CN101407620B - High performance epoxy resins composite material and preparation thereof - Google Patents
High performance epoxy resins composite material and preparation thereof Download PDFInfo
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- CN101407620B CN101407620B CN2007100469620A CN200710046962A CN101407620B CN 101407620 B CN101407620 B CN 101407620B CN 2007100469620 A CN2007100469620 A CN 2007100469620A CN 200710046962 A CN200710046962 A CN 200710046962A CN 101407620 B CN101407620 B CN 101407620B
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Abstract
The invention belongs to the technical field of nano materials, and particularly relates to a high-performance epoxide resin composite material and a preparation method. Carboxylic acid, chloroformylation, amination or hydroxylation are carried out to the carbon nano tube; and the carbon nano tube is modified by small molecular aromatic polyanhydride compound so as to prepare the carbon nano tube which carries acid anhydride group. The carbon nano tube is dispersed in epoxide resin substrate by ultrasonic oscillation and high-speed stirring, is cured by adopting organic acid anhydride curing agent so as to obtain the carbon nano tube/epoxide resin composite material. The invention leads the preparation of the carbon nano tube/epoxide resin composite material to be more convenient, the activity of taking part in reaction of the carbon nano tube is endowed, and acid anhydride group of the carbon nano tube and the epoxide resin group of the epoxide resin generate chemical cross linking, thus improving the dispersion of the carbon nano tube in the epoxide resin and obtaining high-performance epoxide resin composite material. Compared with the control sample, all the mechanical performance indexes of the cured composite material are improved by 5 percent to 300 percent and the volume resistivity is reduced by 3 to 9 order of magnitude.
Description
Technical field
The invention belongs to technical field of nano material, be specifically related to the technology of preparing of carbon nano tube compound material, be meant a kind of preparation method of the carbon nano tube/epoxy resin matrix material as usefulness such as surface tissue material, coating or tackiness agents.
Background technology
Since Iijima in 1991 found carbon nanotube, just because of its particular structure, good electrical properties and mechanical property were the focuses of Recent study to carbon nanotube.Carbon nanotube has nanometer grade diameter micron order length, and length-to-diameter ratio can reach 100～1000, and intensity is high, has the ideal Young's modulus, is a kind of perfect filamentary material, and its performance is better than current any fiber.Therefore can be used as super fiber, be used for the enhancing body of advanced composite materials; Because carbon nanotube combines the quantum rule of the semi-metal character of graphite and energy level and electronic wave, and has nano level yardstick, makes it also boundless in the application prospect of person in electronics; The huge specific surface area of carbon nanotube and the adsorbable a large amount of hydrogen of the pore texture that has, so carbon nanotube has also become the focus of research as best hydrogen storage material; Owing to the vestibule structure and the absorption property of carbon nanotube uniqueness, therefore can be used as the carrier of catalyzer, the katalysis that improves catalyzer has to greatest extent also shown good prospects for application aspect catalysis.
The carbon nano tube/epoxy resin matrix material is the heterogeneous system that Resins, epoxy and carbon nanotube are composited.Performance such as its adhesive property that Resins, epoxy is good, erosion resistance, dielectric properties, solidified after-product cure shrinkage are low, combine with characteristics such as the high-modulus of carbon nanotube, low density, heat-conductivity conductings, by rational coupling and synergy, show the performance more excellent than pure epoxy resin cured article.Utilize compound various materials, the Application Areas of having extended carbon nanotube greatly of preparing of carbon nanotube and polymkeric substance.
Yet the carbon nanotube geometry is regular, stable in properties, and surface energy is big, has very strong self aggregation tendency.If the scattering problem of carbon nanotube in macromolecule resin can not solve, its modified effect to resin will be influenced greatly.At present, external existing many about improve the report of Resins, epoxy performance with carbon nanotube.Made the carbon nano tube/epoxy resin matrix material as Allaoui J, Schadler, Breton etc. with blending method, find to add the mechanical property that carbon nanotube can improve matrix, but because the dispersion problem of carbon nanotube fails better to be solved, cause the increase rate of mechanical property of matrix material little, even decrease.
Summary of the invention
It is inhomogeneous to exist carbon nanotube to disperse in body material in the prior art, carbon nano tube modified and the not strong problem of body material interface interaction.The object of the invention is to provide the preparation method of simple relatively, easy to operate, the capable of being industrialized carbon nano tube/epoxy resin matrix material of a kind of technology, and the high performance composite that obtain of this method.
A kind of preparation method of high-performance epoxy resin composite material is characterized in that: this preparation method mainly is at first with carbon nanotube carboxylic acidization, chloride, amination or hydroxylation, again by the compound-modified carbon nanotube of small molecules aromatic series multi-anhydride.By suitable ultra-sonic oscillation and high-speed stirring, carbon nanotube is scattered in the epoxy resin-base, adopt acid anhydride type curing agent to solidify, obtain high-performance carbon nanotube/epoxy resin composite material.Its concrete steps comprise:
Step 1: the carboxylic acidization of carbon nanotube
Add carbon nanometer tube material in the mixed strong acids solution of the 50ml vitriol oil and concentrated nitric acid (volume ratio is 3: 1) composition with 0.1～100 weight part, sonic oscillation was handled 3～12 hours, poured in the deionized water, with the filter membrane suction filtration, repetitive scrubbing is repeatedly to neutrality, vacuum-drying.Again above-mentioned product is placed H
2SO
4With H
2O
2Mixing solutions (98%H
2SO
4: 30%H
2O
2=4: 1) in 70 ℃ of following backflow 2h.Be the inclined to one side fluorine membrane filtration of 0.45 μ m with the aperture then, be washed to pH and be neutral.Product places vacuum drying oven, obtains carboxylic acidifying carbon nanotube after the vacuum-drying.
Step 2: the chloride of carbon nanotube
Learn from else's experience above-mentioned acidifying carbon nanotube 1 weight part and low molecule chloride reagent 1～100 weight part, 20～160 ℃ of following stirring and refluxing 5～100h.Filter and remove unreacted chloride reagent, obtain the carbon nanotube of chloride with the polar organic solvent repetitive scrubbing.
Step 3: the hydroxylation of carbon nanotube or amination
Chloride carbon nanotube 1 weight part and diamine or polyamine or dibasic alcohol or polyvalent alcohol 1～50 weight part are mixed, 50～150 ℃ of following oil bath mechanical stirring, 12～96h refluxes, with unreacted small molecule amine of polar organic solvent flush away or alcohol, 40～80 ℃ of following vacuum-drying 3～12 hours obtains ammonification or hydroxylation carbon nanotube.
Wherein diamine or polyamine or dibasic alcohol or polyvalent alcohol comprise C
2-C
6Diamine or C
2-C
6Dibasic alcohol or C
2-C
6Polyamine or C
2-C
6Polyvalent alcohol; Specifically comprise: quadrol, propylene diamine, hexanediamine, ethylene glycol, hexylene glycol, butyleneglycol, pentanediol, glycerol, tetramethylolmethane.
Step 4: the compound-modified carbon nanotube of aromatic series multi-anhydride
With the above-mentioned amination of 1 weight part or the hydroxylation carbon nanotube aromatic anhydride compound of agitation and dropping 1～100 weight part at a slow speed in the polar organic solvent ice bath, being warming up to 100～150 ℃ after dropwising refluxed 3～12 hours, with the unreacted aromatic anhydride compound of polar organic solvent flush away, 40～80 ℃ of following vacuum-drying 3～12 hours obtains having the carbon nanotube of anhydride group.
Step 5: curing reaction
The carbon nanotube that will have anhydride group joins 10～1000 weight part Resins, epoxy to be mixed, at 60～100 ℃, ultrasonic dispersing 1～12 hour, add organic acid anhydride class solidifying agent, above curing system is poured in the mould, vacuum condition removes bubble down, at 100～250 ℃ of following curing moldings, obtains epoxy resin composite material.
Described carbon nanotube is meant single wall, double-walled and the multi-walled carbon nano-tubes of catalytic pyrolysis, arc-over, template and the preparation of laser evaporation method, wherein one or more.
Described Resins, epoxy is liquid bisphenol A type, and oxirane value 0.37-0.55eq/100g, the trade mark comprise E-54 (616), E-51 (618), E-52-D, E-44 (6101), E-45, E-42 (634), E-39-D.
React used polar solvent and be meant ethanol or methyl alcohol or acetone or N, dinethylformamide and composition thereof.
Described chloride reagent is meant thionyl chloride or oxalyl chloride.
Described aromatic anhydride compound is meant pyromellitic acid anhydride (PDMA), the affixture of pyromellitic acid anhydride and caprolactone, benzophenone tetracarboxylic dianhydride, the affixture of benzophenone tetracarboxylic dianhydride and caprolactone, N, N '-dicarboxylic anhydride ditan, one or more in mellitic acid three acid anhydrides.
Described organic acid anhydride class solidifying agent comprises Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl carbic anhydride, dodecyl succinic anhydride, chlorendic anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic dianhydride, tetrahydrotoluene tetracarboxylic dianhydride, phenyl ether tetracarboxylic dianhydride, trimellitic acid 1,2-anhydride, poly-nonane diacid acid anhydride.
The compound-modified used polar organic solvent of described anhydrides is meant one or more in methyl-sulphoxide, tetrahydrofuran (THF), the methyl alcohol.
The carbon nano tube/epoxy resin matrix material for preparing of method as mentioned above, the carbon nano-tube modified 0.2-1wt% that accounts for total amount in this matrix material.
The present invention compared with prior art has following outstanding advantage:
1, the present invention is by the compound-modified carbon nanotube of small molecules aromatic anhydride, avidity between the destroying carbon nanometer tube and self aggregation tendency, not only help carbon nanotube and in macromolecule resin, disperse, make the preparation of carbon nano tube/epoxy resin matrix material more convenient; More give carbon nanotube and participate in reactive activity.Carbon nano tube modified and same composition, the epoxy resin cured product that does not add carbon nanotube are compared, and the every mechanical performance index that solidifies the back matrix material improves 5%～300%, and volume specific resistance reduces by 3～9 orders of magnitude.Relative forefathers' method, technology of the present invention is simple, has more practicality.
2, the carbon nano tube/epoxy resin matrix material compound word material of the present invention's preparation can be applicable to prepare device housings, coating or the tackiness agent in fields such as electrical equipment motor, chemical machinery.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.Carbon nanotube used among the embodiment is all available from the organic institute in Chinese Academy of Sciences Chengdu.Resins, epoxy is available from Xinhua Resin Factory, Shanghai.
Embodiment 1:
The first step: with the average caliber of 500mg is 8～15nm, the multi-walled carbon nano-tubes of length 50 μ m and 150ml H
2SO
4With HNO
3Mixing solutions (98%H
2SO
4: 68%HNO
3=3: 1) mix, back flow reaction is 4 hours under 35～40 ℃ and ultra-sonic oscillation condition.Be the inclined to one side fluorine membrane filtration of 0.45 μ m with the aperture then, be washed to pH and be neutral.Product places vacuum drying oven, 40 ℃ of following vacuum-drying 24h.Again an above-mentioned step acidifying and the product through cleaning are placed H
2SO
4With H
2O
2Mixing solutions (98%H
2SO
4: 30%H
2O
2=4: 1) in 70 ℃ of following backflow 2h.Be the inclined to one side fluorine membrane filtration of 0.45 μ m with the aperture then, be washed to pH and be neutral.Product places vacuum drying oven, 40 ℃ of following vacuum-drying 24h.
Second step: get above-mentioned acidifying carbon nanotube 400mg and place reaction flask, add 20ml SOCl
2With 1ml DMF, 70 ℃ of following stirring and refluxing 24h.Filter and wash to being neutral with tetrahydrofuran (THF).Obtain the carbon nanotube of chloride.
The 3rd step: chloride carbon nanotube 0.2g and quadrol 30g are mixed, at 96 ℃ of oil bath reflux 36h.After reaction is finished,, filter with millipore filtration (diameter is 0.45 μ m) with the ultrasonic flush away of dehydrated alcohol unnecessary amine, repeated washing several times, vacuum-drying obtains the carbon nanotube that the surface has amino.400mg amino-carbon nanotube is dissolved in the dimethyl sulfoxide (DMSO), and ultrasonic concussion 30min adds the 4g pyromellitic acid anhydride; add catalyzer vitriol oil 1ml, stir under 90 ℃ nitrogen protection; magnetic agitation, the reaction times is 48h, obtains the carbon nanotube that anhydride group is contained on the surface.
The 4th step: get 60 ℃ of following preheatings of 30g E-51 type Resins, epoxy.According to the 1wt% of the total amount carbon nanotube 0.3g that pyromellitic acid anhydride modifies that learns from else's experience, add in the Resins, epoxy of preheating, the powerful 8h that stirs, ultrasonic dispersing 4h mixes.Add 16g solidifying agent Tetra hydro Phthalic anhydride, mechanical stirring is even; Place 50 ℃ of following vacuum stripping bubbles of vacuum drying oven, cast, 200 ℃ solidified 1 hour, and the demoulding gets epoxy resin composite material.
Embodiment 2:
In first and second step, prepare the chloride carbon nanotube by embodiment 1 described method.
The 3rd step: chloride carbon nanotube 0.2g and ethylene glycol 30g are mixed, at 96 ℃ of oil bath reflux 36h.After reaction is finished, filter with millipore filtration (diameter is 0.45 μ m), vacuum-drying obtains the carbon nanotube that the surface has hydroxyl.400mg hydroxyl carbon nanotube is dissolved in the dimethyl sulfoxide (DMSO), and ultrasonic concussion 30min adds 4g benzophenone tetracarboxylic dianhydride; add catalyzer vitriol oil 1ml, stir under 90 ℃ nitrogen protection; magnetic agitation, the reaction times is 48 hours, obtains the carbon nanotube that anhydride group is contained on the surface.
The 4th step: get 60 ℃ of following preheatings of 30g E-51 type Resins, epoxy.According to the 1wt% of the total amount carbon nanotube 0.3g that the benzophenone tetracarboxylic dianhydride modifies that learns from else's experience, add in the Resins, epoxy of preheating, the powerful 8h that stirs, ultrasonic dispersing 4h mixes.Add 16g solidifying agent Tetra hydro Phthalic anhydride, mechanical stirring is even; Place vacuum drying oven vacuum stripping bubble, cast, 200 ℃ solidified 1 hour, and the demoulding gets epoxy resin composite material.
Embodiment 3:
In first to three step, press the carbon nanotube that embodiment 1 described method preparation is modified through pyromellitic acid anhydride.
The 4th step: get 60 ℃ of following preheatings of 30g E-51 type Resins, epoxy.According to 1% of the total amount carbon nanotube 0.3g that pyromellitic acid anhydride modifies that learns from else's experience, add in the Resins, epoxy of preheating, the powerful 8h that stirs, ultrasonic dispersing 4h mixes.Add 16g solidifying agent phenyl ether tetracarboxylic dianhydride, mechanical stirring is even; Place vacuum drying oven vacuum stripping bubble, cast, 200 ℃ solidified 1 hour, and the demoulding gets epoxy resin composite material.
Comparative example 1:
Get 60 ℃ of preheatings of 30g E-51 type Resins, epoxy, add 16g solidifying agent Tetra hydro Phthalic anhydride, mechanical stirring is even; Place vacuum drying oven vacuum stripping bubble back cast, condition of cure be 150 ℃ following 1 hour, the demoulding, epoxide resin material.
Comparative example 2:
Get 60 ℃ of preheatings of 30g E-51 type Resins, epoxy.Take by weighing the carbon nanotube 0.3g of purifying according to 1% of total amount, add in the Resins, epoxy of preheating, the powerful 8h that stirs, ultrasonic dispersing 4h mixes; Add 16g solidifying agent tetrahydrotoluene tetracarboxylic dianhydride, mechanical stirring is even; Place vacuum drying oven vacuum stripping bubble back cast cured explosive, condition of cure is 150 ℃ of following 1h, and the demoulding gets epoxy resin composite material.
Embodiment 4:
In first to three step, press the carbon nanotube that embodiment 1 described method preparation is modified through pyromellitic acid anhydride.
The 4th step: get 60 ℃ of following preheatings of 30g E-54 type Resins, epoxy.According to 1% of the total amount carbon nanotube 0.3g that pyromellitic acid anhydride modifies that learns from else's experience, add in the Resins, epoxy of preheating, the powerful 8h that stirs, ultrasonic dispersing 4h mixes.Add 16.96g solidifying agent phenyl ether tetracarboxylic dianhydride, mechanical stirring is even; Place vacuum drying oven vacuum stripping bubble, cast, 200 ℃ solidified 1 hour, and the demoulding gets epoxy resin composite material.
Embodiment 5:
In first to three step, press the carbon nanotube that embodiment 2 described method preparations are modified through the benzophenone tetracarboxylic dianhydride.
The 4th step: get 60 ℃ of following preheatings of 30g E-44 type Resins, epoxy.According to 1% of the total amount carbon nanotube 0.3g that the benzophenone tetracarboxylic dianhydride modifies that learns from else's experience, add in the Resins, epoxy of preheating, the powerful 8h that stirs, ultrasonic dispersing 4h mixes.Add 36.48g solidifying agent trimellitic acid 1,2-anhydride, mechanical stirring is even; Place vacuum drying oven vacuum stripping bubble, cast, 200 ℃ solidified 1 hour, and the demoulding gets epoxy resin composite material.
Embodiment 6:
In first and second step, prepare the chloride carbon nanotube by embodiment 1 described method.
The 3rd step: chloride carbon nanotube 0.2g and hexanediamine 30g are mixed, at 96 ℃ of oil bath reflux 36h.After reaction is finished, with the unnecessary amine of dehydrated alcohol flush away, filter with millipore filtration (diameter is 0.45 μ m), vacuum-drying obtains the surface and has amino carbon nanotube.400mg hydroxyl carbon nanotube is dissolved in the dimethyl sulfoxide (DMSO), and ultrasonic concussion 30min adds 4g six phenylformic acid three acid anhydrides; add catalyzer vitriol oil 1ml, stir under 90 ℃ nitrogen protection; magnetic agitation, the reaction times is 48 hours, obtains the carbon nanotube that anhydride group is contained on the surface.
The 4th step: get 60 ℃ of following preheatings of 30g E-39-D type Resins, epoxy.According to the 1wt% of the total amount carbon nanotube 0.3g that the benzophenone tetracarboxylic dianhydride modifies that learns from else's experience, add in the Resins, epoxy of preheating, the powerful 8h that stirs, ultrasonic dispersing 4h mixes.Add 23.68g solidifying agent trimellitic acid 1,2-anhydride, mechanical stirring is even; Place vacuum drying oven vacuum stripping bubble, cast, 200 ℃ solidified 1 hour, and the demoulding gets epoxy resin composite material.
Subordinate list 1: the mechanical property of above-mentioned all kinds of epoxide resin materials relatively.
| Mechanical performance index | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 |
| Shock strength (J/m 2)? | 50.85? | 53.52? | 65.36? | 14.50? | 45.80? |
| Tensile strength (Mpa) | 78.52? | 80.68? | 83.23? | 56.80? | 68.42? |
| Elongation at break (%) | 12.62? | 13.60? | 15.24? | 3.15? | 6.93? |
| Flexural strength (Mpa) | 118.36? | 126.34? | 130.50? | 90.45? | 95.32? |
(1) tensile property:, adopt DXLL-5000 type microcomputer control universal testing machine (going up the outstanding plant and instrument of Heiden company limited) to measure according to GB/T1040-92 " plastic tensile method for testing performance ";
(2) bending property:, adopt DXLL-5000 type microcomputer control universal testing machine (going up the outstanding plant and instrument of Heiden company limited) to measure according to GB9341-88 " plastics bending property test method ";
(3) impact property:, adopt CharpyXCJ-50 simply supported beam impact experiment instrument (Chengde trier factory) to measure according to GB1043-93 " plastic impact method for testing performance ".
Subordinate list 2: the electric property of above-mentioned all kinds of epoxide resin materials relatively.
| The electric property index | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 |
| Volume specific resistance (Ω cm) | 3.5×10 7 | ?7.4×10 8 | ?6.2×10 8 | ?5.1×10 15 | ?3.7×10 11 |
| Surface resistivity (Ω) | 4.2×10 8 | ?2.6×10 9 | ?3.9×10 9 | ?3.5×10 15 | ?7.3×10 12 |
According to standard GB/T15662 " conduction, antistatic plastic volume specific resistance testing method ", adopt four electrode method to measure the volume specific resistance and the surface resistivity of sample.
Electrostatic voltmeter EST103:100mV～± 200V, input resistance 〉=10
14Ω (100T Ω), the Beijing City Inst. of Labour Safety Science;
Skin peace reometer EST122:1 * 10
-15A, 0.5%, the Beijing City Inst. of Labour Safety Science;
Numeral variable voltage source WYJ0-25A: 0-30V is adjustable in single channel output, and 0.5%, the outstanding Electrical Appliances Co., Ltd of last seamount;
Test shielded cell and self-control copper electrode anchor clamps;
Insulcrete 〉=100T Ω .m (10
14Ω .m).
By above-mentioned table data as seen, and to comparing in the same old way, the every mechanical performance index that solidifies the back matrix material improves 5%～300%, and volume specific resistance reduces by 3～9 orders of magnitude.
Claims (12)
1. the preparation method of high-performance epoxy resin composite material is characterized in that: at first carbon nanotube is carried out carboxylic acidization, chloride, amination or hydroxylation successively; Again by the compound-modified carbon nanotube of aromatic series multi-anhydride; By ultra-sonic oscillation and high-speed stirring, carbon nanotube is scattered in the epoxy resin-base then, adopts acid anhydride type curing agent to solidify, obtain the carbon nano tube/epoxy resin matrix material.
2. the method for claim 1 is characterized in that concrete steps comprise:
(1) carboxylic acidization of carbon nanotube;
(2) chloride of carbon nanotube;
(3) hydroxylation of carbon nanotube or amination;
(4) the compound-modified carbon nanotube of aromatic series multi-anhydride:
With the above-mentioned amination of 1 weight part or the hydroxylation carbon nanotube aromatic anhydride compound of agitation and dropping 1～100 weight part at a slow speed in the polar organic solvent ice bath, being warming up to 100～150 ℃ after dropwising refluxed 3～12 hours, with the unreacted aromatic anhydride compound of polar organic solvent flush away, 40～80 ℃ of following vacuum-drying 3～12 hours obtains having the carbon nanotube of anhydride group;
(5) curing reaction
1 part of carbon nanotube that has anhydride group is joined the mixing of 80-100 weight part Resins, epoxy, at 60～100 ℃, ultrasonic dispersing 1～12 hour, add 40-50 weight part organic acid anhydride class solidifying agent, above curing system is poured in the mould, vacuum condition removes bubble down, at 100～250 ℃ of following curing moldings, obtains epoxy resin composite material.
3. method according to claim 2, it is characterized in that: the hydroxylation or the amination process of step (3) carbon nanotube specifically comprise: chloride carbon nanotube 1 weight part and diamine or polyamine or dibasic alcohol or polyvalent alcohol 1～50 weight part are mixed, stir down at 50～150 ℃, 12～96h refluxes, with unreacted small molecule amine of polar organic solvent flush away or alcohol, 40～80 ℃ of following vacuum-drying 3～12 hours obtains ammonification or hydroxylation carbon nanotube;
Wherein diamine or polyamine or dibasic alcohol or polyvalent alcohol comprise: C
2-C
6Diamine or C
2-C
6Dibasic alcohol or C
2-C
6Polyamine or C
2-C
6Polyvalent alcohol.
4. preparation method according to claim 1 and 2, it is characterized in that: described carbon nanotube comprises single wall, double-walled and the multi-walled carbon nano-tubes of catalytic pyrolysis, arc-over, template and the preparation of laser evaporation method, one or more of above-mentioned carbon nanotube.
5. preparation method according to claim 2 is characterized in that: Resins, epoxy is liquid bisphenol A type described in step (5) curing reaction, oxirane value 0.37-0.55eq/100g.
6. preparation method according to claim 2 is characterized in that: react used polar organic solvent and comprise ethanol, methyl alcohol, acetone, N, dinethylformamide, wherein a kind of or mixture.
7. preparation method according to claim 2 is characterized in that: thionyl chloride or oxalyl chloride are adopted in the chloride of described carbon nanotube.
8. preparation method according to claim 2, it is characterized in that: the described aromatic anhydride compound of step (4) comprises affixture, the N of affixture, benzophenone tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride and the caprolactone of pyromellitic acid anhydride PDMA, pyromellitic acid anhydride and caprolactone, one or more in N '-dicarboxylic anhydride ditan, mellitic acid three acid anhydrides.
9. preparation method according to claim 2 is characterized in that: the described organic acid anhydride class of step (5) solidifying agent comprises in Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl carbic anhydride, dodecyl succinic anhydride, chlorendic anhydride, pyromellitic acid anhydride, benzophenone tetracarboxylic dianhydride, tetrahydrotoluene tetracarboxylic dianhydride, phenyl ether tetracarboxylic dianhydride, trimellitic acid 1,2-anhydride, the poly-nonane diacid acid anhydride one or more mixture.
10. preparation method according to claim 2 is characterized in that: the compound-modified used polar organic solvent of the described anhydrides of step (4) comprises one or more in methyl-sulphoxide, tetrahydrofuran (THF), the methyl alcohol.
11. preparation method according to claim 3 is characterized in that: described diamine or polyamine or dibasic alcohol or polyvalent alcohol specifically comprise: quadrol, propylene diamine, hexanediamine, ethylene glycol, hexylene glycol, butyleneglycol, pentanediol, glycerol, tetramethylolmethane.
12. the carbon nano tube/epoxy resin matrix material that the described method of claim 1-2 prepares is characterised in that the carbon nano-tube modified 0.2-1wt% that accounts for total amount in this matrix material.
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