CN109251529B - Synthesis preparation method and product of multilayer nano graphite sheet hybrid transparent polyimide film - Google Patents
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Abstract
The invention discloses a multilayer nano graphite sheet hybrid transparent polyimide film, which comprises the following substances in parts by weight: 500 parts of polyimide 200-200, 3-12 parts of nano graphite and 3-12 parts of microcrack discoloring agent. The multilayer nano graphite sheet hybrid transparent polyimide film adopts the technical scheme of compounding the nano graphite and the microcrack discoloring agent, so that the material is sensitive to grains with tiny cracks, shows observable changes by naked eyes, is easy to identify, has clear and visible color changes within a range of a few millimeters around the cracks, can effectively monitor the safety condition of the composite material used in airplanes and automobiles, and further avoids sudden accidents.
Description
Technical Field
The invention belongs to the technical field of polyimide film preparation, and particularly relates to a multilayer nano graphite sheet hybrid transparent polyimide film and a preparation method thereof.
Background
Minor damage to critical components of aircraft, automobiles, etc. can result in serious consequences. At present, the method of human eye observation and scanning instrument scanning is mainly adopted for tiny fission of components, human eyes can observe large cracks but cannot effectively observe the tiny fission, equipment scanning needs a large amount of time, and parts with complex components are difficult to scan.
The structural damage of the material usually begins from some tiny cracks and deformation, the distortion deformation of the natural materials such as shells of colored crustaceans can cause the color change, because the shells contain microcrack discoloring substances, if the polyimide film material is added with artificial microcrack discoloring substances in the preparation process, the polyimide film material is prepared into a 'microcrack Early-Warning transparent polyimide film', the hidden damage can be warned for the cracks and the perceived defects which are in micron order and difficult to detect, and the damage Sensitivity and Early Warning (Early Warning) and other fields are used for monitoring the safety condition of the composite materials used in airplanes and automobiles, thereby avoiding the occurrence of sudden accidents. The technology is not found to have a breakthrough at present, and is a technology which urgently needs to be developed and applied.
Disclosure of Invention
The invention aims to provide a multilayer nano graphite sheet hybrid transparent polyimide film and a preparation method thereof.
A multilayer nano graphite sheet hybrid transparent polyimide film comprises the following substances in parts by weight: 500 parts of polyimide 200-200, 3-12 parts of nano graphite and 3-12 parts of microcrack discoloring agent.
The microcrack discoloring agent is 1,2,3,10 b-tetrahydrofluoranthene, 9-ethyl fluorene or 9-benzyl fluorene.
The microcrack color-changing agent is a compound having the following molecular formula:
wherein X is methyl, ethyl, halogen or phenyl.
The polyimide is prepared from diamine and dianhydride by a two-step solution polycondensation method.
The diamine is 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, α, omega-bis (methylamino) polydimethylsiloxane, 2' -bis (trifluoromethyl) benzidine, 2, 4-diaminofluorobenzene, 2- (trifluoromethyl) -1, 4-phenylenediamine, 4-trifluoromethyl-1, 2-phenylenediamine or 4, 5-difluorobenzene-1, 2-diamine.
The dianhydride is 3, 3 ', 4, 4 ' -biphenyl tetracarboxylic dianhydride, 4, 4 ' -oxydiphthalic anhydride, pyromellitic dianhydride, bisphenol A dianhydride or hexafluoroisopropylidene diphthalic dianhydride.
The preparation method of the multilayer nano graphite sheet hybrid transparent polyimide film comprises the following steps:
(1) at room temperature, adding diamine and dianhydride into a reaction kettle, adding m-cresol under the protection of nitrogen, uniformly stirring, adding isoquinoline, heating to 170-200 ℃, reacting for 10-14 hours, cooling, and then pouring the reaction liquid into ethanol for precipitation to prepare polyimide resin;
(2) placing the nano graphite in an organic solvent, carrying out high-temperature treatment by a high-shear disperser, and then dispersing in advance, wherein the treatment temperature is 200-800 ℃;
(3) adding the synthesized polyimide resin and the treated nano-graphite into a reaction kettle, stirring at the stirring speed of 800-1200rpm for 1-2h to prepare a membrane liquid;
(4) adding a microcrack discoloring agent into the membrane liquid, and continuously stirring at the stirring speed of 300-500rpm for 2-5h to prepare a discoloring membrane liquid;
(5) pressing the color-changing film into a defoaming kettle, removing bubbles in the color-changing film liquid under a vacuum condition, and casting the defoamed color-changing film liquid into a casting machine to form a polyimide film with uniform thickness;
(6) putting the polyimide film into an imidization furnace for imidization, and processing the polyimide film by a winding machine and a splitting machine to prepare a finished product.
The organic solvent is dimethyl acetamide, dimethyl sulfoxide, N-dimethyl acetamide, N-dimethyl formamide, dimethyl sulfoxide or N-methyl pyrrolidone.
The invention has the beneficial effects that: the multilayer nano graphite sheet hybrid transparent polyimide film adopts the technical scheme of compounding the nano graphite and the microcrack discoloring agent, so that the material is sensitive to grains with tiny cracks, shows observable changes by naked eyes, is easy to identify, has clear and visible color changes within a range of a few millimeters around the cracks, can effectively monitor the safety condition of the composite material used in airplanes and automobiles, and further avoids sudden accidents.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
A multilayer nano graphite sheet hybrid transparent polyimide film comprises the following substances in parts by weight: 350g of polyimide, 5g of nano graphite and 8g of 1,2,3,10 b-tetrahydrofluoranthene.
The preparation method of the multilayer nano graphite sheet hybrid transparent polyimide film comprises the following steps:
(1) at room temperature, 1180g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane and 990g of 4, 4' -oxydiphthalic anhydride are added into a reaction kettle, 15000g of m-cresol is added under the protection of nitrogen, after uniform stirring, 500g of isoquinoline is added, the temperature is increased to 190 ℃, the reaction is carried out for 12 hours, and after cooling, the reaction solution is poured into ethanol for precipitation to prepare polyimide resin;
(2) placing 5g of nano graphite in 500g N-methyl pyrrolidone, and pre-dispersing the nano graphite after high-temperature treatment by a high-shear disperser, wherein the treatment temperature is 500 ℃;
(3) adding 350g of prepared polyimide resin into the nano graphite dispersion liquid prepared in the step (2), and stirring the mixture by a reaction kettle at the stirring speed of 1000rpm for 1.5h to prepare a membrane liquid;
(4) adding 8g of 1,2,3,10 b-tetrahydrofluoranthene into the membrane liquid, and continuously stirring at the stirring speed of 400rpm for 3 hours to prepare a color-changing membrane liquid;
(5) pressing the color-changing film into a defoaming kettle, removing bubbles in the color-changing film liquid under a vacuum condition, and casting the defoamed color-changing film liquid into a casting machine to form a polyimide film with uniform thickness;
(6) putting the polyimide film into an imidization furnace for imidization, and processing the polyimide film by a winding machine and a splitting machine to prepare a finished product.
Example 2
A multilayer nano graphite sheet hybrid transparent polyimide film comprises the following substances in parts by weight: 200g of polyimide, 3g of nano graphite and 3g of 9-ethyl fluorene.
The preparation method of the multilayer nano graphite sheet hybrid transparent polyimide film comprises the following steps:
(1) at room temperature, adding 1108g of 2, 2' -bis (trifluoromethyl) benzidine and 880g of pyromellitic dianhydride into a reaction kettle, adding 13000g of m-cresol under the protection of nitrogen, stirring uniformly, adding 400g of isoquinoline, heating to 170 ℃, reacting for 10 hours, cooling, and then pouring the reaction solution into ethanol for precipitation to prepare polyimide resin;
(2) putting 3g of nano graphite in 300g N-methyl pyrrolidone, and pre-dispersing the nano graphite after high-temperature treatment by a high-shear disperser, wherein the treatment temperature is 300 ℃;
(3) adding 200g of prepared polyimide resin into the nano graphite dispersion liquid prepared in the step (2), and stirring the mixture by a reaction kettle at the stirring speed of 800rpm for 1h to prepare a membrane liquid;
(4) adding 8g of 9-ethyl fluorene into the membrane liquid, and continuously stirring at the stirring speed of 400rpm for 3 hours to prepare a color-changing membrane liquid;
(5) pressing the color-changing film into a defoaming kettle, removing bubbles in the color-changing film liquid under a vacuum condition, and casting the defoamed color-changing film liquid into a casting machine to form a polyimide film with uniform thickness;
(6) putting the polyimide film into an imidization furnace for imidization, and processing the polyimide film by a winding machine and a splitting machine to prepare a finished product.
Example 3
A multilayer nano graphite sheet hybrid transparent polyimide film comprises the following substances in parts by weight: 500g of polyimide, 12g of nano graphite and 12g of 9-benzylfluorene.
The preparation method of the multilayer nano graphite sheet hybrid transparent polyimide film comprises the following steps:
(1) at room temperature, adding 1320g of α, omega-bis (methylamino) polydimethylsiloxane and 1010g of bisphenol A type dianhydride into a reaction kettle, adding 15000g of m-cresol under the protection of nitrogen, stirring uniformly, adding 500g of isoquinoline, heating to 200 ℃, reacting for 14 hours, cooling, and then pouring the reaction liquid into ethanol for precipitation to prepare polyimide resin;
(2) placing 12g of nano graphite in 600g of N-methyl pyrrolidone, carrying out high-temperature treatment by a high-shear disperser, and then dispersing in advance, wherein the treatment temperature is 800 ℃;
(3) adding the synthesized polyimide resin and the processed nano-graphite into a reaction kettle, stirring at the stirring speed of 1200rpm for 2 hours, and preparing a membrane liquid;
(4) adding 12g of 9-benzylfluorene into the membrane liquid, and continuously stirring at the stirring speed of 500rpm for 5 hours to prepare a color-changing membrane liquid;
(5) pressing the color-changing film into a defoaming kettle, removing bubbles in the color-changing film liquid under a vacuum condition, and casting the defoamed color-changing film liquid into a casting machine to form a polyimide film with uniform thickness;
(6) putting the polyimide film into an imidization furnace for imidization, and processing the polyimide film by a winding machine and a splitting machine to prepare a finished product.
Example 4
A multilayer nano graphite sheet hybrid transparent polyimide film comprises the following substances in parts by weight: 350g of polyimide, 5g of nano graphite and 8g of (3-chloropentane-1, 5-diacyl) diphenyl.
The preparation method of the multilayer nano graphite sheet hybrid transparent polyimide film comprises the following steps:
(1) at room temperature, 1180g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane and 990g of 4, 4' -oxydiphthalic anhydride are added into a reaction kettle, 15000g of m-cresol is added under the protection of nitrogen, after uniform stirring, 500g of isoquinoline is added, the temperature is increased to 190 ℃, the reaction is carried out for 12 hours, and after cooling, the reaction solution is poured into ethanol for precipitation to prepare polyimide resin;
(2) placing 5g of nano graphite in 500g N-methyl pyrrolidone, and pre-dispersing the nano graphite after high-temperature treatment by a high-shear disperser, wherein the treatment temperature is 500 ℃;
(3) adding 350g of prepared polyimide resin into the nano graphite dispersion liquid prepared in the step (2), and stirring the mixture by a reaction kettle at the stirring speed of 1000rpm for 1.5h to prepare a membrane liquid;
(4) adding 8g of (3-chloropentane-1, 5-diacyl) diphenyl into the membrane liquid, and continuously stirring at the stirring speed of 400rpm for 3 hours to prepare a color-changing membrane liquid;
(5) pressing the color-changing film into a defoaming kettle, removing bubbles in the color-changing film liquid under a vacuum condition, and casting the defoamed color-changing film liquid into a casting machine to form a polyimide film with uniform thickness;
(6) putting the polyimide film into an imidization furnace for imidization, and processing the polyimide film by a winding machine and a splitting machine to prepare a finished product.
Example 5
A multilayer nano graphite sheet hybrid transparent polyimide film comprises the following substances in parts by weight: 350g of polyimide, 5g of nano graphite and 8g of pentane-1, 3, 5-trinitrobenzene.
The preparation method of the multilayer nano graphite sheet hybrid transparent polyimide film comprises the following steps:
(1) at room temperature, 1180g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane and 990g of 4, 4' -oxydiphthalic anhydride are added into a reaction kettle, 15000g of m-cresol is added under the protection of nitrogen, after uniform stirring, 500g of isoquinoline is added, the temperature is increased to 190 ℃, the reaction is carried out for 12 hours, and after cooling, the reaction solution is poured into ethanol for precipitation to prepare polyimide resin;
(2) placing 5g of nano graphite in 500g N-methyl pyrrolidone, and pre-dispersing the nano graphite after high-temperature treatment by a high-shear disperser, wherein the treatment temperature is 500 ℃;
(3) adding 350g of prepared polyimide resin into the nano graphite dispersion liquid prepared in the step (2), and stirring the mixture by a reaction kettle at the stirring speed of 1000rpm for 1.5h to prepare a membrane liquid;
(4) adding 8g of pentane-1, 3, 5-trinitrobenzene into the membrane liquid, and continuously stirring at the stirring speed of 400rpm for 3 hours to prepare a color-changing membrane liquid;
(5) pressing the color-changing film into a defoaming kettle, removing bubbles in the color-changing film liquid under a vacuum condition, and casting the defoamed color-changing film liquid into a casting machine to form a polyimide film with uniform thickness;
(6) putting the polyimide film into an imidization furnace for imidization, and processing the polyimide film by a winding machine and a splitting machine to prepare a finished product.
Example 6
A multilayer nano graphite sheet hybrid transparent polyimide film comprises the following substances in parts by weight: 350g of polyimide, 5g of nano-graphite and 8g of 1- (2-chloroethyl) -3- (4 beta-chloromethylcyclohexane-1 alpha-yl) -1-nitrosourea.
The preparation method of the multilayer nano graphite sheet hybrid transparent polyimide film comprises the following steps:
(1) at room temperature, 1180g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane and 990g of 4, 4' -oxydiphthalic anhydride are added into a reaction kettle, 15000g of m-cresol is added under the protection of nitrogen, after uniform stirring, 500g of isoquinoline is added, the temperature is increased to 190 ℃, the reaction is carried out for 12 hours, and after cooling, the reaction solution is poured into ethanol for precipitation to prepare polyimide resin;
(2) placing 5g of nano graphite in 500g N-methyl pyrrolidone, and pre-dispersing the nano graphite after high-temperature treatment by a high-shear disperser, wherein the treatment temperature is 500 ℃;
(3) adding 350g of prepared polyimide resin into the nano graphite dispersion liquid prepared in the step (2), and stirring the mixture by a reaction kettle at the stirring speed of 1000rpm for 1.5h to prepare a membrane liquid;
(4) adding 8g of 1- (2-chloroethyl) -3- (4 beta-chloromethylcyclohexane-1 alpha-yl) -1-nitrosourea into the membrane liquid, and continuously stirring at the stirring speed of 400rpm for 3h to prepare a color-changing membrane liquid;
(5) pressing the color-changing film into a defoaming kettle, removing bubbles in the color-changing film liquid under a vacuum condition, and casting the defoamed color-changing film liquid into a casting machine to form a polyimide film with uniform thickness;
(6) putting the polyimide film into an imidization furnace for imidization, and processing the polyimide film by a winding machine and a splitting machine to prepare a finished product.
Example 7
A multilayer nano graphite sheet hybrid transparent polyimide film comprises the following substances in parts by weight: 350g of polyimide, 5g of nano graphite, 8g of pentane-1, 3, 5-trinitrobenzene and 3g of shell extract of the shell of the ballistic-resistant cocklebur beetle.
The extraction method of the shell extract of the Canarium album comprises the following steps: grinding shell of Ardisia perforata, sieving with 60 mesh sieve, adding 8 times weight parts of 75% ethanol water solution, reflux extracting for 3 times, mixing filtrates, decolorizing with active carbon, and evaporating to dryness.
The preparation method of the multilayer nano graphite sheet hybrid transparent polyimide film comprises the following steps:
(1) at room temperature, 1180g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane and 990g of 4, 4' -oxydiphthalic anhydride are added into a reaction kettle, 15000g of m-cresol is added under the protection of nitrogen, after uniform stirring, 500g of isoquinoline is added, the temperature is increased to 190 ℃, the reaction is carried out for 12 hours, and after cooling, the reaction solution is poured into ethanol for precipitation to prepare polyimide resin;
(2) placing 5g of nano graphite in 500g N-methyl pyrrolidone, and pre-dispersing the nano graphite after high-temperature treatment by a high-shear disperser, wherein the treatment temperature is 500 ℃;
(3) adding 350g of prepared polyimide resin into the nano graphite dispersion liquid prepared in the step (2), and stirring the mixture by a reaction kettle at the stirring speed of 1000rpm for 1.5h to prepare a membrane liquid;
(4) adding 8g of pentane-1, 3, 5-trinitrobenzene and 3g of shell extract of the shooting and blasting step into the membrane liquid, and continuously stirring at the stirring speed of 400rpm for 3 hours to prepare a color-changing membrane liquid;
(5) pressing the color-changing film into a defoaming kettle, removing bubbles in the color-changing film liquid under a vacuum condition, and casting the defoamed color-changing film liquid into a casting machine to form a polyimide film with uniform thickness;
(6) putting the polyimide film into an imidization furnace for imidization, and processing the polyimide film by a winding machine and a splitting machine to prepare a finished product.
Comparative example 1
A multilayer nano graphite sheet hybrid transparent polyimide film comprises the following substances in parts by weight: 350g of polyimide and 5g of nano graphite.
The preparation method of the multilayer nano graphite sheet hybrid transparent polyimide film comprises the following steps:
(1) at room temperature, 1180g of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane and 990g of 4, 4' -oxydiphthalic anhydride are added into a reaction kettle, 15000g of m-cresol is added under the protection of nitrogen, after uniform stirring, 500g of isoquinoline is added, the temperature is increased to 190 ℃, the reaction is carried out for 12 hours, and after cooling, the reaction solution is poured into ethanol for precipitation to prepare polyimide resin;
(2) placing 5g of nano graphite in 500g N-methyl pyrrolidone, and pre-dispersing the nano graphite after high-temperature treatment by a high-shear disperser, wherein the treatment temperature is 500 ℃;
(3) adding 350g of prepared polyimide resin into the nano graphite dispersion liquid prepared in the step (2), and stirring the mixture by a reaction kettle at the stirring speed of 1000rpm for 1.5h to prepare a membrane liquid;
(4) pressing the membrane liquid into a defoaming kettle, removing bubbles in the membrane liquid under a vacuum condition, and casting the defoamed membrane liquid into a casting machine to form a polyimide membrane with uniform thickness;
(5) putting the polyimide film into an imidization furnace for imidization, and processing the polyimide film by a winding machine and a splitting machine to prepare a finished product.
Experimental example:
taking the polyimide films prepared in the examples 1 to 7 and the comparative example 1, scratching a micro scratch with the length of 1cm and the width of 0.2mm by using a sharp knife, observing whether the color change exists around the scratch of the polyimide film, calculating the width of a color band, and obtaining the experimental result shown in the table 1:
TABLE 1
Note: represents P <0.05 compared to the example 1 group.
As can be seen from table 1, the microcrack discoloring agent was not added in comparative example 1, no color band was generated, the colored bands of examples 1 to 5 were generated, the colored bands of examples 6 to 7 were generated, and the width of the color band was significantly higher than that of example 1.
Claims (6)
1. The multilayer nano graphite sheet hybrid transparent polyimide film is characterized by comprising the following substances in parts by weight: 500 parts of polyimide 200-one, 3-12 parts of nano graphite and 3-12 parts of a microcrack discoloring agent; the microcrack discoloring agent is 1,2,3,10 b-tetrahydrofluoranthene, 9-ethylfluorene, 9-benzylfluorene, (3-chloropentane-1, 5-diacyl) diphenyl, pentane-1, 3, 5-trinitrobenzene, 1- (2-chloroethyl) -3- (4 beta-chloromethylcyclohexane-1 alpha-yl) -1-nitrosourea or a shell extract of a barberry beetle.
2. The multilayer graphite nanoplatelet hybrid transparent polyimide film as claimed in claim 1, wherein the polyimide is prepared from diamine and dianhydride by a two-step solution polycondensation method.
3. The multi-layered graphite nanoplatelet hybrid transparent polyimide film of claim 1, wherein the diamine is 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane, α, ω -bis (methylamino) polydimethylsiloxane, 2' -bis (trifluoromethyl) benzidine, 2, 4-diaminofluorobenzene, 2- (trifluoromethyl) -1, 4-phenylenediamine, 4-trifluoromethyl-1, 2-phenylenediamine or 4, 5-difluorobenzene-1, 2-diamine.
4. The multi-layered nanographitic plate hybrid transparent polyimide film according to claim 1, wherein the dianhydride is 3, 3 ', 4, 4 ' -biphenyltetracarboxylic dianhydride, 4, 4 ' -oxydiphthalic anhydride, pyromellitic dianhydride, bisphenol a type dianhydride, or hexafluoroisopropylidene diphthalic dianhydride.
5. The method for preparing the multilayer graphite nanoplatelet hybrid transparent polyimide film as recited in claim 1, comprising the following steps:
(1) at room temperature, adding diamine and dianhydride into a reaction kettle, adding m-cresol under the protection of nitrogen, uniformly stirring, adding isoquinoline, heating to 170-200 ℃, reacting for 10-14 hours, cooling, and then pouring the reaction liquid into ethanol for precipitation to prepare polyimide resin;
(2) placing the nano graphite in an organic solvent, carrying out high-temperature treatment by a high-shear disperser, and then dispersing in advance, wherein the treatment temperature is 200-800 ℃;
(3) adding the synthesized polyimide resin and the treated nano-graphite into a reaction kettle, stirring at the stirring speed of 800-1200rpm for 1-2h to prepare a membrane liquid;
(4) adding a microcrack discoloring agent into the membrane liquid, and continuously stirring at the stirring speed of 300-500rpm for 2-5h to prepare a discoloring membrane liquid;
(5) pressing the color-changing film into a defoaming kettle, removing bubbles in the color-changing film liquid under a vacuum condition, and casting the defoamed color-changing film liquid into a casting machine to form a polyimide film with uniform thickness;
(6) putting the polyimide film into an imidization furnace for imidization, and processing the polyimide film by a winding machine and a splitting machine to prepare a finished product.
6. The method for preparing the multilayer graphite nanoplatelet hybrid transparent polyimide film according to claim 5, wherein the organic solvent is N, N-dimethylacetamide, N-dimethylformamide, dimethylsulfoxide or N-methylpyrrolidone.
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| PCT/CN2018/107191 WO2020029391A1 (en) | 2018-08-07 | 2018-09-25 | Method for preparing multilayer nanographite flake hybrid transparent polyimide thin film synthesis and product thereof |
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| JP2009025625A (en) * | 2007-07-20 | 2009-02-05 | Ricoh Co Ltd | Electrophotographic seamless belt, intermediate transfer belt, and image forming apparatus and full-color image forming apparatus using the same |
| WO2009069715A1 (en) * | 2007-11-30 | 2009-06-04 | Gunze Limited | Semielectroconductive polyimide resin belt and process for producing semielectroconductive polyimide resin belt |
| CN103145987B (en) * | 2013-03-29 | 2014-12-17 | 黑龙江大学 | Preparation method of polyimide and graphene oxide compounded photoelectric material |
| CN106496611A (en) * | 2016-09-26 | 2017-03-15 | 安徽国风塑业股份有限公司 | A kind of preparation method of high heat conduction Kapton |
-
2018
- 2018-08-07 CN CN201810887929.9A patent/CN109251529B/en active Active
- 2018-09-25 WO PCT/CN2018/107191 patent/WO2020029391A1/en active Application Filing
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| WO2020029391A1 (en) | 2020-02-13 |
| CN109251529A (en) | 2019-01-22 |
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Inventor after: Xu Weiwei Inventor after: Gao Shanglin Inventor after: Wang Yong Inventor after: Qi Xiaodong Inventor after: Jiang Xin Inventor after: Chen Chen Inventor before: Xu Weiwei Inventor before: Gao Shanglin Inventor before: Wang Yong Inventor before: Xiao Dong Qi Inventor before: Jiang Xin Inventor before: Chen Chen |
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Application publication date: 20190122 Assignee: YANGZHOU YABAO NEW MATERIAL TECHNOLOGY CO.,LTD. Assignor: JIANGSU YABAO INSULATION MATERIAL Co.,Ltd. Contract record no.: X2023980036321 Denomination of invention: Preparation method and product of multilayer nano graphite hybrid transparent polyimide film Granted publication date: 20200522 License type: Common License Record date: 20230608 |