CN104277421A - Preparation method of multicomponent-modified carbon-fiber-reinforced epoxy resin composite material - Google Patents
Preparation method of multicomponent-modified carbon-fiber-reinforced epoxy resin composite material Download PDFInfo
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Abstract
The invention relates to a preparation method of a multicomponent-modified carbon-fiber-reinforced epoxy resin composite material, which comprises the following steps: oxidizing carbon nanotubes (CNTs) with strong acid; carrying out acyl-chlorination and amination on the oxidized CNTs sequentially with thionyl chloride and diamine to introduce amino functional group; oxidizing carbon fiber with strong oxidizing acid, and carrying out acyl-chlorination treatment with thionyl chloride to introduce acyl chloro group; mixing the prepared modifying CNTs and modifying carbon fiber to perform graft reaction, thereby obtaining the CNTs-grafted carbon fiber; mixing the CNTs-grafted carbon fiber with polyhedral oligomeric silsesquioxane (POSS) to perform graft reaction, thereby obtaining the binary POSS-grafted carbon fiber; and sufficiently infiltrating the binary POSS-grafted carbon fiber in the base resin, and carrying out hot pressing to perform curing formation. The CNTs and POSS cografted on the carbon fiber surface can improve the surface topography of the carbon fiber, increase the contact area with the resin base and penetrate into the resin base under the anchoring action, so that the interfacial mechanical mesh action is higher.
Description
Technical field
The present invention relates to a kind of preparation method of modified carbon fiber reinforced epoxy matrix material, belong to carbon-fibre composite technical field.
Background technology
Carbon fiber (CF) is by organic fibre in rare gas element, the fibrous carbon material that the carbon content obtained through high temperature cabonization is higher, and it has the intrinsic characteristics of carbon material and the soft workability of textile fibres, is fortifying fibre of new generation.The excellent properties such as carbon fiber has high strength, high-modulus, high temperature resistant, density is low, rub resistance, corrosion-resistant and conductive and heat-conductive.When same volume, its weight is less than 1/4 of steel.Carbon fiber resin composite material tensile strength is general all at more than 3500Mpa, and be firm 7-9 times, tensile modulus of elasticity is that 230 ~ 430Gpa is also higher than steel.Therefore the specific tenacity of carbon fiber resin composite material and the intensity of material can reach more than 2000Mpa/ (g/cm3) with the ratio of its density, and the specific tenacity of A3 steel is only 59Mpa/ (g/cm
3) left and right.The specific modulus of material is higher, then the intensity of component is larger, and specific tenacity is higher, then member dead weight is less.Just because of the performance of its uniqueness, advanced carbon-fibre composite plays an important role in fields such as space flight and aviation, military affairs, automobile and buildings.
But, due to carbon fiber be through 1300 DEG C ~ 1600 DEG C high temperature cabonizations and obtained carbon content up to more than 90% carbon material, carbonization in high temperature inert gas, along with the effusion of non-carbon and the enrichment of carbon, its surfactivity is reduced, surface tension declines, and is deteriorated with the wetting property of resin matrix.In addition, in order to the tensile strength improving carbon fiber needs to reduce surface imperfection as far as possible, therefore, its surface volume is also less.Level and smooth surface make the holdfast of itself and resin matrix and mechanical bond effect more weak, cause the interlaminar shear strength of matrix material to reduce, therefore, adopt carbon fiber to be strongthener when preparing matrix material, all need to carry out surface modification treatment to carbon fiber.Surface treatment not only can improve carbon fiber surface surface roughness and specific surface area, increase and the holdfast of resin matrix and mechanical bond effect, also can improve the content of fiber surface activity atom, improve the functional group content participating in reaction, increase the chemical bond quantity formed with resin matrix in preparation composite material.Meanwhile, the change of carbon fiber surface activity, can reduce the contact angle between itself and resin, improves its wetting property, and this can be combined (hydrogen bond, Van der Waals force etc.) effect by the secondary valence bond of fortifying fibre surface between resin matrix.Wherein carbon fiber surface chemical graft process can be introduced at fiber surface and produce new active site and functional group, and can select the material of grafting according to the actual requirements, is the focus of research at present.
Summary of the invention
The process that the present invention seeks to solve existing carbon fibre reinforced composite interface lacks controlled effective method for activating surface, and cause the problem that fibre reinforced non-polar resin matrix material interlayer shearing resistance is low, thus provide the preparation method of a kind of interfacial adhesion firmly multicomponent modified carbon fiber reinforced epoxy matrix material.
The technical scheme that the present invention takes is:
A preparation method for multicomponent modified carbon fiber reinforced epoxy matrix material, comprises step as follows:
(1) carbon nanotube strong acid is oxidized;
(2) the carbon nanotube priority sulfur oxychloride after oxidation, diamine are carried out chloride and aminated process, introduce amido functional group;
(3) carbon fiber is used Strong oxdiative acid oxidase, then use sulfur oxychloride chloride process, introduce acid chloride group;
(4) the modifying carbon fibers mixed grafting that carbon nano-tube modified and step (3) obtained for step (2) obtains is reacted, obtain the carbon fiber of grafting carbon nanotube;
(5) by grafting, the carbon fiber of carbon nanotube and half times of siloxanes POSS mixed grafting react, and obtain the carbon fiber of binary grafting POSS;
(6) carbon fiber of binary grafting POSS and matrix resin are fully infiltrated rear hot-press solidifying shaping.
The preparation method of described multicomponent modified carbon fiber reinforced epoxy matrix material, preferably includes step as follows:
(1) carbon nanotube (CNTs) is added the mixed acid solution of the vitriol oil and concentrated nitric acid, stirring reaction 2 ~ 4h under 60 ~ 80 DEG C of waters bath with thermostatic control, filter, washing, under vacuum condition dry must be oxidized after carbon nanotube;
(2) carbon nanotube after oxidation is added sulfur oxychloride and organic solvent, be heated to 70-80 DEG C of reaction 48-72h, terminate rear underpressure distillation and remove unnecessary SOCl
2, then add diamine, be heated to 75-80 DEG C of reaction 36-48h, with distilled water diluting, suction filtration is until filtrate is in neutral, and obtain aminated carbon nanotube, vacuum-drying is for subsequent use;
(3) by carbon fiber (CF) acetone reflux extracting post-drying, then Strong oxdiative acid is added, heating in water bath is to 60-70 DEG C of oxidation 2 ~ 6h, cleaning is to neutral repeatedly, dries, and obtains the carbon fiber be oxidized, the carbon fiber of oxidation is added SOCl2 and organic solvent, heating in water bath is to 70-80 DEG C of reaction 36-48h, and forced air drying after taking out, obtains the carbon fiber of chloride;
(4) by aminated carbon nanotube dispersed in organic solvent, the carbon fiber of chloride is added after being uniformly dispersed, 60-72h is reacted under 50-60 DEG C of water bath with thermostatic control, every 1 ~ 3h reaction soln shaken again in reaction process and point to spread, to ensure that aminated carbon nanotube dispersed evenly fully can contact with carbon fiber, have neither part nor lot in the aminated carbon nanotube of reaction after taking out with acetone reflux extracting removing fiber surface, vacuum drying oven is dry, obtains the carbon fiber of grafting carbon nanotube;
(5) half times of siloxanes POSS is placed in organic solvent, add the carbon fiber of grafting carbon nanotube, 24h-36h is reacted under 50-60 DEG C of water bath with thermostatic control, have neither part nor lot in the POSS molecule of reaction with acetone reflux extracting removing fiber surface after taking out, vacuum drying oven is dry, obtains the carbon fiber of binary grafting POSS;
(6) configure the Homogeneous phase mixing liquid of epoxy resin and solidifying agent, the carbon fiber of binary grafting POSS is mixed fully to infiltrate with it be placed in mould, mould is put on thermocompressor and solidifies.
The vitriol oil in above-mentioned preparation method described in step (1) and concentrated nitric acid volume ratio are 3:1, and the ratio of carbon nanotube and mixed acid solution is 0.04-0.05g/ml.Carbon nanotube is any one single armed prepared in arc-over, chemical gaseous phase deposition, template, sun power method or laser evaporation or multi-walled carbon nano-tubes.
Carbon nanotube in step (2) after oxidation and the ratio of sulfur oxychloride are 0.02-0.03g/ml, the volume ratio of sulfur oxychloride, organic solvent, diamine is 100:5:100, described diamine is quadrol, choose any one kind of them in 1,2-propylene diamine, 1,3-propylene diamine.The ratio 3:100-150 of carbon fiber and Strong oxdiative acid in step (3), g/ml; The volume ratio of sulfur oxychloride, organic solvent is 100:5.The carbon fiber of oxidation and the ratio 3:100-200 of sulfur oxychloride, g/ml; Strong oxdiative acid is for choosing any one kind of them in concentrated nitric acid, the vitriol oil, hypochlorous acid, nitration mixture (concentrated nitric acid and the vitriol oil).
In step (4), the carbon fiber of aminated carbon nanotube and chloride, the ratio of organic solvent are 1:6-15:150-300, g:g:ml; The method of dispersing Nano carbon tubes can adopt ultrasonic vibration method, magnetic agitation method is chosen any one kind of them in (needing to carry out suspension process to fiber).
Organic solvent described in above-mentioned steps (2)-(4) be in DMF, tetrahydrofuran (THF), acetone any one.Half times of siloxanes POSS, the carbon fiber of grafting carbon nanotube, the ratio 1:6-15:150-300 of organic solvent, g:g:ml in step (5); Described organic solvent is choose any one kind of them in tetrahydrofuran (THF), acetone, sherwood oil.
Step (6) described epoxy resin is choose any one kind of them in epoxy resin E-51, epoxy resin E-44; Described solidifying agent is choose any one kind of them in aromatic diamines, methyl tetrahydrophthalic anhydride, imidazoles.Described thermocompressor is cured as and starts timing when die temperature rises to 90 DEG C and observe glue state, insulation 10min-1h, resin is pressurized to 5MPa when starting gel, after be warming up to 120 DEG C, pressure increases to 10MPa, after insulation 2h, continue to be warming up to 150 DEG C, pressure is constant, insulation 4h, keep pressure to mold cools down to room temperature, molding.Suitable proportion described in step (6) is epoxy resin, aromatic liquid diamines H-256 mass ratio is 100:(30 ~ 40); Epoxy resin, methyl tetrahydro phthalic anhydride and N, N-dimethyl benzylamine mass ratio are 100:(65 ~ 75): 1; Epoxy resin, imidazoles mass ratio are 100:6.Carbon fiber and epoxy resin mass ratio are (60-70): (30-40), preferred 65:35.
Matrix material prepared by aforesaid method.
The present invention is at the CNTs of carbon fiber surface grafting one dimension, carbon fiber surface Grafting Structure and grafting density controllability and order can be realized, again based on CF/CNTs composite reinforcement, further grafting containing different activities end group POSS, formed and there is different modulus gradient CF/CNTs/POSS bielement nano grafting reinforcement.CNTs and POSS can improve the surface topography of carbon fiber at carbon fiber surface cografting, and POSS is grafted to CNTs surface and forms " mace " shape, more can expand the contact area with resin matrix, be deep in resin matrix with holdfast effect, make interfacial mechanical engagement stronger.Simultaneously, CNTs and POSS chemical graft, to fiber surface, can improve the content of fiber surface activity atom, can reduce the contact angle between resin like this, improve its wetting property, the secondary valence bond increased between resin matrix is combined (hydrogen bond, Van der Waals force etc.) effect.In addition, CNTs and POSS surface have neither part nor lot in reaction functional group can with resin reaction, increase the chemical bond quantity formed with resin matrix.Thus the bonding of carbon fiber and interlaminar resin is strengthened, the comprehensive mechanical property of the matrix material of preparation is improved significantly.Therefore, the present invention has important science and technology value and actual application value.
POSS is a kind of omnipotent molecule, any organic group can be connected to its surface by chemical reaction, and this molecule customization is easy, controllability is strong, produce POSS initial feed advantage of lower cost and productive rate is very high, this makes POSS cheap, large-scale commercial applications can be carried out, POSS molecular center is rigid inorganic nano core, around around the unique molecular structure of reactive functionality can define firmly chemistry and physical action at composite material interface simultaneously, boundary strength is significantly improved, is better than common anhydride molecule.
Accompanying drawing explanation
Fig. 1 is the schema of the carbon fiber surface chemical graft reaction of embodiment 1.
Fig. 2 is the SEM pattern of the carbon fiber surface in different treatment stage, b) except slurry CF, e) grafting CNTs, f) binary grafting POSS;
Fig. 3 is shearing resistance between embodiment 1 different treatment stage carbon fiber composite layer.
Fig. 4 be surface that the present invention obtains be connected to carbon nanotube/POSS carbon fiber composite layer between the SEM figure of shear fracture pattern.
Embodiment
Further illustrate of the present invention below in conjunction with embodiment, instead of limit the scope of the invention.
Embodiment 1:
A preparation method for multicomponent modified carbon fiber reinforced epoxy matrix material, comprises the following steps:
(1): the round-bottomed flask that the CNTs taking 4g drying is placed in, the volume ratio adding the 100ml vitriol oil and concentrated nitric acid is the mixing solutions of 3:1, stirring reaction 4h under 60 DEG C of waters bath with thermostatic control, distilled water diluting is added in solution after the reaction, with porous membrane suction filtration to washings in neutral, at 100 DEG C under vacuum condition dry must be oxidized after CNTs;
(2): the CNTs after the oxidation obtained by 2g step (1), adds 100ml SOCl respectively
2with 5ml DMF (DMF) solution, be heated to 76 DEG C of reaction 72h, terminate rear underpressure distillation and remove unnecessary SOCl
2, add 100ml quadrol, be heated to 80 DEG C of reaction 48h, with distilled water diluting, suction filtration is until filtrate is in neutral, and obtain aminated CNTs, at 100 DEG C, vacuum-drying is for subsequent use;
(3): CF is placed in apparatus,Soxhlet's, acetone reflux extracting 72h under 75 DEG C of conditions, takes out and puts into the dry 4h of 100 DEG C of vacuum drying box, obtain the CF after except slurry.Be placed in round-bottomed flask by except the CF after slurry, add 100ml concentrated nitric acid, heating in water bath to 60 DEG C oxidation 3h, repeatedly clean reacted CF to washing lotion in neutral with distilled water, 100 DEG C of oven dry, obtain the CF be oxidized; To in the CF (3g) of the oxidation of gained, add 100ml SOCl respectively
2with 5ml DMF solution, heating in water bath to 76 DEG C reaction 48h, forced air drying after taking out, obtains the CF of chloride;
(4): take the aminated CNTs of 0.2g step (2) gained as in 100ml tetrahydrofuran THF solution, sonic oscillation obtains finely dispersed amidized CNTs solution for 15 minutes, the CF of the chloride of 3g step (3) gained is put into this solution, 72h is reacted under 50 DEG C of waters bath with thermostatic control, every 2h, reaction soln is had children outside the state plan vibration again in reaction process fully to contact with CF to ensure that aminated CNTs is uniformly dispersed, remove with being placed in the extracting of apparatus,Soxhlet's acetone reflux the aminated CNTs that fiber surface has neither part nor lot in reaction after taking-up, put into the dry 4h of 100 DEG C of vacuum drying box, obtain CF/CNTs,
(5): take 0.5g POSS and be placed in 100mlTHF solution, the CF/CNTs of 3g step (4) gained is put into this solution, 24h is reacted under 50 DEG C of waters bath with thermostatic control, have neither part nor lot in the POSS molecule of reaction with acetone reflux extracting removing fiber surface after taking out, 100 DEG C of dry 4h of vacuum drying oven, obtain CF/CNTs/POSS bielement nano grafting reinforcement;
(6): the CF/CNTs/POSS being wound around step (5) gained of the suitable number of turns on the glass holder that 200mm is long, the ratio that matrix resin is 100:32 in epoxy resin, aromatic liquid diamines H-256 mass ratio mixes, by carbon fiber and matrix resin in mass ratio 65:35 fully infiltrate and be placed in mould, mould is put on thermocompressor and solidifies by following technique.Start timing when die temperature rises to 90 DEG C and observe glue state, insulation about 30min, be pressurized to 5MPa when epoxy resin starts gel, after be warming up to 120 DEG C, pressure increases to 10MPa, after insulation 2h, continue to be warming up to 150 DEG C, pressure is constant, insulation 4h, keep pressure to mold cools down to room temperature, molding, obtains resin content and controls the CF/CNTs/POSS reinforced epoxy matrix material in 35 ± 1.5% scopes.
In the present embodiment step (1), the specification of CNTs is TNM3, is that Chengdu organic chemistry company limited of the Chinese Academy of Sciences produces.The specification of CF is 3K in the present embodiment step (3), be the specification that Carbon fibe company limited of Jilin divine boat produces POSS in the present embodiment step (6) is analytical pure, is that Hybrid Plastics company of the U.S. produces.
Table 1 is the constituent content of fiber surface after CNTs/POSS binary grafting CF.
Fig. 1 is the schema of the carbon fiber surface chemical graft reaction of embodiment 1.
Fig. 2 is the SEM pattern of the carbon fiber surface in different treatment stage, and after showing grafting CNTs and POSS, carbon fiber/epoxy resin composite material improves 6.7% and 11.8% respectively with except the carbon fibre surface energy starched compared with carbon fiber after grafting.
Fig. 3 is shearing resistance between different treatment stage carbon fiber composite layer, and after showing grafting CNTs and POSS, the interlaminar shear strength of carbon fiber/epoxy resin composite material improves 21.6% and 31.6% respectively with except starching compared with carbon fiber.Except the carbon fiber ILSS after slurry is lower, only has 65.99GPa.After oxidation, its ILSS brings up to 71.4GPa, this is because oxygenizement generates hydroxyl, carboxyl isoreactivity group at fiber surface, fiber wetness can be improved, and strong oxidizer has certain etching action to fiber surface, add the roughness of fiber surface, improve the bonding strength of fiber and resin.Carbon fiber ILSS after chloride is 77.2GPa, this generates acid chloride groups because chloride acts on fiber surface, and sulfur oxychloride also can produce etching action by fiber surface, and fiber surface activity number of functional groups is increased, fiber surface roughness increases further, and ILSS is improved.After grafting CNTs, the ILSS of matrix material is 80.27GPa, 21.6% is improved compared with blank sample, known in conjunction with XPS ultimate analysis, after grafting CNTs, fiber surface contains a large amount of oxygen element, show fiber surface still containing a large amount of oxygen-containing functional group, certain effect is served to the bonding strength improving fiber and resin, in addition due to the introducing of CNTs, its surperficial unreacted amino group can occur crosslinked with epoxy molecule, strengthen the chemical action at interface, and the CNTs of carbon fiber surface grafting is different in size, direction is different, in the process of fiber and resin compounded, these CNTs can thrust resin matrix, firmly can lock the molecular resin near it, the motion of restriction interface zone molecule, form powerful mechanical engagement, interface bond strength is strengthened further.Increase further through the matrix material ILSS of CNTs and POSS binary grafting, reach 86.84MPa, improve 8.2% than the composite sample of simple CNTs grafting, improve 31.6% than blank style.The combination of the two better can play mechanical holdfast and Chemical bond effect.POSS can react with the functional group on carbon fiber surface and CNTs surface, fiber surface after grafting POSS, it is more coarse that CNTs surface becomes, POSS molecule and accumulation body thereof add the roughness of carbon fiber modifying surface, particulate firmly can lock the molecular resin near it, the motion of further restriction interface zone molecule, forms powerful mechanical engagement, boundary strength is significantly improved.Simultaneously, POSS side base contains a large amount of epoxide groups, these epoxide groups can improve the surface energy of fiber, improve the wetting property of fiber and resin, fiber surface is made to be combined with matrix resin tightr, decrease the generation of boundary defect, chemical bond can also be generated with matrix resin generation chemical reaction, make between fiber surface and resin, to form powerful chemical action.
Fig. 4 be surface be connected to carbon nanotube/POSS carbon fiber composite layer between the SEM figure of shear fracture pattern.
Embodiment 2: the present embodiment adds 100ml 1,2-propylene diamine in step (2) as different from Example 1 and carries out aminated process to CNTs, other step and parameter identical with embodiment 1.
Embodiment 3: the present embodiment adds the 100ml vitriol oil in step (3) as different from Example 1 and carries out oxide treatment to CF, other step and parameter identical with embodiment 1.
Embodiment 4: the present embodiment as different from Example 1 middle magnetic agitation of step (4) obtains finely dispersed amidized CNTs solution for 20 minutes, this solution is put into after suspension process is carried out to CF, react 72h under 50 DEG C of waters bath with thermostatic control, every 2h, reaction soln being stirred to ensure that aminated CNTs is uniformly dispersed again in reaction process fully can contact with CF.Other step and parameter identical with embodiment 1.
Embodiment 5: the present embodiment as different from Example 1 step (6) epoxy resin, aromatic liquid diamines H-256 mass ratio is that the ratio of 100:35 mixes.Other step and parameter identical with embodiment 1.
Embodiment 6: the present embodiment as different from Example 1 middle matrix resin of step (6) presses epoxy resin, methyl tetrahydro phthalic anhydride and N, N-dimethyl benzylamine mass ratio is that the ratio of 100:70:1 mixes, carbon fiber and matrix resin fully being infiltrated is placed in mould, is put in by mould on thermocompressor and solidifies by following technique.Start timing when die temperature rises to 90 DEG C and observe glue state, between 10min-30min, when epoxy resin starts gel, be pressurized to 5MPa, after insulation 2h, be warming up to 120 DEG C, pressure increases to 10MPa, after insulation 2h, continue to be warming up to 150 DEG C, pressure is constant, insulation 4h, keep pressure to mold cools down to room temperature, molding, obtains resin content and controls the CF/CNTs/POSS reinforced epoxy matrix material in 35 ± 1.5% scopes.Other step and parameter identical with embodiment 1.
Embodiment 7: the present embodiment as different from Example 1 middle matrix resin of step (6) mixes in the ratio that epoxy resin, imidazoles mass ratio are 100:6, carbon fiber and matrix resin fully being infiltrated is placed in mould, is put in by mould on thermocompressor and solidifies by following technique.Start timing when die temperature rises to 50 DEG C when die temperature rises to and observe glue state, insulation about 30min, be pressurized to 5MPa when epoxy resin starts gel, after be warming up to 100 DEG C, pressure increases to 10MPa, after insulation 3h, continue to be warming up to 150 DEG C, pressure is constant, insulation 4h, keep pressure to mold cools down to room temperature, molding, obtains resin content and controls the CF/CNTs/POSS reinforced epoxy matrix material in 35 ± 1.5% scopes.Other step and parameter identical with embodiment 1.
Above-mentioned understands and applies the invention for the ease of those skilled in the art the description of embodiment.Those of ordinary skill in the art obviously easily can make various amendment to these embodiments, and General Principle described herein are applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art are according to announcement of the present invention, and the improvement make the present invention and amendment all should within protection scope of the present invention.
Claims (10)
1. a preparation method for multicomponent modified carbon fiber reinforced epoxy matrix material, is characterized in that, comprise step as follows: carbon nanotube strong acid is oxidized by (1);
(2) the carbon nanotube priority sulfur oxychloride after oxidation, diamine are carried out chloride and aminated process, introduce amido functional group;
(3) carbon fiber is used Strong oxdiative acid oxidase, then use sulfur oxychloride chloride process, introduce acid chloride group;
(4) the modifying carbon fibers mixed grafting that carbon nano-tube modified and step (3) obtained for step (2) obtains is reacted, obtain the carbon fiber of grafting carbon nanotube;
(5) by grafting, the carbon fiber of carbon nanotube and half times of siloxanes POSS mixed grafting react, and obtain the carbon fiber of binary grafting POSS;
(6) carbon fiber of binary grafting POSS and matrix resin are fully infiltrated rear hot-press solidifying shaping.
2. the preparation method of multicomponent modified carbon fiber reinforced epoxy matrix material according to claim 1, is characterized in that, comprise step as follows:
(1) carbon nanotube is added the mixed acid solution of the vitriol oil and concentrated nitric acid, stirring reaction 2 ~ 4h under 60 ~ 80 DEG C of waters bath with thermostatic control, filter, washing, under vacuum condition dry must be oxidized after carbon nanotube;
(2) carbon nanotube after oxidation is added sulfur oxychloride and organic solvent, be heated to 70-80 DEG C of reaction 48-72h, after terminating, underpressure distillation removes unnecessary SOCl2, then binary ammonia is added, be heated to 70-80 DEG C of reaction 36-48h, with distilled water diluting, suction filtration is until filtrate is in neutral, obtain aminated carbon nanotube, vacuum-drying is for subsequent use;
(3) by carbon fiber acetone reflux extracting post-drying, then Strong oxdiative acid is added, heating in water bath to 60 DEG C oxidation 2 ~ 6h, cleaning is to neutral repeatedly, and 100 DEG C of oven dry obtain the carbon fiber be oxidized, the carbon fiber of oxidation is added SOCl2 and organic solvent, heating in water bath is to 70-80 DEG C of reaction 36-48h, and forced air drying after taking out, obtains the carbon fiber of chloride;
(4) by aminated carbon nanotube dispersed in organic solvent, the carbon fiber of chloride is added after being uniformly dispersed, 60-72h is reacted under 50-60 DEG C of water bath with thermostatic control, every 1 ~ 3h reaction soln shaken again in reaction process and point to spread, to ensure that aminated carbon nanotube dispersed evenly fully can contact with carbon fiber, have neither part nor lot in the aminated carbon nanotube of reaction after taking out with acetone reflux extracting removing fiber surface, vacuum drying oven is dry, obtains the carbon fiber of grafting carbon nanotube;
(5) half times of siloxanes POSS is placed in organic solvent, add the carbon fiber of grafting carbon nanotube, 24h-36h is reacted under 50-60 DEG C of water bath with thermostatic control, have neither part nor lot in the POSS molecule of reaction with acetone reflux extracting removing fiber surface after taking out, vacuum drying oven is dry, obtains the carbon fiber of binary grafting POSS;
(6) configure the Homogeneous phase mixing liquid of epoxy resin and solidifying agent, the carbon fiber of binary grafting POSS is mixed fully to infiltrate with it be placed in mould, mould is put on thermocompressor and solidifies.
3. the preparation method of multicomponent modified carbon fiber reinforced epoxy matrix material according to claim 2, it is characterized in that, the vitriol oil described in step (1) and concentrated nitric acid volume ratio are 3:1, and the ratio of carbon nanotube and mixed acid solution is 0.04-0.05g/ml.
4. the preparation method of multicomponent modified carbon fiber reinforced epoxy matrix material according to claim 2, is characterized in that, the ratio 3:100 of carbon fiber and Strong oxdiative acid in step (3), g/ml; The volume ratio of sulfur oxychloride, organic solvent is 100:5, the carbon fiber of oxidation and the ratio 3:100 of sulfur oxychloride, g/ml.
5. the preparation method of multicomponent modified carbon fiber reinforced epoxy matrix material according to claim 2, it is characterized in that, in step (4), the carbon fiber of aminated carbon nanotube and chloride, the ratio of organic solvent are 1:6-15:150-300, g:g:ml.
6. the preparation method of multicomponent modified carbon fiber reinforced epoxy matrix material according to claim 2, is characterized in that, described Strong oxdiative acid is choosing any one kind of them in the nitration mixture of concentrated nitric acid, the vitriol oil, hypochlorous acid, concentrated nitric acid and the vitriol oil.
7. the preparation method of multicomponent modified carbon fiber reinforced epoxy matrix material according to claim 2, it is characterized in that, half times of siloxanes POSS, the carbon fiber of grafting carbon nanotube, the ratio 1:6-15:150-300 of organic solvent, g:g:ml in step (5); Described organic solvent is choose any one kind of them in tetrahydrofuran (THF), acetone, sherwood oil.
8. the preparation method of multicomponent modified carbon fiber reinforced epoxy matrix material according to claim 2, is characterized in that, step (6) described epoxy resin is choose any one kind of them in epoxy resin E-51, epoxy resin E-44; Described solidifying agent is choose any one kind of them in aromatic diamines, methyl tetrahydrophthalic anhydride, imidazoles.
9. the preparation method of multicomponent modified carbon fiber reinforced epoxy matrix material according to claim 2, is characterized in that, described thermocompressor is cured as and starts timing when die temperature rises to 90 DEG C and observe glue state, insulation 10min-1h, resin is pressurized to 5MPa when starting gel, after be warming up to 120 DEG C, pressure increases to 10MPa, after insulation 2h, continue to be warming up to 150 DEG C, pressure is constant, insulation 4h, keep pressure to mold cools down to room temperature, molding.
10. matrix material prepared by the method described in claim 1 or 2.
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