CN113150545B - Polymer film containing nano fullerene and preparation method thereof - Google Patents
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Abstract
The invention relates to a polyimide film containing nano fullerene, which contains amino acid ester or substituted amino acid ester modified nano fullerene, and the addition amount of the nano fullerene is 0.2-5% of the mass of polyimide. The preparation method comprises the following steps: firstly, diamine and dianhydride react in an organic solvent to obtain polyamic acid; then adding amino acid ester or substituted amino acid ester modified nano fullerene, and uniformly mixing to obtain polyamic acid/fullerene precursor solution; and coating the precursor solution to prepare a membrane, and performing high-temperature thermal imidization to obtain the polyimide/fullerene hybrid membrane. The technology of the invention eliminates the charge accumulation phenomenon on the surface of the film material by introducing the nano fullerene with a special structure into the polyimide film, avoids the adverse effect on the luminous display layer and reduces the deviation of the threshold voltage in the display device.
Description
Technical Field
The invention belongs to the field of polymer materials, and relates to a polyimide film containing nano fullerene and a preparation method thereof.
Background
Polyimide is an important high-performance polymer material and has wide application in the fields of electronics, microelectronics, new energy, aviation, aerospace and the like. Particularly in the fields of integrated circuits, photoelectric displays, and the like, polyimide films are important as interlayer dielectric and heat-resistant substrate materials because of their excellent heat resistance, mechanical properties, chemical stability, and the like.
The imidization method of polyimide includes both thermal imidization and chemical imidization, and since most of polyimides have poor solubility, they can be prepared only by subjecting polyamic acid or acid derivative thereof to high-temperature thermal imidization. For flexible display devices, the transparent polyimide as a flexible polymer substrate is the key to achieving flexibility, lightness and thinness of the device. During the fabrication of the device, the transparent polyimide film upper layer is subjected to a series of high temperature deposition layers, such as a buffer layer, an active layer, a gate insulating layer, and the like. The performance of the polyimide substrate material has an important influence on the upper light-emitting display layer, and in the past, much research has been focused on the matching between the thermal expansion of polyimide and the inorganic layer, and so on, but at present, more problems reflect the electrical performance of the polyimide substrate material, and particularly, the charge accumulation effect on the surface affects the performance of the display device, and causes serious problems of threshold voltage shift, display accuracy reduction, even image retention, and so on. Therefore, on the basis of maintaining the good insulating property of the polyimide film material, eliminating the charge accumulation on the surface of the film and releasing the accumulated charge in time possibly brings about damage, which is a technical challenge to be solved at present.
The fullerene is a cage-shaped all-carbon molecule consisting of pentagons and hexagons and has unique chemical and physical properties. C60 and C70 fullerenes are the most common species, and are the two species which have the most stable physicochemical properties and are most widely studied. Among them, C60 fullerene has a perfectly symmetrical structure like a football, and the synthesis yield is also the highest. The fullerene material shows excellent performances in the aspects of superconductivity, magnetism, optics, catalysis, biology and the like, particularly the characteristics of unique pi electron structure, low electron recombination energy, high electron mobility and the like of fullerene molecules, and is increasingly and widely applied to the fields of new materials, new energy sources, photoelectric display, biomedicine and the like.
In order to solve the problems, the invention provides a polyimide film containing nano fullerene and a preparation method thereof, which eliminate the charge accumulation phenomenon on the surface of a polyimide film material by introducing the nano fullerene with a special structure into the film, avoid the adverse effect on a light-emitting display layer and improve the stability of threshold voltage in a display device.
Disclosure of Invention
The invention provides a polyimide film containing nano fullerene, which eliminates the charge accumulation phenomenon on the surface of a polyimide film material by introducing the nano fullerene with a special structure into the film.
The invention aims to provide a polyimide film containing nano fullerene, which is characterized in that the content of the nano fullerene is 0.2-5% of the mass of the polyimide.
The nano fullerene is amino acid ester or substituted amino acid ester modified nano fullerene, preferably amino acid ester, methyl amino acid ester, ethyl amino acid ester or benzyl amino acid ester modified C 60 Or C 70 A fullerene. The polyimide film containing nano fullerene is characterized in that the charge aggregation phenomenon on the surface of the polyimide film is effectively relieved.
When the addition amount of the nano fullerene is too low, the problem of charge aggregation on the surface of the polyimide film is not obviously improved; when the addition amount is too high, effective dispersion of nano fullerene becomes a problem, and simultaneously, the color of the polyamic acid solution is deepened, and the light transmittance and the yellowness of the prepared film are influenced.
The invention further relates to a preparation method of the polyimide film containing the nano fullerene, which is prepared by blending the polyamic acid solution and the nano fullerene and carrying out high-temperature thermal imidization treatment, and specifically comprises the following steps:
(1) Dissolving diamine and dianhydride in an organic solvent, and reacting to obtain a polyamic acid solution;
(2) Adding nano fullerene into the polyamic acid solution, and mixing to obtain polyamic acid/fullerene precursor solution;
(3) And coating the precursor solution to prepare a film, and performing high-temperature thermal imidization to obtain the polyimide/fullerene hybrid film.
In addition, after the temperature is reduced to room temperature after the step (3), the prepared polyimide/fullerene hybrid film can be soaked in water for stripping, dried and then stored for standby.
In step (1), the diamine is 4,4' -diaminodiphenyl sulfone, 3,4' -diaminodiphenyl sulfone, 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl, 2,2' -bis (methyl) -4,4' -diaminobiphenyl, 2,2' -bis-fluorine-4,4 ' -diaminobiphenyl, 2,2' -bis (trifluoromethyl) -4,4' -diaminophenyl ether, 3575-bis (2 ' -trifluoromethyl-4 ' -aminophenoxy) benzene, 1,4-bis (2 ' -trifluoromethyl-4 ' -aminophenoxy) biphenyl, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2' -bis (4-aminophenoxy phenyl) hexafluoropropane, 3925-5425-azft 544 ' -aminophenyl) cyclohexane, 8696-bis (3-aminophenyl) phenylfluorene, 963-bis (3-aminophenyl) phenylfluorene, 56963-964-diaminobenzofluorene, 3-bis (3-azftf-7496-aminobenzene, 8696-bis (3-aminobenzene) fluorene, 963-bis (3-963-aminobenzene) fluorene, N ' -bis (2-trifluoromethyl-4-aminophenyl) -terephthalamide, N ' -bis (3-trifluoromethyl-4-aminophenyl) -terephthalamide, N ' -3,3' -bis (trifluoromethyl) - (1,1-biphenyl) -4,4' -diaminobenzamide, and mixtures thereof, any one or more of N, N '-2,2' -bis (trifluoromethyl) - (1,1-biphenyl) -4,4 '-diaminobenzamide, N' -2,6-bis (trifluoromethyl) - (1,1-biphenyl) -4,4 '-diaminobenzamide, 4,4' -diaminodiphenyl ether, 1,4-p-phenylenediamine.
In step (1), the dianhydride is selected from 1,2,4,5-pyromellitic dianhydride, 2,5,7,10-naphthalenetetracarboxylic dianhydride, 3,3',4,4' -biphenyltetracarboxylic dianhydride, 2,3,3',4' -biphenyltetracarboxylic dianhydride, 3,3',4,4' -benzophenonetetracarboxylic dianhydride, 3,3',4,4' -diphenylsulfonetetracarboxylic dianhydride, 7984 zxft 3584 ',4,4' -diphenylethertetracarboxylic dianhydride, 3,3',4,4' -dibenzoic acid terephthalamide tetracarboxylic dianhydride, 4,4'- (3256 zxft 3556-hexafluoroisopropylidene) diphthalic dianhydride, norbornane-2-spiro- α -cyclopentanone- α' -norbornane-2 "-norbornane-34zft-3456" -pyromellitic dianhydride, hydrogenated naphthalene-tetracarboxylic dianhydride, 355749 hydrogenated tetracarboxylic dianhydride, 35xlft-tetracarboxylic dianhydride, 355738-cyclohexane-2-tetracarboxylic dianhydride, 35xlft-tetracarboxylic dianhydride, and hydrogenated naphthalene-2-tetracarboxylic dianhydride.
In the step (1), the organic solvent is any one or more of N, N '-dimethylformamide, N' -dimethylacetamide, N '-diethylformamide, N' -diethylacetamide, dimethylpropionamide, diethylpropionamide, N-methylpyrrolidone, N-ethylpyrrolidone, butyrolactone, cyclopentanone, dimethyl sulfoxide and m-cresol; the molar ratio of diamine to dianhydride is 1: (0.96-1.04) and the reaction temperature is-10 ℃ to 120 ℃; the solid content of the polyamic acid solution is 10-40% by mass.
The selected diamine and dianhydride are beneficial to the performance requirements of the flexible photoelectric display device on different polyimide substrate materials, and a polyimide structure with flexibly adjustable performance can be obtained through homopolymerization and copolymerization reaction modes, so that a series of polyimide films for flexible substrates with different heat resistance, transparency, mechanical properties and other requirements can be obtained.
In the step (2), the nano fullerene is amino acid ester or substituted amino acid ester surface modified nano fullerene, and preferably amino acid ester, methyl amino acid ester, ethyl amino acid ester, benzyl amino acid ester modified C 60 Or C 70 A fullerene. The nano fullerene with the surface modified by amino acid ester or substituted amino acid ester can bring the beneficial effects of improving the solubility and eliminating the accumulation of surface charges. On one hand, the problem that the traditional fullerene has poor solubility in an organic solvent can be effectively solved, and secondary amine (-NH-) or quaternary amine (-N-) groups and carboxylic ester groups (-COOR) brought by amino acid ester modification are very helpful for obtaining good dispersibility and compatibility of the fullerene in a polyamide acid solution. On the other hand, the strong electron capture capability of the nano fullerene can effectively eliminate the charges on the surface of the polyimide film in time, and the damage to the photoelectric display layer caused by the excessive accumulation of the charges is avoided. Meanwhile, the nano fullerene is not conductive per se, so that the insulating property of the polyimide film is not influenced.
In the step (2), the addition amount of the nano fullerene is 0.2 to 5 percent of the mass of the polyimide.
In step (3), the coating to make a film may be performed by any suitable coating method known in the art, such as spraying, blade coating, spin coating, and the like. The high-temperature thermal imidization process comprises the steps of baking for 2-6 hours at the temperature of 80-350 ℃; baking at 350-450 deg.c for 0.5-4 hr. On one hand, the high-temperature heat drying of the rear section is beneficial to improving the imidization degree of the polyimide film and improving the comprehensive performance of the polyimide film; on the other hand, the method is favorable for eliminating the agglomeration problem of the nano fullerene in the film, improving the dispersion performance in the matrix and reducing the influence on the light transmittance of the film.
The invention further relates to application of the nano fullerene containing polyimide film in the fields of flexible electronics, microelectronics, optical display, integrated circuits and the like.
Fullerenes are generally soluble in only a few aromatic benzene-based solvents, such as toluene, xylene, chlorobenzene, and the like. The fullerene derivatives with different structure types obtained by surface chemical modification improve the solubility of fullerene in organic solvent by introducing different functional groups. The invention selects amino acid ester or nano fullerene for replacing amino acid ester surface modification, effectively solves the problem that the traditional fullerene has poor solubility in organic solvent, can be directly added into solution of polyamic acid and derivatives thereof, does not change the conventional synthesis and film preparation process of polyimide, effectively realizes the dispersion of nano fullerene by utilizing high-temperature thermal imidization treatment in the polyimide film preparation process, and can simply, conveniently and quickly prepare the polyimide film containing nano fullerene.
In the invention, the added amino acid ester or substituted amino acid ester surface modified fullerene is in a nano-scale size and has good dispersibility in a polyamic acid solution, so that the prepared polyimide film has good surface quality, and meanwhile, the fullerene is a good electron acceptor for capturing free radicals and has smaller recombination energy in an electron transfer reaction, so that the nano fullerene has the capability of absorbing a large number of active free radicals and charges and the anti-oxidation characteristic, thereby being capable of eliminating any free radicals or electronic active groups possibly existing on the surface of the polyimide film in time and avoiding the excessive accumulation of the charges on the surface of the film.
Drawings
FIG. 1 is a photograph of a nano-fullerene containing polyimide film having a thickness of 10 μm prepared in examples 1 to 3.
Detailed Description
The following examples are intended to illustrate the present invention more specifically, but the present invention is not limited to these examples at all, and those skilled in the art can make various modifications within the technical idea of the present invention.
EXAMPLE 1 Nanofuerene-containing polyimide film PI/C 60 -1％
Step (1): 10.81 g (0.10 mol) of 1,4-p-phenylenediamine and 230 g of N, N-diethylacetamide are added into a three-mouth bottle with a mechanical stirring device, a nitrogen inlet and a nitrogen outlet and a thermometer, and stirred under the protection of nitrogen until the N, N-diethylacetamide is completely dissolved; 29.42 g (0.10 mol) of 3,3',4,4' -biphenyltetracarboxylic dianhydride was added, stirred until completely dissolved, and reacted at 25 ℃ for 16 hours to obtain a polyamic acid solution having a solid content of about 15 wt%.
Step (2): 0.36 g of methyl carbamate-modified C are weighed out 60 And adding fullerene into the polyamide acid solution, and quickly stirring until the fullerene and the polyamide acid solution are uniformly mixed.
And (3): and filtering the polyamic acid/fullerene precursor solution, defoaming in vacuum, and coating on a glass plate or a stainless steel plate with a flat surface. Baking at 60 deg.C for 2 hr, at 250 deg.C for 1 hr, and at 400 deg.C for 1 hr under nitrogen atmosphere. Cooling to room temperature, soaking in water, stripping, and drying to obtain polyimide film containing nano fullerene.
EXAMPLE 2 Nanofulefin-containing polyimide film PI/C 60 -3.0％
Step (1): 32.02 g (0.10 mol) of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl and 340 g of N, N-dimethylacetamide are added into a three-necked flask with a mechanical stirrer, a nitrogen inlet and outlet and a thermometer, and stirred under the protection of nitrogen until the N, N-dimethylacetamide is completely dissolved; 29.42 g (0.10 mole) of 3,3',4,4' -biphenyltetracarboxylic dianhydride was added, stirred until all dissolved, and reacted at 15 ℃ for 24 hours to give a polyamic acid solution with a solid content of about 15 wt%.
Step (2): 1.73 g of methyl carbamate-modified C are weighed out 60 And adding fullerene into the polyamide acid solution, and quickly stirring until the fullerene and the polyamide acid solution are uniformly mixed.
And (3): and filtering the polyamic acid/fullerene precursor solution, defoaming in vacuum, and coating on a glass plate or a stainless steel plate with a smooth surface. Baking at 80 deg.C for 1 hr, 200 deg.C for 2 hr, and 420 deg.C for 0.5 hr under nitrogen atmosphere. Cooling to room temperature, soaking in water, stripping, and drying to obtain polyimide film containing nano fullerene.
EXAMPLE 3 Nanofulefin-containing polyimide film PI/C 60 -5.0％
Step (1): 32.02 g (0.10 mol) of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl and 275 g of N-methyl-2-pyrrolidone are added into a three-mouth bottle with a mechanical stirring device, a nitrogen inlet and a nitrogen outlet and a thermometer, and stirred under the protection of nitrogen until the materials are completely dissolved; 14.71 g (0.05 mole) of 3,3',4,4' -biphenyltetracarboxylic dianhydride and 22.21 g (0.05 mole) of 4,4' - (2,2-hexafluoroisopropylidene) diphthalic anhydride were added, stirred until all dissolved, and reacted at 25 ℃ for 24 hours to give a polyamic acid solution with a solid content of about 20 wt%.
Step (2): 3.27 g of methyl urethane modified C are weighed 60 And adding fullerene into the polyamide acid solution, and quickly stirring until the fullerene and the polyamide acid solution are uniformly mixed.
And (3): and filtering the polyamic acid/fullerene precursor solution, defoaming in vacuum, and coating on a glass plate or a stainless steel plate with a smooth surface. Baking at 80 deg.C for 1 hr, at 350 deg.C for 0.5 hr, and at 450 deg.C for 0.5 hr under nitrogen atmosphere. Cooling to room temperature, soaking in water, stripping, and drying to obtain polyimide film containing nano fullerene.
Comparative example 1 simple polyimide film PI
Step (1): 10.81 g (0.10 mol) of 1,4-p-phenylenediamine and 210 g of N-methyl-2-pyrrolidone are added into a three-mouth bottle with a mechanical stirrer, a nitrogen inlet and a nitrogen outlet and a thermometer, and stirred under the protection of nitrogen until the materials are completely dissolved; 29.42 g (0.10 mole) of 3,3',4,4' -biphenyltetracarboxylic dianhydride was added, stirred until all dissolved, and reacted at 25 ℃ for 24 hours to give a polyamic acid solution with a solids content of about 16 wt%.
Step (2): and filtering the polyamic acid solution, defoaming in vacuum, and coating on a glass plate or a stainless steel plate with a smooth surface. Baking at 80 deg.C for 0.5 hr, at 250 deg.C for 2 hr, and at 430 deg.C for 0.5 hr under nitrogen atmosphere. Cooling to room temperature, soaking in water, stripping and drying to obtain the pure polyimide film.
Qualitative test of threshold voltage shift ratio of Nanofulefin-containing polyimide films prepared in examples 1 to 3 and of pure polyimide film prepared in comparative example 1
First, a Thin Film Transistor (TFT) was prepared based on the above polyimide film, and a threshold voltage (V) was obtained by testing a current-voltage curve (I-V curve) th ). Continuously applying voltage to the test sample to obtain threshold voltage deviation amount, i.e. delta V th . Because the test equipment can not complete long-time test, accurate quantitative delta V can not be obtained th Numerical values. Therefore, the experiment was conducted with respect to Δ V by periodically applying a voltage for a shorter time (1 to 10 hours) th The values were assessed qualitatively or semi-quantitatively.
The results show that the test samples prepared based on examples 1 to 3 exhibit lower Δ V th Values, estimated in the range of about 0.51 to 1.47V; whereas the test specimens prepared on the basis of comparative example 1 have a distinctly higher Δ V th The estimated value is in the range of about 2.2 to 3.6V. Although the precise Δ V cannot be obtained th The test value, but the overall rule of the test result proves that the introduction of the nano fullerene is helpful for reducing the offset of threshold voltage and the current fluctuation caused by the offset, thereby effectively inhibiting the influence on the light-emitting display layer and solving the problem of residual image in the display. FIG. 1 is a photo of a polyimide film containing nano-fullerene prepared in examples 1 to 3, which shows that the film has good optical transparency and low turbidity, indicating that nano-fullerene does not significantly agglomerate in the film, and the film preparation process provided by the surface modification and the technical method effectively improves the dispersibility of the nano-fullerene in a matrix and reduces the influence of the nano-fullerene on the light transmittance of the film.
Claims (9)
1. A polyimide film containing nano fullerene, wherein the content of the nano fullerene is 0.2% -5% of the mass of the polyimide, the nano fullerene is amino acid ester or nano fullerene modified by substituted amino acid ester, and the polyimide film containing the nano fullerene is subjected to high-temperature treatment at 350-450 ℃.
2. The nano-fullerene containing polyimide film according to claim 1, wherein the nano-fullerene is an amino acid ester, methyl amino acid ester, ethyl amino acid ester, benzyl amino acid ester modified C 60 Or C 70 A fullerene.
3. The process for preparing a nano-fullerene containing polyimide film according to any one of the preceding claims, comprising the steps of:
(1) Dissolving diamine and dianhydride in an organic solvent, and reacting to obtain a polyamic acid solution;
(2) Adding nano fullerene into the polyamic acid solution, and mixing to obtain polyamic acid/fullerene precursor solution;
(3) And coating the precursor solution to prepare a film, and performing high-temperature thermal imidization to obtain the polyimide/fullerene hybrid film.
4. The process according to claim 3, wherein in step (1) the diamine is 4,4' -diaminodiphenyl sulfone, 3,4' -diaminodiphenyl sulfone, 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl, 2,2' -bis (methyl) -4,4' -diaminobiphenyl, 2,2' -bis-fluoro-4,4 ' -diaminobiphenyl, 2,2' -bis (trifluoromethyl) -4,4' -diaminophenyl ether, 1,4-bis (2 ' -trifluoromethyl-4 ' -aminophenoxy) benzene, 1,4-bis (2 ' -trifluoromethyl-4 ' -aminophenoxy) biphenyl, 2,2-bis (3-aminophenyl) hexafluoropropane, 3828 ' bis (4-aminophenoxy) 5425, bis (2 ' -aminophenyl) -8696-bis (3-aminophenyl) fluorene, bis (74963-aminophenyl) 8696, bis (3-aminophenyl) -74964 ' -diaminofluorene, 3-bis (3-aminophenyl) fluorene, 567-bis (3-aminobenzene) fluorene, 964-bis (3-aminobenzene-8696, bis (3-aminobenzene) fluorene, N ' -bis (2-trifluoromethyl-4-aminophenyl) -terephthalamide, N ' -bis (3-trifluoromethyl-4-aminophenyl) -terephthalamide, N ' -3,3' -bis (trifluoromethyl) - (1,1-biphenyl) -4,4' -diaminobenzamide, any one or more of N, N ' -2,2' -bis (trifluoromethyl) - (1,1-biphenyl) -4,4' -diaminobenzamide, N ' -2,6-bis (trifluoromethyl) - (1,1-biphenyl) -4,4' -diaminobenzamide, 4,4' -diaminodiphenyl ether, 1,4-p-phenylenediamine;
the dianhydride is selected from 1,2,4,5-pyromellitic dianhydride, 2,5,7,10-naphthalene tetracarboxylic dianhydride, 3,3',4,4' -biphenyl tetracarboxylic dianhydride, 2,3,3',4' -biphenyl tetracarboxylic dianhydride, 3,3',4,4' -benzophenone tetracarboxylic dianhydride, 3,3',4,4' -diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride, 3,3',4,4' -dibenzoic acid terephthalamide tetracarboxylic dianhydride, 4,4'- (56 zxft 3256-hexafluoroisopropylidene) diphthalic dianhydride, norbornane-2-spiro-alpha-cyclopentanone-alpha' -spiro-2 '-norbornane-5,5' -3238-cyclohexane-tetracarboxylic dianhydride, hydrogenated cyclohexane-2-tetracarboxylic dianhydride, hydrogenated cyclohexane-5738-tetracarboxylic dianhydride, hydrogenated naphthalene-2-tetracarboxylic dianhydride [ 5 ] dianhydride, or hydrogenated cyclohexane-2-naphthalene-2-tetracarboxylic dianhydride [ 385749 ];
the molar ratio of diamine to dianhydride is 1: 0.96-1.04.
5. The method according to claim 3, wherein in the step (1), the organic solvent is any one or more of N, N-dimethylformamide, N-dimethylacetamide, N-diethylformamide, N-diethylacetamide, dimethylpropionamide, diethylpropionamide, N-methylpyrrolidone, N-ethylpyrrolidone, butyrolactone, cyclopentanone, dimethylsulfoxide, and m-cresol.
6. The method according to claim 3, wherein in the step (2), the solid content of the polyamic acid solution is 10-40%, and the reaction temperature is-10 ℃ to 120 ℃.
7. The method as claimed in claim 3, wherein in step (2), the nano fullerene is added in an amount of 0.2-5% by mass of the polyimide.
8. The method according to claim 3, wherein in the step (3), the high temperature thermal imidization process comprises a heat-baking at 80-350 ℃ for 2-6 hours; and baking at 350-450 deg.c for 0.5-4 hr.
9. Use of a nano-fullerene containing polyimide film as claimed in any one of claims 1 to 2 in the fields of flexible electronics, microelectronics, optical displays, integrated circuits.
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| CN101418079A (en) * | 2008-11-27 | 2009-04-29 | 同济大学 | Method for preparing polyimide lubrication film containing fullerene additives |
| CN103739840A (en) * | 2013-12-12 | 2014-04-23 | 青岛海洋新材料科技有限公司 | Preparation method of fullerene-polyimide conductive film |
| CN106083626A (en) * | 2016-06-03 | 2016-11-09 | 厦门大学 | One fullerene amino-acid ester self assembly carried medicine sustained-release vesicle material and its preparation method and application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101418079A (en) * | 2008-11-27 | 2009-04-29 | 同济大学 | Method for preparing polyimide lubrication film containing fullerene additives |
| CN103739840A (en) * | 2013-12-12 | 2014-04-23 | 青岛海洋新材料科技有限公司 | Preparation method of fullerene-polyimide conductive film |
| CN106083626A (en) * | 2016-06-03 | 2016-11-09 | 厦门大学 | One fullerene amino-acid ester self assembly carried medicine sustained-release vesicle material and its preparation method and application |
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