CN101979436A - Method for preparing carbon nanofiber and carbon nanotube modified carbon fiber/epoxy resin multi-dimensional hybrid composite - Google Patents
Method for preparing carbon nanofiber and carbon nanotube modified carbon fiber/epoxy resin multi-dimensional hybrid composite Download PDFInfo
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Abstract
The invention belongs to the technical field of nano materials and particularly relates to a method for preparing a carbon nanofiber and carbon nanotube modified carbon fiber/epoxy resin multi-dimensional hybrid composite. The method comprises the following steps of: performing surface carboxylation and acylation treatment on carbon nanotubes, carbon nanofibers and carbob fibers; introducing diamine or polyamine to the obtained product; modifying amino carbon nanofibers and carbon nanotubes with an aromatic polyanhydride compound to prepare the carbon fibers, the carbon nanofibers and the carbon nanotubes carrying anhydride radicals; and ultrasonically oscillating the carbon nanofibers, the carbon nanotubes and the epoxy resin with the anhydride and stirring the mixed materials at a high speed to make the carbon nanofibers and the carbon nanotubes uniformly dispersed in the epoxy resin matrix and make the carbon nanofibers and the carbon nanotubes grafted with the anhydride and the epoxy resin fully undergo a chemical crosslinking reaction so as to obtain an epoxy resin linear block polymer, and combining the epoxy resin linear block polymer serving as a matrix and the carbon fibers to form multi-dimensional hybrid composite structures connected by covalent bonds. In the invention, by using the carbon nanotubes, the carbon nanofibers and the strength and toughness toughened epoxy resin, the bonding strength of carbon fiber interfaces is improved, so that the integral performance of the carbon fiber/epoxy resin multi-dimensional hybrid composite is improved, and the application range of the carbon fibers and the epoxy resin is widened.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to the preparation method of the fine dimension of a kind of Nano carbon fibers peacekeeping carbon nano-tube modification carbon ∕ epoxy resin multi-dimensional hybrid composite.
Background technology
The thermostability that Resins, epoxy is good, dimensional stability as composite matrix resin, in recent years, are subjected to paying attention to widely, are widely used in high-tech areas such as aerospace, mechano-electronic, printed circuit board (PCB).Resins, epoxy is a kind of thermoset oligopolymer, and poor performance except as the stablizer of polyvinyl chloride, does not have direct use value; When itself and solidifying agent are cured after reaction forms the three-dimensional crosslinked network structure, then present the performance of a series of excellences.Behavior and the performance of cured article of Resins, epoxy 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 solidifying agent.Therefore, be applied in is exactly the problem of solidification of studying Resins, epoxy research Resins, epoxy in a way.
Carbon nano fiber (Carbon Nanofibers is called for short CNF) is a kind of form of chemical meteorological grown carbon fiber, and it is by the discontinuous graphite fibre by the preparation of cracking gaseous hydrocarbon.From physical size, performance with produce and see that originally it is that to constitute with carbon ink, soccerballene, single wall and multiple-wall carbon nanotube be an end, with the continuous carbon fibre ring in the other end chain link.The diameter of carbon nano fiber is a kind of novel submicron strongthener between 10 ~ 500nm.But at present many research workers are referred to as carbon nanotube to the tubular fibre of diameter below 100nm, that is the diameter of carbon nano fiber is between carbon nanotube and gas-phase growth of carbon fibre.The preparation of comparing carbon nano fiber with CNT (carbon nano-tube) is easier to realize suitability for industrialized production.Carbon nano fiber is except having the characteristic of general carbon fiber, outside performances such as low density, high specific strength, high ratio modulus, high conduction and heat conduction, also have advantages such as tubular structure, defects count is considerably less, specific surface area is big, length-to-diameter ratio is big, have broad application prospects in fields such as enhancing body, antistatic material, catalyzer and the support of the catalyst of matrix material, lithium-ion secondary cell anode material, electrical double layer capacitor electrodes, hydrogen storage material, absorbing materials.Carbon nano fiber can reach the same reinforced effects of continuous carbon fibre, and price then is equivalent to adopt glass fibre to make toughener.The cost for preparing matrix material with carbon nano fiber is very low, can adopt the such low cost production technology of for example injection molding.
Carbon nanotube (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 applied research, gained great popularity.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 homodisperse Nano carbon fibers peacekeeping 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.
The excellent properties of Tan Xian Wei ∕ epoxy resin composite material has obtained widespread use in every profession and trade, can utilize the fine dimension of the mechanical property modification carbon ∕ epoxy resin composite material of Nano carbon fibers peacekeeping carbon nanotube excellence, the fine dimension of preparation Nano carbon fibers peacekeeping carbon nano-tube modification carbon ∕ epoxy resin multi-dimensional hybrid composite, the prospect that can predict the fine dimension of Nano carbon fibers peacekeeping carbon nano-tube modification carbon ∕ epoxy resin multi-dimensional hybrid composite will be very wide.
Summary of the invention
The object of the present invention is to provide a kind of good dispersity, the firm Nano carbon fibers peacekeeping carbon nano-tube modification carbon fibre of interface bonding to tie up the preparation method of ∕ epoxy resin multi-dimensional hybrid composite.
The preparation method of the fine dimension of a kind of Nano carbon fibers peacekeeping carbon nano-tube modification carbon ∕ epoxy resin multi-dimensional hybrid composite that the present invention proposes, with carbon nanotube, Nano carbon fibers peacekeeping carbon fiber is carboxylated through the surface, after the chloride, introduce diamine or polyamine more thereon, amidized Nano carbon fibers peacekeeping carbon nanotube is compound-modified with small molecules aromatic series multi-anhydride, the Nano carbon fibers peacekeeping carbon nanotube of anhydride group is carried in preparation, the Nano carbon fibers peacekeeping carbon nanotube and the Resins, epoxy that are connected to this acid anhydrides are carried out sonic oscillation and high-speed stirring, be being scattered in the epoxy resin-base of Nano carbon fibers peacekeeping even carbon nanotube, and make the Nano carbon fibers peacekeeping carbon nanotube and the Resins, epoxy that are connected to acid anhydrides fully carry out chemical crosslink reaction, compound with the Resins, epoxy linear block polymer that contains Nano carbon fibers peacekeeping carbon nanotube that obtains as matrix and carbon fiber, formation obtains the fine dimension of the carbon ∕ epoxy resin multi-dimensional hybrid composite of Nano carbon fibers peacekeeping carbon nano-tube modification with the multi-dimensional hybrid composite structure that covalent linkage links to each other.Concrete steps are as follows:
(1) takes by weighing 1～1 * 10
2G 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 1～80 hour, is heated to 20～180 ℃ then, reacts 1～48 hour, and with the microfiltration membrane suction filtration, repetitive scrubbing is to neutral, and vacuum-drying is 1～48 hour under 25～150 ℃ of temperature, obtains the carbon nanotube of purifying;
(2) with 1～1 * 10
2G exsiccant carbon fiber, 1～1 * 10
2G exsiccant carbon nano fiber, 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 repetitive scrubbing to solution is, and vacuum-drying is 1～48 hour under 25～200 ℃ of temperature, obtains acidifying carbon fiber, Nano carbon fibers peacekeeping carbon nanotube respectively;
(3) with step (2) gained acidifying carbon fiber 1～1 * 10
2G, carbon nano fiber 1～1 * 10
2G and carbon nanotube 1～1 * 10
2G respectively with acylating reagent l0～1 * 10
4G mixes, and after 0.1 ~ 10 hour, is heated to 25～220 ℃ with 1 ~ 120kHz ultrasonication, stirring and back flow reaction 0.5～100 hour, and suction filtration and repetitive scrubbing are removed acylating reagent, obtain carbon fiber, the Nano carbon fibers peacekeeping carbon nanotube of acylations respectively;
(4) with step (3) gained acidylate carbon fiber 1～1 * 10
2G, carbon nano fiber 1～1 * 10
2G and carbon nanotube 1～1 * 10
2G respectively with diamine or polyamine 10～1 * 10
4G mixes, with 1 ~ 100kHz ultrasonication 1～100 hour, under 25～200 ℃ of temperature, reacted 0.5～100 hour then, suction filtration and repetitive scrubbing, vacuum-drying is 1～48 hour under 25 ~ 200 ℃ of temperature, obtains graft type carbon fiber, Nano carbon fibers peacekeeping carbon nanotube that the surface has active amino respectively;
(5) step (4) gained surface is had the carbon fiber 1～1 * 10 of active amino
2G, carbon nanotube 1～1 * 10
2G and carbon nano fiber 1～1 * 10
2G is agitation and dropping 1～100g aromatic anhydride compound in the polar organic solvent ice bath, be warming up to 100～150 ℃ after dropwising, under this temperature, refluxed 3～16 hours, with the unreacted aromatic anhydride compound of polar organic solvent flush away, 40～80 ℃ of following vacuum-drying 3～12 hours obtains having carbon fiber, carbon nanotube and the carbon nano fiber of activity anhydride group;
(6) step (5) gained surface is had the carbon nanotube 1～1 * 10 of activity anhydride group
2G and carbon nano fiber 1～1 * 10
2G and Resins, epoxy 10～1 * 10
4G, be warming up to certain temperature 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 carbon nanotube/nano carbon fiber;
(7) carbon fiber 20～100g mechanically mixing that the resultant epoxide resin polymer 20 ~ 25g that contains the carbon nanotube/nano carbon fiber of step (6) is obtained as matrix and step (4) or step (5), under 60 ~ 100 ℃, ultrasonic dispersing 1～12 hour, add 30～50g organic acid anhydride class solidifying agent, and in forming mould, the vacuum stripping bubble at 100 ℃～250 ℃ following curing moldings, obtains the fine dimension of the carbon ∕ epoxy resin multi-dimensional hybrid composite of Nano carbon fibers peacekeeping carbon nano-tube modification.
Among the present invention, carbon nanotube described in the step (1) be arc-over, chemical gaseous phase deposition, template, sun power method with or the laser evaporation method in the single wall or the multi-walled carbon nano-tubes of any preparation.
Among the present invention, organic acid described in the step (1) is any or its 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, 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 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, in 1 ∕ 100～100 ∕, 1 mol ratio hydrogen peroxide and nitric acid mixed solution or 15～95% weight concentration superoxols 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 quadrol, polyethyene diamine, 1,2-propylene diamine, 1,3-propylene diamine, 1, in the 2-butanediamine, 1,3-butanediamine, hexanediamine, Ursol D, mphenylenediamine, m-xylene diamine, diaminodiphenyl-methane, the Meng alkane diamines, divinyl propylamine, diaminodiphenyl-methane, chlorination hexanediamine, chlorination nonamethylene diamine, chlorination decamethylene diamine, 12 carbon diamines or 13 carbon diamines any; Described polyamine is fourth triamine, N-aminoethyl piperazine, Dyhard RU 100, adipic dihydrazide, N, in N-dimethyl dipropyl triamine, tetraethylene pentamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines or six ethene, seven amine any.
Among the present invention, the quantitative analysis of carboxyl-content in acidifying carbon nanotube, the Nano carbon fibers peacekeeping 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 graft type carbon nanotube, the Nano carbon fibers peacekeeping 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 carbon nanotube and the carbon fiber of activity anhydride group, and its anhydride group is the aromatic anhydride compound.Described aromatic anhydride compound comprises affixture, the sulfobenzide-3 of affixture, 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), sulfobenzide-3,3 ', 4, the affixture of 4 '-tetracarboxylic dianhydride, N, N
,In-dicarboxylic anhydride ditan or mellitic acid three acid anhydrides one or more.
Among the present invention, polar organic solvent comprises ethanol, methyl alcohol, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), acetone or N, N described in the step (5)
,One or more mixtures of-dimethyl formamide.
Among the present invention, Resins, epoxy described in the step (6) is meant in all Resins, epoxy that comprise Racemic glycidol ethers, Racemic glycidol lipid, Racemic glycidol amine, alicyclic ring class, epoxidation of olefins class, imide ring epoxy resins or glycolylurea epoxide resin any.
Among the present invention, organic acid anhydride class solidifying agent comprises organic acid anhydride type curing agent described in the step (7), as one or several mixture in Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl carbic anhydride, dodecyl succinic anhydride, chlorendic anhydride, adjacent pyromellitic dianhydride, phthalic anhydride tetracarboxylic dianhydride, tetrahydrotoluene tetracarboxylic dianhydride, phenyl ether tetracarboxylic dianhydride, trimellitic acid 1,2-anhydride, the poly-nonane diacid acid anhydride.
Among the present invention, carbon fiber described in the step (7) be in unidirectional macrofiber cloth, two-way textile sheet, three-phase textile sheet or the random staple fibre cloth any.
Among the present invention, the processing of carbon nanotube and carbon nano fiber can separate treatment or can select combination treatment in any step in step (2) ~ (6) in step (2) ~ (6).
Preparation method provided by the invention is simple, gained be the carbon fiber multi-dimensional hybrid mixture that the surface is connected to Resins, epoxy, Nano carbon fibers peacekeeping carbon nanotube.The anhydride group of Nano carbon fibers peacekeeping carbon nano tube surface is by producing chemical crosslink reaction with Resins, epoxy, make Nano carbon fibers peacekeeping carbon nanotube 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 containing the fine dimension of Nano carbon fibers peacekeeping carbon nano-tube modification carbon ∕ epoxy resin multi-dimensional hybrid composite.Because the effect of the mixed and modified Resins, epoxy of Tan Na Mi Guan ∕ carbon nano fiber has increased the boundary strength between matrix resin and the carbon fiber, makes matrix material have good interlaminar shear strength.
The present invention is at carbon nanotube, Nano carbon fibers peacekeeping carbon fiber surface is introduced the anhydride group with feature structure, utilize this structure and Resins, epoxy to carry out chemical crosslink reaction, carbon nanotube then, Nano carbon fibers peacekeeping carbon fiber surface will be wound with a large amount of polymkeric substance, because polymkeric substance has avidity and carbon nanotube to matrix resin, the characteristic of carbon nano fiber itself, thereby improve the shortcoming of the interlaminar shear strength deficiency etc. of carbon fiber, this multi-dimensional hybrid mixture has the interface bonding firmly, strength and toughness is good, multiple performances such as easy curing are improved significantly the comprehensive mechanical property of matrix material.Therefore, the present invention has important science and technology value and actual application value.
Description of drawings
Figure l is connected to the carbon nanotube and the carbon nano fiber hybrid composite transmission electron microscope picture of Resins, epoxy for the surface.
Fig. 2 is a kind of Resins, epoxy linearity block carbon nanotube polymer XPS figure.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
EXAMPLE l: with the multi-walled carbon nano-tubes of arc discharge method preparation (OD＜8nm), Nano carbon fibers peacekeeping carbon fiber is an initial raw material, multi-walled carbon nano-tubes is earlier through purifying, again respectively with the carbon nanotube after the acidifying, Nano carbon fibers peacekeeping carbon fiber carries out acidifying, chloride, amination, after using the pyromellitic acid anhydride acid anhydridesization again, Nano carbon fibers peacekeeping carbon nanotube and liquid bisphenol A type Resins, epoxy (E-51) are carried out chemical crosslink reaction, then obtain the Nano carbon fibers peacekeeping multi-walled carbon nano-tubes that the surface is connected to liquid bisphenol A type Resins, epoxy, again that the carbon fiber of itself and pyromellitic acid anhydride acid anhydridesization is compound in a certain way, obtain the fine dimension of the carbon ∕ epoxy resin multi-dimensional hybrid composite of Nano carbon fibers peacekeeping carbon nano-tube modification.
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, 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, 25 ℃ of following vacuum-dryings obtained the multi-walled carbon nano-tubes of purifying after 24 hours;
Step (2): in three single neck round-bottomed flasks of the 250mL that agitator has been housed, one of them adds the carbon nanometer tube material 1g and the 100mL of the purifying that obtains in the step (1), 60% weight concentration concentrated nitric acid, one adds carbon nano fiber 1g and 100mL, 60% weight concentration concentrated nitric acid, another adds the carbon fiber 20g and the 100mL of drying, 60% weight concentration concentrated nitric acid, three flasks are handled through following the same terms: add through 1 hour post-heating to 25 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, with deionized water repetitive scrubbing 3-10 time to neutral, 80 ℃ of vacuum-dryings obtained carboxylic acidifying multi-walled carbon nano-tubes respectively after 48 hours, Nano carbon fibers peacekeeping carbon fiber;
Step (3): in three 250mL three neck round-bottomed flasks that agitator has been housed, one of them adds step (2) gained acidifying carbon nanotube 1g and thionyl chloride 10g, one adds acidifying carbon nano fiber 1g and thionyl chloride 10g, another adds acidifying carbon fiber 20g and thionyl chloride 100g, three flasks are handled through following the same terms: use the 100Hz ultrasonication after 1 hour, be heated to 80 ℃, the stirring and the reaction down 100 hours that refluxes, suction filtration and repetitive scrubbing are removed thionyl chloride, obtain the multi-walled carbon nano-tubes of chloride respectively, Nano carbon fibers peacekeeping carbon fiber;
Step (4): in three 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, a carbon nano fiber 1g and 12 carbon diamine 10g that add acidylate, another adds the carbon fiber 20g and the 12 carbon diamine 100g of acidylate, three flasks are handled through following the same terms: use the 100kHz ultrasonication after 1 hour, 200 ℃ of following stirring reactions 0.5 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 surface respectively and has amino multi-walled carbon nano-tubes, Nano carbon fibers peacekeeping carbon fiber;
Step (5): in three 250mL three neck round-bottomed flasks that agitator has been housed, one of them adds the carbon nanotube 1g and the dimethyl sulfoxide (DMSO) 150mL of step (4) gained ammonification, a carbon nano fiber 1g and a dimethyl sulfoxide (DMSO) 150mL who adds step (4) gained ammonification, another adds the carbon fiber 20g and the dimethyl sulfoxide (DMSO) 150mL of ammonification, three flasks are handled through following the same terms: ultrasonic concussion 30min, add the 10g pyromellitic acid anhydride, add catalyzer vitriol oil 10ml, stir under 90 ℃, nitrogen protection, magnetic agitation, the reaction times is 48 hours, obtains the carbon nano fiber that anhydride group is contained on the surface respectively, carbon nanotube and carbon fiber;
Step (6): in the 500mL three neck round-bottomed flasks that agitator is housed, carbon nanotube 1g, the carbon nano fiber 1g and liquid bisphenol A type Resins, epoxy (E-51) 20g that add step (4) acid anhydridesization, heating is also stirred, with the 60kHz ultrasonication after 2 hours, reacted 12 hours down at 230 ℃, obtain multi-walled carbon nano-tubes and carbon nano fiber mixture that the surface is connected to liquid bisphenol A type Resins, epoxy (E-51);
Step (6): the carbon fiber 20g that gets multi-walled carbon nano-tubes that the surface is connected to liquid bisphenol A type Resins, epoxy (E-51) and carbon nano fiber mixture 20g and step (4) acid anhydridesization is compound in a certain way, de-bubble under vacuum condition obtains the fine dimension of Nano carbon fibers peacekeeping carbon nano-tube modification carbon ∕ epoxy resin multi-dimensional hybrid composite.
Fig. 1 has provided surperficial carbon nanotube and the carbon nano fiber hybrid composite transmission electron microscope picture that is connected to Resins, epoxy.
It is 4.8% that the XPS data that provide from Fig. 2 can draw Nano carbon fibers peacekeeping multi-walled carbon nano-tubes surface amino groups content.
Embodiment 2: with the Single Walled Carbon Nanotube of chemical Vapor deposition process preparation (OD＜8nm), Nano carbon fibers peacekeeping carbon fiber is an initial raw material, Single Walled Carbon Nanotube is through purifying, respectively with carbon nanotube, Nano carbon fibers peacekeeping carbon fiber carries out acidifying, chloride, after the amination, after using benzophenone tetracarboxylic dianhydride acid anhydridesization again, Nano carbon fibers peacekeeping carbon nanotube and liquid bisphenol A type Resins, epoxy (E-54) are carried out chemical crosslink reaction, then obtain the Nano carbon fibers peacekeeping Single Walled Carbon Nanotube that the surface is connected to liquid bisphenol A type Resins, epoxy (E-54), again that the carbon fiber of itself and benzophenone tetracarboxylic dianhydride acid anhydridesization is compound in a certain way, obtain the fine dimension of the carbon ∕ epoxy resin multi-dimensional hybrid composite of Nano carbon fibers peacekeeping carbon nano-tube modification.
Step (1): in the single neck round-bottomed flask of the 500mL that the magnetic agitation rotor is housed, add 1.1g Single Walled Carbon Nanotube raw material, the sulfuric acid of 200mL, 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, 100 ℃ of vacuum-dryings obtained the carbon nanotube of purifying after 24 hours with deionized water repetitive scrubbing 3-10 time;
Step (2): in three single neck round-bottomed flasks of the 500mL that the magnetic agitation rotor has been housed, one of them adds the carbon nanometer tube material 1g and the 200mL of the purifying that obtains in the step (1), 98% concentrated sulfuric acid solution, a carbon nano fiber 1g and a 200mL who adds drying, 98% concentrated sulfuric acid solution, another adds the carbon fiber and the 200mL of 100g drying, 98% concentrated sulfuric acid solution, three flasks are handled through following the same terms: with 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, with deionized water repetitive scrubbing 3-10 time to neutral, 100 ℃ of vacuum-dryings obtained carboxylic acidifying carbon nanotube respectively after 24 hours, Nano carbon fibers peacekeeping carbon fiber;
Step (3): in three 500mL three neck round-bottomed flasks that the magnetic agitation rotor has been housed, one of them adds step (2) gained acidifying carbon nanotube 1g and phosphorus trichloride 10g, one adds acidifying carbon nano fiber 1g and phosphorus trichloride 10g, another adds acidifying carbon fiber 100g and phosphorus trichloride 200g, three flasks are handled through following the same terms: use the 120Hz ultrasonication after 10 hours, be heated to 25 ℃, the stirring and the reaction down 48 hours that refluxes, suction filtration and repetitive scrubbing are repeatedly removed phosphorus trichloride, obtain the carbon nanotube of chloride respectively, Nano carbon fibers peacekeeping carbon fiber;
Step (4): in three 500mL three neck round-bottomed flasks that the magnetic agitation rotor has been housed, one of them adds step (3) gained acylated carbon nano-tube 1g and N, N-dimethyl dipropyl triamine 20g, a carbon nano fiber 1g and a N who adds acidylate, N-dimethyl dipropyl triamine 20g, another adds the carbon nano fiber 100g and the phosphorus trichloride 100g of acidylate, three flasks are handled through following the same terms: use the 1kHz ultrasonication after 100 hours, reacted 12 hours down at 200 ℃, 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 surface respectively and has amino carbon nanotube, Nano carbon fibers peacekeeping carbon fiber;
Step (5): in two 500mL three neck round-bottomed flasks that the magnetic agitation rotor has been housed, one of them adds the amidized carbon nanotube 1g of step (4), carbon nano fiber 1g and dimethyl sulfoxide (DMSO) 300mL, another adds the amidized carbon fiber 100g of step (4), two flasks are handled through following the same terms: use the 100kHz ultrasonication after 1 hour, 250 ℃ of following stirring reactions 12 hours, obtain the surface respectively and be connected to the Nano carbon fibers peacekeeping carbon mano-tube composite of anhydride group and the carbon fiber that the surface is connected to anhydride group;
Step (6): in the 500mL three neck round-bottomed flasks that agitator is housed, the Nano carbon fibers peacekeeping carbon nano tube hybrid thing 2g and liquid bisphenol A type Resins, epoxy (E-54) 20g that add step (5) acid anhydridesization, heating is also stirred, with the 60kHz ultrasonication after 2 hours, reacted 12 hours down at 220 ℃, obtain the carbon nanotube that the surface is connected to liquid bisphenol A type Resins, epoxy (E-54);
Step (7): it is compound in a certain way under 100 ℃ to get in Nano carbon fibers peacekeeping carbon mano-tube composite 20g that surface in the step (6) is connected to liquid bisphenol A type Resins, epoxy (E-54) and the step (4) amidized carbon fiber 100g, remove bubble under vacuum condition, compression molding obtains the fine dimension of the carbon ∕ epoxy resin multi-dimensional hybrid composite of Nano carbon fibers peacekeeping carbon nano-tube modification under 8MPa.
XPS result shows that carbon fiber, Nano carbon fibers peacekeeping Single Walled Carbon Nanotube mishmash surface amino groups content are 5.1%.
Embodiment 3: (OD＜8nm), Nano carbon fibers peacekeeping carbon fiber are initial raw material with the Single Walled Carbon Nanotube of laser evaporation method preparation, Single Walled Carbon Nanotube is through purifying, and respectively that carbon nano fiber, carbon nanotube and carbon fiber is acidified, chloride are after the amination, use N again, N
,After-dicarboxylic anhydride diphenylmethyl the alkanoic acid anhydrideization, Nano carbon fibers peacekeeping carbon nanotube and liquid bisphenol A type Resins, epoxy (E-44) are carried out chemical crosslink reaction, then obtain the Nano carbon fibers peacekeeping Single Walled Carbon Nanotube that the surface is connected to liquid bisphenol A type Resins, epoxy (E-44), again with itself and N, N
,The carbon fiber of-dicarboxylic anhydride diphenylmethyl alkanoic acid anhydrideization is compound in a certain way, obtains the fine dimension of the carbon ∕ epoxy resin multi-dimensional hybrid composite of Nano carbon fibers peacekeeping carbon nano-tube modification.
Step (1): in the single neck round-bottomed flask of churned mechanically 500mL 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 180 ℃ then, reacted 48 hours, with the poly-inclined to one side tetrafluoroethylene microfiltration membrane suction filtration of ψ 0.8 μ m, to neutrality, 100 ℃ 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 three single neck round-bottomed flasks of the 500mL that the magnetic agitation rotor is housed, one of them adds the carbon nanometer tube material and the 250mL of 9.8g purifying, volume ratio is concentrated nitric acid and the vitriol oil mixed solution of 2:1, one adds 9.8g Nano carbon fibers peacekeeping 250mL, volume ratio is concentrated nitric acid and the vitriol oil mixed solution of 2:1, another adds exsiccant carbon fiber 100g and 250mL, volume ratio is concentrated nitric acid and the vitriol oil mixed solution of 2:1, three flasks are handled through following the same terms: with 80 hours post-heating to 25 of 120kHz 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, extremely neutral with the deionized water repetitive scrubbing, 25 ℃ of vacuum-dryings obtained carboxylic acidifying Single Walled Carbon Nanotube respectively after 48 hours, Nano carbon fibers peacekeeping carbon fiber;
Step (3): in three 500mL three neck round-bottomed flasks that the magnetic agitation rotor is housed, one of them adds step (2) gained acidifying carbon nanotube 9.8g and phosphorus pentachloride 100g, one adds step (2) gained acidifying carbon nano fiber 9.8g and phosphorus pentachloride 100g, another adds acidifying carbon fiber 100g and phosphorus pentachloride 200g, three flasks are handled through following the same terms: use the 120Hz ultrasonication after 1 hour, be heated to 25 ℃, the stirring and the reaction down 100 hours that refluxes, suction filtration and repetitive scrubbing remove and repeatedly remove phosphorus pentachloride, obtain the Single Walled Carbon Nanotube of chloride respectively, Nano carbon fibers peacekeeping carbon fiber;
Step (4): in three 500mL three neck round-bottomed flasks that the magnetic agitation rotor is housed, one of them adds step (3) gained acidylate carbon nanotube 9.8g and tetraethylene pentamine 50g, one adds step (3) gained acidylate carbon nano fiber 9.8g and tetraethylene pentamine 50g, another adds the carbon fiber 100g and the tetraethylene pentamine 200g of chloride, three flasks are handled through following the same terms: use the 100kHz ultrasonication after 1 hour, three flasks reacted 24 hours down at 25 ℃, suction filtration is removed unreacted reactant and byproduct of reaction, repeatedly with deionized water wash repeatedly after, 200 ℃ of vacuum-drying 1 hour obtains the surface respectively and has amino Single Walled Carbon Nanotube, Nano carbon fibers peacekeeping carbon fiber;
Step (5): in two 500mL three neck round-bottomed flasks that the magnetic agitation rotor has been housed, add the amidized carbon nanotube 2g of step (4), carbon nano fiber 9.8g and dimethyl sulfoxide (DMSO) 300mL, another adds the carbon fiber 100g and the dimethyl sulfoxide (DMSO) 300mL of ammonification, two flasks are handled through following the same terms: under 90 ℃, ultrasonic concussion 30min, add 100gN, N
,-dicarboxylic anhydride ditan and catalyzer vitriol oil 10ml, nitrogen protection, reaction is 48 hours under the even stirring condition of magnetic force, obtains the surface respectively and contains the Nano carbon fibers peacekeeping carbon mano-tube composite of anhydride group and the carbon fiber that anhydride group is contained on the surface.
Step (6): in the 500mL three neck round-bottomed flasks that agitator is housed, the Nano carbon fibers peacekeeping carbon nanotube 9.8g and liquid bisphenol A type Resins, epoxy (E-44) 100g that add step (5) acid anhydridesization, heating is also stirred, with the 80kHz ultrasonication after 2 hours, reacted 12 hours down at 240 ℃, obtain the Nano carbon fibers peacekeeping carbon nanotube that the surface is connected to liquid bisphenol A type Resins, epoxy (E-44);
Step (7): the carbon fiber 100g that gets Nano carbon fibers peacekeeping carbon mano-tube composite 25g that the surface is connected to liquid bisphenol A type Resins, epoxy (E-44) and step (5) acid anhydridesization is compound down at 100 ℃, de-bubble under vacuum condition, compression molding obtains the fine dimension of the carbon ∕ epoxy resin multi-dimensional hybrid composite of Nano carbon fibers peacekeeping carbon nano-tube modification under 13MPa.
XPS analysis result shows that carbon fiber and Single Walled Carbon Nanotube mishmash surface anhydride content are 6.3%.
Embodiment 4: (OD＜8nm), Nano carbon fibers peacekeeping carbon fiber are initial raw material with the multi-walled carbon nano-tubes of laser evaporation method preparation, the walled carbon nanotubes purifying carries out acidifying, chloride with multi-walled carbon nano-tubes, Nano carbon fibers peacekeeping carbon fiber respectively, after the amination, use N again, N
,After-dicarboxylic anhydride diphenylmethyl the alkanoic acid anhydrideization, Nano carbon fibers peacekeeping multi-walled carbon nano-tubes and liquid bisphenol A type Resins, epoxy (E-44) are carried out chemical crosslink reaction, then obtain the Nano carbon fibers peacekeeping multi-walled carbon nano-tubes mixture that the surface is connected to liquid bisphenol A type Resins, epoxy (E-44), again with itself and N, N
,The carbon fiber of-dicarboxylic anhydride diphenylmethyl alkanoic acid anhydrideization is compound in a certain way, obtains the fine dimension of the carbon ∕ epoxy resin multi-dimensional hybrid composite of Nano carbon fibers peacekeeping carbon nano-tube modification.
Step (1): in the single neck round-bottomed flask of the 500mL that the magnetic agitation rotor is housed, add 1.1g multi-walled carbon nano-tubes raw material, the sulfuric acid of 200mL, 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, 100 ℃ of vacuum-dryings obtained the carbon nanotube of purifying after 24 hours with the deionized water repetitive scrubbing;
Step (2): in two single neck round-bottomed flasks of the 500mL that the magnetic agitation rotor has been housed, one of them adds carbon nanometer tube material 1g and the carbon nano fiber 1g and the 200mL of the purifying that obtains in the step (1), volume ratio is concentrated nitric acid and the vitriol oil mixed solution of 2:1, another adds the carbon fiber and the 200mL of 100g drying, volume ratio is concentrated nitric acid and the vitriol oil mixed solution of 2:1, two flasks are handled through following the same terms: with 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, with deionized water repetitive scrubbing 3-10 time to neutral, 100 ℃ of vacuum-dryings are after 24 hours, obtain respectively carboxylic acidifying carbon nanotube and carbon nano fiber and and carboxylic acidifying carbon fiber;
Step (3): in two 500mL three neck round-bottomed flasks that the magnetic agitation rotor has been housed, one of them adds step (2) gained acidifying carbon nanotube and carbon nano fiber 2g and phosphorus trichloride 10g, another adds acidifying carbon fiber 100g and phosphorus trichloride 200g, two flasks are handled through following the same terms: use the 120Hz ultrasonication after 10 hours, be heated to 25 ℃, the stirring and the reaction down 48 hours that refluxes, suction filtration and repetitive scrubbing are repeatedly removed phosphorus trichloride, obtain the carbon nanotube of chloride and the carbon fiber of carbon nano fiber and chloride respectively;
Step (4): in two 500mL three neck round-bottomed flasks that the magnetic agitation rotor has been housed, one of them adds step (3) gained acylated carbon nano-tube and carbon nano fiber 2g and tetraethylene pentamine 20g, another adds the carbon fiber 100g and the tetraethylene pentamine 100g of acidylate, two flasks are handled through following the same terms: use the 1kHz ultrasonication after 100 hours, reacted 12 hours down at 200 ℃, suction filtration is removed unreacted reactant and byproduct of reaction, use deionized water wash 3 ~ 8 times repeatedly to neutrality, 200 ℃ of vacuum-dryings 1 hour, obtain the surface respectively and have amino carbon nanotube and carbon nano fiber mixture and surface and have amidized carbon fiber;
Step (5): in two 500mL three neck round-bottomed flasks that the magnetic agitation rotor has been housed, one of them adds the amidized carbon nanotube of step (4) and carbon nano fiber mixture 2g and dimethyl sulfoxide (DMSO) 300mL, another adds the carbon fiber 100g and the dimethyl sulfoxide (DMSO) 300mL of ammonification, two flasks are handled through following the same terms: under 90 ℃, ultrasonic concussion 30min, add 100gN, N
,-dicarboxylic anhydride ditan and catalyzer vitriol oil 10ml, nitrogen protection, reaction is 48 hours under the even stirring condition of magnetic force, obtains the surface respectively and contains the Nano carbon fibers peacekeeping carbon mano-tube composite of anhydride group and the carbon fiber that anhydride group is contained on the surface.
Step (6): in the 500mL three neck round-bottomed flasks that agitator is housed, the Nano carbon fibers peacekeeping carbon nanotube 2g and liquid bisphenol A type Resins, epoxy (E-44) 20g that add step (5) acid anhydridesization, heating is also stirred, with the 80kHz ultrasonication after 2 hours, reacted 12 hours down at 240 ℃, obtain the Nano carbon fibers peacekeeping carbon nanotube that the surface is connected to liquid bisphenol A type Resins, epoxy (E-44);
Step (7): the carbon fiber 100g that gets Nano carbon fibers peacekeeping carbon mano-tube composite 20g that the surface is connected to liquid bisphenol A type Resins, epoxy (E-44) and step (5) acid anhydridesization is compound down at 100 ℃, de-bubble under vacuum condition, compression molding obtains the fine dimension of the carbon ∕ epoxy resin multi-dimensional hybrid composite of Nano carbon fibers peacekeeping carbon nano-tube modification under 10MPa.
XPS result shows that carbon fiber and multi-walled carbon nano-tubes mishmash surface anhydride content are 6.7%.
Embodiment 5: (OD＜8nm), Nano carbon fibers peacekeeping carbon fiber are initial raw material with the double-walled carbon nano-tube of arc discharge method preparation, double-walled carbon nano-tube carries out acidifying, chloride with carbon nanotube, Nano carbon fibers peacekeeping carbon fiber respectively, after the amination again through behind the purifying, use N again, N
,After-dicarboxylic anhydride diphenylmethyl the alkanoic acid anhydrideization, Nano carbon fibers peacekeeping carbon nanotube and liquid bisphenol A type Resins, epoxy (E-51) are carried out chemical crosslink reaction, then obtain the Nano carbon fibers peacekeeping carbon nanotube that the surface is connected to liquid bisphenol A type Resins, epoxy (E-51), again with itself and N, N
,The carbon fiber of-dicarboxylic anhydride diphenylmethyl alkanoic acid anhydrideization is compound in a certain way, obtains the fine dimension of the carbon ∕ epoxy resin multi-dimensional hybrid composite of Nano carbon fibers peacekeeping carbon nano-tube modification.
Step (1): in the single neck round-bottomed flask of the 250mL that agitator is housed, the double-walled carbon nano-tube 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, 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, 25 ℃ of following vacuum-dryings obtained the double-walled carbon nano-tube of purifying after 24 hours;
Step (2): in three 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), 98% concentrated sulfuric acid solution, one adds carbon nano fiber 1g and 100mL, 98% concentrated sulfuric acid solution, another adds the carbon fiber 20g and the 100mL of drying, 98% concentrated sulfuric acid solution, three flasks are handled through following the same terms: add through 1 hour post-heating to 25 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, with deionized water repetitive scrubbing 3-10 time to neutral, 80 ℃ of vacuum-dryings obtained carboxylic acidifying double-walled carbon nano-tube respectively after 48 hours, Nano carbon fibers peacekeeping carbon fiber;
Step (3): in three 250mL three neck round-bottomed flasks that agitator has been housed, one of them adds step (2) gained acidifying carbon nanotube 1g and thionyl chloride 10g, one adds acidifying carbon nano fiber 1g and thionyl chloride 10g, another adds acidifying carbon fiber 20g and thionyl chloride 100g, three flasks are handled through following the same terms: use the 100Hz ultrasonication after 1 hour, be heated to 80 ℃, the stirring and the reaction down 100 hours that refluxes, suction filtration and repetitive scrubbing are removed thionyl chloride, obtain the double-walled carbon nano-tube of chloride respectively, Nano carbon fibers peacekeeping carbon fiber;
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, carbon nano fiber 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: use the 100kHz ultrasonication after 1 hour, 200 ℃ of following stirring reactions 0.5 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, obtain respectively the surface have amino double-walled carbon nano-tube and carbon nano fiber mixture and and the surface have amino carbon fiber;
Step (5): in two 250mL three neck round-bottomed flasks that agitator has been housed, one of them adds the amidized carbon nanotube of step (4) and carbon nano fiber 2g and dimethyl sulfoxide (DMSO) 120mL, another adds the carbon fiber 100g and the dimethyl sulfoxide (DMSO) 120mL of step (4) ammonification, two flasks are handled through following the same terms: under 90 ℃, ultrasonic concussion 30min, add 50gN, N
,-dicarboxylic anhydride ditan and catalyzer vitriol oil 10ml, nitrogen protection, reaction is 48 hours under the even stirring condition of magnetic force, obtains the surface respectively and contains the Nano carbon fibers peacekeeping carbon nanotube of anhydride group and the carbon fiber that anhydride group is contained on the surface;
Step (6): in the 250mL three neck round-bottomed flasks that agitator is housed, the Nano carbon fibers peacekeeping carbon nanotube 2g and liquid bisphenol A type Resins, epoxy (E-51) 20g that add step (5) acid anhydridesization, heating is also stirred, with the 80kHz ultrasonication after 2 hours, reacted 12 hours down at 240 ℃, obtain the Nano carbon fibers peacekeeping carbon mano-tube composite that the surface is connected to liquid bisphenol A type Resins, epoxy (E-51);
Step (7): the carbon fiber 100g that gets Nano carbon fibers peacekeeping carbon mano-tube composite 20g that the surface is connected to liquid bisphenol A type Resins, epoxy (E-51) and step (5) acid anhydridesization is compound down at 110 ℃, de-bubble under vacuum condition, compression molding obtains the fine dimension of the carbon ∕ epoxy resin multi-dimensional hybrid composite of Nano carbon fibers peacekeeping carbon nano-tube modification under 11MPa.
XPS result shows that carbon fiber and double-walled carbon nano-tube mishmash surface anhydride content are 5.9%.
The 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. Nano carbon fibers peacekeeping carbon nano-tube modification carbon fibre is tieed up the preparation method of ∕ epoxy resin multi-dimensional hybrid composite, it is characterized in that concrete steps are as follows:
(1) takes by weighing 1～1 * 10
2G exsiccant carbon nanotube and 10～1 * 10
4The mL organic acid mixes, at 1-120kHz ultrasonic wave or 10 r/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 microfiltration membrane suction filtration, repetitive scrubbing is to neutral, and vacuum-drying is 1～48 hour under 25～150 ℃ of temperature, obtains the carbon nanotube of purifying;
(2) with 1～1 * 10
2G exsiccant carbon fiber, 1～1 * 10
2G exsiccant carbon nano fiber, 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 the 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 repetitive scrubbing to solution is, and vacuum-drying is 1～48 hour under 25～200 ℃ of temperature, obtains acidifying carbon fiber, Nano carbon fibers peacekeeping carbon nanotube respectively;
(3) with step (2) gained acidifying carbon fiber 1～1 * 10
2G, carbon nano fiber 1～1 * 10
2G and carbon nanotube 1～1 * 10
2G respectively with acylating reagent l0～1 * 10
4G mixes, and after 0.1-10 hour, is heated to 25～220 ℃ with the 1-120kHz ultrasonication, stirring and back flow reaction 0.5～100 hour, and suction filtration and repetitive scrubbing are removed acylating reagent, obtain carbon fiber, the Nano carbon fibers peacekeeping carbon nanotube of acylations respectively;
(4) with step (3) gained acidylate carbon fiber 1～1 * 10
2G, carbon nano fiber 1～1 * 10
2G and carbon nanotube 1～1 * 10
2G respectively with diamine or polyamine 10～1 * 10
4G mixes, with 1-100kHz ultrasonication 1～100 hour, under 25～200 ℃ of temperature, reacted 0.5～100 hour then, suction filtration and repetitive scrubbing, vacuum-drying is 1～48 hour under 25-200 ℃ of temperature, obtains graft type carbon fiber, Nano carbon fibers peacekeeping carbon nanotube that the surface has active amino respectively;
(5) step (4) gained surface is had the carbon fiber 1～1 * 10 of active amino
2G, carbon nanotube 1～1 * 10
2G and carbon nano fiber 1～1 * 10
2G is agitation and dropping 1～100g aromatic anhydride compound in the polar organic solvent ice bath, be warming up to 100～150 ℃ after dropwising, under this temperature, refluxed 3～16 hours, with the unreacted aromatic anhydride compound of polar organic solvent flush away, 40～80 ℃ of following vacuum-drying 3～12 hours obtains having carbon fiber, carbon nanotube and the carbon nano fiber of activity anhydride group;
(6) step (5) gained surface is had the carbon nanotube 1～1 * 10 of activity anhydride group
2G and carbon nano fiber 1～1 * 10
2G and Resins, epoxy 10～1 * 10
4G, be warming up to 120 ℃ 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 carbon nanotube/nano carbon fiber;
(7) carbon fiber 20～100g mechanically mixing that the resultant epoxide resin polymer 20-25g that contains the carbon nanotube/nano carbon fiber of step (6) is obtained as matrix and step (4) or step (5), under 60-100 ℃, ultrasonic dispersing 1～12 hour, add 30～50g organic acid anhydride class solidifying agent, and in forming mould, the vacuum stripping bubble at 100 ℃～250 ℃ following curing moldings, obtains the fine dimension of the carbon ∕ epoxy resin multi-dimensional hybrid composite of Nano carbon fibers peacekeeping carbon nano-tube modification.
2. the preparation method of the fine dimension of Nano carbon fibers peacekeeping carbon nano-tube modification carbon according to claim 1 ∕ epoxy resin multi-dimensional hybrid composite is characterized in that carbon nanotube described in the step (1) comprises the single wall or the multi-walled carbon nano-tubes of any preparation in chemical Vapor deposition process, arc discharge method, sun power method, template or the laser evaporation method; Organic acid described in the step (1) is any or its 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.
3. the preparation method of the fine dimension of Nano carbon fibers peacekeeping carbon nano-tube modification carbon according to claim 1 ∕ epoxy resin multi-dimensional hybrid composite 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 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, in 1 ∕ 100～100 ∕, 1 mol ratio hydrogen peroxide and nitric acid mixed solution or 15～95% weight concentration superoxols any.
4. the preparation method of the fine dimension of Nano carbon fibers peacekeeping carbon nano-tube modification carbon according to claim 1 ∕ epoxy resin multi-dimensional hybrid composite, 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.
5. the preparation method of the fine dimension of Nano carbon fibers peacekeeping carbon nano-tube modification carbon according to claim 1 ∕ epoxy resin multi-dimensional hybrid composite, it is characterized in that diamine is a quadrol described in the step (4), polyethyene diamine, 1, the 2-propylene diamine, 1, the 3-propylene diamine, 1, the 2-butanediamine, 1, the 3-butanediamine, hexanediamine, Ursol D, mphenylenediamine, m-xylene diamine, diaminodiphenyl-methane, the Meng alkane diamines, the divinyl propylamine, diaminodiphenyl-methane, the chlorination hexanediamine, the chlorination nonamethylene diamine, the chlorination decamethylene diamine, in 12 carbon diamines or the 13 carbon diamines any; Described polyamine is fourth triamine, N-aminoethyl piperazine, Dyhard RU 100, adipic dihydrazide, N, in N-dimethyl dipropyl triamine, tetraethylene pentamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines or six ethene, seven amine any.
6. the preparation method of the fine dimension of Nano carbon fibers peacekeeping carbon nano-tube modification carbon according to claim 1 ∕ epoxy resin multi-dimensional hybrid composite, it is characterized in that aromatic anhydride compound described in the step (5) comprises affixture, the sulfobenzide-3 of affixture, benzophenone tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride and the caprolactone of pyromellitic acid anhydride, pyromellitic acid anhydride and caprolactone, 3 ', 4-4 '-tetracarboxylic dianhydride, sulfobenzide-3,3 ', the affixture of 4-4 '-tetracarboxylic dianhydride, N, N
,-One or more mixtures in dicarboxylic anhydride ditan or mellitic acid three acid anhydrides; Polar organic solvent described in the step (5) comprises ethanol, methyl alcohol, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), acetone or N, N
,One or more mixtures in the-dimethyl formamide.
7. the preparation method of the fine dimension of Nano carbon fibers peacekeeping carbon nano-tube modification carbon according to claim 1 ∕ epoxy resin multi-dimensional hybrid composite is characterized in that the Resins, epoxy described in the step (6) comprises in Racemic glycidol lipid, Racemic glycidol ethers, Racemic glycidol amine, finger ring class, epoxidation of olefins class, imide ring epoxy resins or the glycolylurea epoxide resin any.
8. the preparation method of the fine dimension of Nano carbon fibers peacekeeping carbon nano-tube modification carbon according to claim 1 ∕ epoxy resin multi-dimensional hybrid composite is characterized in that the organic acid anhydride class solidifying agent described in the step (7) is a Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, the methyl carbic anhydride, dodecyl succinic anhydride, chlorendic anhydride, adjacent pyromellitic dianhydride, the phthalic anhydride tetracarboxylic dianhydride, the tetrahydrotoluene tetracarboxylic dianhydride, the phenyl ether tetracarboxylic dianhydride, one or more mixtures in trimellitic acid 1,2-anhydride or the poly-nonane diacid acid anhydride.
9. the preparation method of the fine dimension of Nano carbon fibers peacekeeping carbon nano-tube modification carbon according to claim 1 ∕ epoxy resin multi-dimensional hybrid composite is characterized in that carbon fiber described in the step (7) is any in unidirectional macrofiber cloth, two-way textile sheet, three-phase textile sheet or the random staple fibre cloth.
10. the preparation method of the fine dimension of Nano carbon fibers peacekeeping carbon nano-tube modification carbon according to claim 1 ∕ epoxy resin multi-dimensional hybrid composite, it is characterized in that the carbon nanotube of purifying and carbon nano fiber can separate treatment or in step (2)-(6) combination treatment in any step.
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