CN102108634A - Method for preparing functional carbon fibers - Google Patents
Method for preparing functional carbon fibers Download PDFInfo
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- CN102108634A CN102108634A CN 201110000233 CN201110000233A CN102108634A CN 102108634 A CN102108634 A CN 102108634A CN 201110000233 CN201110000233 CN 201110000233 CN 201110000233 A CN201110000233 A CN 201110000233A CN 102108634 A CN102108634 A CN 102108634A
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Abstract
The invention belongs to the technical field of nanomaterials, and in particular relates to a method for preparing functional carbon fibers. The method comprises the following steps of: performing carboxylation functionalization on carbon nanotubes; introducing diamine or polyamine onto the carbon nanotubes to obtain amino-coated carbon nanotubes; reacting the amino-coated carbon nanotubes with carboxyl-coated carbon fibers, and controlling reaction time; and introducing diamine or polyamine onto the surfaces of the carbon fibers to obtain the amino functional carbon fibers of which the surfaces are grafted with the carbon nanotubes. The reaction steps are simple and controllable; the carbon fibers are toughened through the strength and toughness of the carbon nanotubes; the adhesive property between the carbon fibers and a resin matrix is improved; the interfacial bond strength of a composite material is improved; and defects that the interfacial rigidity is increased and the toughness is reduced after the carbon fibers are treated by the conventional carbon fiber treatment method are well overcome. The prepared carbon fibers of which the surfaces are grafted with the carbon nanotubes have wide application range.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of preparation method of functionalization carbon fiber.
Background technology
CNT (CNTs) is since 1991 are found by Japanese scientist Iijima, caused countries in the world chemistry, physics, the personage's of material educational circles very big concern with its distinctive mechanical property, electric property, thermal property and chemical property, in scientific basic research and application study, gained great popularity.Though CNT has 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 CNT is higher, reunites easily, makes it be difficult to even dispersion in polymer.How evenly dispersing Nano carbon tubes and strengthen CNT with the matrix material interface between combination, be the key of the every performance of raising composite.
Carbon fiber has the performance of a series of excellences such as high specific strength, high ratio modulus, endurance, creep resistant and thermal coefficient of expansion are little, make it become one of most important reinforcing material in recent years, oneself is widely used in fields such as Aero-Space, war industry and athletic sports appliance.But because the carbon fiber surface inertia is big, surface energy is low, has chemically active functional group few, reactivity 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.
At present carbon fiber handle is adopted high-temperature heat treatment, vapour deposition, gaseous oxidation, liquid phase oxidation, anodic oxidation, immersion coating, electropolymerization coating and technical method such as cold, though these methods have improved the surface area of carbon fiber to a certain extent, increased the quantity of surface functional group, improve the wettability of carbon fiber and resin, improved the interlaminar strength of carbon fibre composite to a certain extent; But these methods make the interface rigidity increase simultaneously, toughness of material reduces, and fail to improve between the fiber and the carbon fiber laminate between the performance of resin matrix, therefore the impact property of the composite made of the carbon fiber of handling through above method is well improved.
The functionalization carbon fiber that the surface has CNT can increase the meshing effect of machinery at the interface on the one hand, significantly improves interface performance, can also improve the mechanical property of resin matrix between fiber on the other hand.Be connected by covalent bond with resin matrix with carbon fiber through the CNT after the chemical modification simultaneously, Stress Transfer ability height can significantly improve interaction and boundary strength between the two-phase.
Summary of the invention
The object of the present invention is to provide the preparation method of the functionalization carbon fiber of the firm surface grafting CNT of a kind of interface bonding and diamine or polyamine.
The preparation method of a kind of functionalization carbon fiber that the present invention proposes, be with the carbon nano tube surface purifying, after the carbon nano tube surface of purifying carried out acidifying, introducing has the diamine or the polyamine of feature structure, obtain the graft type CNT that the surface has active amine, with the carbon fiber reaction of aminated CNT and surperficial acidification, the carbon fiber surface that obtains is grafted with diamine or polyamine and CNT again.Its concrete steps are as follows:
(1) takes by weighing the CNT and 10～1 * 10 of 0.1～1 * 10g drying
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 miillpore filter suction filtration, cyclic washing is neutral to filtrate repeatedly, is 25～150 ℃ of following vacuumizes 1～48 hour in temperature, obtains the CNT of purifying;
(2) with 1～1 * 10
2The carbon fiber of g drying 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 the deionized water washing, filter paper suction filtration, cyclic washing repeatedly are neutral to filtrate, vacuumize is 1～48 hour under 25～150 ℃ of temperature, obtains the carbon fiber of acidifying;
(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, cyclic washing repeatedly are neutral to filtrate, vacuumize is 1～48 hour under 25～200 ℃ of temperature, obtains the CNT of acidifying;
(4) with CNT 0.1～1 * 10g, diamine or the polyamine 1～1 * 10 of step (3) gained acidifying
3G, organic solvent 1～1 * 10
3ML and condensing agent 0.1～1 * 10g mix, with 1 ~ 120kHz ultrasonic Treatment 0.1～96 hour, under 25～220 ℃ of temperature, reacted 1～96 hour suction filtration and cyclic washing, vacuumize is 1～48 hour under 25 ~ 200 ℃ of temperature, obtains aminated CNT;
(5) CNT 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 ultrasonic Treatment 0.1～12 hour, reaction temperature 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 cyclic washing, and vacuumize is 1～48 hour under 25 ~ 200 ℃ of temperature, and the carbon fiber surface that obtains is grafted with amido and CNT.
Among the present invention, CNT described in the step (1) is the single wall or the multi-walled carbon nano-tubes of any preparation in arc discharge, chemical gaseous phase deposition, template, solar energy method or the laser evaporation method.
Among the present invention, organic acid described in the step (1) is any or its mixed liquor 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 long fiber cloth, two-way textile sheet, three-phase textile sheet or the random staple fibre.
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 mixed solution, 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 liquor or 15～95% weight concentration hydrogenperoxide steam generators.
Among the present invention, diamine described in step (4), (5) is ethylenediamine, polyethyene diamine, 1,2-propane diamine, 1,3-propane diamine, 1,2-butanediamine, 1, in the 3-butanediamine, 1,6-hexamethylene diamine, p-phenylenediamine (PPD), cyclohexanediamine, m-phenylene diamine (MPD), m-xylene diamine, two amido diphenyl methanes, the Meng alkane diamines, divinyl propylamine, two amido diphenyl methanes, chlorination hexamethylene diamine, chlorination nonamethylene diamine, chlorination decamethylene diamine, 12 carbon diamines or 13 carbon diamines any; Described polyamine is triethylamine, fourth triamine, N-amine ethyl piperazidine, dicyandiamide, 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, styrene, butyl toluene, perchloroethylene, trichloro-ethylene, vinyltoluene, ethylene glycol ether, carrene, carbon disulfide, the tricresyl phosphate orthoresol, methyl alcohol, ethanol, isopropyl alcohol, cyclohexane, cyclohexanone, the toluene cyclohexanone, ether, expoxy propane, acetone, espeleton, methylisobutylketone, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, chlorobenzene, dichloro-benzenes, carrene, chloroform, carbon tetrachloride, trichloro-ethylene, tetrachloro-ethylene, trichloropropane, dichloroethanes, N, dinethylformamide, dimethyl sulfoxide (DMSO), any or its multiple combination in dioxane or the oxolane.
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 CNT, is that the carbon fiber surface of functionalization is grafted with diamine or polyamine and CNT.
Preparation method provided by the invention is simple, gained be that the carbon fiber surface of functionalization is grafted with diamine or polyamine and CNT.The amido of carbon nano tube surface by with the carboxyl reaction of carbon fiber surface, make CNT be grafted to carbon fiber surface, in reaction system, add the carboxyl reaction of diamine or polyamine and carbon fiber surface again, obtain the functionalization carbon fiber surface and be grafted with CNT.Can significantly improve boundary strength between matrix resin and the carbon fiber through the carbon fiber of functionalization of the present invention, make composite have good interlaminar shear strength.Therefore, the present invention has important science and technology value and actual application value.
Description of drawings
Figure l is grafted with the sem photograph of CNT for the carbon fiber surface that provides among the embodiment 1.
Fig. 2 is CNT XPS figure among the embodiment 1.
The CNT transmission electron microscope picture that Fig. 3 modifies for the triethylene tetramine that provides among the embodiment 5.
The specific 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 carbon fiber reaction of walled carbon nanotubes purifying, acidifying and aminated back and acidifying, behind the reaction certain hour, in system, add decamethylene diamine again, make the carboxyl of the complete and not aminated CNT reaction of carbon fiber surface fully aminated, the carbon fiber surface that obtains is grafted with CNT and decamethylene diamine.
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, and, spent deionised water 3-10 time to neutrality with the poly-inclined to one side tetrafluoroethylene micro-filtration membrane suction filtration of ψ 0.45 μ m, 25 ℃ of following vacuumizes 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 red fuming nitric acid (RFNA), be heated to 25 ℃ after 0.1 hour through the 120kHz ultrasonic Treatment, the stirring and the reaction down 12 hours that refluxes, through the filter paper suction filtration, to neutral, 150 ℃ of following vacuumizes obtained the carbon fiber of acidifying after 48 hours with deionized water cyclic washing 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 red fuming nitric acid (RFNA), be heated to 25 ℃ after 1 hour through the 120kHz ultrasonic Treatment, the stirring and the reaction down 48 hours that refluxes, with the poly-inclined to one side tetrafluoroethylene milipore filter suction filtration of ψ 1.2 μ m, to neutral, 80 ℃ of vacuumizes obtained the multi-walled carbon nano-tubes of acidifying after 48 hours with deionized water cyclic washing 3-10 time;
Step (4): in the 250mL three neck round-bottomed flasks that agitator is housed, the CNT 1g, the decamethylene diamine 10g that add step (3) gained acidifying,, acetone 100mL and N, N-dicyclohexylcarbodiimide 10g is with the 100kHz ultrasonic Treatment after 24 hours, 50 ℃ of following stirring reactions 1 hour, suction filtration is removed unreacted reactant and byproduct of reaction, after spending deionised water 3-10 time repeatedly, 80 ℃ of vacuumize 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 CNT 1g, carbon fiber 20g, acetone 100mL and the N of step (2) acidifying of step (4), N-dicyclohexylcarbodiimide 10g, heating is also stirred, with the 60kHz ultrasonic Treatment 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 cyclic washing, 70 ℃ of following vacuumizes 24 hours, the carbon fiber surface that obtains was grafted with CNT and decamethylene diamine;
Fig. 1 has provided the sem photograph that carbon fiber surface is grafted with CNT and decamethylene diamine.
It is 5.6% that the XPS data that Fig. 2 provides can draw multi-wall carbon nano-tube tube-surface amido content.
Embodiment 2: (OD＜8nm) is an initial raw material with the Single Walled Carbon Nanotube of chemical vapour deposition technique preparation, Single Walled Carbon Nanotube is through the carbon fiber reaction with acidifying of purifying, acidifying and aminated back, behind the reaction certain hour, in system, add hexamethylene diamine again, make the carboxyl of the complete and not aminated CNT reaction of carbon fiber surface fully aminated, the carbon fiber surface that obtains is grafted with CNT and hexamethylene diamine.
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 ultrasonic Treatment 12 hours, be heated to 180 ℃ then, reacted 48 hours, with the poly-inclined to one side tetrafluoroethylene micro-filtration membrane suction filtration of ψ 0.8 μ m, to neutral, 100 ℃ of vacuumizes obtained the CNT of purifying after 24 hours with the deionized water cyclic washing;
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 red fuming nitric acid (RFNA), be heated to 120 ℃ after 0.1 hour through the 120kHz ultrasonic Treatment, the stirring and the reaction down 3 hours that refluxes, through the filter paper suction filtration, to neutral, 150 ℃ of following vacuumizes obtained the carbon fiber of acidifying after 48 hours with deionized water cyclic washing 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, be heated to 80 ℃ after 2 hours through the 70kHz ultrasonic Treatment, the stirring and the reaction down 80 hours that refluxes, with the poly-inclined to one side tetrafluoroethylene milipore filter suction filtration of ψ 1.2 μ m, to neutral, 100 ℃ of vacuumizes obtained the Single Walled Carbon Nanotube of acidifying after 24 hours with deionized water cyclic washing 3-10 time;
Step (4): in the 500mL three neck round-bottomed flasks that the magnetic agitation rotor is housed, the Single Walled Carbon Nanotube 3g, hexamethylene diamine 20g, the N that add step (3) gained acidifying, dinethylformamide 20g and and N, N-dicyclohexylcarbodiimide 2g, reacted 12 hours down at 120 ℃ after 96 hours through the 1kHz ultrasonic Treatment, suction filtration is removed unreacted reactant and byproduct of reaction, after spending deionised water repeatedly, 100 ℃ of vacuumize 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 3g of step (4), the carbon fiber 30g of step (2) acidifying, N, dinethylformamide 20g and N, N-dicyclohexylcarbodiimide 3g, heating is also stirred, with the 100kHz ultrasonic Treatment after 1 hour, after reacting 12 hours under 120 ℃, in beaker, add hexamethylene diamine 5g and N, N-dicyclohexylcarbodiimide 2g reacted 24 hours again, suction filtration and cyclic washing repeatedly, in 70 ℃ of following vacuum 36 hours, the carbon fiber surface that obtains was grafted with CNT and hexamethylene diamine.
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 the carbon fiber reaction with acidifying of purifying, acidifying and aminated back, behind the reaction certain hour, in system, add ethylenediamine again, make the carboxyl of the complete and not aminated CNT reaction of carbon fiber surface fully aminated, the carbon fiber surface that obtains is grafted with CNT and ethylenediamine.
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 sulfuric acid solution, with 120kHz ultrasonic Treatment 80 hours, heating and stirring and backflow under 150 ℃ then, reacted 48 hours, with the poly-inclined to one side tetrafluoroethylene micro-filtration membrane suction filtration of ψ 0.8 μ m, to neutrality, 100 ℃ of vacuumizes obtain the Single Walled Carbon Nanotube of purifying after 48 hours with deionized water cyclic washing 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 red fuming nitric acid (RFNA), adding is heated to 35 ℃ through the 120kHz ultrasonic Treatment after 0.5 hour, the stirring and the reaction down 12 hours that refluxes, through the filter paper suction filtration, to neutral, 120 ℃ of following vacuumizes obtained the carbon fiber of acidifying after 48 hours with deionized water cyclic washing 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 red fuming nitric acid (RFNA) and the concentrated sulfuric acid mixed liquor that 250mL, volume ratio are 3:1, be heated to 55 ℃ after 80 hours through the 120kHz ultrasonic Treatment, the stirring and the reaction down 1 hour that refluxes, with the poly-inclined to one side tetrafluoroethylene milipore filter suction filtration of ψ 1.2 μ m, to neutral, 65 ℃ of vacuumizes obtained the Single Walled Carbon Nanotube of acidifying after 48 hours with the deionized water cyclic washing;
Step (4): in the 1000mL three neck round-bottomed flasks that the magnetic agitation rotor is housed, CNT 9.7g, the ethylenediamine 100g, acetone 600mL and the N that add step (3) gained acidifying, N '-DIC 10g, through the 120Hz ultrasonic Treatment after 10 hours, be heated to 55 ℃, the reaction down 96 hours of stirring and reflux is after suction filtration and cyclic washing remove repeatedly, 100 ℃ of vacuumize 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 9.6g that adds step (4) gained, the carbon fiber 100g of step (2) acidifying, acetone 600mL and N, N '-DIC 10g, heating is also stirred, with the 60kHz ultrasonic Treatment after 0.1 hour, after reacting 8 hours under 55 ℃, in flask, add ethylenediamine 10g and N again, N '-DIC 10g reacted 72 hours again, suction filtration and cyclic washing, 70 ℃ of following vacuumizes 48 hours, the carbon fiber surface that obtains was grafted with CNT and ethylenediamine.
XPS analysis result shows that Single Walled Carbon Nanotube surface amido content is 6.9%.
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 the carbon fiber reaction with acidifying of purifying, acidifying and aminated back, behind the reaction certain hour, in system, add tetraethylene pentamine again, make the carboxyl of the complete and not aminated CNT reaction of carbon fiber surface fully aminated, the carbon fiber surface that obtains is connected to multi-walled carbon nano-tubes and tetraethylene pentamine.
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 ultrasonic Treatment 10 hours, be heated to 100 ℃ then, reacted 48 hours, with the poly-inclined to one side tetrafluoroethylene micro-filtration membrane suction filtration of ψ 0.8 μ m, to neutral, 100 ℃ of vacuumizes obtained the CNT of purifying after 24 hours with the deionized water cyclic washing;
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 red fuming nitric acid (RFNA), be heated to 45 ℃ after 0.1 hour through the 120kHz ultrasonic Treatment, the stirring and the reaction down 12 hours that refluxes, through the filter paper suction filtration, to neutral, 150 ℃ of following vacuumizes obtained the carbon fiber of acidifying after 48 hours with deionized water cyclic washing 3-10 time;
Step (3): in the single neck round-bottomed flask of the 500mL that the magnetic agitation rotor is housed, the CNT 2g of adding step (1) gained acidifying and 100mL, 60% weight concentration red fuming nitric acid (RFNA), be heated to 65 ℃ after 1 hour through the 120kHz ultrasonic Treatment, the stirring and the reaction down 24 hours that refluxes, with the poly-inclined to one side tetrafluoroethylene milipore filter suction filtration of ψ 1.2 μ m, to neutral, 70 ℃ of vacuumizes obtained the Single Walled Carbon Nanotube of acidifying after 48 hours with deionized water cyclic washing 3-10 time;
Step (4): in the 500mL three neck round-bottomed flasks that the magnetic agitation rotor is housed, the CNT 2g and tetraethylene pentamine 10g, acetone 100mL and the N that add step (3) gained acidifying, N-dicyclohexylcarbodiimide 2g, with the 1kHz ultrasonic Treatment after 96 hours, 55 ℃ of down reactions 12 hours, suction filtration is removed unreacted reactant and byproduct of reaction, spend deionised water repeatedly after, 200 ℃ of vacuumize 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 CNT 2g, carbon fiber 40g, acetone 300mL, the N of step (2) acidifying of step (4), N-dicyclohexylcarbodiimide 2g heating is also stirred, after 100kHz ultrasonic Treatment reaction 0.1 hour, add tetraethylene pentamine 2g again, reacted 64 hours down at 40 ℃, suction filtration and cyclic washing, 70 ℃ of following vacuumizes 24 hours, the carbon fiber surface that obtains was grafted with CNT and tetraethylene pentamine.
XPS result shows that carbon nano tube 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 carbon fiber reaction of walled carbon nanotubes purifying, acidifying and aminated back and acidifying, behind the reaction certain hour, in system, add triethylene tetramine again, make the carboxyl of the complete and not aminated CNT reaction of carbon fiber surface fully aminated, the carbon fiber surface that obtains is connected to multi-walled carbon nano-tubes and triethylene tetramine.
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, and, spent deionised water 3-10 time to neutrality with the poly-inclined to one side tetrafluoroethylene micro-filtration membrane suction filtration of ψ 0.8 μ m, 85 ℃ of following vacuumizes 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 red fuming nitric acid (RFNA), adding is heated to 25 ℃ through the 120kHz ultrasonic Treatment after 12 hours, the stirring and the reaction down 1 hour that refluxes, through the filter paper suction filtration, to neutral, 150 ℃ of following vacuumizes obtained the carbon fiber of acidifying after 48 hours with deionized water cyclic washing 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, be heated to 65 ℃ after 1 hour through the 60kHz ultrasonic Treatment, the stirring and the reaction down 24 hours that refluxes, with the poly-inclined to one side tetrafluoroethylene milipore filter suction filtration of ψ 1.2 μ m, to neutral, 80 ℃ of vacuumizes obtained the multi-walled carbon nano-tubes of acidifying after 48 hours with deionized water cyclic washing 3-10 time;
Step (4): in the 250mL three neck round-bottomed flasks that agitator is housed, CNT 1g, the triethylene tetramine 10g, acetone 100mL and the N that add step (3) gained acidifying, N '-DIC 1g, through the 100kHz ultrasonic Treatment after 1 hour, 50 ℃ of following stirring reactions 0.5 hour, suction filtration was removed unreacted reactant and byproduct of reaction, spend deionised water 3-10 time repeatedly after, 80 ℃ of vacuumize 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, the carbon fiber 25g that adds aminated multi-walled carbon nano-tubes 1g step (2) acidifying of step (4), acetone 100mL and N, N '-DIC 2g, heating is also stirred, with the 1kHz ultrasonic Treatment after 2 hours, after reacting 12 hours under 70 ℃, in flask, add triethylene tetramine 2g and N again, N '-DIC 1g reacted 48 hours again, suction filtration and cyclic washing, 70 ℃ of following vacuumizes 24 hours, the carbon fiber surface that obtains was grafted with CNT and triethylene tetramine.
XPS result shows that multi-wall carbon nano-tube tube-surface amido content is 7.2%.
Fig. 3 has provided the CNT transmission electron microscope picture that triethylene tetramine 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 (9)
1. the preparation method of a functionalization carbon fiber is characterized in that concrete steps are as follows:
(1) takes by weighing the CNT and 10～1 * 10 of 0.1～1 * 10g drying
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 miillpore filter suction filtration, cyclic washing is neutral to filtrate repeatedly, is 25～150 ℃ of following vacuumizes 1～48 hour in temperature, obtains the CNT of purifying;
(2) with 1～1 * 10
2The carbon fiber of g drying 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 the deionized water washing, filter paper suction filtration, cyclic washing repeatedly are neutral to filtrate, vacuumize is 1～48 hour under 25～150 ℃ of temperature, obtains the carbon fiber of acidifying;
(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, cyclic washing repeatedly are neutral to filtrate, vacuumize is 1～48 hour under 25～200 ℃ of temperature, obtains the CNT of acidifying;
(4) with CNT 0.1～1 * 10g, diamine or the polyamine 1～1 * 10 of step (3) gained acidifying
3G, organic solvent 1～1 * 10
3ML and condensing agent 0.1～1 * 10g mix, with 1 ~ 120kHz ultrasonic Treatment 0.1～96 hour, after reacting 1～96 hour under 25～220 ℃ of temperature, suction filtration and cyclic washing, vacuumize is 1～48 hour under 25 ~ 200 ℃ of temperature, obtains the CNT of amination;
(5) CNT 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 ultrasonic Treatment 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 cyclic washing, and vacuumize is 1～48 hour under 25 ~ 200 ℃ of temperature, and the carbon fiber surface that obtains is grafted with amido and CNT.
2. the preparation method of a kind of functionalization carbon fiber according to claim 1 is characterized in that CNT described in the step (1) comprises single wall or multi-walled carbon nano-tubes or its mixture that mixes with arbitrary proportion of any preparation in chemical vapour deposition technique, arc discharge method, solar energy method, template or the laser evaporation method.
3. the preparation method of a kind of functionalization carbon fiber according to claim 1 is characterized in that organic acid described in the step (1) is any or its multiple mixed liquor 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 a kind of functionalization carbon fiber according to claim 1 is characterized in that carbon fiber described in the step (2) is any or its multiple combination in unidirectional long fiber cloth, two-way textile sheet, three-phase textile sheet or the random staple fibre.
5. the preparation method of a kind of functionalization carbon fiber according to claim 1 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 mixed solution, 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 liquor or 15～95% weight concentration hydrogenperoxide steam generators.
6. the preparation method of a kind of functionalization carbon fiber according to claim 1, it is characterized in that diamine described in step (4), (5) is ethylenediamine, polyethyene diamine, 1,2-propane diamine, 1,3-propane diamine, 1,2-butanediamine, 1, in the 3-butanediamine, 1,6-hexamethylene diamine, p-phenylenediamine (PPD), cyclohexanediamine, m-phenylene diamine (MPD), m-xylene diamine, two amido diphenyl methanes, the Meng alkane diamines, divinyl propylamine, two amido diphenyl methanes, chlorination hexamethylene diamine, chlorination nonamethylene diamine, chlorination decamethylene diamine, 12 carbon diamines or 13 carbon diamines any; Described polyamine is triethylamine, fourth triamine, N-amine ethyl piperazidine, dicyandiamide, 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 a kind of functionalization carbon fiber according to claim 1, it is characterized in that step (4), (5) organic solvent described in is a benzene, toluene, dimethylbenzene, styrene, butyl toluene, perchloroethylene, trichloro-ethylene, vinyltoluene, ethylene glycol ether, carrene, carbon disulfide, the tricresyl phosphate orthoresol, methyl alcohol, ethanol, isopropyl alcohol, cyclohexane, cyclohexanone, the toluene cyclohexanone, ether, expoxy propane, acetone, espeleton, methylisobutylketone, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, acetonitrile, pyridine, chlorobenzene, dichloro-benzenes, carrene, chloroform, carbon tetrachloride, trichloro-ethylene, tetrachloro-ethylene, trichloropropane, dichloroethanes, N, dinethylformamide, dimethyl sulfoxide (DMSO), any or its multiple combination in dioxane or the oxolane.
8. the preparation method of a kind of functionalization carbon fiber according to claim 1, 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 a kind of functionalization carbon fiber according to claim 1, it is characterized in that the carbon fiber surface that obtains described in the step (5) is grafted with amido and CNT, is the carbon fiber that the carbon fiber surface of functionalization is grafted with diamine or polyamine and CNT.
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