained is aminated, the acidifying carbon fiber 1～1 * 10 of step (2) gained
2G, organic solvent 1～1 * 10
3ML and condensing agent 0.1～1 * 10g mix, and with 1 ~ 120kHz ultrasonication 0.1～12 hour, are 25～220 ℃ of reactions after 0.1～96 hour, toward wherein adding diamine or polyamine 0.1～1 * 10 down in temperature
2G and condensing agent 0～1 * 10g reacted 1～96 hour again, suction filtration and repetitive scrubbing, and vacuum-drying is 1～48 hour under 25 ~ 200 ℃ of temperature, and the carbon fiber surface that obtains is grafted with amido and carbon nanotube;
(6) carbon fiber surface with step (5) gained is grafted with amido and carbon nanotube 0.1～1 * 10g and Resins, epoxy 1～1 * 10
3G is compound, and reaction through organic solvent washing, was removed unreacted Resins, epoxy after 0.1～24 hour under temperature is 25～150 ℃, obtained the enhancing body that the functionalization carbon fiber surface is grafted with Resins, epoxy;
(7) carbon nanotube 0.1～1 * 10g, Resins, epoxy 1～1 * 10 that step (4) gained is aminated
3G and solidifying agent 1～1 * 10
3G is compound under 5～150 ℃ in temperature, and magnetic force or mechanical stirring are disperseed and froth in vacuum was reacted 0.1～24 hour, obtain the matrix of the Resins, epoxy of carbon nanotube highly malleablized;
(8) the functionalization carbon fiber surface that step (6) is obtained is grafted with the enhancing body 1～1 * 10 of Resins, epoxy
2The matrix 1～1 * 10 of the Resins, epoxy of the carbon nanotube highly malleablized that g and step (7) obtain
3G is 50～180 ℃ of following froth in vacuum reactions 0.5～48 hour through the mold pressing composite molding in temperature, obtains carbon nanotube and functionalization carbon-fibre reinforced epoxy resin composite material.
2. the preparation method of carbon nanotube according to claim 1 and functionalization carbon-fibre reinforced epoxy resin composite material is characterized in that carbon nanotube described in the step (1) comprises the single wall of any preparation in chemical Vapor deposition process, arc discharge method, sun power method, template or the laser evaporation method or multi-walled carbon nano-tubes or with its arbitrary proportion blended mixture.
3. the preparation method of carbon nanotube according to claim 1 and functionalization carbon-fibre reinforced epoxy resin composite material is characterized in that organic acid described in the step (1) is any or its multiple mixed solution in the hydrochloric acid of the sulfuric acid of nitric acid, 1～55% weight acid concentration of 1～35% weight acid concentration or 1～50% weight acid concentration.
4. the preparation method of carbon nanotube according to claim 1 and functionalization carbon-fibre reinforced epoxy resin composite material is characterized in that carbon fiber described in the step (2) is any or its multiple combination in unidirectional macrofiber cloth, two-way textile sheet, three-phase textile sheet or the random staple fibre.
5. the preparation method of carbon nanotube according to claim 1 and functionalization carbon-fibre reinforced epoxy resin composite material is characterized in that step (2), (3) acid with strong oxidizing property described in is 0.1～70% weight acid concentration nitric acid, 1～100% weight acid concentration sulfuric acid, 1 ∕, 100～100 ∕, 1 mol ratio potassium permanganate and sulfuric acid mixed solution, 1 ∕, 100～100 ∕, 1 mol ratio nitric acid and sulfuric acid mixed solution, 1 ∕ 100～100 ∕, 1 mol ratio potassium permanganate and nitric acid mixing solutions, 1 ∕, 100～100 ∕, 1 mol ratio hydrogen peroxide and sulfuric acid mixture liquid, 1 ∕, 100～100 ∕, 1 mol ratio hydrogen peroxide and hydrochloric acid mixed solution, any or its multiple combination in 1 ∕ 100～100 ∕, 1 mol ratio hydrogen peroxide and nitric acid mixed solution or 15～95% weight concentration superoxols.
6. the preparation method of carbon nanotube according to claim 1 and functionalization carbon-fibre reinforced epoxy resin composite material, it is characterized in that step (4), (5) diamine is quadrol described in, polyethyene diamine, 1, the 2-propylene diamine, 1, the 3-propylene diamine, 1, the 2-butanediamine, 1, the 3-butanediamine, 1, the 6-hexanediamine, Ursol D, cyclohexanediamine, mphenylenediamine, m-xylene diamine, two amido ditans, the Meng alkane diamines, the divinyl propylamine, two amido ditans, the chlorination hexanediamine, the chlorination nonamethylene diamine, the chlorination decamethylene diamine, in 12 carbon diamines or the 13 carbon diamines any; Described polyamine is triethylamine, fourth triamine, N-amine ethyl piperazidine, Dyhard RU 100, adipic dihydrazide, N, N-dimethyl dipropyl triamine, pentamethyl-diethylenetriamine, N, N, N, N, any or its multiple combination in N-five methyl diethylentriamine, tetraethylene pentamine, diethylenetriamine, triethylene tetramine, five ethene hexamines or six ethene, seven amine.
7. the preparation method of carbon nanotube according to claim 1 and functionalization carbon-fibre reinforced epoxy resin composite material, it is characterized in that step (4), (5), (6) organic solvent is benzene described in, toluene, dimethylbenzene, vinylbenzene, butyl toluene, tetrachloroethylene, trieline, Vinyl toluene, ethylene glycol ether, methylene dichloride, dithiocarbonic anhydride, the tricresyl phosphate ortho-cresol, methyl alcohol, ethanol, Virahol, hexanaphthene, pimelinketone, the toluene pimelinketone, ether, propylene oxide, acetone, espeleton, mibk, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, chlorobenzene, dichlorobenzene, methylene dichloride, trichloromethane, tetracol phenixin, trieline, zellon, trichloropropane, ethylene dichloride, N, dinethylformamide, dimethyl sulfoxide (DMSO), any or its multiple combination in dioxane or the tetrahydrofuran (THF).
8. the preparation method of carbon nanotube according to claim 1 and functionalization carbon-fibre reinforced epoxy resin composite material, it is characterized in that condensing agent is N described in step (4), (5), N '-dicyclohexylcarbodiimide, N, any or its multiple combination in N '-DIC or 1-ethyl-3-dimethylamine propyl carbodiimide.
9. the preparation method of carbon nanotube according to claim 1 and functionalization carbon-fibre reinforced epoxy resin composite material is characterized in that Resins, epoxy described in step (6), (7) all is meant among arbitrary in all Resins, epoxy that comprise Racemic glycidol ethers, glycidyl ester class, Racemic glycidol amine, alicyclic, epoxidation of olefins class, imide ring epoxy resins or glycolylurea epoxide resin or its multiple combination.
10. the preparation method of carbon nanotube according to claim 1 and functionalization carbon-fibre reinforced epoxy resin composite material is characterized in that solidifying agent described in the step (7) is m-xylene diamine, mphenylenediamine, two amido ditanes, 4,4
'The affixture of the affixture of-two amido sulfobenzides, methyl tetrahydro phthalic anhydride, methyl tetrahydrophthalic anhydride, pyromellitic acid anhydride, pyromellitic acid anhydride and caprolactone, benzophenone tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride and caprolactone, sulfobenzide-3,3
', 4,4
'-tetracarboxylic dianhydride, sulfobenzide-3,3
', 4,4
'The affixture of-tetracarboxylic dianhydride, N, N
'Any or its multiple combination in-dicarboxylic anhydride ditan or mellitic acid three acid anhydrides.
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| CN105778424A (en) * | 2016-04-22 | 2016-07-20 | 武汉理工大学 | Carbon nanotube and carbon fiber synergistically modified epoxy resin composite material and preparation method thereof |
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| CN111171757B (en) * | 2020-02-26 | 2021-07-27 | 广州市白云化工实业有限公司 | Modified carbon nanotube, epoxy conductive adhesive and preparation method thereof |
| CN114181494A (en) * | 2020-09-14 | 2022-03-15 | 中国科学院福建物质结构研究所 | Preparation method of anti-delamination high-conductivity polymer matrix composite material prepared by carbon nano tube bucky paper in-situ deposition of carbon fibers |
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| CN114164647A (en) * | 2021-12-21 | 2022-03-11 | 长春工业大学 | Carbon fiber with multi-component bionic hierarchical structure, preparation method and composite material |
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