CN101811661A - Preparation method of carbon fiber/carbon nano tube/epoxy resin multi-dimensional hybrid composite - Google Patents
Preparation method of carbon fiber/carbon nano tube/epoxy resin multi-dimensional hybrid composite Download PDFInfo
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Abstract
The invention belongs to the technical field of nano materials, and in particular relates to a preparation method of a carbon fiber/carbon nano tube/epoxy resin multi-dimensional hybrid composite. The invention comprises the following steps: carrying out surface carboxylation and chloride acetylation on carbon nano tubes and carbon fibers, introducing diamine or polyamine, and modifying the amino-grafted carbon nano tubes with small-molecule aromatic polyanhydride compounds to prepare carbon nano tubes carrying with anhydride groups; carrying out ultrasonic oscillation, stirring at a high speed to dispersing the carbon nano tubes in an epoxy resin matrix, and curing with organic anhydride curing agent to obtain an epoxy resin polymer containing carbon nano tubes; and using the epoxy resin polymer containing the carbon nano tubes as the matrix for being compounded with the carbon fibers to form the covalently-bonded multi-dimensional hybrid composite structure. The invention has the advantage of convenient preparation; the carbon nano tubes are endued with activity for participating in the reaction, and the anhydride groups on the carbon nano tubes and the epoxy groups in the epoxy resin generate chemical crosslink, thereby promoting the dispersion of the carbon nano tubes in the epoxy resin; and the epoxy resin is toughened by using the strength and the toughness of the carbon nano tubes to enhance the bonding strength with the carbon fiber substrate, thus improving the overall performance of the carbon fiber/carbon nano tube/epoxy resin multi-dimensional hybrid composite, and widening the application of the carbon fibers, the carbon nano tubes and the epoxy resin.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to a kind of preparation method of carbon fiber/carbon nano tube/epoxy resin multi-dimensional hybrid composite.
Background technology
Epoxy resin is a kind of thermosetting oligomer, poor performance.Except as the stabilizing agent of polyvinyl chloride, there is not direct use value.But, then present the performance of a series of excellences when it and curing agent are cured after reaction forms the three-dimensional crosslinked network structure.So the chemical reaction performance of curing agent and epoxy resin is basis, the core that epoxy resin is used.Behavior and the performance of solidfied material of epoxy resin in solidification process depends on to a great extent and interacts between curing agents and it and the resin and rationally cooperate, and these depend on the molecular structure of curing agent.Therefore, be applied in is exactly the problem of solidification of studying epoxy resin research epoxy resin in a way.
CNT (CNTs) just with its excellent mechanical property, electric property, thermal property and chemical property etc., has become the focus of each scientific domain research rapidly since being found.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 of CNT can be higher, reunites easily, makes it be difficult to realize even dispersion in polymer.CNT will must be combined closely with polymer backbone as reinforcing material, and stress is transferred on the CNT effectively.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.The excellent properties of carbon fibre composite has obtained extensive use in every profession and trade.Can utilize the excellent separately mechanical property modified epoxy of carbon fiber and CNT, preparation carbon fiber/carbon nano tube/epoxy resin multi-dimensional hybrid composite, the prospect that can predict carbon fiber/carbon nano tube/epoxy resin hybrid composite will be very wide.
Summary of the invention
The object of the present invention is to provide the preparation method of the firm carbon fiber/carbon nano tube/epoxy resin multi-dimensional hybrid composite of a kind of good dispersion, interface bonding.
The preparation method of carbon fiber/carbon nano tube/epoxy resin multi-dimensional multi-dimensional hybrid composite that the present invention proposes, be with the carbon nano tube surface purifying, after the carbon nano tube surface of purifying carried out carboxylated, chloride, introducing has the diamine or the polyamine of feature structure, obtain the graft type CNT that the surface has active amino, it is compound-modified with little molecule aromatic series multi-anhydride to be connected to this amino CNT again, and the CNT of anhydride group is carried in preparation.Supersonic oscillations and high-speed stirred, CNT is scattered in the epoxy resin-base, adopt organic acid anhydride class curing agent to solidify, compound by certain way with the epoxide resin polymer that obtains containing CNT as matrix and carbon fiber, form the multi-dimensional hybrid composite structure that links to each other with covalent bond at last, then carbon fiber and carbon nano tube surface will be wound with a large amount of polymer.Its concrete steps are as follows:
(1) takes by weighing 1～1 * 10
2The CNT of g drying and 10g～1 * 10
3The g organic acid mixes, in 1～120kHz ultrasonic wave or 10r/min～10
6The centrifugal speed of r/min stirs down and handled 1～80 hour, is heated to 20～180 ℃ then, reacts 1～48 hour, and with the micro-filtration membrane suction filtration, cyclic washing is to neutral, and vacuum drying is 1～48 hour under 25～150 ℃ of temperature, obtains the CNT of purifying;
(2) with 1～1 * 10
2The carbon fiber of g drying, step obtain purifying carbon nano-tube 1～1 * 10 in (1)
2G respectively with acid with strong oxidizing property 1～1 * 10
4ML mixes, under 1～120kHz ultrasonic wave, handled 1～80 hour, be heated to 25～120 ℃ then, stirring and back flow reaction 1～80 hour, ultramicropore filter membrane suction filtration, it is neutral that cyclic washing to solution is, and vacuum drying is 1～48 hour under 25～200 ℃ of temperature, obtains the carbon fiber and the CNT of acidifying respectively;
(3) with the carbon fiber and the CNT 1～1 * 10 of step (2) gained acidifying
2G respectively with acylating reagent 1～1 * 10
4ML after 0.1～10 hour, is heated to 25～220 ℃ with the processing of 1～120kHz ultrasonic wave, stirring and back flow reaction 0.5～100 hour, and suction filtration and cyclic washing are removed acylating reagent, obtain the carbon fiber and the CNT of acyl groupization respectively;
(4) with step (3) gained acidylate carbon fiber and CNT 1～1 * 10
2G respectively with diamine or polyamine 10～1 * 10
4G, handled 1～100 hour with 1～100kHz ultrasonic wave, under 25～200 ℃ of temperature, reacted 0.5～100 hour suction filtration and cyclic washing then, vacuum drying is 1～48 hour under 25～200 ℃ of temperature, obtains graft type carbon fiber and CNT that the surface has active amino respectively;
(5) step (4) gained surface is had the carbon fiber and the CNT 1～1 * 10 of active amino
2G aromatic anhydride compound of agitation and dropping 1～100g at a slow speed in the polar organic solvent ice bath, being warming up to 100～150 ℃ after dropwising refluxed 3～12 hours, with the unreacted aromatic anhydride compound of polar organic solvent flush away, 40～80 ℃ of following vacuum drying 3～12 hours obtain having the carbon fiber and the CNT of activity anhydride group;
(6) step (5) gained surface is had the CNT 1～1 * 10 of activity anhydride group
2G and epoxy resin 10～1 * 10
4G, be warming up to the resin matrix fusion after, dispersed with stirring evenly and remove bubble under vacuum condition is carried out chemical crosslink reaction simultaneously, obtains containing the epoxide resin polymer of CNT;
(7) with the resultant epoxide resin polymer 20g-25g that contains CNT of step (6) as matrix and carbon fiber 20g-100g with mechanical mixture, at 60～100 ℃, ultrasonic wave disperseed 1～12 hour, add 40～50g organic acid anhydride class curing agent, above curing system is poured in the mould, vacuum condition removes bubble down, at 100～250 ℃ of following curing moldings, obtains carbon fiber-containing/carbon nano tube/epoxy resin multi-dimensional hybrid composite.
Among the present invention, CNT described in the step (1) is single wall, double-walled or the multi-walled carbon nano-tubes of any preparation in arc discharge, chemical gaseous phase deposition, template, solar energy method and 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, acid with strong oxidizing property described in the step (2) 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, in 1/100～100/1 mol ratio hydrogen peroxide and nitric acid mixed liquor or 15～95% weight concentration hydrogenperoxide steam generators any.
Among the present invention, acylating reagent described in the step (3) be in thionyl chloride, phosphorus trichloride or phosphorus pentachloride, thionyl chloride, phosphorus tribromide, phosphorus pentabromide or the thionyl bromide any.
Among the present invention, diamine described in the step (4) is ethylenediamine, polyethyene diamine, 1,2-propane diamine, 1,3-propane diamine, 1, in the 2-butanediamine, 1,3-butanediamine, hexamethylene diamine, p-phenylenediamine (PPD), m-phenylene diamine (MPD), m-xylene diamine, diaminodiphenyl-methane, the Meng alkane diamines, divinyl propylamine, diaminodiphenyl-methane, chlorination hexamethylene diamine, chlorination nonamethylene diamine, chlorination decamethylene diamine, 12 carbon diamines or 13 carbon diamines any; Described polyamine is fourth triamine, N-aminoethyl piperazine, dicyandiamide, adipic dihydrazide, N, in N-dimethyl dipropyl triamine, TEPA, diethylenetriamine, triethylene tetramine, TEPA, five ethene hexamines or six ethene, seven amine any.
Among the present invention, the quantitative analysis of carboxyl-content in the CNT of acidifying and the carbon fiber can be adopted TGA, XPS or nuclear magnetic resonance method in the step (2).
Among the present invention, the surface that obtains described in the step (4) has the graft type CNT and the carbon fiber of active amino, and its amino is diamine or polyamine.
Among the present invention, the surface that obtains described in the step (5) has the graft type CNT and the carbon fiber of activity anhydride group, and its anhydride group is the aromatic anhydride compound.Described aromatic anhydride compound comprises addition product, the diphenyl sulfone-3 of addition product, benzophenone tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride and the caprolactone of pyromellitic acid anhydride PDMA, pyromellitic acid anhydride and caprolactone, 3 ', 4,4 '-tetracarboxylic dianhydride DSDA, diphenyl sulfone-3,3 ', 4, the addition product of 4 '-tetracarboxylic dianhydride, N, one or more in N '-dicarboxylic anhydride diphenyl methane, mellitic acid three acid anhydrides.
Among the present invention, the polar organic solvent described in the step (5) comprises ethanol, methyl alcohol, dimethyl sulfoxide (DMSO), oxolane, acetone or N, one or more mixtures of N '-dimethyl formamide.
Among the present invention, the epoxy resin described in the step (6) is meant in all epoxy resin that comprise glycidol ethers, glycidol lipid, glycidol amine, alicyclic ring class, epoxidation of olefins class, imide ring epoxy resins or glycolylurea epoxide resin any.
Among the present invention, the linear block polymer of the carbon nanotubes that obtains described in the step (6) is the linear block polymer of CNT that is connected to the block polymer of epoxy resin on the CNT of acid anhydridesization.
Among the present invention, organic acid anhydride class curing agent described in the step (7) comprises organic acid anhydride type curing agent, as one or several mixture in phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl carbic anhydride, dodecyl succinic anhydride, chlorendic anhydride, adjacent PMDA, phthalic anhydride tetracarboxylic dianhydride, methylcyclohexene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, trimellitic anhydride, the poly-azelaic acid acid anhydride.
Among the present invention, carbon fiber described in the step (7) is any in unidirectional long fibre cloth, two-way woven cloth, three-phase woven cloth or the random short fiber.
Preparation method provided by the invention is simple, gained be the carbon fiber multi-dimensional hybrid compound that the surface is connected to epoxy resin/CNT.The anhydride group of carbon nano tube surface is by producing chemical crosslink reaction with epoxy resin, make CNT become the part of epoxy-resin systems, again by compound in a certain way with the carbon fiber of surface acid anhydridization, froth in vacuum obtains carbon fiber-containing/carbon nano tube/epoxy resin multi-dimensional hybrid composite.Because the effect of carbon nano-tube modification epoxy resin has increased the boundary strength between matrix resin and the carbon fiber, makes composite have good interlaminar shear strength.
The present invention introduces the anhydride group with feature structure at CNT and carbon fiber surface, utilize this structure and epoxy resin to carry out chemical crosslink reaction, then CNT and carbon fiber surface will be wound with a large amount of polymer, because polymer has the characteristic of affinity and CNT itself to matrix resin, thereby improve the shortcoming of the interlaminar shear strength deficiency etc. of carbon fiber, this multi-dimensional hybrid compound has firm, the multiple performances such as strength and toughness is good, easy curing of interface bonding, and the comprehensive mechanical property of composite is improved significantly.Therefore, the present invention has important science and technology value and actual application value.
Description of drawings
Fig. 1 is a kind of epoxy resin linearity block carbon nanotube polymer transmission electron microscope picture.
Fig. 2 is a kind of epoxy resin linearity block carbon nanotube polymer XPS figure.
The specific embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1: (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, respectively CNT and carbon fiber are carried out acidifying, chloride, after the amination, after using the pyromellitic acid anhydride acid anhydridesization again, CNT and liquid bisphenol A type epoxy resin (E-51) are carried out chemical crosslink reaction, then obtain the multi-walled carbon nano-tubes that the surface is connected to liquid bisphenol A type epoxy resin, again that the carbon fiber of itself and pyromellitic acid anhydride acid anhydridesization is compound in a certain way, obtain carbon fiber-containing/carbon nano tube/epoxy resin multi-dimensional hybrid composite.
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 10 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 tetrafluoroethene micro-filtration membrane suction filtration of ψ 0.8 μ m, 25 ℃ of following vacuum drying obtained the multi-walled carbon nano-tubes of purifying after 24 hours;
Step (2): in two single neck round-bottomed flasks of the 250mL that agitator has been housed, one of them goes into the carbon nanometer tube material 1g and the 100mL of the purifying that obtains in the step (1), 60% weight concentration red fuming nitric acid (RFNA), another adds the carbon fiber 20g and the 100mL of drying, 60% weight concentration red fuming nitric acid (RFNA), two flasks are handled through following the same terms: adding is heated to 25 ℃ after the 60kHz ultrasonic wave is handled 1 hour, the stirring and the reaction down 24 hours that refluxes, with the poly-inclined to one side tetrafluoroethene milipore filter suction filtration of ψ 1.2 μ m, with deionized water cyclic washing 3-10 time to neutral, 80 ℃ of vacuum drying obtained the multi-walled carbon nano-tubes and the carbon fiber of carboxylic acidization respectively after 48 hours;
Step (3): in two 250mL three neck round-bottomed flasks that agitator has been housed, one of them adds the CNT 1g and the thionyl chloride 10g of step (2) gained acidifying, another adds the carbon fiber 20g and the thionyl chloride 100g of acidifying, two flasks are handled through following the same terms: after handling 1 hour with the 100Hz ultrasonic wave, be heated to 80 ℃, the stirring and the reaction down 100 hours that refluxes, suction filtration and cyclic washing are removed thionyl chloride, obtain the multi-walled carbon nano-tubes and the carbon fiber of chloride respectively;
Step (4): in two 250mL three neck round-bottomed flasks that agitator has been housed, one of them adds step (3) gained acylated carbon nano-tube 1g and 12 carbon diamine 10g, another adds the carbon fiber 20g and the 12 carbon diamine 100g of acidylate, two flasks are handled through following the same terms: after handling 1 hour with the 100kHz ultrasonic wave, 200 ℃ of following stirring reactions 0.5 hour, suction filtration is removed unreacted reactant and byproduct of reaction, after spending deionised water 3-10 time repeatedly, 80 ℃ of vacuum drying 48 hours obtain the surface respectively and have amino multi-walled carbon nano-tubes and carbon fiber;
Step (5): in two 250mL three neck round-bottomed flasks that agitator has been housed; one of them CNT 1g that adds step (4) gained ammonification is dissolved in the dimethyl sulfoxide (DMSO); another carbon fiber 20g that adds ammonification is dissolved in the dimethyl sulfoxide (DMSO); two flasks are handled through following the same terms: ultrasonic concussion 30min; add the 10g pyromellitic acid anhydride; add catalyst concentrated sulfuric acid 10ml; stir under 90 ℃; nitrogen protection; magnetic agitation; reaction time is 48 hours, obtains carbon fiber and CNT that anhydride group is contained on the surface respectively.
Step (6): in the 250mL three neck round-bottomed flasks that agitator is housed, the CNT 1g and liquid bisphenol A type epoxy resin (E-51) 20g that add step (5) acid anhydridesization, heating is also stirred, after handling 2 hours with the 60kHz ultrasonic wave, reacted 12 hours down at 240 ℃, obtain the multi-walled carbon nano-tubes that the surface is connected to liquid bisphenol A type epoxy resin (E-51);
Step (7): the carbon fiber 20g that gets multi-walled carbon nano-tubes compound 20g that the surface is connected to liquid bisphenol A type epoxy resin (E-51) and step (5) acid anhydridesization is compound down with 150 ℃, de-bubble under vacuum condition, compression molding obtains carbon fiber-containing/carbon nano tube/epoxy resin multi-dimensional hybrid composite under 10MPa.
Fig. 1 has provided the surperficial carbon nano tube hybrid composite transmission electron microscope picture that is connected to epoxy resin, and CNT is enclosed with the polymer of one deck light color as can be seen.
It is 7.0% (with the mol ratio of carbon) that the XPS data that provide from Fig. 2 can draw multi-wall carbon nano-tube tube-surface carboxyl-content.Therefore can calculate and handle back multi-walled carbon nano-tubes surface amino groups content is 7.0%.
Embodiment 2: (OD＜8nm) is an initial raw material with the SWCN of chemical vapour deposition technique preparation, SWCN is through purifying, respectively CNT and carbon fiber are carried out acidifying, chloride, amination, after using benzophenone tetracarboxylic dianhydride acid anhydridesization again, CNT and liquid bisphenol A type epoxy resin (E-54) are carried out chemical crosslink reaction, then obtain the SWCN that the surface is connected to liquid bisphenol A type epoxy resin (E-54), again that the carbon fiber of itself and benzophenone tetracarboxylic dianhydride acid anhydridesization is compound in a certain way, obtain carbon fiber-containing/carbon nano tube/epoxy resin multi-dimensional hybrid composite
Step (1): in the single neck round-bottomed flask of the 500mL that agitator is housed, the sulfuric acid of the SWCN raw material of adding 1.1g drying and 100mL, 20% weight concentration, under the 120kHz ultrasonic wave, handled 12 hours, be heated to 180 ℃ then, reacted 48 hours, and, spent deionised water 3-10 time to neutrality with the poly-inclined to one side tetrafluoroethene micro-filtration membrane suction filtration of ψ 0.8 μ m, 100 ℃ of following vacuum drying obtained the multi-walled carbon nano-tubes of purifying after 24 hours;
Step (2): in two single neck round-bottomed flasks of the 500mL that agitator has been housed, one of them goes into the carbon nanometer tube material 1g and the 200mL of the purifying that obtains in the step (1), 98% concentrated sulfuric acid solution, another adds the carbon fiber 100g and the 200mL of drying, 98% concentrated sulfuric acid solution, two flasks are handled through following the same terms: adding is heated to 80 ℃ after the 70kHz ultrasonic wave is handled 2 hours, the stirring and the reaction down 80 hours that refluxes, with the poly-inclined to one side tetrafluoroethene milipore filter suction filtration of ψ 1.2 μ m, with deionized water cyclic washing 3-10 time to neutral, 100 ℃ of vacuum drying obtained the multi-walled carbon nano-tubes and the carbon fiber of carboxylic acidization respectively after 24 hours;
Step (3): in two 500mL three neck round-bottomed flasks that agitator has been housed, one of them adds the CNT 1g and the trichlorine sulfoxide 10g of step (2) gained acidifying, another adds the carbon fiber 100g and the three torak 200g of acidifying, two flasks are handled through following the same terms: after handling 10 hours with the 120Hz ultrasonic wave, be heated to 25 ℃, the stirring and the reaction down 48 hours that refluxes, suction filtration and cyclic washing are removed three toraks, obtain the SWCN and the carbon fiber of chloride respectively;
Step (4): in two 500mL three neck round-bottomed flasks that agitator has been housed, one of them adds step (3) gained acylated carbon nano-tube 1g and 12 carbon diamine 10g, another adds the carbon fiber 20g and the 12 carbon diamine 100g of acidylate, two flasks are handled through following the same terms: after handling 1 hour with the 100kHz ultrasonic wave, 200 ℃ of following stirring reactions 0.5 hour, suction filtration is removed unreacted reactant and byproduct of reaction, after spending deionised water 3-10 time repeatedly, 80 ℃ of vacuum drying 48 hours obtain the surface respectively and have amino SWCN and carbon fiber;
Step (5): in two 500mL three neck round-bottomed flasks that agitator has been housed; one of them CNT 1g that adds step (4) gained ammonification is dissolved in the dimethyl sulfoxide (DMSO); another carbon fiber 20g that adds ammonification is dissolved in the dimethyl sulfoxide (DMSO); two flasks are handled through following the same terms: ultrasonic concussion 30min; add the acid of 10g benzophenone tetracarboxylic dianhydride; add catalyst concentrated sulfuric acid 10ml; stir under 90 ℃; nitrogen protection; magnetic agitation; reaction time is 48 hours, obtains carbon fiber and CNT that anhydride group is contained on the surface respectively.
Step (6): in the 500mL three neck round-bottomed flasks that agitator is housed, the CNT 1g and liquid bisphenol A type epoxy resin (E-54) 20g that add step (5) acid anhydridesization, heating is also stirred, after handling 2 hours with the 60kHz ultrasonic wave, reacted 12 hours down at 240 ℃, obtain the SWCN that the surface is connected to liquid bisphenol A type epoxy resin (E-54);
Step (7): the carbon fiber 20g that gets single-wall carbon nanotube composite 20g that the surface is connected to liquid bisphenol A type epoxy resin (E-54) and step (5) acid anhydridesization is compound down at 100 ℃, de-bubble under vacuum condition, compression molding obtains carbon fiber-containing/carbon nano tube/epoxy resin multi-dimensional hybrid composite under 8MPa.
XPS result shows that carbon fiber and SWCN impurity surface anhydride content are 6.5%.
Embodiment 3: (OD＜8nm) is an initial raw material with the SWCN of laser evaporation method preparation, SWCN is through purifying, respectively that carbon fiber and CNT is acidified, chloride, after the amination, use N again, after N '-dicarboxylic anhydride diphenylmethyl alkanoic acid anhydrideization, CNT and liquid bisphenol A type epoxy resin (E-44) are carried out chemical crosslink reaction, then obtain the SWCN that the surface is connected to liquid bisphenol A type epoxy resin (E-44), again with itself and N, the carbon fiber of N '-dicarboxylic anhydride diphenylmethyl alkanoic acid anhydrideization is compound in a certain way, obtains carbon fiber-containing/carbon nano tube/epoxy resin multi-dimensional hybrid composite.
Step (1): in the single neck round-bottomed flask of the 500mL that agitator is housed, the sulfuric acid of the SWCN raw material of adding 10g drying and 250mL, 20% weight concentration, under the 120kHz ultrasonic wave, handled 80 hours, heating and stirring and backflow under 180 ℃ then, reacted 48 hours, and, spent deionised water 3-10 time to neutrality with the poly-inclined to one side tetrafluoroethene micro-filtration membrane suction filtration of ψ 0.8 μ m, 100 ℃ of following vacuum drying obtained the SWCN of purifying after 24 hours;
Step (2): in two single neck round-bottomed flasks of the 500mL that agitator has been housed, one of them goes into the carbon nanometer tube material 9.8g and the 250mL of the purifying that obtains in the step (1), volume ratio is 2: 1 red fuming nitric acid (RFNA) and a concentrated sulfuric acid mixed liquor, another adds the carbon fiber 100g and the 250mL of drying, volume ratio is 2: 1 red fuming nitric acid (RFNA) and a concentrated sulfuric acid mixed liquor, two flasks are handled through following the same terms: be heated to 25 ℃ with the processing of 120kHz ultrasonic wave after 80 hours, the stirring and the reaction down 80 hours that refluxes, with the poly-inclined to one side tetrafluoroethene milipore filter suction filtration of ψ 1.2 μ m, extremely neutral with the deionized water cyclic washing, 25 ℃ of vacuum drying obtained the SWCN and the carbon fiber of carboxylic acidization respectively after 48 hours;
Step (3): in two 500mL three neck round-bottomed flasks that the magnetic agitation rotor is housed, one of them adds the CNT 9.8g and the phosphorus pentachloride 100g of step (2) gained acidifying, another adds the carbon fiber 100g and the phosphorus pentachloride 200g of acidifying, two flasks are handled through following the same terms: after handling 1 hour with the 120Hz ultrasonic wave, be heated to 25 ℃, the stirring and the reaction down 100 hours that refluxes, suction filtration and cyclic washing remove and repeatedly remove phosphorus pentachloride, obtain the SWCN and the carbon fiber of chloride respectively;
Step (4): in two 500mL three neck round-bottomed flasks that the magnetic agitation rotor is housed, one of them adds step (3) gained acidylate CNT 9.8g and TEPA 50g, another adds the carbon fiber 100g and the TEPA 200g of chloride, two flasks are handled through following the same terms: after handling 1 hour with the 100kHz ultrasonic wave, two flasks reacted 24 hours down at 25 ℃, suction filtration is removed unreacted reactant and byproduct of reaction, spend repeatedly deionised water repeatedly after, 200 ℃ of vacuum drying 1 hour obtain the surface respectively and have amino SWCN and carbon fiber;
Step (5): in two 500mL three neck round-bottomed flasks that agitator has been housed; one of them CNT 9.8g that adds step (4) gained ammonification is dissolved in the dimethyl sulfoxide (DMSO); another carbon fiber 100g that adds ammonification is dissolved in the dimethyl sulfoxide (DMSO); two flasks are handled through following the same terms: ultrasonic concussion 30min; add 100gN; N '-dicarboxylic anhydride diphenyl methane; add catalyst concentrated sulfuric acid 10ml; stir under 90 ℃; nitrogen protection; magnetic agitation, the reaction time is 48 hours, obtains carbon fiber and CNT that anhydride group is contained on the surface respectively.
Step (6): in the 500mL three neck round-bottomed flasks that agitator is housed, the CNT 9.8g and liquid bisphenol A type epoxy resin (E-44) 100g that add step (5) acid anhydridesization, heating is also stirred, after handling 2 hours with the 80kHz ultrasonic wave, reacted 12 hours down at 240 ℃, obtain the SWCN that the surface is connected to liquid bisphenol A type epoxy resin (E-44);
Step (7): the carbon fiber 100g that gets single-wall carbon nanotube composite 25g that the surface is connected to liquid bisphenol A type epoxy resin (E-44) and step (5) acid anhydridesization is compound down at 100 ℃, de-bubble under vacuum condition, compression molding obtains carbon fiber-containing/carbon nano tube/epoxy resin multi-dimensional hybrid composite under 13MPa.
The XPS analysis result shows that carbon fiber and SWCN impurity surface anhydride content are 8.0%.
Embodiment 4: (OD＜8nm) is an initial raw material with the multi-walled carbon nano-tubes of laser evaporation method preparation, the walled carbon nanotubes purifying, respectively that carbon fiber and CNT is acidified, chloride, after the amination, use N again, after N '-dicarboxylic anhydride diphenylmethyl alkanoic acid anhydrideization, CNT and liquid bisphenol A type epoxy resin (E-44) are carried out chemical crosslink reaction, then obtain the SWCN that the surface is connected to liquid bisphenol A type epoxy resin (E-44), again with itself and N, the carbon fiber of N '-dicarboxylic anhydride diphenylmethyl alkanoic acid anhydrideization is compound in a certain way, obtains carbon fiber-containing/carbon nano tube/epoxy resin multi-dimensional hybrid composite.
Step (1): in the single neck round-bottomed flask of the 500mL that agitator is housed, the sulfuric acid of the multi-walled carbon nano-tubes raw material of adding 10g drying and 250mL, 20% weight concentration, under the 60kHz ultrasonic wave, handled 40 hours, heating and stirring and backflow under 180 ℃ then, reacted 48 hours, and, spent deionised water 3-10 time to neutrality with the poly-inclined to one side tetrafluoroethene micro-filtration membrane suction filtration of ψ 0.8 μ m, 100 ℃ of following vacuum drying obtained the double-walled carbon nano-tube of purifying after 24 hours;
Step (2): in two single neck round-bottomed flasks of the 500mL that agitator has been housed, one of them goes into the carbon nanometer tube material 9.8g and the 250mL of the purifying that obtains in the step (1), volume ratio is 2: 1 red fuming nitric acid (RFNA) and a concentrated sulfuric acid mixed liquor, another adds the carbon fiber 100g and the 250mL of drying, volume ratio is 2: 1 red fuming nitric acid (RFNA) and a concentrated sulfuric acid mixed liquor, two flasks are handled through following the same terms: be heated to 25 ℃ with the processing of 60kHz ultrasonic wave after 40 hours, the stirring and the reaction down 80 hours that refluxes, with the poly-inclined to one side tetrafluoroethene milipore filter suction filtration of ψ 1.2 μ m, extremely neutral with the deionized water cyclic washing, 25 ℃ of vacuum drying obtained the multi-walled carbon nano-tubes and the carbon fiber of carboxylic acidization respectively after 48 hours;
Step (3): in two 500mL three neck round-bottomed flasks that the magnetic agitation rotor is housed, one of them adds the CNT 9.8g and the phosphorus pentachloride 100g of step (2) gained acidifying, another adds the carbon fiber 100g and the phosphorus pentachloride 200g of acidifying, two flasks are handled through following the same terms: after handling 1 hour with the 60Hz ultrasonic wave, be heated to 25 ℃, the stirring and the reaction down 100 hours that refluxes, suction filtration and cyclic washing remove and repeatedly remove phosphorus pentachloride, obtain the multi-walled carbon nano-tubes and the carbon fiber of chloride respectively;
Step (4): in two 500mL three neck round-bottomed flasks that the magnetic agitation rotor is housed, one of them adds step (3) gained acidylate CNT 9.8g and TEPA 50g, another adds the carbon fiber 100g and the TEPA 200g of chloride, two flasks are handled through following the same terms: after handling 1 hour with the 100kHz ultrasonic wave, two flasks reacted 24 hours down at 25 ℃, suction filtration is removed unreacted reactant and byproduct of reaction, spend repeatedly deionised water repeatedly after, 200 ℃ of vacuum drying 1 hour obtain the surface respectively and have amino multi-walled carbon nano-tubes and carbon fiber;
Step (5): in two 500mL three neck round-bottomed flasks that agitator has been housed; one of them CNT 9.8g that adds step (4) gained ammonification is dissolved in the dimethyl sulfoxide (DMSO); another carbon fiber 100g that adds ammonification is dissolved in the dimethyl sulfoxide (DMSO); two flasks are handled through following the same terms: ultrasonic concussion 30min; add 100gN; N '-dicarboxylic anhydride diphenyl methane; add catalyst concentrated sulfuric acid 10ml; stir under 90 ℃; nitrogen protection; magnetic agitation, the reaction time is 48 hours, obtains carbon fiber and CNT that anhydride group is contained on the surface respectively.
Step (6): in the 500mL three neck round-bottomed flasks that agitator is housed, the CNT 9.8g and liquid bisphenol A type epoxy resin (E-44) 100g that add step (5) acid anhydridesization, heating is also stirred, after handling 2 hours with the 80kHz ultrasonic wave, reacted 12 hours down at 240 ℃, obtain the multi-walled carbon nano-tubes that the surface is connected to liquid bisphenol A type epoxy resin (E-44);
Step (7): the carbon fiber 100g that gets single-wall carbon nanotube composite 25g that the surface is connected to liquid bisphenol A type epoxy resin (E-44) and step (5) acid anhydridesization is compound down at 100 ℃, de-bubble under vacuum condition, compression molding obtains carbon fiber-containing/carbon nano tube/epoxy resin multi-dimensional hybrid composite under 13MPa.
XPS result shows that carbon fiber and multi-walled carbon nano-tubes impurity surface anhydride content are 7.4%.
Embodiment 5: (OD＜8nm) is an initial raw material with the multi-walled carbon nano-tubes of chemical gas-phase method preparation, the walled carbon nanotubes purifying, respectively that carbon fiber and CNT is acidified, chloride, after the amination, use N again, after N '-dicarboxylic anhydride diphenylmethyl alkanoic acid anhydrideization, CNT and liquid bisphenol A type epoxy resin (E-51) are carried out chemical crosslink reaction, then obtain the multi-walled carbon nano-tubes that the surface is connected to liquid bisphenol A type epoxy resin (E-51), again with itself and N, the carbon fiber of N '-dicarboxylic anhydride diphenylmethyl alkanoic acid anhydrideization is compound in a certain way, obtains carbon fiber-containing/carbon nano tube/epoxy resin multi-dimensional hybrid composite.
Step (1): in the single neck round-bottomed flask of the 500mL that agitator is housed, the sulfuric acid of the multi-walled carbon nano-tubes raw material of adding 10g drying and 250mL, 20% weight concentration, under the 90kHz ultrasonic wave, handled 60 hours, heating and stirring and backflow under 180 ℃ then, reacted 48 hours, and, spent deionised water 3-10 time to neutrality with the poly-inclined to one side tetrafluoroethene micro-filtration membrane suction filtration of ψ 0.8 μ m, 100 ℃ of following vacuum drying obtained the multi-walled carbon nano-tubes of purifying after 24 hours;
Step (2): in two single neck round-bottomed flasks of the 500mL that agitator has been housed, one of them goes into the carbon nanometer tube material 9.8g and the 250mL of the purifying that obtains in the step (1), volume ratio is 2: 1 red fuming nitric acid (RFNA) and a concentrated sulfuric acid mixed liquor, another adds the carbon fiber 100g and the 250mL of drying, volume ratio is 2: 1 red fuming nitric acid (RFNA) and a concentrated sulfuric acid mixed liquor, two flasks are handled through following the same terms: be heated to 25 ℃ with the processing of 120kHz ultrasonic wave after 80 hours, the stirring and the reaction down 80 hours that refluxes, with the poly-inclined to one side tetrafluoroethene milipore filter suction filtration of ψ 1.2 μ m, extremely neutral with the deionized water cyclic washing, 25 ℃ of vacuum drying obtained the multi-walled carbon nano-tubes and the carbon fiber of carboxylic acidization respectively after 48 hours;
Step (3): in two 500mL three neck round-bottomed flasks that the magnetic agitation rotor is housed, one of them adds the CNT 9.8g and the phosphorus pentachloride 100g of step (2) gained acidifying, another adds the carbon fiber 100g and the phosphorus pentachloride 200g of acidifying, two flasks are handled through following the same terms: after handling 1 hour with the 120Hz ultrasonic wave, be heated to 25 ℃, the stirring and the reaction down 100 hours that refluxes, suction filtration and cyclic washing remove and repeatedly remove phosphorus pentachloride, obtain the multi-walled carbon nano-tubes and the carbon fiber of chloride respectively;
Step (4): in two 500mL three neck round-bottomed flasks that the magnetic agitation rotor is housed, one of them adds step (3) gained acidylate CNT 9.8g and TEPA 50g, another adds the carbon fiber 100g and the TEPA 200g of chloride, two flasks are handled through following the same terms: after handling 5 hours with the 60kHz ultrasonic wave, two flasks reacted 24 hours down at 25 ℃, suction filtration is removed unreacted reactant and byproduct of reaction, spend repeatedly deionised water repeatedly after, 200 ℃ of vacuum drying 1 hour obtain the surface respectively and have amino multi-walled carbon nano-tubes and carbon fiber;
Step (5): in two 500mL three neck round-bottomed flasks that agitator has been housed; one of them CNT 9.8g that adds step (4) gained ammonification is dissolved in the dimethyl sulfoxide (DMSO); another carbon fiber 100g that adds ammonification is dissolved in the dimethyl sulfoxide (DMSO); two flasks are handled through following the same terms: ultrasonic concussion 30min; add 100gN; N '-dicarboxylic anhydride diphenyl methane; add catalyst concentrated sulfuric acid 10ml; stir under 90 ℃; nitrogen protection; magnetic agitation, the reaction time is 48 hours, obtains carbon fiber and CNT that anhydride group is contained on the surface respectively.
Step (6): in the 500mL three neck round-bottomed flasks that agitator is housed, the CNT 9.8g and liquid bisphenol A type epoxy resin (E-51) 100g that add step (5) acid anhydridesization, heating is also stirred, after handling 2 hours with the 80kHz ultrasonic wave, reacted 12 hours down at 240 ℃, obtain the multi-walled carbon nano-tubes that the surface is connected to liquid bisphenol A type epoxy resin (E-51);
Step (7): the carbon fiber 100g that gets multi-walled carbon nano-tubes compound 25g that the surface is connected to liquid bisphenol A type epoxy resin (E-51) and step (5) acid anhydridesization is compound down at 100 ℃, de-bubble under vacuum condition, compression molding obtains carbon fiber-containing/carbon nano tube/epoxy resin multi-dimensional hybrid composite under 13MPa.
XPS result shows that carbon fiber and multi-walled carbon nano-tubes impurity surface anhydride content are 8.3%.
The above-mentioned description to embodiment is to understand and the invention of application benzene 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 (11)
1. the preparation method of a carbon fiber/carbon nano tube/epoxy resin multi-dimensional hybrid composite is characterized in that concrete steps are as follows:
(1) takes by weighing 1～1 * 10
2The CNT of g drying and 10g～1 * 10
3The g organic acid mixes, in 1～120kHz ultrasonic wave or 10r/min～10
6The centrifugal speed of r/min stirs down and handled 1～80 hour, is heated to 20～180 ℃ then, reacts 1～48 hour, and with the micro-filtration membrane suction filtration, cyclic washing is to neutral, and vacuum drying is 1～48 hour under 25～150 ℃ of temperature, obtains the CNT of purifying;
(2) with 1～1 * 10
2The carbon fiber of g drying, step obtain purifying carbon nano-tube 1～1 * 10 in (1)
2G respectively with acid with strong oxidizing property 1～1 * 10
4ML mixes, under 1～120kHz ultrasonic wave, handled 1～80 hour, be heated to 25～120 ℃ then, stirring and back flow reaction 1～80 hour, ultramicropore filter membrane suction filtration, it is neutral that cyclic washing to solution is, and vacuum drying is 1～48 hour under 25～200 ℃ of temperature, obtains the carbon fiber and the CNT of acidifying respectively;
(3) with the carbon fiber and the CNT 1～1 * 10 of step (2) gained acidifying
2G respectively with acylating reagent 10～1 * 10
4G after 0.1～10 hour, is heated to 25～220 ℃ with the processing of 1～120kHz ultrasonic wave, stirring and back flow reaction 0.5～100 hour, and suction filtration and cyclic washing are removed acylating reagent, obtain the carbon fiber and the CNT of acyl groupization respectively;
(4) with step (3) gained acidylate carbon fiber and CNT 1～1 * 10
2G respectively with diamine or polyamine 10～1 * 10
4G, handled 1～100 hour with 1～100kHz ultrasonic wave, under 25～200 ℃ of temperature, reacted 0.5～100 hour suction filtration and cyclic washing then, vacuum drying is 1～48 hour under 25～200 ℃ of temperature, obtains graft type carbon fiber and CNT that the surface has active amino respectively;
(5) step (4) gained surface is had the carbon fiber and the CNT 1～1 * 10 of active amino
2The aromatic anhydride compound of g agitation and dropping 1～100g in the polar organic solvent ice bath, being warming up to 100～150 ℃ after dropwising refluxed 3～12 hours, with the unreacted aromatic anhydride compound of polar organic solvent flush away, 40～80 ℃ of following vacuum drying 3～12 hours obtain having the carbon fiber and the CNT of activity anhydride group;
(6) step (5) gained surface is had the CNT 1～1 * 10 of activity anhydride group
2G and epoxy resin 10～1 * 10
4G, be warming up to the resin matrix fusion after, dispersed with stirring evenly and remove bubble under vacuum condition is carried out chemical crosslink reaction simultaneously, obtains containing the epoxide resin polymer of CNT;
(7) will be with the resultant epoxide resin polymer 20g-25g of CNT that contains of step (6) as matrix and carbon fiber 20g-100g mechanical mixture, at 60～100 ℃, ultrasonic wave disperseed 1～12 hour, add 40～50g organic acid anhydride class curing agent, above curing system is poured in the mould, vacuum condition removes bubble down, at 100～250 ℃ of following curing moldings, obtains carbon fiber-containing/carbon nano tube/epoxy resin multi-dimensional hybrid composite.
2. the preparation method of carbon fiber/carbon nano tube/epoxy resin multi-dimensional hybrid composite according to claim 1 is characterized in that CNT described in the step (1) comprises single wall, double-walled or the multi-walled carbon nano-tubes 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 carbon fiber/carbon nano tube/epoxy resin multi-dimensional hybrid composite according to claim 1 is characterized in that 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.
4. the preparation method of carbon fiber/carbon nano tube/epoxy resin multi-dimensional hybrid composite according to claim 1 is characterized in that acid with strong oxidizing property described in the step (2) 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, in 1/100～100/1 mol ratio hydrogen peroxide and nitric acid mixed liquor or 15～95% weight concentration hydrogenperoxide steam generators any.
5. the preparation method of carbon fiber/carbon nano tube/epoxy resin multi-dimensional hybrid composite according to claim 1, it is characterized in that acylating reagent described in the step (3) be in thionyl chloride, phosphorus trichloride, phosphorus pentachloride, thionyl chloride, phosphorus tribromide, phosphorus pentabromide or the thionyl bromide any.
6. the preparation method of carbon fiber/carbon nano tube/epoxy resin multi-dimensional hybrid composite according to claim 1, it is characterized in that diamine described in the step (4) is ethylenediamine, polyethyene diamine, 1,2-propane diamine, 1,3-propane diamine, 1, in the 2-butanediamine, 1,3-butanediamine, hexamethylene diamine, p-phenylenediamine (PPD), m-phenylene diamine (MPD), m-xylene diamine, diaminodiphenyl-methane, the Meng alkane diamines, divinyl propylamine, diaminodiphenyl-methane, chlorination hexamethylene diamine, chlorination nonamethylene diamine, chlorination decamethylene diamine, 12 carbon diamines or 13 carbon diamines any; Described polyamine is fourth triamine, N-aminoethyl piperazine, dicyandiamide, adipic dihydrazide, N, in N-dimethyl dipropyl triamine, TEPA, diethylenetriamine, triethylene tetramine, TEPA, five ethene hexamines or six ethene, seven amine any.
7. the preparation method of carbon fiber/carbon nano tube/epoxy resin multi-dimensional hybrid composite according to claim 1, it is characterized in that aromatic anhydride compound described in the step (5) comprises addition product, the diphenyl sulfone-3 of addition product, benzophenone tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride and the caprolactone of pyromellitic acid anhydride PDMA, pyromellitic acid anhydride and caprolactone, 3 ', 4,4 '-tetracarboxylic dianhydride DSDA, diphenyl sulfone-3,3 ', 4, the addition product of 4 '-tetracarboxylic dianhydride, N, one or more in N '-dicarboxylic anhydride diphenyl methane or mellitic acid three acid anhydrides.
8. the preparation method of carbon fiber/carbon nano tube/epoxy resin multi-dimensional hybrid composite according to claim 1, it is characterized in that the polar organic solvent described in the step (5) comprises ethanol, methyl alcohol, dimethyl sulfoxide (DMSO), oxolane, acetone or N, one or more mixtures of N '-dimethyl formamide.
9. the preparation method of carbon fiber/carbon nano tube/epoxy resin multi-dimensional hybrid composite according to claim 1 is characterized in that epoxy resin described in the step (6) refers to comprise in glycidol ethers, glycidol lipid, glycidol amine, alicyclic ring class, epoxidation of olefins class, imide ring epoxy resins or the glycolylurea epoxide resin any.
10. the preparation method of carbon fiber/carbon nano tube/epoxy resin multi-dimensional hybrid composite according to claim 1 is characterized in that organic acid anhydride class curing agent is a phthalic anhydride described in the step (7), tetrabydrophthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, the methyl carbic anhydride, dodecyl succinic anhydride, chlorendic anhydride, adjacent PMDA, the phthalic anhydride tetracarboxylic dianhydride, the methylcyclohexene tetracarboxylic dianhydride, the diphenyl ether tetracarboxylic dianhydride, one or several mixture in trimellitic anhydride or the poly-azelaic acid acid anhydride.
11. the preparation method of carbon fiber/carbon nano tube/epoxy resin multi-dimensional hybrid composite according to claim 1 is characterized in that carbon fiber described in the step (7) is any in unidirectional long fibre cloth, two-way woven cloth, three-phase woven cloth or the random staple fibre cloth.
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