WO2020029392A1 - Transparent polyimide film with slight crack early-warning function and preparation method therefor - Google Patents

Transparent polyimide film with slight crack early-warning function and preparation method therefor Download PDF

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WO2020029392A1
WO2020029392A1 PCT/CN2018/107196 CN2018107196W WO2020029392A1 WO 2020029392 A1 WO2020029392 A1 WO 2020029392A1 CN 2018107196 W CN2018107196 W CN 2018107196W WO 2020029392 A1 WO2020029392 A1 WO 2020029392A1
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polyimide film
film
transparent polyimide
warning
add
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PCT/CN2018/107196
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French (fr)
Chinese (zh)
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徐伟伟
高尚林
王勇
祁晓东
姜新
陈晨
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江苏亚宝绝缘材料股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C08K3/045—Fullerenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/02—Halogenated hydrocarbons
    • C08K5/03—Halogenated hydrocarbons aromatic, e.g. C6H5-CH2-Cl

Definitions

  • the invention belongs to the technical field of polyimide film preparation, and particularly relates to a transparent polyimide film for early warning of microcracks and a preparation method thereof.
  • micro fissures of components are mainly observed by human eyes and scanning instruments. Human eyes can observe large fissures, but it is difficult to effectively observe micro fissures. Equipment scanning takes a lot of time, and some parts have complex parts. Difficult to scan.
  • Material structural damage often starts with some small cracks and deformations. Natural materials such as colored beetles' shells can cause color changes due to distortion. Because the shell contains micro-crack color-changing substances, if polyimide film materials are prepared In the process, artificial micro-crack discoloration substance is added to prepare a “transparent polyimide film with early warning of micro-cracks”. The micro-scale cracks and defects that are difficult to detect can be used to warn of hidden damage. Damage sensitivity (Defect Sensitivity), Early Warning (Early Warning) and other fields are used to monitor the safety status of composite materials used in aircraft and automobiles, so as to avoid sudden accidents. This technology has not yet been found to have a breakthrough, and is a technology in urgent need of development and application.
  • the object of the present invention is to provide a transparent polyimide film for early warning of microcracks and a preparation method thereof.
  • a transparent polyimide film for warning of microcracks comprising the following parts by weight: 200-500 parts of polyimide, 3-8 parts of fullerene, and 3-8 parts of microcrack discoloration agent.
  • micro-crack discoloration agent is 3-methylcholanthrene, 7,12-dimethylbenzoanthracene, and fluoranthene-d10.
  • micro-crack discoloration agent is a compound having the following molecular formula:
  • X is methyl, ethyl, halogen or phenyl
  • Y is butyl, halogen or phenyl
  • the polyimide is prepared by using a diamine and a dianhydride as raw materials and adopting a two-step solution polycondensation method.
  • the diamine is 2,2-bis [4- (4-aminophenoxy) phenyl] propane, ⁇ , ⁇ -bis (methylamino) polydimethylsiloxane, 2,2'-bis (Trifluoromethyl) benzidine, 2,4-diaminofluorobenzene, 2- (trifluoromethyl) -1,4-phenylenediamine, 4-trifluoromethyl-1,2-benzenediamine Amine or 4,5-difluorobenzene-1,2-diamine.
  • the dianhydride is 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxybisphthalic anhydride, pyromellitic dianhydride, bisphenol A dianhydride or Hexafluoroisopropylidene diphthalic dianhydride.
  • Fullerene is placed in an organic solvent and pre-dispersed after being subjected to a high-temperature treatment by a high-shear dispersing machine, and the processing temperature is 200-800 ° C;
  • the polyimide film is placed in an imidization furnace for imidization, and processed by a winder and a slitter to produce a finished product.
  • the organic solvent is dimethylacetamide, dimethylsulfoxide, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide or N-methylpyrrolidone.
  • the transparent polyimide film for early warning of microcracks of the present invention adopts the technical solution of fullerene and microcrack discolorant composite technology to make the material sensitive to minute lines of fission, showing changes observable to the naked eye. It is easy to identify. Within a few millimeters around the crack, the color change is clearly visible, which can effectively monitor the safety status of those composite materials used in aircraft and automobiles, thereby avoiding accidents.
  • a transparent polyimide film for warning of microcracks includes the following materials in parts by weight: 350g of polyimide, 5g of fullerene, and 5g of 3-methylcholanthrene.
  • step (3) Take 350 g of the prepared polyimide resin, add it to the fullerene dispersion prepared in step (2), and stir it in a reaction kettle at a stirring speed of 1000 rpm and a stirring time of 1.5 h to prepare a film liquid;
  • the polyimide film is placed in an imidization furnace for imidization, and processed by a winder and a slitter to produce a finished product.
  • a transparent polyimide film for warning of microcracks includes the following parts by weight: 200g of polyimide, 3g of fullerene, and 3g of 7,12-dimethylbenzoanthracene.
  • step (3) Take 200 g of the prepared polyimide resin, add it to the fullerene dispersion prepared in step (2), and stir it in a reaction kettle at a stirring speed of 800 rpm and a stirring time of 1 hour to prepare a film liquid;
  • the polyimide film is placed in an imidization furnace for imidization, and processed by a winder and a slitter to produce a finished product.
  • a transparent polyimide film for early warning of microcracks includes the following parts by weight: 500g of polyimide, 8g of fullerene, and 8g of fluoranthene-d10.
  • the polyimide film is placed in an imidization furnace for imidization, and processed by a winder and a slitter to produce a finished product.
  • a transparent polyimide film for warning of microcracks comprising the following parts by weight: 350g of polyimide, 5g of fullerene, 2- (chloromethyl) -4- (2-chloropentyl)- 1-pentylbenzene 5g.
  • step (3) Take 350 g of the prepared polyimide resin, add it to the fullerene dispersion prepared in step (2), and stir it in a reaction kettle at a stirring speed of 1000 rpm and a stirring time of 1.5 h to prepare a film liquid;
  • the polyimide film is placed in an imidization furnace for imidization, and processed by a winder and a slitter to produce a finished product.
  • a transparent polyimide film for warning of microcracks comprising the following parts by weight: 350g of polyimide, 5g of fullerene, and 5g of 2-phenyl-1-pentyl-4-pentylbenzene.
  • step (3) Take 350 g of the prepared polyimide resin, add it to the fullerene dispersion prepared in step (2), and stir it in a reaction kettle at a stirring speed of 1000 rpm and a stirring time of 1.5 h to prepare a film liquid;
  • the polyimide film is placed in an imidization furnace for imidization, and processed by a winder and a slitter to produce a finished product.
  • a transparent polyimide film for warning of microcracks includes the following materials in parts by weight: 350g of polyimide, 5g of fullerene, and 5g of (2-cyclohexyl) benzene.
  • step (3) Take 350 g of the prepared polyimide resin, add it to the fullerene dispersion prepared in step (2), and stir it in a reaction kettle at a stirring speed of 1000 rpm and a stirring time of 1.5 h to prepare a film liquid;
  • the polyimide film is placed in an imidization furnace for imidization, and processed by a winder and a slitter to produce a finished product.
  • a transparent polyimide film for warning of microcracks comprising the following parts by weight: 350g of polyimide, 5g of fullerene, 5g of 3-methylcholanthrene, and 3g of Lijin turtle shell extract.
  • the extraction method of the beetle shell extract is as follows: the beetle shell is ground, passed through a 60 mesh sieve, and 8 times by weight of 75% ethanol aqueous solution is added for reflux extraction three times. to make.
  • step (3) Take 350 g of the prepared polyimide resin, add it to the fullerene dispersion prepared in step (2), and stir it in a reaction kettle at a stirring speed of 1000 rpm and a stirring time of 1.5 h to prepare a film liquid;
  • the polyimide film is placed in an imidization furnace for imidization, and processed by a winder and a slitter to produce a finished product.
  • a transparent polyimide film for early warning of microcracks includes the following parts by weight: 350g of polyimide and 5g of fullerene.
  • step (3) Take 350 g of the prepared polyimide resin, add it to the fullerene dispersion prepared in step (2), and stir it in a reaction kettle at a stirring speed of 1000 rpm and a stirring time of 1.5 h to prepare a film liquid;
  • the membrane is hydraulically pressured into a defoaming kettle, and the air bubbles in the membrane liquid are removed under a vacuum condition; the defoamed membrane liquid is put into a casting machine and cast to form a polyimide film having a uniform thickness;
  • the polyimide film is placed in an imidization furnace for imidization, and processed by a winder and a slitter to produce a finished product.

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  • Manufacturing & Machinery (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

Disclosed are a transparent polyimide film with a slight crack early-warning function and a preparation method therefor. The transparent polyimide film comprises the following substances in parts by weight: 200-500 parts of a polyimide, 3-8 parts of fullerene, and 3-8 parts of a slight crack color-changing agent. With regard to the transparent polyimide film with a slight crack early-warning function of the present invention, a technical scheme of combining the fullerene and the slight crack color-changing agent is used, such that the material is sensitive to the texture of a slight crack and displays a change that is observable by the naked eye and is easy to identify, and the change in color is clear and visible within a range of several millimeters around the crack. Same can be effective in monitoring the safety conditions of composite materials used in aircrafts and automobiles in order to avoid the occurrence of sudden accidents.

Description

一种预警微裂纹的透明聚酰亚胺薄膜及其制备方法Early warning micro crack transparent polyimide film and preparation method thereof 技术领域Technical field
本发明属于聚酰亚胺薄膜制备技术领域，具体涉及一种预警微裂纹的透明聚酰亚胺薄膜及其制备方法。The invention belongs to the technical field of polyimide film preparation, and particularly relates to a transparent polyimide film for early warning of microcracks and a preparation method thereof.
背景技术Background technique
飞机，汽车等关键部件的微小损害，可能会导致严重的后果发生。而部件的微小裂变目前主要采用人眼观察和扫描器械扫描的办法，人眼可以观察到大的裂口，却难以有效观察到微小的裂变，设备扫描需要花费大量的时间，且有些部件复杂的部位难以扫描。Minor damage to key components such as airplanes and automobiles can lead to serious consequences. At present, the micro fissures of components are mainly observed by human eyes and scanning instruments. Human eyes can observe large fissures, but it is difficult to effectively observe micro fissures. Equipment scanning takes a lot of time, and some parts have complex parts. Difficult to scan.
材料结构性损坏往往始于一些微小的开裂和变形，自然界如彩色甲壳虫的壳等材料扭曲变形会引起颜色的变化，因为其壳中含有微裂纹变色物质，如果将聚酰亚胺薄膜材料在制备过程中添加人工的微裂纹变色物质，制备成“预警微裂纹的透明聚酰亚胺薄膜”后，对微米级的、难以被检测到的裂纹和察觉的缺陷，可警示出隐性损坏，对于损伤敏感(Defect Sensitivity)、早期预警(Early Warning)等领域，用以监测那些在飞机、汽车中所使用的复合材料的安全状况，从而避免突发性事故的发生。该技术目前还未被发现有突破，是急需开发应用的一项技术。Material structural damage often starts with some small cracks and deformations. Natural materials such as colored beetles' shells can cause color changes due to distortion. Because the shell contains micro-crack color-changing substances, if polyimide film materials are prepared In the process, artificial micro-crack discoloration substance is added to prepare a “transparent polyimide film with early warning of micro-cracks”. The micro-scale cracks and defects that are difficult to detect can be used to warn of hidden damage. Damage sensitivity (Defect Sensitivity), Early Warning (Early Warning) and other fields are used to monitor the safety status of composite materials used in aircraft and automobiles, so as to avoid sudden accidents. This technology has not yet been found to have a breakthrough, and is a technology in urgent need of development and application.
发明内容Summary of the invention
本发明的目的在于提供一种预警微裂纹的透明聚酰亚胺薄膜及其制备方法。The object of the present invention is to provide a transparent polyimide film for early warning of microcracks and a preparation method thereof.
一种预警微裂纹的透明聚酰亚胺薄膜，包括如下重量份数的物质：聚酰亚胺200-500份，富勒烯3-8份，微裂纹变色剂3-8份。A transparent polyimide film for warning of microcracks, comprising the following parts by weight: 200-500 parts of polyimide, 3-8 parts of fullerene, and 3-8 parts of microcrack discoloration agent.
所述微裂纹变色剂为3-甲基胆蒽，7,12-二甲基苯并蒽，荧蒽-d10。The micro-crack discoloration agent is 3-methylcholanthrene, 7,12-dimethylbenzoanthracene, and fluoranthene-d10.
所述微裂纹变色剂为具有下述分子式的化合物：The micro-crack discoloration agent is a compound having the following molecular formula:
Figure PCTCN2018107196-appb-000001
Figure PCTCN2018107196-appb-000001
式中，X为甲基，乙基，卤素或苯基，Y为丁基，卤素或苯基。In the formula, X is methyl, ethyl, halogen or phenyl, and Y is butyl, halogen or phenyl.
所述聚酰亚胺的以二胺和二酐为原料，采用二步溶液缩聚法制得。The polyimide is prepared by using a diamine and a dianhydride as raw materials and adopting a two-step solution polycondensation method.
所述二胺为2，2-二[4-(4-氨基苯氧基)苯基]丙烷、α，ω-双(甲基氨基)聚二甲基硅氧烷、2，2’-双(三氟甲基)联苯胺、2，4-二氨基氟苯、2-(三氟甲基)-1，4-亚苯基二胺、4-三氟甲基-1，2-苯二胺或4，5-二氟苯-1，2-二胺。The diamine is 2,2-bis [4- (4-aminophenoxy) phenyl] propane, α, ω-bis (methylamino) polydimethylsiloxane, 2,2'-bis (Trifluoromethyl) benzidine, 2,4-diaminofluorobenzene, 2- (trifluoromethyl) -1,4-phenylenediamine, 4-trifluoromethyl-1,2-benzenediamine Amine or 4,5-difluorobenzene-1,2-diamine.
所述二酐为3，3′，4，4′-联苯四羧酸二酐、4，4′-氧双邻苯二甲酸酐、均苯四甲酸二酐、双酚A型二酐或六氟异亚丙基二酞酸二酐。The dianhydride is 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxybisphthalic anhydride, pyromellitic dianhydride, bisphenol A dianhydride or Hexafluoroisopropylidene diphthalic dianhydride.
上述预警微裂纹的透明聚酰亚胺薄膜的制备方法，按照如下步骤进行：The method for preparing the above-mentioned early warning micro-cracked transparent polyimide film is as follows:
(1)在室温下，将二胺与二酐加入到反应釜，氮气保护下加入间甲酚，搅拌均匀后，加入异喹啉，升温至170-200℃，反应10-14小时，冷却后将反应液倒入乙醇析出，制成聚酰亚胺树脂；(1) At room temperature, add diamine and dianhydride to the reaction kettle, add m-cresol under nitrogen protection, stir well, add isoquinoline, warm to 170-200 ° C, react for 10-14 hours, and cool Pour the reaction solution into ethanol to make a polyimide resin;
(2)将富勒烯放在有机溶剂中，经高剪切分散机加以高温处理后预先分散，处理温度为200-800℃；(2) Fullerene is placed in an organic solvent and pre-dispersed after being subjected to a high-temperature treatment by a high-shear dispersing machine, and the processing temperature is 200-800 ° C;
(3)将合成的聚酰亚胺树脂和处理好的富勒烯加入反应釜搅拌，搅拌速度800-1200rpm，搅拌时间1-2h，制成膜液；(3) adding the synthesized polyimide resin and the treated fullerene to the reaction kettle and stirring, the stirring speed is 800-1200 rpm, and the stirring time is 1-2 hours to prepare a film liquid;
(4)向膜液中加入微裂纹变色剂，继续搅拌，搅拌速度300-500rpm，搅拌时间2-5h，制成变色膜液；(4) Add the micro-crack discoloration agent to the film liquid, continue to stir, the stirring speed is 300-500 rpm, and the stirring time is 2-5 h to make a color-changing film liquid;
(5)将变色膜液压入脱泡釜，在真空条件下脱去变色膜液中的气泡，将脱泡后的变色膜液放入流延机加以流延形成厚度均匀的聚酰亚胺薄膜；(5) Hydraulically change the color-changing film into the defoaming kettle, remove the bubbles in the color-changing film liquid under vacuum conditions, put the decolorized film-changing film liquid into a casting machine and cast to form a polyimide film with uniform thickness ;
(6)将聚酰亚胺薄膜放入亚胺化炉进行亚胺化处理，通过收卷机和分切机进行加工，制成成品。(6) The polyimide film is placed in an imidization furnace for imidization, and processed by a winder and a slitter to produce a finished product.
所述有机溶剂为二甲基乙酰胺，二甲亚砜、N，N-二甲基乙酰胺、N，N-二甲基甲酰胺、二甲基亚砜或N-甲基吡咯烷酮。The organic solvent is dimethylacetamide, dimethylsulfoxide, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide or N-methylpyrrolidone.
本发明的有益效果：本发明的预警微裂纹的透明聚酰亚胺薄膜，采用富勒烯和微裂纹变色剂复合的技术方案，使得材料对裂变微小的纹路敏感，呈现出肉眼可观测的变化，容易识别，在裂纹周围几毫米范围内，颜色变化清晰可见，可以有效监测那些在飞机、汽车中所使用的复合材料的安全状况，从而避免突发性事故的发生。Beneficial effect of the present invention: The transparent polyimide film for early warning of microcracks of the present invention adopts the technical solution of fullerene and microcrack discolorant composite technology to make the material sensitive to minute lines of fission, showing changes observable to the naked eye. It is easy to identify. Within a few millimeters around the crack, the color change is clearly visible, which can effectively monitor the safety status of those composite materials used in aircraft and automobiles, thereby avoiding accidents.
具体实施方式detailed description
下面结合具体实施例对本发明做进一步说明。The present invention is further described below with reference to specific embodiments.
实施例1Example 1
一种预警微裂纹的透明聚酰亚胺薄膜，包括如下重量份数的物质：聚酰亚胺350g，富勒烯5g，3-甲基胆蒽5g。A transparent polyimide film for warning of microcracks includes the following materials in parts by weight: 350g of polyimide, 5g of fullerene, and 5g of 3-methylcholanthrene.
上述预警微裂纹的透明聚酰亚胺薄膜，按照如下步骤进行：The above-mentioned warning micro-cracked transparent polyimide film is performed according to the following steps:
(1)在室温下，将1180g 2，2-二[4-(4-氨基苯氧基)苯基]丙烷与990g 4，4′-氧双邻苯二甲酸酐加入到反应釜，氮气保护下加入15000g间甲酚，搅拌均匀后，加入500g异喹啉，升温至190℃，反应12小时，冷却后将反应液倒入乙醇析出，制成聚酰亚胺树脂；(1) At room temperature, add 1180g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 990g of 4,4′-oxybisphthalic anhydride to the reactor, and protect it with nitrogen. Add 15000g of m-cresol below, stir well, add 500g of isoquinoline, heat up to 190 ° C, and react for 12 hours. After cooling, pour the reaction solution into ethanol to precipitate to make a polyimide resin;
(2)将5g富勒烯放在500g N-甲基吡咯烷酮中，经高剪切分散机加以高温处理后预先分散，处理温度为500℃；(2) 5g of fullerene is placed in 500g of N-methylpyrrolidone, which is pre-dispersed after being subjected to high-temperature treatment by a high-shear disperser, and the treatment temperature is 500 ° C;
(3)取制备好的聚酰亚胺树脂350g，加入步骤(2)制备的富勒烯分散液中，经反应釜搅拌，搅拌速度1000rpm，搅拌时间1.5h，制成膜液；(3) Take 350 g of the prepared polyimide resin, add it to the fullerene dispersion prepared in step (2), and stir it in a reaction kettle at a stirring speed of 1000 rpm and a stirring time of 1.5 h to prepare a film liquid;
(4)向膜液中加入3-甲基胆蒽5g，继续搅拌，搅拌速度400rpm，搅拌时间3h，制成变色膜液；(4) Add 5 g of 3-methylcholanthrene to the film liquid, continue stirring, the stirring speed is 400 rpm, and the stirring time is 3 hours to prepare a color changing film liquid;
(5)将变色膜液压入脱泡釜，在真空条件下脱去变色膜液中的气泡，将脱泡后的变色膜液放入流延机加以流延形成厚度均匀的聚酰亚胺薄膜；(5) Hydraulically change the color-changing film into the defoaming kettle, remove the bubbles in the color-changing film liquid under vacuum conditions, put the decolorized film-changing film liquid into a casting machine and cast to form a polyimide film with uniform thickness ;
(6)将聚酰亚胺薄膜放入亚胺化炉进行亚胺化处理，通过收卷机和分切机进行加工，制成成品。(6) The polyimide film is placed in an imidization furnace for imidization, and processed by a winder and a slitter to produce a finished product.
实施例2Example 2
一种预警微裂纹的透明聚酰亚胺薄膜，包括如下重量份数的物质：聚酰亚胺200g，富勒烯3g，7,12-二甲基苯并蒽3g。A transparent polyimide film for warning of microcracks includes the following parts by weight: 200g of polyimide, 3g of fullerene, and 3g of 7,12-dimethylbenzoanthracene.
上述预警微裂纹的透明聚酰亚胺薄膜的制备方法，按照如下步骤进行：The method for preparing the above-mentioned early warning micro-cracked transparent polyimide film is as follows:
(1)在室温下，将1108g 2，2’-双(三氟甲基)联苯胺与880g均苯四甲酸二酐加入到反应釜，氮气保护下加入13000g间甲酚，搅拌均匀后，加入400g异喹啉，升温至170℃，反应10小时，冷却后将反应液倒入乙醇析出，制成聚酰亚 胺树脂；(1) At room temperature, add 1108g of 2,2'-bis (trifluoromethyl) benzidine and 880g of pyromellitic dianhydride to the reaction kettle, add 13000g of m-cresol under nitrogen protection, stir well, then add 400 g of isoquinoline, heated to 170 ° C., and reacted for 10 hours. After cooling, the reaction solution was poured into ethanol to precipitate out to make a polyimide resin;
(2)将3g富勒烯放在300g N-甲基吡咯烷酮中，经高剪切分散机加以高温处理后预先分散，处理温度为300℃；(2) Put 3g of fullerene in 300g of N-methylpyrrolidone, disperse it in advance by high-temperature treatment in a high-shear disperser, and treat the temperature at 300 ° C;
(3)取制备好的聚酰亚胺树脂200g，加入步骤(2)制备的富勒烯分散液中，经反应釜搅拌，搅拌速度800rpm，搅拌时间1h，制成膜液；(3) Take 200 g of the prepared polyimide resin, add it to the fullerene dispersion prepared in step (2), and stir it in a reaction kettle at a stirring speed of 800 rpm and a stirring time of 1 hour to prepare a film liquid;
(4)向膜液中加入7,12-二甲基苯并蒽3g，继续搅拌，搅拌速度400rpm，搅拌时间3h，制成变色膜液；(4) Add 3g of 7,12-dimethylbenzoanthracene to the film liquid, continue stirring, the stirring speed is 400 rpm, and the stirring time is 3 hours to prepare a color changing film liquid;
(5)将变色膜液压入脱泡釜，在真空条件下脱去变色膜液中的气泡，将脱泡后的变色膜液放入流延机加以流延形成厚度均匀的聚酰亚胺薄膜；(5) Hydraulically change the color-changing film into the defoaming kettle, remove the bubbles in the color-changing film liquid under vacuum conditions, put the decolorized film-changing film liquid into a casting machine and cast to form a polyimide film with uniform thickness ;
(6)将聚酰亚胺薄膜放入亚胺化炉进行亚胺化处理，通过收卷机和分切机进行加工，制成成品。(6) The polyimide film is placed in an imidization furnace for imidization, and processed by a winder and a slitter to produce a finished product.
实施例3Example 3
一种预警微裂纹的透明聚酰亚胺薄膜，包括如下重量份数的物质：聚酰亚胺500g，富勒烯8g，荧蒽-d10 8g。A transparent polyimide film for early warning of microcracks includes the following parts by weight: 500g of polyimide, 8g of fullerene, and 8g of fluoranthene-d10.
上述预警微裂纹的透明聚酰亚胺薄膜的制备方法，按照如下步骤进行：The method for preparing the above-mentioned early warning micro-cracked transparent polyimide film is as follows:
(1)在室温下，将1320gα，ω-双(甲基氨基)聚二甲基硅氧烷与1010g双酚A型二酐加入到反应釜，氮气保护下加入15000g间甲酚，搅拌均匀后，加入500g异喹啉，升温至200℃，反应14小时，冷却后将反应液倒入乙醇析出，制成聚酰亚胺树脂；(1) At room temperature, add 1320 g of α, ω-bis (methylamino) polydimethylsiloxane and 1010 g of bisphenol A dianhydride to the reaction kettle, add 15000 g of m-cresol under nitrogen protection, and stir well 500 g of isoquinoline was added, the temperature was raised to 200 ° C., and the reaction was carried out for 14 hours. After cooling, the reaction solution was poured into ethanol to precipitate out to make a polyimide resin;
(2)将富勒烯8g放在500gN-甲基吡咯烷酮中，经高剪切分散机加以高温处理后预先分散，处理温度为800℃；(2) Put 8g of fullerene in 500g of N-methylpyrrolidone, disperse it in advance by high-temperature treatment in a high-shear disperser, and treat the temperature at 800 ° C;
(3)将合成的聚酰亚胺树脂和处理好的富勒烯加入反应釜搅拌，搅拌速度1200rpm，搅拌时间2h，制成膜液；(3) adding the synthesized polyimide resin and the treated fullerene to the reaction kettle and stirring at a stirring speed of 1200 rpm and a stirring time of 2 hours to prepare a film liquid;
(4)向膜液中加入荧蒽-d10 8g，继续搅拌，搅拌速度500rpm，搅拌时间5h，制成变色膜液；(4) Add 8g of fluoranthene-d10 to the film liquid, continue stirring, and stir at a speed of 500 rpm and a stirring time of 5 hours to prepare a color-changing film liquid;
(5)将变色膜液压入脱泡釜，在真空条件下脱去变色膜液中的气泡，将脱泡后的变色膜液放入流延机加以流延形成厚度均匀的聚酰亚胺薄膜；(5) Hydraulically change the color-changing film into the defoaming kettle, remove the bubbles in the color-changing film liquid under vacuum conditions, put the decolorized film-changing film liquid into a casting machine and cast to form a polyimide film with uniform thickness ;
(6)将聚酰亚胺薄膜放入亚胺化炉进行亚胺化处理，通过收卷机和分切机进行加工，制成成品。(6) The polyimide film is placed in an imidization furnace for imidization, and processed by a winder and a slitter to produce a finished product.
实施例4Example 4
一种预警微裂纹的透明聚酰亚胺薄膜，包括如下重量份数的物质：聚酰亚胺350g，富勒烯5g，2-(氯甲基)-4-(2-氯戊基)-1-戊苯5g。A transparent polyimide film for warning of microcracks, comprising the following parts by weight: 350g of polyimide, 5g of fullerene, 2- (chloromethyl) -4- (2-chloropentyl)- 1-pentylbenzene 5g.
上述预警微裂纹的透明聚酰亚胺薄膜，按照如下步骤进行：The above-mentioned warning micro-cracked transparent polyimide film is performed according to the following steps:
(1)在室温下，将1180g 2，2-二[4-(4-氨基苯氧基)苯基]丙烷与990g 4，4′-氧双邻苯二甲酸酐加入到反应釜，氮气保护下加入15000g间甲酚，搅拌均匀后，加入500g异喹啉，升温至190℃，反应12小时，冷却后将反应液倒入乙醇析出，制成聚酰亚胺树脂；(1) At room temperature, add 1180g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 990g of 4,4′-oxybisphthalic anhydride to the reactor, and protect it with nitrogen. Add 15000g of m-cresol below, stir well, add 500g of isoquinoline, heat up to 190 ° C, and react for 12 hours. After cooling, pour the reaction solution into ethanol to precipitate to make a polyimide resin;
(2)将5g富勒烯放在500g N-甲基吡咯烷酮中，经高剪切分散机加以高温处理后预先分散，处理温度为500℃；(2) 5g of fullerene is placed in 500g of N-methylpyrrolidone, which is pre-dispersed after being subjected to high-temperature treatment by a high-shear disperser, and the treatment temperature is 500 ° C;
(3)取制备好的聚酰亚胺树脂350g，加入步骤(2)制备的富勒烯分散液中，经反应釜搅拌，搅拌速度1000rpm，搅拌时间1.5h，制成膜液；(3) Take 350 g of the prepared polyimide resin, add it to the fullerene dispersion prepared in step (2), and stir it in a reaction kettle at a stirring speed of 1000 rpm and a stirring time of 1.5 h to prepare a film liquid;
(4)向膜液中加入2-(氯甲基)-4-(2-氯戊基)-1-戊苯5g，继续搅拌，搅拌速 度400rpm，搅拌时间3h，制成变色膜液；(4) Add 5 g of 2- (chloromethyl) -4- (2-chloropentyl) -1-pentylbenzene to the film liquid, continue stirring, the stirring speed is 400 rpm, and the stirring time is 3 hours to prepare a color changing film liquid;
(5)将变色膜液压入脱泡釜，在真空条件下脱去变色膜液中的气泡，将脱泡后的变色膜液放入流延机加以流延形成厚度均匀的聚酰亚胺薄膜；(5) Hydraulically change the color-changing film into the defoaming kettle, remove the bubbles in the color-changing film liquid under vacuum conditions, put the decolorized film-changing film liquid into a casting machine and cast to form a polyimide film with uniform thickness ;
(6)将聚酰亚胺薄膜放入亚胺化炉进行亚胺化处理，通过收卷机和分切机进行加工，制成成品。(6) The polyimide film is placed in an imidization furnace for imidization, and processed by a winder and a slitter to produce a finished product.
实施例5Example 5
一种预警微裂纹的透明聚酰亚胺薄膜，包括如下重量份数的物质：聚酰亚胺350g，富勒烯5g，2-苯基-1-戊基-4-戊基苯5g。A transparent polyimide film for warning of microcracks, comprising the following parts by weight: 350g of polyimide, 5g of fullerene, and 5g of 2-phenyl-1-pentyl-4-pentylbenzene.
上述预警微裂纹的透明聚酰亚胺薄膜，按照如下步骤进行：The above-mentioned warning micro-cracked transparent polyimide film is performed according to the following steps:
(1)在室温下，将1180g 2，2-二[4-(4-氨基苯氧基)苯基]丙烷与990g 4，4′-氧双邻苯二甲酸酐加入到反应釜，氮气保护下加入15000g间甲酚，搅拌均匀后，加入500g异喹啉，升温至190℃，反应12小时，冷却后将反应液倒入乙醇析出，制成聚酰亚胺树脂；(1) At room temperature, add 1180g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 990g of 4,4′-oxybisphthalic anhydride to the reactor, and protect it with nitrogen. Add 15000g of m-cresol below, stir well, add 500g of isoquinoline, heat up to 190 ° C, and react for 12 hours. After cooling, pour the reaction solution into ethanol to precipitate to make a polyimide resin;
(2)将5g富勒烯放在500g N-甲基吡咯烷酮中，经高剪切分散机加以高温处理后预先分散，处理温度为500℃；(2) 5g of fullerene is placed in 500g of N-methylpyrrolidone, which is pre-dispersed after being subjected to high-temperature treatment by a high-shear disperser, and the treatment temperature is 500 ° C;
(3)取制备好的聚酰亚胺树脂350g，加入步骤(2)制备的富勒烯分散液中，经反应釜搅拌，搅拌速度1000rpm，搅拌时间1.5h，制成膜液；(3) Take 350 g of the prepared polyimide resin, add it to the fullerene dispersion prepared in step (2), and stir it in a reaction kettle at a stirring speed of 1000 rpm and a stirring time of 1.5 h to prepare a film liquid;
(4)向膜液中加入2-苯基-1-戊基-4-戊基苯5g，继续搅拌，搅拌速度400rpm，搅拌时间3h，制成变色膜液；(4) Add 5 g of 2-phenyl-1-pentyl-4-pentylbenzene to the film liquid, continue stirring, the stirring speed is 400 rpm, and the stirring time is 3 hours to prepare a color changing film liquid;
(5)将变色膜液压入脱泡釜，在真空条件下脱去变色膜液中的气泡，将脱泡后的变色膜液放入流延机加以流延形成厚度均匀的聚酰亚胺薄膜；(5) Hydraulically change the color-changing film into the defoaming kettle, remove the bubbles in the color-changing film liquid under vacuum conditions, put the decolorized film-changing film liquid into a casting machine and cast to form a polyimide film with uniform thickness ;
(6)将聚酰亚胺薄膜放入亚胺化炉进行亚胺化处理，通过收卷机和分切机进行加工，制成成品。(6) The polyimide film is placed in an imidization furnace for imidization, and processed by a winder and a slitter to produce a finished product.
实施例6Example 6
一种预警微裂纹的透明聚酰亚胺薄膜，包括如下重量份数的物质：聚酰亚胺350g，富勒烯5g，(2-环己基)苯5g。A transparent polyimide film for warning of microcracks includes the following materials in parts by weight: 350g of polyimide, 5g of fullerene, and 5g of (2-cyclohexyl) benzene.
上述预警微裂纹的透明聚酰亚胺薄膜，按照如下步骤进行：The above-mentioned warning micro-cracked transparent polyimide film is performed according to the following steps:
(1)在室温下，将1180g 2，2-二[4-(4-氨基苯氧基)苯基]丙烷与990g 4，4′-氧双邻苯二甲酸酐加入到反应釜，氮气保护下加入15000g间甲酚，搅拌均匀后，加入500g异喹啉，升温至190℃，反应12小时，冷却后将反应液倒入乙醇析出，制成聚酰亚胺树脂；(1) At room temperature, add 1180g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 990g of 4,4′-oxybisphthalic anhydride to the reactor, and protect it with nitrogen. Add 15000g of m-cresol below, stir well, add 500g of isoquinoline, heat up to 190 ° C, and react for 12 hours. After cooling, pour the reaction solution into ethanol to precipitate to make a polyimide resin;
(2)将5g富勒烯放在500g N-甲基吡咯烷酮中，经高剪切分散机加以高温处理后预先分散，处理温度为500℃；(2) 5g of fullerene is placed in 500g of N-methylpyrrolidone, which is pre-dispersed after being subjected to high-temperature treatment by a high-shear disperser, and the treatment temperature is 500 ° C;
(3)取制备好的聚酰亚胺树脂350g，加入步骤(2)制备的富勒烯分散液中，经反应釜搅拌，搅拌速度1000rpm，搅拌时间1.5h，制成膜液；(3) Take 350 g of the prepared polyimide resin, add it to the fullerene dispersion prepared in step (2), and stir it in a reaction kettle at a stirring speed of 1000 rpm and a stirring time of 1.5 h to prepare a film liquid;
(4)向膜液中加入(2-环己基)苯5g，继续搅拌，搅拌速度400rpm，搅拌时间3h，制成变色膜液；(4) Add 5 g of (2-cyclohexyl) benzene to the film liquid, continue stirring, the stirring speed is 400 rpm, and the stirring time is 3 hours to prepare a color changing film liquid;
(5)将变色膜液压入脱泡釜，在真空条件下脱去变色膜液中的气泡，将脱泡后的变色膜液放入流延机加以流延形成厚度均匀的聚酰亚胺薄膜；(5) Hydraulically change the color-changing film into the defoaming kettle, remove the bubbles in the color-changing film liquid under vacuum conditions, put the decolorized film-changing film liquid into a casting machine and cast to form a polyimide film with uniform thickness ;
(6)将聚酰亚胺薄膜放入亚胺化炉进行亚胺化处理，通过收卷机和分切机进行加工，制成成品。(6) The polyimide film is placed in an imidization furnace for imidization, and processed by a winder and a slitter to produce a finished product.
实施例7Example 7
一种预警微裂纹的透明聚酰亚胺薄膜，包括如下重量份数的物质：聚酰亚胺350g，富勒烯5g，3-甲基胆蒽5g，丽金龟壳提取物3g。A transparent polyimide film for warning of microcracks, comprising the following parts by weight: 350g of polyimide, 5g of fullerene, 5g of 3-methylcholanthrene, and 3g of Lijin turtle shell extract.
所述丽金龟壳提取物的提取方法为：将丽金龟的壳磨碎，过60目筛，加入8倍重量份数的75％乙醇水溶液回流提取3次，合并滤液，活性炭脱色，蒸干制成。The extraction method of the beetle shell extract is as follows: the beetle shell is ground, passed through a 60 mesh sieve, and 8 times by weight of 75% ethanol aqueous solution is added for reflux extraction three times. to make.
上述预警微裂纹的透明聚酰亚胺薄膜，按照如下步骤进行：The above-mentioned warning micro-cracked transparent polyimide film is performed according to the following steps:
(1)在室温下，将1180g 2，2-二[4-(4-氨基苯氧基)苯基]丙烷与990g 4，4′-氧双邻苯二甲酸酐加入到反应釜，氮气保护下加入15000g间甲酚，搅拌均匀后，加入500g异喹啉，升温至190℃，反应12小时，冷却后将反应液倒入乙醇析出，制成聚酰亚胺树脂；(1) At room temperature, add 1180g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 990g of 4,4′-oxybisphthalic anhydride to the reactor, and protect it with nitrogen. Add 15000g of m-cresol below, stir well, add 500g of isoquinoline, heat up to 190 ° C, and react for 12 hours. After cooling, pour the reaction solution into ethanol to precipitate to make a polyimide resin;
(2)将5g富勒烯放在500g N-甲基吡咯烷酮中，经高剪切分散机加以高温处理后预先分散，处理温度为500℃；(2) 5g of fullerene is placed in 500g of N-methylpyrrolidone, which is pre-dispersed after being subjected to high-temperature treatment by a high-shear disperser, and the treatment temperature is 500 ° C;
(3)取制备好的聚酰亚胺树脂350g，加入步骤(2)制备的富勒烯分散液中，经反应釜搅拌，搅拌速度1000rpm，搅拌时间1.5h，制成膜液；(3) Take 350 g of the prepared polyimide resin, add it to the fullerene dispersion prepared in step (2), and stir it in a reaction kettle at a stirring speed of 1000 rpm and a stirring time of 1.5 h to prepare a film liquid;
(4)向膜液中加入3-甲基胆蒽5g，丽金龟壳提取物3g，继续搅拌，搅拌速度400rpm，搅拌时间3h，制成变色膜液；(4) Add 5 g of 3-methylcholanthrene and 3 g of turquoise shell extract to the film liquid, continue stirring, stirring speed at 400 rpm, and stirring time for 3 h to prepare a color changing film liquid;
(5)将变色膜液压入脱泡釜，在真空条件下脱去变色膜液中的气泡，将脱泡后的变色膜液放入流延机加以流延形成厚度均匀的聚酰亚胺薄膜；(5) Hydraulically change the color-changing film into the defoaming kettle, remove the bubbles in the color-changing film liquid under vacuum conditions, put the decolorized film-changing film liquid into a casting machine and cast to form a polyimide film with uniform thickness ;
(6)将聚酰亚胺薄膜放入亚胺化炉进行亚胺化处理，通过收卷机和分切机进行加工，制成成品。(6) The polyimide film is placed in an imidization furnace for imidization, and processed by a winder and a slitter to produce a finished product.
对比例1Comparative Example 1
一种预警微裂纹的透明聚酰亚胺薄膜，包括如下重量份数的物质：聚酰亚胺350g，富勒烯5g。A transparent polyimide film for early warning of microcracks includes the following parts by weight: 350g of polyimide and 5g of fullerene.
上述预警微裂纹的透明聚酰亚胺薄膜，按照如下步骤进行：The above-mentioned warning micro-cracked transparent polyimide film is performed according to the following steps:
(1)在室温下，将1180g 2，2-二[4-(4-氨基苯氧基)苯基]丙烷与990g 4，4′-氧双邻苯二甲酸酐加入到反应釜，氮气保护下加入15000g间甲酚，搅拌均匀后，加入500g异喹啉，升温至190℃，反应12小时，冷却后将反应液倒入乙醇析出，制成聚酰亚胺树脂；(1) At room temperature, add 1180g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 990g of 4,4′-oxybisphthalic anhydride to the reactor, and protect it with nitrogen. Add 15000g of m-cresol below, stir well, add 500g of isoquinoline, heat up to 190 ° C, and react for 12 hours. After cooling, pour the reaction solution into ethanol to precipitate to make a polyimide resin;
(2)将5g富勒烯放在500g N-甲基吡咯烷酮中，经高剪切分散机加以高温处理后预先分散，处理温度为500℃；(2) 5g of fullerene is placed in 500g of N-methylpyrrolidone, which is pre-dispersed after being subjected to high-temperature treatment by a high-shear disperser, and the treatment temperature is 500 ° C;
(3)取制备好的聚酰亚胺树脂350g，加入步骤(2)制备的富勒烯分散液中，经反应釜搅拌，搅拌速度1000rpm，搅拌时间1.5h，制成膜液；(3) Take 350 g of the prepared polyimide resin, add it to the fullerene dispersion prepared in step (2), and stir it in a reaction kettle at a stirring speed of 1000 rpm and a stirring time of 1.5 h to prepare a film liquid;
(4)将膜液压入脱泡釜，在真空条件下脱去膜液中的气泡，将脱泡后的膜液放入流延机加以流延形成厚度均匀的聚酰亚胺薄膜；(4) the membrane is hydraulically pressured into a defoaming kettle, and the air bubbles in the membrane liquid are removed under a vacuum condition; the defoamed membrane liquid is put into a casting machine and cast to form a polyimide film having a uniform thickness;
(6)将聚酰亚胺薄膜放入亚胺化炉进行亚胺化处理，通过收卷机和分切机进行加工，制成成品。(6) The polyimide film is placed in an imidization furnace for imidization, and processed by a winder and a slitter to produce a finished product.
实验例：Experimental example:
取实施例1-7及对比例1制备的聚酰亚胺薄膜，采用尖刀划一道长1cm，宽0.2mm的微小划痕，观察聚酰亚胺薄膜划痕周围有无颜色变化，计算颜色带的宽度，实验结果见表1：Take the polyimide films prepared in Examples 1-7 and Comparative Example 1, and use a sharp knife to make a small scratch with a length of 1 cm and a width of 0.2 mm. Observe whether there is a color change around the polyimide film and calculate the color band. Width, the experimental results are shown in Table 1:
表1Table 1
Figure PCTCN2018107196-appb-000002
Figure PCTCN2018107196-appb-000002
注：*代表与实施例1组比较P<0.05。Note: * represents P <0.05 compared with the group of Example 1.
由表1可以看出，对比例1中未加入微裂纹变色剂，没有色带产生，实施例1-4有色带产生，实施例5-7有色带产生，且色带的宽度显著高于实施例1。It can be seen from Table 1 that the micro-crack discoloration agent was not added in Comparative Example 1, and no color band was generated. The color band was generated in Example 1-4, and the color band was generated in Example 5-7. example 1.

Claims (8)

  1. 一种预警微裂纹的透明聚酰亚胺薄膜，其特征在于，包括如下重量份数的物质：聚酰亚胺200-500份，富勒烯3-8份，微裂纹变色剂3-8份。A transparent polyimide film for warning of microcracks, which is characterized by comprising the following parts by weight: 200-500 parts of polyimide, 3-8 parts of fullerene, and 3-8 parts of microcrack discoloration agent .
  2. 根据权利要求1所述预警微裂纹的透明聚酰亚胺薄膜，其特征在于，所述微裂纹变色剂为3-甲基胆蒽，7,12-二甲基苯并蒽，荧蒽-d10。The transparent polyimide film for warning of microcracks according to claim 1, wherein the microcrack discoloration agent is 3-methylcholanthrene, 7,12-dimethylbenzoanthracene, and fluoranthene-d10 .
  3. 根据权利要求1所述预警微裂纹的透明聚酰亚胺薄膜，其特征在于，所述微裂纹变色剂为具有下述分子式的化合物：The transparent polyimide film for warning of microcracks according to claim 1, wherein the microcrack discoloration agent is a compound having the following molecular formula:
    Figure PCTCN2018107196-appb-100001
    Figure PCTCN2018107196-appb-100001
    式中，X为甲基，乙基，卤素或苯基，Y为丁基，卤素或苯基。In the formula, X is methyl, ethyl, halogen or phenyl, and Y is butyl, halogen or phenyl.
  4. 根据权利要求1所述预警微裂纹的透明聚酰亚胺薄膜，其特征在于，所述聚酰亚胺的以二胺和二酐为原料，采用二步溶液缩聚法制得。The transparent polyimide film for warning of microcracks according to claim 1, wherein the polyimide is prepared by using a diamine and a dianhydride as raw materials and adopting a two-step solution polycondensation method.
  5. 根据权利要求1所述预警微裂纹的透明聚酰亚胺薄膜，其特征在于，所述二胺为2，2-二[4-(4-氨基苯氧基)苯基]丙烷、α，ω-双(甲基氨基)聚二甲基硅氧烷、2，2’-双(三氟甲基)联苯胺、2，4-二氨基氟苯、2-(三氟甲基)-1，4-亚苯基二胺、4-三氟甲基-1，2-苯二胺或4，5-二氟苯-1，2-二胺。The transparent polyimide film for warning of microcracks according to claim 1, wherein the diamine is 2,2-bis [4- (4-aminophenoxy) phenyl] propane, α, ω -Bis (methylamino) polydimethylsiloxane, 2,2'-bis (trifluoromethyl) benzidine, 2,4-diaminofluorobenzene, 2- (trifluoromethyl) -1, 4-phenylene diamine, 4-trifluoromethyl-1,2-phenylenediamine or 4,5-difluorobenzene-1,2-diamine.
  6. 根据权利要求1所述预警微裂纹的透明聚酰亚胺薄膜，其特征在于，所述二酐为3，3′，4，4′-联苯四羧酸二酐、4，4′-氧双邻苯二甲酸酐、均苯四甲酸二酐、双酚A型二酐或六氟异亚丙基二酞酸二酐。The transparent polyimide film for warning of microcracks according to claim 1, wherein the dianhydride is 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 4,4′-oxygen Diphthalic anhydride, pyromellitic dianhydride, bisphenol A dianhydride or hexafluoroisopropylidene diphthalic dianhydride.
  7. 权利要求1所述预警微裂纹的透明聚酰亚胺薄膜的制备方法，其特征在于，按照如下步骤进行：The method for preparing a transparent polyimide film for early warning of microcracks according to claim 1, characterized in that it is performed as follows:
    (1)在室温下，将二胺与二酐加入到反应釜，氮气保护下加入间甲酚，搅拌均匀后，加入异喹啉，升温至170-200℃，反应10-14小时，冷却后将反应液倒入乙醇析出，制成聚酰亚胺树脂；(1) At room temperature, add diamine and dianhydride to the reaction kettle, add m-cresol under nitrogen protection, stir well, add isoquinoline, warm to 170-200 ° C, react for 10-14 hours, and cool Pour the reaction solution into ethanol to make a polyimide resin;
    (2)将富勒烯放在有机溶剂中，经高剪切分散机加以高温处理后预先分散，处理温度为200-800℃；(2) Fullerene is placed in an organic solvent and pre-dispersed after being subjected to high-temperature treatment by a high-shear dispersing machine, and the processing temperature is 200-800 ° C;
    (3)将合成的聚酰亚胺树脂和处理好的富勒烯加入反应釜搅拌，搅拌速度800-1200rpm，搅拌时间1-2h，制成膜液；(3) adding the synthesized polyimide resin and the treated fullerene to the reaction kettle and stirring, the stirring speed is 800-1200 rpm, and the stirring time is 1-2 hours to prepare a film liquid;
    (4)向膜液中加入微裂纹变色剂，继续搅拌，搅拌速度300-500rpm，搅拌时间2-5h，制成变色膜液；(4) Add the micro-crack discoloration agent to the film liquid, continue to stir, the stirring speed is 300-500 rpm, and the stirring time is 2-5 h to make a color-changing film liquid;
    (5)将变色膜液压入脱泡釜，在真空条件下脱去变色膜液中的气泡，将脱泡后的变色膜液放入流延机加以流延形成厚度均匀的聚酰亚胺薄膜；(5) Hydraulically change the color-changing film into the defoaming kettle, remove the bubbles in the color-changing film liquid under vacuum conditions, put the decolorized film-changing film liquid into a casting machine and cast to form a polyimide film with uniform thickness ;
    (6)将聚酰亚胺薄膜放入亚胺化炉进行亚胺化处理，通过收卷机和分切机进行加工，制成成品。(6) The polyimide film is placed in an imidization furnace for imidization, and processed by a winder and a slitter to produce a finished product.
  8. 根据权利要求1所述预警微裂纹的透明聚酰亚胺薄膜的制备方法的制备方法，其特征在于，所述有机溶剂为二甲基乙酰胺，二甲亚砜、N，N-二甲基乙酰胺、N，N-二甲基甲酰胺、二甲基亚砜或N-甲基吡咯烷酮。The method for preparing a transparent polyimide film with early warning microcracks according to claim 1, wherein the organic solvent is dimethylacetamide, dimethylsulfoxide, N, N-dimethyl Acetamide, N, N-dimethylformamide, dimethylsulfoxide or N-methylpyrrolidone.
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