CN103602065A - Preparation method of reduced graphene and polyimide nano composite material - Google Patents
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Abstract
The invention relates to a preparation method of a reduced graphene and polyimide nano composite material. The preparation method comprises the following steps: firstly performing ultrasonic dispersion on oxidized graphene in deionized water by adopting a solution mixing method to prepare an oxidized graphene waterborne suspension with high dispersion and stability; then directly mixing a polyamic acid solution subjected to neutralization with the oxidized graphene waterborne suspension to realize the high dispersion of the oxidized graphene in polyamic acid; and finally performing and synchronous thermal reduction on the oxidized graphene through thermal imidization to prepare the reduced graphene and polyimide nano composite material. The preparation method provided by the invention has the advantages of good reduced graphene dispersion and good thermal stability.
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, every profession and trade improves constantly the requirement of polyimide performance, simple polyimide resin cannot meet people's application demand.Under this background, nano-material modified polyimide resin, i.e. polyimide nano-composite material, comes into people's sight line gradually, becomes the reliable method that improves and expand polyimide performance.
Graphene is a kind of new carbon of monatomic bed thickness, because of its bigger serface and outstanding mechanics, electricity and thermal property, becomes one of strongthener the most attractive in current nano composite material.For reducing the production cost of graphene nanocomposite material, the common method of adding Graphene at present in resin is first to add graphene oxide cheaply, then in resin, obtains 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 of preparing reduced graphene/polyimide nano-composite material, the method utilizes graphene oxide in polar solvent, to have the feature of certain dispersiveness, graphene oxide is first distributed in solvent, again diamines and dianhydride monomer are joined and in solvent, carry out polymerization, finally, at synchronous thermal reduction graphene oxide of hot imidization stage, 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 of chemical modification graphene oxide (as: CN 20110100930), can obviously increase the dispersion stabilization of graphene oxide in polar solvent, but the various modifying agent temperature tolerances that adopt are starkly lower than polyimide itself, and the heat resistance of matrix material is existed to disadvantageous effect.
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, graphene oxide is disperseed to preparation high dispersing and stable graphene oxide waterborne suspension in deionized water for ultrasonic; 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.
Preparation method of the present invention specifically realizes by following steps:
(1) graphene oxide is joined in deionized water, utilize ultra-sonic generator ultrasonic dispersion 60～180min under ultrasonic power 100～150W and room temperature, the water-based graphene oxide dispersion liquid that preparation concentration is 0.5～5mg/ml;
(2) press dianhydride and diamines equimolar ratio, dianhydride and diamines are joined in solvent, making dianhydride and dianhydride quality sum massfraction in solution is 11%～24%, stirring reaction 2～24h under the condition of 0～25 ℃ and protection of inert gas, obtain polyamic acid solution, to adding mole number in this solution, it is the neutralization reagent of 2.2～2.4 times of diamines, continue reaction 0.5～2h, obtain hydrophilic polyamide acid solution, then, under the condition stirring, in this hydrophilic polyamide acid solution, add the water-based graphene oxide dispersion liquid of preparing in step (1), control the add-on of water-based graphene oxide dispersion liquid, the mass ratio that makes graphene oxide addition and dianhydride and diamines total amount is 1:50～200, then stir 30～60min, obtain graphene oxide polyamic acid solution,
(3) by graphene oxide polyamic acid solution vacuum drying under 60～80 ℃ of conditions, obtain graphene oxide and polyamic acid matrix material;
(4) under protection of inert gas; by graphene oxide and polyamic acid matrix material; according to following heating schedule, carry out hot imidization and graphene oxide thermal reduction: 100 ℃ of constant temperature 0.5～2h; 150 ℃ of constant temperature 0.5～2h; 200 ℃ of constant temperature 0.5～2h, 250 ℃ of constant temperature 0.5～2h, 300 ℃ of constant temperature 0.5～2h; constant temperature finishes 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 dianhydride, 2,3,3', 4-bibenzene tetracarboxylic dianhydride, 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 oxide, 3,3'-diaminodiphenyl oxide 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 reacting of neutralization reagent and carboxyl in polyamic acid main chain, make polyamic acid lose the reactive hydrogen that in carboxyl, autocatalysis polyamic acid decomposes, increase the stability of polyamic acid to water, overcome and introduce the disadvantageous effect that water causes polyamic acid to decompose.
(3) preparation method of thermal reduction Graphene provided by the present invention and polyimide nano-composite material, by reacting of neutralization reagent and carboxyl in polyamic acid main chain, improve the wetting ability of solution, thereby can utilize the dispersed optimum dispersion system of Graphene, by solution mixing method, obtaining the stable and homogeneous of graphene oxide in polyamic acid solution disperses, and the π-π interaction between aromatic ring in aromatic ring and graphene oxide in polyamic acid, can further improve the dispersion stabilization of graphene oxide in system after mixing.
Accompanying drawing explanation
Fig. 1 is the thermogravimetric analysis curve of thermal reduction Graphene/Kapton and pure Kapton.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.
It should be noted that embodiment is herein only for illustrating the present invention rather than limiting the scope of the invention.It is example that processing thermal reduction Graphene and polyimide composite film are take in the present invention, 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, various changes or modification that those skilled in the art make the present invention, these equivalent form of values belong in the limited range of appended claims equally.
5.0g graphene oxide is joined in 1L deionized water, utilize ultra-sonic generator ultrasonic dispersion 180min under ultrasonic power 150W and room temperature, the water-based graphene oxide dispersion liquid that preparation concentration is 5mg/ml, standby.
Take 4 of 200.24g, the pyromellitic acid anhydride of 4'-diaminodiphenyl oxide and 218.12g, joins the N of 1.77L, and in N'-dimethyl formamide, stirring reaction 24h under the condition of 25 ℃ and nitrogen protection, obtains polyamic acid solution.To the triethylamine that adds 306.64ml in this solution, continue reaction 1h, obtain hydrophilic polyamic acid solution.Then, under the condition stirring, in this hydrophilic solution, add the 1L water-based graphene oxide dispersion liquid having prepared, stir 60min, realize dispersed in polyamic acid of graphene oxide.By above-mentioned soln using whirler masking, vacuum drying under 60 ℃ of conditions, obtains graphene oxide/polyamic acid laminated film.Finally, under nitrogen protection, by this film, at 100 ℃, 150 ℃, 200 ℃, 250 ℃ and 300 ℃ of difference constant temperature 0.5h, constant temperature finishes rear naturally cooling, just obtains the polyimide nano composite thin film that thermal reduction Graphene strengthens.
Embodiment 2
0.52g graphene oxide is joined in 260ml deionized water, utilize ultra-sonic generator ultrasonic dispersion 60min under ultrasonic power 100W and room temperature, the water-based graphene oxide dispersion liquid that preparation concentration is 2mg/ml, standby.
Take 3 of 32.22g, 3', 4; 3 of 4'-benzophenone tetracarboxylic dianhydride and 20.02g, 3'-diaminodiphenyl oxide joins the N of 300ml under the condition stirring; in N'-dimethyl formamide, stirring reaction 2h under the condition of 0 ℃ and argon shield, synthesizing polyamides acid solution.To the triethylamine that adds 30.67ml in this solution, continue reaction 0.5h, obtain hydrophilic polyamic acid solution.Then, under the condition stirring, the water-based graphene oxide dispersion liquid to adding above-mentioned preparation in this hydrophilic solution, stirs 30min, realizes dispersed in polyamic acid of graphene oxide.Get the above-mentioned solution of 100ml and film on the sheet glass of 20cm * 20cm, and under 80 ℃ of conditions vacuum drying, obtain graphene oxide/polyamic acid laminated film.Finally, under nitrogen protection, by this film, at 100 ℃, 150 ℃, 200 ℃, 250 ℃ and 300 ℃ of difference constant temperature 2h, constant temperature finishes rear naturally cooling, obtains the polyimide nano composite thin film that thermal reduction Graphene strengthens.
Embodiment 3
0.03g graphene oxide is joined in 60ml deionized water, utilize ultra-sonic generator ultrasonic dispersion 120min under ultrasonic power 120W and room temperature, the water-based graphene oxide dispersion liquid that preparation concentration is 0.5mg/ml, standby.
Take the bisphenol A-type dianhydride of 5.02g and the mphenylenediamine of 1.08g, under the condition stirring, join the N of 50ml, in N'-dimethyl formamide, stirring reaction 6h under the condition of 15 ℃ and argon shield, synthesizing polyamides acid solution.To the Tributylamine that adds 1.15ml in this solution, continue reaction 1h, obtain hydrophilic polyamic acid solution.Then, under the condition stirring, in this hydrophilic solution, add above-mentioned water-based graphene oxide dispersion liquid, stir 45min, realize dispersed in polyamic acid of graphene oxide.By above-mentioned solution coating, vacuum drying under 70 ℃ of conditions, obtains graphene oxide/polyamic acid laminated film.Finally, under nitrogen protection, by this film at 100 ℃ of constant temperature 0.5h, 150 ℃ of constant temperature 1h, 200 ℃ of constant temperature 0.5h, 250 ℃ of constant temperature 1h, 300 ℃ of constant temperature 0.5h, constant temperature finishes rear naturally cooling, obtains the polyimide nano composite thin film that thermal reduction Graphene strengthens.
Embodiment 4
3g graphene oxide is joined in 1.5L deionized water, utilize ultra-sonic generator ultrasonic dispersion 150min under ultrasonic power 130W and room temperature, the water-based graphene oxide dispersion liquid that preparation concentration is 2mg/ml, standby.
Take 3 of 294.22g, 3', the Ursol D of 4,4'-bibenzene tetracarboxylic dianhydride and 108.14g joins in N-methyl-2-pyrrolidone of 3L under the condition stirring, and under 25 ℃ and the condition that stirs, reacts 12h, synthesizing polyamides acid solution.To the Tributylamine that adds 220.35ml in this solution, continue reaction 1h, obtain hydrophilic polyamic acid solution.Then, under the condition stirring, in this hydrophilic solution, add above-mentioned water-based graphene oxide dispersion liquid, stir 50min, realize dispersed in polyamic acid of graphene oxide.By above-mentioned solution coating, vacuum drying under 75 ℃ of conditions, obtains graphene oxide/polyamic acid laminated film.Finally, under nitrogen protection, by this film at 100 ℃ of constant temperature 1h, 150 ℃ of constant temperature 1h, 200 ℃ of constant temperature 1h, 250 ℃ of constant temperature 1h, 300 ℃ of constant temperature 0.5h, constant temperature finishes rear naturally cooling, obtains the polyimide nano composite thin film that thermal reduction Graphene strengthens.
Embodiment 5
5.0g graphene oxide is joined in 1L deionized water, utilize ultra-sonic generator ultrasonic dispersion 100min under ultrasonic power 140W and room temperature, the water-based graphene oxide dispersion liquid that preparation concentration is 5mg/ml, standby.
Take 3 of 200.24g, 3 of 4'-diaminodiphenyl oxide and 310.21g, 3', 4,4'-phenyl ether tetracarboxylic dianhydride, joins the N of 1.77L, and in N'-dimethyl formamide, stirring reaction 24h under the condition of 25 ℃ and nitrogen protection, obtains polyamic acid solution.To the Tributylamine that adds 220.35ml in this solution, continue reaction 1h, obtain hydrophilic polyamic acid solution.Then, under the condition stirring, in this hydrophilic solution, add the 1L water-based graphene oxide dispersion liquid having prepared, stir 60min, realize dispersed in polyamic acid of graphene oxide.By above-mentioned soln using whirler masking, vacuum drying under 60 ℃ of conditions, obtains graphene oxide/polyamic acid laminated film.Finally, under nitrogen protection, by this film, at 100 ℃, 150 ℃, 200 ℃, 250 ℃ and 300 ℃ of difference constant temperature 0.5h, constant temperature finishes rear naturally cooling, just obtains the polyimide nano composite thin film that thermal reduction Graphene strengthens.
Embodiment 6
5.0g graphene oxide is joined in 1L deionized water, utilize ultra-sonic generator ultrasonic dispersion 160min under ultrasonic power 110W and room temperature, the water-based graphene oxide dispersion liquid that preparation concentration is 5mg/ml, standby.
Take 2,3 of 294.22g, 3', the O-Phenylene Diamine of 4-bibenzene tetracarboxylic dianhydride and 108.14g, joins the N of 1.84L, and in N'-N,N-DIMETHYLACETAMIDE, stirring reaction 8h under the condition of 25 ℃ and nitrogen protection, obtains polyamic acid solution.To the triethylamine that adds 306.64ml in this solution, continue reaction 1h, obtain hydrophilic polyamic acid solution.Then, under the condition stirring, in this hydrophilic solution, add the 1L water-based graphene oxide dispersion liquid having prepared, stir 60min, realize dispersed in polyamic acid of graphene oxide.By above-mentioned soln using whirler masking, vacuum drying under 60 ℃ of conditions, obtains graphene oxide/polyamic acid laminated film.Finally, under nitrogen protection, by this film, at 100 ℃, 150 ℃, 200 ℃, 250 ℃ and 300 ℃ of difference constant temperature 0.5h, constant temperature finishes rear naturally cooling, just obtains the polyimide nano composite thin film that thermal reduction Graphene strengthens.
Embodiment 7
3g graphene oxide is joined in 1.5L deionized water, utilize ultra-sonic generator ultrasonic dispersion 150min under ultrasonic power 130W and room temperature, the water-based graphene oxide dispersion liquid that preparation concentration is 2mg/ml, standby.
Take 3 of 294.22g, 3', 2 of 4,4'-bibenzene tetracarboxylic dianhydride and 200.24g, 4'-diaminodiphenyl oxide joins in N-methyl-2-pyrrolidone of 3L under the condition stirring, and under 25 ℃ and the condition that stirs, reacts 12h, synthesizing polyamides acid solution.To the Tributylamine that adds 220.35ml in this solution, continue reaction 1h, obtain hydrophilic polyamic acid solution.Then, under the condition stirring, in this hydrophilic solution, add above-mentioned water-based graphene oxide dispersion liquid, stir 50min, realize dispersed in polyamic acid of graphene oxide.By above-mentioned solution coating, vacuum drying under 75 ℃ of conditions, obtains graphene oxide/polyamic acid laminated film.Finally, under nitrogen protection, by this film at 100 ℃ of constant temperature 1h, 150 ℃ of constant temperature 1h, 200 ℃ of constant temperature 1h, 250 ℃ of constant temperature 1h, 300 ℃ of constant temperature 0.5h, constant temperature finishes rear naturally cooling, obtains the polyimide nano composite thin film that thermal reduction Graphene strengthens.
For the advantage of checking the method for the invention with at present existing method contrast, 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, under room temperature, ultrasonic dispersion 60min, obtains graphene oxide at N, the dispersion liquid in N'-dimethyl formamide.
Under nitrogen protection; take 3 of 32.22g; 3'; 4; 4 of 4'-benzophenone tetracarboxylic dianhydride and 20.02g, 4'-diaminodiphenyl oxide joins in above-mentioned graphene oxide dispersion liquid under the condition stirring; under 15 ℃ and the condition that stirs, react 2h, the polyamic acid solution of synthetic graphene oxide hydridization.Then,, by above-mentioned solution coating, vacuum drying under 80 ℃ of conditions, obtains graphene oxide/polyamic acid laminated film.Finally, under nitrogen protection, by this film at 100 ℃ of constant temperature 0.5h, 150 ℃ of constant temperature 1h, 200 ℃ of constant temperature 1h, 250 ℃ of constant temperature 1h, 300 ℃ of constant temperature 0.5h, constant temperature finishes rear naturally cooling, obtains reduced graphene/polyimide composite film.
Comparative example 2
Under nitrogen protection, 2g graphene oxide is joined to the N of 100ml, in N'-dimethyl formamide, stir, then to the ethyl isocyanate that adds 0.16ml in system, stirring reaction 12h.After reaction finishes, in system, add methylene dichloride to clean, and repeat 10 times, finally the ethyl isocyanate modified graphite oxide obtaining is dried under 60 ℃ of conditions.
The graphite oxide that takes 0.52g modification joins the N of 300ml, in N'-dimethyl formamide, utilizes 100W ultra-sonic generator, ultrasonic dispersion 60min under room temperature.Under nitrogen protection; take 3 of 32.22g; 3'; 4; 4 of 4'-benzophenone tetracarboxylic dianhydride and 20.02g, 4'-diaminodiphenyl oxide joins in above-mentioned graphene oxide dispersion liquid under the condition stirring; under 15 ℃ and the condition that stirs, react 2h, the polyamic acid solution of synthetic graphene oxide hydridization.Then,, by above-mentioned solution coating, vacuum drying under 80 ℃ of conditions, obtains graphene oxide/polyamic acid laminated film.Finally, under nitrogen protection, by this film at 100 ℃ of constant temperature 0.5h, 150 ℃ of constant temperature 1h, 200 ℃ of constant temperature 1h, 250 ℃ of constant temperature 1h, 300 ℃ of constant temperature 0.5h, constant temperature finishes rear naturally cooling, obtains reduced graphene/polyimide composite film.
For verifying the validity of method provided by the present invention, carry out following test:
Adopt Q600 type thermal analyzer, under the temperature rise rate of air atmosphere and 10 ℃/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 liquid) in test implementation 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 STM D638, tensile strength, Young's modulus and the elongation at break of test Graphene/polyimide nano composite thin film.
The result of test 2 and 3, lists in table 1.By contrast, can find, the reduced graphene that adopts the inventive method to prepare is compared with comparative example with polyimide nano-composite material, and Young's modulus and elongation at break are substantially suitable, and specific conductivity and tensile strength obviously improve.
The main oxidated Graphene thermal reduction 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: the synchronous thermal reduction graphene oxide of (1) polyamic acid hot imidization process, and method is feasible and reducing degree is higher; (2) the invention provides thermal reduction Graphene and polyimide prepared by method, 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 subject to the impact of reduced graphene degree of scatter, and reduced graphene degree of scatter is higher, and its enhancing efficiency is higher, and the tensile strength of nano compound film is just larger.The rising of nano compound film tensile strength, has further proved the raising of the method that the invention provides to redox graphene degree of scatter in polyimide.In addition, nano compound film mechanical experimental results is directly explanation also, and the reduced graphene that the method that the invention provides is prepared and polyimide nano-composite material mechanical property are better than existing technology of preparing.
Table 1
Claims (6)
1. a preparation method for reduced graphene and polyimide nano-composite material, is characterized in that comprising the steps:
(1) graphene oxide is joined in deionized water to ultrasonic dispersion 60～180min under ultrasonic power 100～150W and room temperature, the water-based graphene oxide dispersion liquid that preparation concentration is 0.5～5mg/ml;
(2) press dianhydride and diamines equimolar ratio, dianhydride and diamines are joined in solvent, making dianhydride and dianhydride quality sum massfraction in solution is 11%～24%, stirring reaction 2～24h under the condition of 0～25 ℃ and protection of inert gas, obtain polyamic acid solution, to adding mole number in this solution, it is the neutralization reagent of 2.2～2.4 times of diamines, continue reaction 0.5～2h, obtain hydrophilic polyamide acid solution, then, under the condition stirring, in this hydrophilic polyamide acid solution, add the water-based graphene oxide dispersion liquid of preparing in step (1), control the add-on of water-based graphene oxide dispersion liquid, the mass ratio that makes graphene oxide addition and dianhydride and diamines total amount is 1:50～200, then stir 30～60min, obtain graphene oxide polyamic acid solution,
(3) by graphene oxide polyamic acid solution vacuum drying under 60～80 ℃ of conditions, obtain graphene oxide and polyamic acid matrix material;
(4) under protection of inert gas; by graphene oxide and polyamic acid matrix material; according to following heating schedule, carry out hot imidization and graphene oxide thermal reduction: 100 ℃ of constant temperature 0.5～2h; 150 ℃ of constant temperature 0.5～2h; 200 ℃ of constant temperature 0.5～2h, 250 ℃ of constant temperature 0.5～2h, 300 ℃ of constant temperature 0.5～2h; constant temperature finishes rear naturally cooling, obtains reduced graphene and polyimide nano-composite material.
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 dianhydride is bisphenol A-type dianhydride, pyromellitic acid anhydride, 3,3', 4,4'-bibenzene tetracarboxylic dianhydride, 2,3,3', 4-bibenzene tetracarboxylic dianhydride, 3,3', 4,4'-phenyl ether tetracarboxylic dianhydride or 3,3', 4,4'-benzophenone tetracarboxylic dianhydride.
3. the preparation method of a kind of reduced graphene as claimed in claim 1 and polyimide nano-composite material, it is characterized in that described diamines is 4,4'-diaminodiphenyl oxide, 3,4'-diaminodiphenyl oxide, 3,3'-diaminodiphenyl oxide or 2,4'-diaminodiphenyl oxide, mphenylenediamine, O-Phenylene Diamine or Ursol D.
4. the preparation method of a kind of reduced graphene as claimed in claim 1 and polyimide nano-composite material, is characterized in that described solvent is N, N'-dimethyl formamide, N, N'-N,N-DIMETHYLACETAMIDE or N-Methyl pyrrolidone.
5. the preparation method of a kind of reduced graphene as claimed in claim 1 and polyimide nano-composite material, is characterized in that described neutralization reagent is triethylamine or Tributylamine.
6. 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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| CN103881124A (en) * | 2014-03-06 | 2014-06-25 | 河海大学 | Polyamide film loading graphene oxide nanometer sheet and preparation method and application thereof |
| CN104355302A (en) * | 2014-10-21 | 2015-02-18 | 复旦大学 | Preparation method of graphene/polyimide-based carbon aerogel |
| 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 |
| CN104672900A (en) * | 2015-02-10 | 2015-06-03 | 北京化工大学常州先进材料研究院 | High dielectric constant polyimide/multiwalled carbon nanotube/nano barium titanate composite film and preparation method thereof |
| CN105733002A (en) * | 2016-03-08 | 2016-07-06 | 华南师范大学 | Polyimide/PEG-b-PE/carbon material composite film with capacitance function and preparation method thereof |
| CN107488348A (en) * | 2017-09-04 | 2017-12-19 | 杭州高烯科技有限公司 | A kind of preparation method of graphene polyimides black film |
| CN107963623A (en) * | 2016-10-18 | 2018-04-27 | 中国科学院山西煤炭化学研究所 | The method for preparing carbon material-graphene composite material film |
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| CN111349255A (en) * | 2020-04-14 | 2020-06-30 | 安徽宇航派蒙健康科技股份有限公司 | Graphene-polyimide conductive film and preparation method thereof |
| CN111490233A (en) * | 2019-01-25 | 2020-08-04 | 南京大学 | Polyimide and graphene composite-based rechargeable magnesium battery positive electrode material and preparation method thereof |
| CN113831734A (en) * | 2021-09-30 | 2021-12-24 | 浙江中科玖源新材料有限公司 | Antistatic polyimide/graphene composite film and preparation method thereof |
| CN115216055A (en) * | 2022-06-23 | 2022-10-21 | 浙江美之源化妆品有限公司 | Preparation method of perfume volatilization medium graphite core rod |
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| CN103881124A (en) * | 2014-03-06 | 2014-06-25 | 河海大学 | Polyamide film loading graphene oxide nanometer sheet and preparation method and application thereof |
| CN104355302A (en) * | 2014-10-21 | 2015-02-18 | 复旦大学 | Preparation method of graphene/polyimide-based carbon aerogel |
| 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 |
| CN104672900B (en) * | 2015-02-10 | 2017-10-31 | 北京化工大学常州先进材料研究院 | A kind of high dielectric constant polyimide/multi-walled carbon nanotube/nano barium phthalate laminated film and preparation method thereof |
| CN104672900A (en) * | 2015-02-10 | 2015-06-03 | 北京化工大学常州先进材料研究院 | High dielectric constant polyimide/multiwalled carbon nanotube/nano barium titanate composite film and preparation method thereof |
| CN105733002B (en) * | 2016-03-08 | 2018-11-09 | 华南师范大学 | A kind of polyimides with capacitive function/PEG-b-PE/ carbon material laminated films and preparation method thereof |
| CN105733002A (en) * | 2016-03-08 | 2016-07-06 | 华南师范大学 | Polyimide/PEG-b-PE/carbon material composite film with capacitance function and preparation method thereof |
| CN107963623A (en) * | 2016-10-18 | 2018-04-27 | 中国科学院山西煤炭化学研究所 | The method for preparing carbon material-graphene composite material film |
| CN107488348A (en) * | 2017-09-04 | 2017-12-19 | 杭州高烯科技有限公司 | A kind of preparation method of graphene polyimides black film |
| CN108395576A (en) * | 2018-04-19 | 2018-08-14 | 太仓美克斯机械设备有限公司 | A kind of graphite acrylamide dispersion liquid and its application in anti-oxidant Polypyrrole Conducting Materials |
| CN111490233A (en) * | 2019-01-25 | 2020-08-04 | 南京大学 | Polyimide and graphene composite-based rechargeable magnesium battery positive electrode material and preparation method thereof |
| CN111349255A (en) * | 2020-04-14 | 2020-06-30 | 安徽宇航派蒙健康科技股份有限公司 | Graphene-polyimide conductive film and preparation method thereof |
| CN113831734A (en) * | 2021-09-30 | 2021-12-24 | 浙江中科玖源新材料有限公司 | Antistatic polyimide/graphene composite film and preparation method thereof |
| CN115216055A (en) * | 2022-06-23 | 2022-10-21 | 浙江美之源化妆品有限公司 | Preparation method of perfume volatilization medium graphite core rod |
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