CN104277421B - A kind of preparation method of multicomponent modified carbon fiber reinforced epoxy composite - Google Patents
A kind of preparation method of multicomponent modified carbon fiber reinforced epoxy composite Download PDFInfo
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Abstract
The preparation method who the present invention relates to a kind of multicomponent modified carbon fiber reinforced epoxy composite, is oxidized CNT CNTs with strong acid; CNT after oxidation is successively carried out to chloride and aminated processing with thionyl chloride, diamine, introduce amido functional group; Carbon fiber is oxidized with strong oxidizing acid, then uses thionyl chloride chloride processing, introduce acid chloride group; Carbon nano-tube modified and the modifying carbon fibers mixed grafting making is reacted to the carbon fiber of CNT that obtained grafting; By grafting the carbon fiber of CNT react with half times of siloxanes POSS mixed grafting, obtain the carbon fiber of binary grafting POSS; The carbon fiber of binary grafting POSS and matrix resin are fully infiltrated to after heat pressure curing molding. CNTs and POSS can improve the surface topography of carbon fiber at carbon fiber surface cograft, the contact area of expansion and resin matrix, is deep in resin matrix with holdfast effect, makes interface mechanical engagement effect stronger.
Description
Technical field
The preparation method who the present invention relates to a kind of modified carbon fiber reinforced epoxy composite, belongs to carbon fibre composite skillArt field.
Background technology
Carbon fiber (CF) be by organic fiber in inert gas, through high temperature cabonization and higher fibrous of the phosphorus content that makesMaterial with carbon element, it has the soft machinability of intrinsic characteristics and the textile fabric of material with carbon element, is fortifying fibre of new generation. Carbon fiber toolHave high strength, high-modulus, the excellent properties such as high temperature resistant, density is low, rub resistance, corrosion-resistant and conductive and heat-conductive. At same volumeSituation under, its weight is less than 1/4 of steel. Carbon fiber resin composite material tensile strength generally all more than 3500Mpa,Be firm 7-9 times, tensile modulus of elasticity is that 230～430Gpa is also higher than steel. Therefore the specific strength of carbon fiber resin composite materialBe more than the intensity of material and the ratio of its density can reach 2000Mpa/ (g/cm3), and the specific strength of A3 steel is only 59Mpa/ (g/cm3)Left and right. The specific modulus of material is higher, and the intensity of member is larger, and specific strength is higher, and member dead weight is less. Just because of itUnique performance, advanced carbon fibre composite plays an important role in fields such as space flight and aviation, military affairs, automobile and buildings.
But, because carbon fiber is that the carbon content that makes through 1300 DEG C～1600 DEG C high temperature cabonizations is up to more than 90% carbon materialMaterial, carbonization in high temperature inert gas, along with the effusion of non-carbon and the enrichment of carbon, reduces its surface-active, surfacePower declines, with the wellability variation of resin matrix. In addition, for the hot strength that improves carbon fiber need to reduce surface as far as possibleDefect, therefore, its surface volume is also less. A little less than level and smooth surface makes the holdfast and mechanical bond effect of itself and resin matrix,Cause the interlaminar shear strength of composite to reduce, therefore, adopting carbon fiber is reinforcing material while preparing composite, all needsCarbon fiber is carried out to surface modification treatment. Surface treatment not only can improve carbon fiber surface surface roughness and specific area, increase withThe holdfast of resin matrix and mechanical bond effect, also can improve the content of fiber surface activity atom, improves the sense that participates in reactionMass contg, increases the chemical bond quantity forming with resin matrix in preparation composite material. Meanwhile, carbon fiber surface activityChange, can reduce the contact angle between itself and resin, improve its wetting property, this can fortifying fibre surface and resin matrixBetween secondary bond in conjunction with (hydrogen bond, Van der Waals force etc.) effect. Wherein carbon fiber surface chemical graft process can be at fiber surfaceIntroducing and produce new active site and functional group, and can select according to the actual requirements the material of grafting, is the focus of studying at present.
Summary of the invention
The processing the present invention seeks in order to solve existing carbon fibre reinforced composite interface lacks controlled effective surface active sideMethod, and cause carbon fiber to strengthen the low problem of non-polar resin composite interlayer shear strength, thus provide a kind of interface stickyTie the firmly preparation method of multicomponent modified carbon fiber reinforced epoxy composite.
The technical scheme that the present invention takes is:
A preparation method for multicomponent modified carbon fiber reinforced epoxy composite, comprises that step is as follows:
(1) CNT is oxidized with strong acid;
(2) CNT after oxidation is successively carried out to chloride and aminated processing with thionyl chloride, diamine, introduce amino-functionalGroup;
(3) carbon fiber is oxidized with strong oxidizing acid, then uses thionyl chloride chloride processing, introduce acid chloride group;
(4) the modifying carbon fibers mixed grafting that the carbon nano-tube modified and step (3) step (2) being made obtains reacts, and has obtained graftingThe carbon fiber of CNT;
(5) by grafting the carbon fiber of CNT react with half times of siloxanes POSS mixed grafting, obtain the carbon fibre of binary grafting POSSDimension;
(6) carbon fiber of binary grafting POSS and matrix resin are fully infiltrated to after heat pressure curing molding.
The preparation method of described multicomponent modified carbon fiber reinforced epoxy composite, preferably includes step as follows:
(1) CNT (CNTs) is added to the mixed acid solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), under 60～80 DEG C of waters bath with thermostatic control, stirReaction 2～4h, filters, washing, the CNT under vacuum condition after dry oxidation;
(2) CNT after oxidation is added to thionyl chloride and organic solvent, be heated to 70-80 DEG C of reaction 48-72h, after finishing, subtractPress distillation to remove unnecessary SOCl2, then add diamine, be heated to 75-80 DEG C of reaction 36-48h, with distilled water diluting, take outFilter, until filtrate is neutral, obtains aminated CNT, and vacuum drying is for subsequent use;
(3) by acetone backflow extracting post-drying for carbon fiber (CF), then add strong oxidizing acid, heating water bath is to 60-70 DEG C of oxidation2～6h, cleans repeatedly to neutral, dries, and obtains the carbon fiber of oxidation, and the carbon fiber of oxidation is added to SOCl2 and organic solvent,Heating water bath, to 70-80 DEG C of reaction 36-48h, takes out rear forced air drying, obtains the carbon fiber of chloride;
(4) by aminated carbon nanotube dispersed in organic solvent, after being uniformly dispersed, add the carbon fiber of chloride, 50-60 DEG C of perseveranceUnder tepidarium, react 60-72h, in course of reaction, every 1～3h, reaction solution is again shaken and point spread, to ensure aminated carbonNanotube is uniformly dispersed and can fully contacts with carbon fiber, removes fiber surface and have neither part nor lot in the amine of reaction after taking-up with acetone backflow extractingThe CNT of base, vacuum drying chamber is dry, obtains the carbon fiber of grafting carbon nanotube;
(5) half times of siloxanes POSS is placed in to organic solvent, adds the carbon fiber of grafting carbon nanotube, under 50-60 DEG C of water bath with thermostatic controlReaction 24h-36h, removes fiber surface and has neither part nor lot in the POSS molecule of reaction with acetone backflow extracting after taking-up, vacuum drying oven is dry,Obtain the carbon fiber of binary grafting POSS;
(6) the even mixed liquor of configuration epoxy resin and curing agent, after mixing the carbon fiber of binary grafting POSS and fully infiltrate with itBe placed in mould, mould is put on hot press and is solidified.
The described concentrated sulfuric acid and the red fuming nitric acid (RFNA) volume ratio of step in above-mentioned preparation method (1) is 3:1, the ratio of CNT and mixed acid solutionExample is 0.04-0.05g/ml. CNT is arc discharge, chemical gaseous phase deposition, template, solar energy method or laser evaporationIn any single armed of preparing or multi-walled carbon nano-tubes.
CNT in step (2) after oxidation and the ratio of thionyl chloride are 0.02-0.03g/ml, thionyl chloride, organic solvent,The volume ratio of diamine is 100:5:100, and described diamine is ethylenediamine, 1, and 2-propane diamine, 1 is chosen any one kind of them in 3-propane diamine.The ratio 3:100-150 of carbon fiber and strong oxidizing acid in step (3), g/ml; The volume ratio of thionyl chloride, organic solvent is100:5. The carbon fiber of oxidation and the ratio 3:100-200 of thionyl chloride, g/ml; Strong oxidizing acid be red fuming nitric acid (RFNA), the concentrated sulfuric acid,In hypochlorous acid, nitration mixture (red fuming nitric acid (RFNA) and the concentrated sulfuric acid), choose any one kind of them.
In step (4), aminated CNT and the carbon fiber of 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 concussion method, magnetic agitation method (need to hang processing to fiber)In choose any one kind of them.
The described organic solvent in above-mentioned steps (2)-(4) is any one in DMF, oxolane, acetone.Half times of siloxanes POSS, the carbon fiber of grafting carbon nanotube, the ratio 1:6-15:150-300 of organic solvent in step (5),G:g:ml; Described organic solvent is to choose any one kind of them in oxolane, acetone, benzinum.
The described epoxy resin of step (6) is to choose any one kind of them in epoxy resin E-51, epoxy resin E-44; Described curing agent is fragrance twoIn amine, methyl tetrahydrophthalic anhydride, imidazoles, choose any one kind of them. On described hot press, be cured as and rise to 90 DEG C when mold temperatureIn time, starts timing and observes glue state, insulation 10min-1h, when resin starts gel, be pressurized to 5MPa, after be warming up to 120 DEG C,Pressure increases to 10MPa, after insulation 2h, continues to be warming up to 150 DEG C, and pressure is constant, and insulation 4h keeps pressure to mold cools downTo room temperature, molding. Proper proportion described in step (6) is that epoxy resin, aromatic liquid diamines H-256 mass ratio are 100:(30～40); Epoxy resin, methyl tetrahydro phthalic anhydride and N, N-dimethyl benzylamine mass ratio is 100:(65～75): 1; EpoxyResin, imidazoles mass ratio are 100:6. Carbon fiber and epoxy resin mass ratio are (60-70): (30-40), and preferably 65:35.
Composite prepared by said method.
The present invention is at the CNTs of carbon fiber surface grafting one dimension, can realize carbon fiber surface Grafting Structure and grafting density controllability andOrder, then taking CF/CNTs composite reinforcement as basis, further grafting contain different activities end group POSS, form toolThere is different modulus gradient CF/CNTs/POSS bielement nano grafting reinforcement. CNTs and POSS are in the meeting of carbon fiber surface cograftImprove the surface topography of carbon fiber, and POSS is grafted to CNTs surface and forms " mace " shape, more can expand and treeThe contact area of fat matrix, is deep in resin matrix with holdfast effect, makes interface mechanical engagement effect stronger. Meanwhile, CNTsTo fiber surface, can improve the content of fiber surface activity atom with POSS chemical graft, can reduce between resin like thisContact angle, improve its wetting property, increase with resin matrix between secondary bond be combined (hydrogen bond, Van der Waals force etc.) act on.In addition, CNTs and POSS surface have neither part nor lot in reaction functional group can with resin reaction, increase with resin matrix form chemistryBond number amount. Thereby the bonding of carbon fiber and interlaminar resin is strengthened, and the comprehensive mechanical property of the composite 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, and any organic group can be connected to its surface by chemical reaction, and this pointSon customization is easy, controllability is strong, produces that the initial feed cost of POSS is relatively low and productive rate is very high, and this makes POSSCheap, can carry out large-scale business application, it is rigid inorganic nano core that POSS divides subcenter, around around reactingThe unique molecular structure of functional group has formed firmly chemistry and physical action at composite material interface simultaneously, makes boundary strength remarkableImprove, be better than common acid anhydrides molecule.
Brief description of the drawings
Fig. 1 is the flow chart of the carbon fiber surface chemical graft reaction of embodiment 1.
Fig. 2 is the SEM pattern of the carbon fiber surface in different disposal stage, b) except slurry CF, e) grafting CNTs, f) binary grafting POSS;
Fig. 3 is embodiment 1 different disposal stage carbon fibre composite interlaminar shear strength.
Fig. 4 is the SEM that surface that the present invention makes is connected to the carbon fibre composite interlayer shear fracture apperance of CNT/POSSFigure.
Detailed description of the invention
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 composite, comprises the following steps:
(1): take the round-bottomed flask that CNTs that 4g is dry is placed in, the volume ratio that adds the 100ml concentrated sulfuric acid and red fuming nitric acid (RFNA) is 3:1Mixed solution, stirring reaction 4h under 60 DEG C of waters bath with thermostatic control adds distilled water diluting in reacted solution, uses porous membraneIt is neutral that suction filtration to cleaning solution is, the CNTs after dry oxidation under vacuum condition at 100 DEG C;
(2): the CNTs after the oxidation that 2g step (1) is made, adds respectively 100mlSOCl2And 5mlN, N-dimethyl formylAmine (DMF) solution, is heated to 76 DEG C of reaction 72h, finishes rear decompression distillation and removes unnecessary SOCl2, add 100ml second twoAmine, is heated to 80 DEG C of reaction 48h, and with distilled water diluting, suction filtration, until filtrate is neutral, obtains aminated CNTs, 100 DEG CLower vacuum drying is for subsequent use;
(3): CF is placed in to apparatus,Soxhlet's, and acetone backflow extracting 72h under 75 DEG C of conditions, takes out and put into 100 DEG C of vacuum drying boxDry 4h, obtains except the CF after slurry. By being placed in round-bottomed flask except the CF after slurry, add 100ml red fuming nitric acid (RFNA), heating water bathTo 60 DEG C of oxidation 3h, reacted CF repeatedly to be cleaned to washing lotion and is neutral with distilled water, 100 DEG C of oven dry, obtain oxidationCF; In the CF (3g) of the oxidation of gained, add respectively 100mlSOCl2With 5mlDMF solution, heating water bath to 76 DEG CReaction 48h, takes out rear forced air drying, obtains the CF of chloride;
(4): take the aminated CNTs of 0.2g step (2) gained as in 100ml tetrahydrofuran THF solution, sonic oscillationWithin 15 minutes, obtain finely dispersed amidized CNTs solution, the CF of the chloride of 3g step (3) gained is put into this solutionIn, under 50 DEG C of waters bath with thermostatic control, react 72h, in course of reaction every 2h by reaction solution again have children outside the state plan vibration aminated to ensureCNTs is uniformly dispersed and can fully contacts with CF, after taking out, removes fiber surface not with being placed in apparatus,Soxhlet's acetone backflow extractingParticipate in the aminated CNTs of reaction, put into the dry 4h of 100 DEG C of vacuum drying box, obtain CF/CNTs;
(5): take 0.5gPOSS and be placed in 100mlTHF solution, the CF/CNTs of 3g step (4) gained is put into this solution,Under 50 DEG C of waters bath with thermostatic control, react 24h, after taking-up, remove fiber surface and have neither part nor lot in the POSS molecule of reaction with acetone backflow extracting,100 DEG C of dry 4h of vacuum drying oven, obtain CF/CNTs/POSS bielement nano grafting reinforcement;
(6): on the long instrument bezel of 200mm, be wound around the CF/CNTs/POSS of step (5) gained of the suitable number of turns, matrix resin is pressedThe ratio that epoxy resin, aromatic liquid diamines H-256 mass ratio are 100:32 mixes, and carbon fiber and matrix resin are pressedMass ratio 65:35 fully infiltrates and is placed in mould, and mould is put on hot press and is solidified by following technique. When mold temperature literDuring to 90 DEG C, start timing and observe glue state, insulation 30min left and right, is pressurized to 5MPa when epoxy resin starts gel, afterBe warming up to 120 DEG C, pressure increases to 10MPa, after insulation 2h, continues to be warming up to 150 DEG C, and pressure is constant, and insulation 4h, keepsPressure is to mold cools down to room temperature, and molding, obtains resin content and be controlled at the CF/CNTs/POSS enhancing in 35 ± 1.5% scopesEpoxy resin composite material.
In the present embodiment step (1), the specification of CNTs is TNM3, is that Chengdu organic chemistry Co., Ltd of the Chinese Academy of Sciences produces. ThisIn embodiment step (3), the specification of CF is 3K, is that charcoal fiber Co., Ltd of Jilin divine boat produces in the present embodiment step (6)The specification of POSS is pure for analyzing, and is that HybridPlastics 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 flow chart of the carbon fiber surface chemical graft reaction of embodiment 1.
Fig. 2 is the SEM pattern of the carbon fiber surface in different disposal stage, shows that carbon fiber/epoxy resin is multiple after grafting CNTs and POSSCondensation material has improved respectively 6.7% and 11.8% with the carbon fibre surface energy after grafting compared with slurry carbon fiber.
Fig. 3 is different disposal stage carbon fibre composite interlaminar shear strength, show carbon fiber after grafting CNTs and POSS/The interlaminar shear strength of epoxy resin composite material has promoted respectively 21.6% and 31.6% compared with removing slurry carbon fiber. Except the carbon after slurryFiber ILSS is lower, only has 65.99GPa. After oxidation, its ILSS brings up to 71.4GPa, and this is at fiber because of oxidationSurface Creation hydroxyl, carboxyl isoreactivity group, fiber wetness can be improved, and strong oxidizer has fiber surfaceCertain etching action, has increased the roughness of fiber surface, has improved the bond strength of fiber and resin. Carbon after chlorideFiber ILSS is 77.2GPa, and this is to have generated acid chloride groups because chloride acts on fiber surface, and thionyl chloride also canFiber surface produces etching action, and fiber surface activity number of functional groups is increased, and fiber surface roughness further increases, ILSSBe improved. After grafting CNTs, the ILSS of composite is 80.27GPa, has promoted 21.6% compared with blank sample, in conjunction withXPS elementary analysis is known, and after grafting CNTs, fiber surface contains a large amount of oxygen elements, shows that fiber surface still contains a large amount of containing oxygenFunctional group, has played certain effect to the bond strength that improves fiber and resin, and due to the introducing of CNTs, its surface is not in additionThe amino group of reaction can occur to be cross-linked with epoxy resin molecule, strengthens the chemical action at interface, and carbon fiber surface graftingCNTs is different in size, direction is different, and in the process of fiber and resin compounded, these CNTs can thrust resin matrix, energyNear enough its molecular resins that firmly locks, the motion of restriction interface zone molecule, forms powerful mechanical engagement, makes boundaryFace bond strength further strengthens. Composite ILSS through CNTs and the grafting of POSS binary further increases, and has reached86.84MPa, has improved 8.2% than the composite sample of simple CNTs grafting, has improved 31.6% than blank style. The twoCombination can better bring into play mechanical holdfast and chemical bond effect. POSS can with the sense on carbon fiber surface and CNTs surfaceGroup reacts, fiber surface after grafting POSS, and it is more coarse that CNTs surface becomes, and POSS molecule and accumulation body thereof increaseThe roughness of carbon fiber modifying surface, particulate can firmly lock near the molecular resin it, further limits interfaceThe motion of region molecule, forms powerful mechanical engagement, and boundary strength is significantly improved. Meanwhile, POSS side group contains a large amount ofEpoxide group, these epoxide groups can improve fiber surface can, improve the wellability of fiber and resin, make fiber surface andMatrix resin, in conjunction with tightr, has reduced the generation of boundary defect, can also generate chemical bond with matrix resin generation chemical reaction,Make to form between fiber surface and resin powerful chemical action.
Fig. 4 is the SEM figure of the surface carbon fibre composite interlayer shear fracture apperance that is connected to CNT/POSS.
Embodiment 2: the present embodiment adds 100ml1 in step (2) as different from Example 1, and 2-propane diamine carries out amine to CNTsBase processing, other step and parameter are identical with embodiment 1.
Embodiment 3: the present embodiment adds the 100ml concentrated sulfuric acid to carry out oxidation processes to CF in step (3) as different from Example 1,Other step and parameter are identical with embodiment 1.
Embodiment 4: the present embodiment as different from Example 1 middle magnetic agitation of step (4) obtains finely dispersed amino for 20 minutesChange CNTs solution, to CF hangs processing after put into this solution, under 50 DEG C of waters bath with thermostatic control, react 72h, course of reactionIn every 2h, reaction solution is stirred to ensure that aminated CNTs is uniformly dispersed can fully contact with CF again. Other stepAnd parameter is identical with embodiment 1.
Embodiment 5: the present embodiment is the middle epoxy resin of step (6), aromatic liquid diamines H-256 mass ratio as different from Example 1For the ratio of 100:35 mixes. Other step and parameter are identical with embodiment 1.
Embodiment 6: the present embodiment as different from Example 1 in step (6) matrix resin press epoxy resin, methyl tetrahydro phthalic anhydride andN, the ratio that N-dimethyl benzylamine mass ratio is 100:70:1 mixes, and carbon fiber and matrix resin are fully infiltrated and are placed onIn mould, mould is put on hot press and is solidified by following technique. In the time that mold temperature rises to 90 DEG C, start timing and observe glueState, between 10min-30min, is pressurized to 5MPa when epoxy resin starts gel, after insulation 2h, be warming up to 120 DEG C, pressesPower increases to 10MPa, insulation 2h after, continue to be warming up to 150 DEG C, pressure is constant, insulation 4h, keep pressure to mold cools down extremelyRoom temperature, molding, obtains resin content and is controlled at the CF/CNTs/POSS reinforced epoxy composite in 35 ± 1.5% scopes.Other step and parameter are identical with embodiment 1.
Embodiment 7: the present embodiment as different from Example 1 middle matrix resin of step (6) is 100 by epoxy resin, imidazoles mass ratio:6 ratio mixes, carbon fiber and matrix resin are fully infiltrated and are placed in mould, by mould be put on hot press by asLower technique is solidified. In the time that mold temperature rises to 50 DEG C, start timing and observe glue state when mold temperature rises to, insulation 30minLeft and right, is pressurized to 5MPa when epoxy resin starts gel, after be warming up to 100 DEG C, pressure increases to 10MPa, insulation 3h after, continueContinue and be warming up to 150 DEG C, pressure is constant, and insulation 4h keeps pressure to mold cools down to room temperature, and molding, obtains resin content controlCF/CNTs/POSS reinforced epoxy composite in 35 ± 1.5% scopes. Other step and parameter and embodiment 1Identical.
The above-mentioned description to embodiment understands and applies the invention for the ease of those skilled in the art. Be familiar with this areaTechnical staff obviously can easily make various amendments to these embodiment, and General Principle described herein is applied to itIn he embodiment and needn't pass through performing creative labour. Therefore, the invention is not restricted to the embodiment here, those skilled in the artAccording to announcement of the present invention, the improvement that the present invention is made and amendment all should be within protection scope of the present invention.
Claims (10)
1. a preparation method for multicomponent modified carbon fiber reinforced epoxy composite, is characterized in that, comprises that step is as follows:
(1) CNT is oxidized with strong acid;
(2) CNT after oxidation is successively carried out to chloride and aminated processing with thionyl chloride, diamine, introduce amido functional group;
(3) carbon fiber is oxidized with strong oxidizing acid, then uses thionyl chloride chloride processing, introduce acid chloride group;
(4) the carbon nano-tube modified and step (3) step (2) being made modifying carbon fibers mixed grafting react, the carbon fiber of CNT that obtained grafting;
(5) by grafting the carbon fiber of CNT react with half times of siloxanes POSS mixed grafting, obtain the carbon fiber of binary grafting POSS;
(6) carbon fiber of binary grafting POSS and matrix resin are fully infiltrated to after heat pressure curing molding; The ratio that described matrix resin is 100:32 in epoxy resin, aromatic liquid diamines H-256 mass ratio mixes, or the ratio that is 100:35 in epoxy resin, aromatic liquid diamines H-256 mass ratio mixes, or press epoxy resin, methyl tetrahydro phthalic anhydride and N, the ratio that N-dimethyl benzylamine mass ratio is 100:70:1 mixes, or the ratio that is 100:6 in epoxy resin, imidazoles mass ratio mixes.
2. the preparation method of multicomponent modified carbon fiber reinforced epoxy composite according to claim 1, is characterized in that, comprises that step is as follows:
(1) CNT is added to the mixed acid solution of the concentrated sulfuric acid and red fuming nitric acid (RFNA), stirring reaction 2～4h under 60～80 DEG C of waters bath with thermostatic control, filters, washing, the CNT under vacuum condition after dry oxidation;
(2) CNT after oxidation is added to thionyl chloride and organic solvent, be heated to 70-80 DEG C of reaction 48-72h, finish rear decompression distillation and remove unnecessary SOCl2, then add diamine, be heated to 70-80 DEG C of reaction 36-48h, with distilled water diluting, suction filtration, until filtrate is neutral, obtains aminated CNT, and vacuum drying is for subsequent use;
(3) by acetone backflow extracting post-drying for carbon fiber, then add strong oxidizing acid, heating water bath to 60 DEG C oxidation 2～6h, cleans repeatedly to neutral, and 100 DEG C of oven dry obtain the carbon fiber of oxidation, and the carbon fiber of oxidation is added to SOCl2And organic solvent, heating water bath, to 70-80 DEG C of reaction 36-48h, takes out rear forced air drying, obtains the carbon fiber of chloride;
(4) by aminated carbon nanotube dispersed in organic solvent, after being uniformly dispersed, add the carbon fiber of chloride, under 50-60 DEG C of water bath with thermostatic control, react 60-72h, in course of reaction, every 1～3h, reaction solution is again shaken and point spread, to ensure that aminated carbon nanotube dispersed evenly can fully contact with carbon fiber, the aminated CNT of removing fiber surface and have neither part nor lot in reaction after taking-up with acetone backflow extracting, vacuum drying chamber is dry, obtains the carbon fiber of grafting carbon nanotube;
(5) half times of siloxanes POSS is placed in to organic solvent, add the carbon fiber of grafting carbon nanotube, under 50-60 DEG C of water bath with thermostatic control, react 24h-36h, after taking-up, remove fiber surface and have neither part nor lot in the POSS molecule of reaction with acetone backflow extracting, vacuum drying oven is dry, obtains the carbon fiber of binary grafting POSS;
(6) the even mixed liquor of configuration epoxy resin and curing agent, mixes the carbon fiber of binary grafting POSS fully to infiltrate being placed in mould with it, and mould is put on hot press and is solidified.
3. the preparation method of multicomponent modified carbon fiber reinforced epoxy composite according to claim 2, it is characterized in that, the described concentrated sulfuric acid and the red fuming nitric acid (RFNA) volume ratio of step (1) is 3:1, and the ratio of CNT and mixed acid solution is 0.04-0.05g/mL.
4. the preparation method of multicomponent modified carbon fiber reinforced epoxy composite according to claim 2, it is characterized in that, the ratio 3:100g/mL of carbon fiber and strong oxidizing acid in step (3), the volume ratio of thionyl chloride, organic solvent is 100:5, the carbon fiber of oxidation and the ratio 3:100g/mL of thionyl chloride.
5. the preparation method of multicomponent modified carbon fiber reinforced epoxy composite according to claim 2, it is characterized in that, in step (4), aminated CNT and the carbon fiber of chloride, the ratio of organic solvent are 1:6-15:150-300g:g:mL.
6. the preparation method of multicomponent modified carbon fiber reinforced epoxy composite according to claim 2, is characterized in that, described strong oxidizing acid is choosing any one kind of them in the nitration mixture of red fuming nitric acid (RFNA), the concentrated sulfuric acid, hypochlorous acid, red fuming nitric acid (RFNA) and the concentrated sulfuric acid.
7. the preparation method of multicomponent modified carbon fiber reinforced epoxy composite according to claim 2, it is characterized in that, half times of siloxanes POSS, the carbon fiber of grafting carbon nanotube, the ratio 1:6-15:150-300g:g:mL of organic solvent in step (5), described organic solvent is to choose any one kind of them in oxolane, acetone, benzinum.
8. the preparation method of multicomponent modified carbon fiber reinforced epoxy composite according to claim 2, is characterized in that, the described epoxy resin of step (6) is to choose any one kind of them in epoxy resin E-51, epoxy resin E-44.
9. the preparation method of multicomponent modified carbon fiber reinforced epoxy composite according to claim 2, is characterized in that, concrete steps curing on described hot press are: in the time that mold temperature rises to 90 DEG C, start timing and observe glue state, insulation 10min-1h, when resin starts gel, be pressurized to 5MPa, 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. the composite that prepared by the method described in claim 1 or 2.
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| CN102140230A (en) * | 2011-01-12 | 2011-08-03 | 同济大学 | Preparation method of composite material consisting of carbon nanotube and functional carbon fiber-reinforced epoxy resin |
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