CN103602065B - The method for making of a kind of reduced graphene and polyimide nano-composite material - Google Patents
The method for making of a kind of reduced graphene and polyimide nano-composite material Download PDFInfo
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- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
The preparation method of reduced graphene and polyimide nano-composite material adopts a solution mixing method, first by graphene oxide ultrasonic disperse in deionized water, prepares high dispersing and stable graphene oxide waterborne suspension; Then the polyamic acid solution after neutralization is directly mixed with this graphene oxide waterborne suspension, realize the high dispersing of graphene oxide in polyamic acid; Finally by the synchronous thermal reduction graphene oxide of hot imidization, prepare reduced graphene and polyimide nano-composite material.The present invention has reduced graphene good dispersity, the advantage of Heat stability is good.
Description
Technical field
The invention belongs to a kind of nano composite material, be specifically related to the preparation method of a kind of reduced graphene and polyimide nano-composite material.
Background technology
Polyimide has high-temperature resistant grade, strong mechanical performance and outstanding chemical stability, is widely used in the fields such as aerospace, electron device and automotive industry.But along with the development of modern civilization, the requirement of every profession and trade to polyimide performance improves constantly, and simple polyimide resin cannot meet the application demand of people.Under this background, nano-material modified polyimide resin, i.e. polyimide nano-composite material, come into the sight line of people gradually, becomes the reliable method improving and expand polyimide performance.
Graphene is a kind of new carbon of monatomic thickness, because of mechanics, electricity and thermal property that its large specific surface sum is outstanding, becomes one of strongthener of most magnetism in current nano composite material.For reducing the production cost of graphene nanocomposite material, the common method of adding Graphene at present in resin first adds the graphene oxide of low cost, then in resin, obtain reduced graphene by the mode of chemical reduction or thermal reduction.Different graphene oxide addition meanss, directly affects the degree of scatter of final reduced graphene in matrix resin, and the overall performance of nano composite material.Situ aggregation method is the common method preparing reduced graphene/polyimide nano-composite material, the method utilizes graphene oxide in polar solvent, have certain dispersed feature, graphene oxide is first distributed in solvent, again diamines and dianhydride monomer are joined in solvent and be polymerized, final at hot imidization stage synchronous thermal reduction graphene oxide, obtain reduced graphene/polyimide nano-composite material.But the dispersion stabilization of graphene oxide in polar organic solvent is poor, in polymerization process, there is graphene oxide agglomeration again, limit the degree of scatter of final Graphene in polyimide matrix.In addition, the method (as: CN20110100930) of chemical modification graphene oxide, obviously can increase the dispersion stabilization of graphene oxide in polar solvent, but the various modifying agent temperature tolerances adopted are starkly lower than polyimide itself, there is disadvantageous effect to the heat resistance of matrix material.
Summary of the invention
For the shortcoming of existing Graphene and polyimide nano-composite material, the invention provides a kind of reduced graphene good dispersity, the reduced graphene of Heat stability is good and the preparation method of polyimide nano-composite material.
Preparation method of the present invention adopts solution mixing method, first, by graphene oxide ultrasonic disperse in deionized water, prepares high dispersing and stable graphene oxide waterborne suspension; Then, the polyamic acid solution after neutralization is directly mixed with this graphene oxide waterborne suspension, realizes the high dispersing of graphene oxide in polyamic acid; Finally, by the synchronous thermal reduction graphene oxide of hot imidization, reduced graphene and polyimide nano-composite material is prepared.
Preparation method of the present invention realizes particular by following steps:
(1) join in deionized water by graphene oxide, utilize ultra-sonic generator ultrasonic disperse 60 ~ 180min under ultrasonic power 100 ~ 150W and room temperature, preparation concentration is the water-based graphene oxide dispersion of 0.5 ~ 5mg/ml;
(2) by dianhydride and diamines equimolar ratio, dianhydride and diamines are joined in solvent, make dianhydride and dianhydride quality sum in the solution massfraction be 11% ~ 24%, stirring reaction 2 ~ 24h under 0 ~ 25 DEG C of condition with protection of inert gas, obtain polyamic acid solution, the neutralization reagent that mole number is 2.2 ~ 2.4 times of diamines is added in this solution, continue reaction 0.5 ~ 2h, obtain hydrophilic polyamide acid solution, then, under the condition stirred, the water-based graphene oxide dispersion of preparation in step (1) is added in this hydrophilic polyamide acid solution, control the add-on of water-based graphene oxide dispersion, the mass ratio of graphene oxide addition and dianhydride and diamines total amount is made to be 1:50 ~ 200, then 30 ~ 60min is stirred, obtain graphene oxide polyamic acid solution,
(3) by graphene oxide polyamic acid solution vacuum drying under 60 ~ 80 DEG C of conditions, graphene oxide and polyamic acid matrix material is obtained;
(4) under protection of inert gas; by graphene oxide and polyamic acid matrix material; hot imidization and graphene oxide thermal reduction is carried out: 100 DEG C of constant temperature 0.5 ~ 2h according to following heating schedule; 150 DEG C of constant temperature 0.5 ~ 2h; 200 DEG C of constant temperature 0.5 ~ 2h, 250 DEG C of constant temperature 0.5 ~ 2h, 300 DEG C of constant temperature 0.5 ~ 2h; constant temperature terminates rear naturally cooling, obtains reduced graphene and polyimide nano-composite material.
Described dianhydride can be bisphenol A-type dianhydride, pyromellitic acid anhydride, 3,3', 4,4'-bibenzene tetracarboxylic dianhydrides, 2,3,3', 4-bibenzene tetracarboxylic dianhydrides, 3,3', 4,4'-phenyl ether tetracarboxylic dianhydride or 3,3', 4,4'-benzophenone tetracarboxylic dianhydride.
Described diamines can be 4,4'-diaminodiphenyl oxide, 3,4'-diaminodiphenyl oxides, 3,3'-diaminodiphenyl oxides or 2,4'-diaminodiphenyl oxide, mphenylenediamine, O-Phenylene Diamine or Ursol D.
Described solvent can be N, N'-dimethyl formamide, N, N'-N,N-DIMETHYLACETAMIDE or N-Methyl pyrrolidone.
Described neutralization reagent can be triethylamine or Tributylamine.
Described rare gas element can be nitrogen or argon gas.
Beneficial effect of the present invention is as follows:
(1) preparation method of thermal reduction Graphene provided by the present invention and polyimide nano-composite material, technological process is simple and reliable, conveniently realizes industrial applications.
(2) preparation method of thermal reduction Graphene provided by the present invention and polyimide nano-composite material, by the reaction of carboxyl in neutralization reagent and polyamic acid main chain, polyamic acid is made to lose the reactive hydrogen that in carboxyl, autocatalysis polyamic acid decomposes, increase polyamic acid to the stability of water, overcome the disadvantageous effect introduced water and cause polyamic acid to decompose.
(3) preparation method of thermal reduction Graphene provided by the present invention and polyimide nano-composite material, by the reaction of carboxyl in neutralization reagent and polyamic acid main chain, improve the wetting ability of solution, thus the dispersion system of graphene dispersion optimum can be utilized, stable and the homogeneous dispersion of graphene oxide in polyamic acid solution is obtained by solution mixing method, and the π-π after blending in polyamic acid in aromatic ring and graphene oxide between aromatic ring interacts, and can improve the dispersion stabilization of graphene oxide in system further.
Accompanying drawing explanation
Fig. 1 is the thermal gravimetric analysis curve of thermal reduction Graphene/Kapton and pure Kapton.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.
It should be noted that embodiment herein only for illustration of the present invention instead of limit the scope of the invention.The present invention is to process thermal reduction Graphene and polyimide composite film, a kind of application form of the most frequently used Graphene modified polyimide is described, but the method for Graphene modified polyimide provided by the invention is not only confined to the processing of thin-film material, be equally applicable to the processing of other form thermal reduction Graphenes and polyimide composite based material, as sheet material, particulate material and powder etc.
It shall yet further be noted that, after reading content of the present invention, the various change that those skilled in the art make the present invention or amendment, these equivalent form of values belong in the limited range of appended claims equally.
Embodiment 1
Joined in 1L deionized water by 5.0g graphene oxide, utilize ultra-sonic generator ultrasonic disperse 180min under ultrasonic power 150W and room temperature, preparation concentration is the water-based graphene oxide dispersion of 5mg/ml, for subsequent use.
Take 4, the 4'-diaminodiphenyl oxides of 200.24g and the pyromellitic acid anhydride of 218.12g, join the N of 1.77L, in N'-dimethyl formamide, stirring reaction 24h under 25 DEG C of conditions with nitrogen protection, obtains polyamic acid solution.In this solution, add the triethylamine of 306.64ml, continue reaction 1h, obtain hydrophilic polyamic acid solution.Then, under the condition stirred, in this hydrophilic solution, add the 1L water-based graphene oxide dispersion prepared, stir 60min, realize dispersed in polyamic acid of graphene oxide.By above-mentioned soln using whirler masking, vacuum drying under 60 DEG C of conditions, obtains graphene oxide/polyamic acid laminated film.Finally, under nitrogen protection, by this film at 100 DEG C, 150 DEG C, 200 DEG C, 250 DEG C and 300 DEG C of difference constant temperature 0.5h, constant temperature terminates rear naturally cooling, just obtains the polyimide nano composite thin film that thermal reduction Graphene strengthens.
Embodiment 2
Joined in 260ml deionized water by 0.52g graphene oxide, utilize ultra-sonic generator ultrasonic disperse 60min under ultrasonic power 100W and room temperature, preparation concentration is the water-based graphene oxide dispersion of 2mg/ml, for subsequent use.
Take 3,3' of 32.22g, 4; 3, the 3'-diaminodiphenyl oxides of 4'-benzophenone tetracarboxylic dianhydride and 20.02g, join the N of 300ml under the condition stirred; in N'-dimethyl formamide, stirring reaction 2h under the condition of 0 DEG C and argon shield, synthesizing polyamides acid solution.In this solution, add the triethylamine of 30.67ml, continue reaction 0.5h, obtain hydrophilic polyamic acid solution.Then, under the condition stirred, in this hydrophilic solution, add the water-based graphene oxide dispersion of above-mentioned preparation, stir 30min, realize dispersed in polyamic acid of graphene oxide.Get the above-mentioned solution of 100ml film on the sheet glass of 20cm × 20cm, and under 80 DEG C of conditions vacuum drying, obtain graphene oxide/polyamic acid laminated film.Finally, under nitrogen protection, by this film at 100 DEG C, 150 DEG C, 200 DEG C, 250 DEG C and 300 DEG C of difference constant temperature 2h, constant temperature terminates rear naturally cooling, obtains the polyimide nano composite thin film that thermal reduction Graphene strengthens.
Embodiment 3
Joined in 60ml deionized water by 0.03g graphene oxide, utilize ultra-sonic generator ultrasonic disperse 120min under ultrasonic power 120W and room temperature, preparation concentration is the water-based graphene oxide dispersion of 0.5mg/ml, for subsequent use.
Take the bisphenol A-type dianhydride of 5.02g and the mphenylenediamine of 1.08g, under the condition stirred, join the N of 50ml, in N'-dimethyl formamide, stirring reaction 6h under the condition of 15 DEG C and argon shield, synthesizing polyamides acid solution.In this solution, add the Tributylamine of 1.15ml, continue reaction 1h, obtain hydrophilic polyamic acid solution.Then, under the condition stirred, in this hydrophilic solution, add above-mentioned water-based graphene oxide dispersion, stir 45min, realize dispersed in polyamic acid of graphene oxide.By above-mentioned solution coating, vacuum drying under 70 DEG C of conditions, obtains graphene oxide/polyamic acid laminated film.Finally, under nitrogen protection, by this film at 100 DEG C of constant temperature 0.5h, 150 DEG C of constant temperature 1h, 200 DEG C of constant temperature 0.5h, 250 DEG C of constant temperature 1h, 300 DEG C of constant temperature 0.5h, constant temperature terminates rear naturally cooling, obtains the polyimide nano composite thin film that thermal reduction Graphene strengthens.
Embodiment 4
Joined in 1.5L deionized water by 3g graphene oxide, utilize ultra-sonic generator ultrasonic disperse 150min under ultrasonic power 130W and room temperature, preparation concentration is the water-based graphene oxide dispersion of 2mg/ml, for subsequent use.
Take the Ursol D of 3,3' of 294.22g, 4,4'-bibenzene tetracarboxylic dianhydrides and 108.14g, stir condition under join in the N-Methyl pyrrolidone of 3L, 25 DEG C and stir condition under react 12h, synthesizing polyamides acid solution.In this solution, add the Tributylamine of 220.35ml, continue reaction 1h, obtain hydrophilic polyamic acid solution.Then, under the condition stirred, in this hydrophilic solution, add above-mentioned water-based graphene oxide dispersion, stir 50min, realize dispersed in polyamic acid of graphene oxide.By above-mentioned solution coating, vacuum drying under 75 DEG C of conditions, obtains graphene oxide/polyamic acid laminated film.Finally, under nitrogen protection, by this film at 100 DEG C of constant temperature 1h, 150 DEG C of constant temperature 1h, 200 DEG C of constant temperature 1h, 250 DEG C of constant temperature 1h, 300 DEG C of constant temperature 0.5h, constant temperature terminates rear naturally cooling, obtains the polyimide nano composite thin film that thermal reduction Graphene strengthens.
Embodiment 5
Joined in 1L deionized water by 5.0g graphene oxide, utilize ultra-sonic generator ultrasonic disperse 100min under ultrasonic power 140W and room temperature, preparation concentration is the water-based graphene oxide dispersion of 5mg/ml, for subsequent use.
Take 3, the 4'-diaminodiphenyl oxides of 200.24g and 3,3', 4, the 4'-phenyl ether tetracarboxylic dianhydrides of 310.21g, join the N of 1.77L, in N'-dimethyl formamide, stirring reaction 24h under 25 DEG C of conditions with nitrogen protection, obtains polyamic acid solution.In this solution, add the Tributylamine of 220.35ml, continue reaction 1h, obtain hydrophilic polyamic acid solution.Then, under the condition stirred, in this hydrophilic solution, add the 1L water-based graphene oxide dispersion prepared, stir 60min, realize dispersed in polyamic acid of graphene oxide.By above-mentioned soln using whirler masking, vacuum drying under 60 DEG C of conditions, obtains graphene oxide/polyamic acid laminated film.Finally, under nitrogen protection, by this film at 100 DEG C, 150 DEG C, 200 DEG C, 250 DEG C and 300 DEG C of difference constant temperature 0.5h, constant temperature terminates rear naturally cooling, just obtains the polyimide nano composite thin film that thermal reduction Graphene strengthens.
Embodiment 6
Joined in 1L deionized water by 5.0g graphene oxide, utilize ultra-sonic generator ultrasonic disperse 160min under ultrasonic power 110W and room temperature, preparation concentration is the water-based graphene oxide dispersion of 5mg/ml, for subsequent use.
Take 2,3,3', the 4-bibenzene tetracarboxylic dianhydrides of 294.22g and the O-Phenylene Diamine of 108.14g, join the N of 1.84L, in N'-N,N-DIMETHYLACETAMIDE, stirring reaction 8h under 25 DEG C of conditions with nitrogen protection, obtains polyamic acid solution.In this solution, add the triethylamine of 306.64ml, continue reaction 1h, obtain hydrophilic polyamic acid solution.Then, under the condition stirred, in this hydrophilic solution, add the 1L water-based graphene oxide dispersion prepared, stir 60min, realize dispersed in polyamic acid of graphene oxide.By above-mentioned soln using whirler masking, vacuum drying under 60 DEG C of conditions, obtains graphene oxide/polyamic acid laminated film.Finally, under nitrogen protection, by this film at 100 DEG C, 150 DEG C, 200 DEG C, 250 DEG C and 300 DEG C of difference constant temperature 0.5h, constant temperature terminates rear naturally cooling, just obtains the polyimide nano composite thin film that thermal reduction Graphene strengthens.
Embodiment 7
Joined in 1.5L deionized water by 3g graphene oxide, utilize ultra-sonic generator ultrasonic disperse 150min under ultrasonic power 130W and room temperature, preparation concentration is the water-based graphene oxide dispersion of 2mg/ml, for subsequent use.
Take 2, the 4'-diaminodiphenyl oxides of 3,3' of 294.22g, 4,4'-bibenzene tetracarboxylic dianhydrides and 200.24g, stir condition under join in the N-Methyl pyrrolidone of 3L, 25 DEG C and stir condition under react 12h, synthesizing polyamides acid solution.In this solution, add the Tributylamine of 220.35ml, continue reaction 1h, obtain hydrophilic polyamic acid solution.Then, under the condition stirred, in this hydrophilic solution, add above-mentioned water-based graphene oxide dispersion, stir 50min, realize dispersed in polyamic acid of graphene oxide.By above-mentioned solution coating, vacuum drying under 75 DEG C of conditions, obtains graphene oxide/polyamic acid laminated film.Finally, under nitrogen protection, by this film at 100 DEG C of constant temperature 1h, 150 DEG C of constant temperature 1h, 200 DEG C of constant temperature 1h, 250 DEG C of constant temperature 1h, 300 DEG C of constant temperature 0.5h, constant temperature terminates rear naturally cooling, obtains the polyimide nano composite thin film that thermal reduction Graphene strengthens.
For the advantage that checking the method for the invention contrasts with the method that has at present, carry out contrast verification.
Comparative example 1
Take the N that 0.52g graphene oxide joins 300ml, in N'-dimethyl formamide, utilize 100W ultra-sonic generator, ultrasonic disperse 60min under room temperature, obtain the dispersion liquid of graphene oxide in N, N'-dimethyl formamide.
Under nitrogen protection; take 3 of 32.22g; 3'; 4; 4, the 4'-diaminodiphenyl oxides of 4'-benzophenone tetracarboxylic dianhydride and 20.02g, join in above-mentioned graphene oxide dispersion under the condition stirred; 2h is reacted, the polyamic acid solution of synthesis graphene oxide hydridization under 15 DEG C and the condition that stirs.Then, by above-mentioned solution coating, vacuum drying under 80 DEG C of conditions, obtains graphene oxide/polyamic acid laminated film.Finally, under nitrogen protection, by this film at 100 DEG C of constant temperature 0.5h, 150 DEG C of constant temperature 1h, 200 DEG C of constant temperature 1h, 250 DEG C of constant temperature 1h, 300 DEG C of constant temperature 0.5h, constant temperature terminates rear naturally cooling, obtains reduced graphene/polyimide composite film.
Comparative example 2
Under nitrogen protection, 2g graphene oxide is joined the N of 100ml, stir in N'-dimethyl formamide, in system, then add the ethyl isocyanate of 0.16ml, stirring reaction 12h.After reaction terminates, in system, add methylene dichloride cleaning, and repeat 10 times, finally the ethyl isocyanate modified graphite oxide obtained is dried under 60 DEG C of conditions.
The graphite oxide taking 0.52g modification joins the N of 300ml, in N'-dimethyl formamide, utilizes 100W ultra-sonic generator, ultrasonic disperse 60min under room temperature.Under nitrogen protection; take 3 of 32.22g; 3'; 4; 4, the 4'-diaminodiphenyl oxides of 4'-benzophenone tetracarboxylic dianhydride and 20.02g, join in above-mentioned graphene oxide dispersion under the condition stirred; 2h is reacted, the polyamic acid solution of synthesis graphene oxide hydridization under 15 DEG C and the condition that stirs.Then, by above-mentioned solution coating, vacuum drying under 80 DEG C of conditions, obtains graphene oxide/polyamic acid laminated film.Finally, under nitrogen protection, by this film at 100 DEG C of constant temperature 0.5h, 150 DEG C of constant temperature 1h, 200 DEG C of constant temperature 1h, 250 DEG C of constant temperature 1h, 300 DEG C of constant temperature 0.5h, constant temperature terminates rear naturally cooling, obtains reduced graphene/polyimide composite film.
For verifying the validity of method provided by the present invention, carry out following test:
Test 1
Adopt Q600 type thermal analyzer, under the temperature rise rate of air atmosphere and 10 DEG C/min, the thermogravimetric curve of thermal reduction Graphene/Kapton and pure Kapton (preparation method and the different of embodiment 1 are, do not add water-based graphene oxide dispersion) in testing example 1.
Test 2
Adopt four probe method, detect the specific conductivity of reduced graphene/polyimide nano composite thin film.
Test 3
According to standard A STMD638, test the tensile strength of Graphene/polyimide nano composite thin film, Young's modulus and elongation at break.
Test 1 the results are shown in Figure of description 1, can obviously find out from figure, compared with pure Kapton, 5% and 10% thermal weight loss temperature of the thermal reduction Graphene/Kapton adopting method provided by the present invention to prepare, not only do not decline, and due to the modification of thermal reduction Graphene, occur rising by a small margin, show that thermal reduction Graphene/Kapton prepared by method provided by the present invention can not affect the original outstanding heat resistance of polyimide.
The result of test 2 and 3, lists in table 1.Can be found by contrast, the reduced graphene adopting the inventive method to prepare is with polyimide nano-composite material compared with comparative example, and Young's modulus and elongation at break are substantially suitable, and specific conductivity and tensile strength significantly improve.
The main oxidated graphene thermal reducing degree of specific conductivity of nano compound film and the impact of degree of scatter, the significantly lifting of specific conductivity mainly illustrates 2 points: (1) polyamic acid hot imidization course synchronization thermal reduction graphene oxide, and method is feasible and reducing degree is higher; (2) thermal reduction Graphene prepared by the method that the invention provides and polyimide, the degree of scatter of reduced graphene in body material polyimide is obviously better than existing method.
The tensile strength of nano compound film is mainly by the impact of reduced graphene degree of scatter, and reduced graphene degree of scatter is higher, then its enhancing efficiency is higher, and the tensile strength of nano compound film is larger.The rising of nano compound film tensile strength, has proved the raising of the method that the invention provides to redox graphene degree of scatter in polyimide further.In addition, nano compound film mechanical experimental results also directly illustrates, the invention provides reduced graphene prepared by method and polyimide nano-composite material mechanical property is better than existing technology of preparing.
Table 1
Claims (2)
1. a preparation method for reduced graphene and polyimide nano-composite material, is characterized in that comprising the steps:
(1) join in deionized water by graphene oxide, ultrasonic disperse 60 ~ 180min under ultrasonic power 100 ~ 150W and room temperature, preparation concentration is the water-based graphene oxide dispersion of 0.5 ~ 5mg/ml;
(2) by dianhydride and diamines equimolar ratio, dianhydride and diamines are joined in solvent, make dianhydride and diamines quality sum in the solution massfraction be 11% ~ 24%, stirring reaction 2 ~ 24h under 0 ~ 25 DEG C of condition with protection of inert gas, obtain polyamic acid solution, the neutralization reagent that mole number is 2.2 ~ 2.4 times of diamines is added in this solution, continue reaction 0.5 ~ 2h, obtain hydrophilic polyamide acid solution, then, under the condition stirred, the water-based graphene oxide dispersion of preparation in step (1) is added in this hydrophilic polyamide acid solution, control the add-on of water-based graphene oxide dispersion, the mass ratio of graphene oxide addition and dianhydride and diamines total amount is made to be 1:50 ~ 200, then 30 ~ 60min is stirred, obtain graphene oxide polyamic acid solution,
(3) by graphene oxide polyamic acid solution vacuum drying under 60 ~ 80 DEG C of conditions, graphene oxide and polyamic acid matrix material is obtained;
(4) under protection of inert gas, by graphene oxide and polyamic acid matrix material, hot imidization and graphene oxide thermal reduction is carried out: 100 DEG C of constant temperature 0.5 ~ 2h according to following heating schedule, 150 DEG C of constant temperature 0.5 ~ 2h, 200 DEG C of constant temperature 0.5 ~ 2h, 250 DEG C of constant temperature 0.5 ~ 2h, 300 DEG C of constant temperature 0.5 ~ 2h, constant temperature terminates rear naturally cooling, obtains reduced graphene and polyimide nano-composite material;
Described dianhydride is bisphenol A-type dianhydride, pyromellitic acid anhydride, 3,3', 4,4'-bibenzene tetracarboxylic dianhydrides, 2,3,3', 4-bibenzene tetracarboxylic dianhydrides, 3,3', 4,4'-phenyl ether tetracarboxylic dianhydride or 3,3', 4,4'-benzophenone tetracarboxylic dianhydride;
Described diamines is 4,4'-diaminodiphenyl oxide, 3,4'-diaminodiphenyl oxides, 3,3'-diaminodiphenyl oxides or 2,4'-diaminodiphenyl oxide, mphenylenediamine, O-Phenylene Diamine or Ursol D;
Described solvent is N, N'-dimethyl formamide, N, N'-N,N-DIMETHYLACETAMIDE or N-Methyl pyrrolidone;
Described neutralization reagent is triethylamine or Tributylamine.
2. the preparation method of a kind of reduced graphene as claimed in claim 1 and polyimide nano-composite material, is characterized in that described rare gas element can be nitrogen or argon gas.
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| CN104448312A (en) * | 2014-11-27 | 2015-03-25 | 北京化工大学常州先进材料研究院 | High-dielectric-constant polyimide film provided with multiwalled carbon nanotubes and preparation method of high-dielectric-constant polyimide film |
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