WO2018171000A1 - 一种改性聚酰亚胺薄膜及其制备方法 - Google Patents

一种改性聚酰亚胺薄膜及其制备方法 Download PDF

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WO2018171000A1
WO2018171000A1 PCT/CN2017/082048 CN2017082048W WO2018171000A1 WO 2018171000 A1 WO2018171000 A1 WO 2018171000A1 CN 2017082048 W CN2017082048 W CN 2017082048W WO 2018171000 A1 WO2018171000 A1 WO 2018171000A1
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film
modified polyimide
polyimide film
temperature
formula
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柯霖波
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Wuhan China Star Optoelectronics Technology Co Ltd
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Wuhan China Star Optoelectronics Technology Co Ltd
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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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1075—Partially aromatic polyimides
    • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
    • 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

Definitions

  • the invention relates to the field of transparent flexible display technology, in particular to a modified polyimide film and a preparation method thereof.
  • the film substrate made of polymer material has the characteristics of light weight, flexibility, transparency and excellent comprehensive performance, and can well meet the requirements of display technology.
  • polyimide polyimide
  • Polyimide has excellent heat resistance, radiation resistance, chemical resistance, electrical insulation, mechanical properties, etc., but the traditional commercial PI film is brownish yellow, which is mainly due to the alternating two in the main chain of the macromolecule.
  • CTC intramolecular and intermolecular charge transfer complex
  • the present invention copolymerizes an aliphatic dianhydride monomer with a fluorine-containing diamine monomer to prepare a modified polyimide film, which improves flexibility and colorless transparency and visible light while maintaining good heat resistance.
  • the transmittance can be used as a substrate material for transparent flexible display technology.
  • the present invention provides a method for preparing a modified polyimide film, comprising the steps of:
  • the film obtained in the step (2) is heated and solidified at 80 to 120 ° C in a nitrogen atmosphere, and after being cooled to room temperature, the film is peeled off from the glass substrate to obtain a modified polyimide film.
  • the temperature of the copolymerization reaction is 10 to 40 °C. It is preferably 15 to 30 °C.
  • the aprotic polar solvent is selected from the group consisting of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2- One or more of pyrrolidone (NMP) and dimethyl sulfoxide (DMSO).
  • the molar ratio of the aliphatic dianhydride to the fluorine-containing aromatic diamine is 1: (0.95 to 1.05).
  • the molar ratio of the aliphatic dianhydride to the fluorine-containing aromatic diamine is 1:1.
  • the method further comprises: subjecting the reaction liquid to vacuum defoaming treatment for 12 to 24 hours.
  • the vacuum defoaming treatment is carried out under stirring, and the defoaming can facilitate subsequent formation of a flat, bubble-free film surface on the glass substrate.
  • the coating thickness formed on the glass substrate is 50 to 200 ⁇ m.
  • the baking time is 4 to 10 minutes.
  • the purpose of the baking is to volatilize the solvent in the reaction liquid, and the solvent is evaporated under vacuum to allow the volatile solvent to not drip on the surface of the film by cooling to room temperature; then, when the temperature is solidified in the step (3), The solvent is almost non-existent, so it is only necessary to cure at a high temperature under nitrogen, and no further pumping is required.
  • the temperature of the baking film formation is 90 to 115 °C.
  • the film is heated at a temperature of from 90 to 115 ° C.
  • the experimental equipment such as an oven protected by nitrogen is first heated to a temperature at which the temperature is solidified (for example, 90, 100 or 110 ° C), and then the film obtained in the step (2) is placed at such a temperature. In the oven, the temperature rise is started according to a preset procedure.
  • the heat curing method is one of hot air heating and infrared heating.
  • the curing temperature is 360 to 450 ° C, and the curing time is 10 to 60 min.
  • the film is cured at the temperature.
  • the quality loss is less.
  • curing at this temperature further strengthens the high temperature resistance of the modified PI film.
  • the modified polyimide is mainly used for the manufacture of flexible film substrates, and the process is as high as 400 ° C. Left and right, high temperature resistant modified PI film is more conducive to application.
  • the curing rate of the curing is 10 to 20 ° C / min.
  • the film obtained in the step (2) is heated and cured from 80 to 120 ° C, the film obtained in the step (2) is first kept at 120 ° C for 15 to 30 minutes. This insulation further ensures that the residual solvent can be completely evaporated.
  • the peeling and peeling is performed by laser peeling or mechanical peeling.
  • the mechanical peeling is manual peeling.
  • the obtained reaction liquid contains a polyamic acid, and its structural formula is as follows:
  • n is the degree of polymerization, and n is a natural number.
  • n is a natural number of 1 to 1000.
  • n is a natural number from 100 to 1000.
  • it may be 200, 300, 400, 500, 600, 700, 800 or 900, and the like.
  • n is the degree of polymerization, and n is a natural number.
  • n is a natural number of 1 to 1000.
  • a method for preparing a modified polyimide film provided by the first aspect of the present invention the cyclic aliphatic dianhydride monomer represented by the formula (I) and the fluorine-containing aromatic diamine monomer represented by the formula (II) Copolymerization, obtaining a reaction liquid containing a polyamic acid, and then undergoing a special thermal imidation process (before vacuum curing at 50-120 ° C, and then curing at a temperature of 80-120 ° C), and a stripping process to obtain a modified poly Imide film.
  • the reaction process is as follows:
  • the aliphatic dianhydride uses an alicyclic structure instead of the usual aromatic ring structure, which can effectively interrupt the conjugation of the final product polyimide molecule, reduce the probability of CTC formation, and improve the colorless transparency of the material. And showed superior flexibility.
  • a trifluoromethyl group (-CF 3 ) and a group R 2 having an ether bond (-O-) introduced into the molecule of the fluorine-containing aromatic diamine monomer, which have strong electron-withdrawing properties and can also reduce the final product aggregation.
  • the intermolecular conjugation of imide effectively inhibits the formation of CTC, significantly improves the colorless transparency of the polyimide film and improves its solubility and thermal stability.
  • the polyimide film obtained by the present invention allows the polyimide film obtained by the present invention to have both good high temperature resistance characteristics, excellent colorless transparency and flexibility, visible light transmittance, and the like.
  • the preparation method is simple and easy, and the reaction degree is controllable.
  • the modified polyimide film has a smooth and smooth film surface, less solvent residue, high purity, and can realize industrial production.
  • the present invention provides a modified polyimide film, the chemical structure of the material of the modified polyimide film is as shown in the following formula (III):
  • n is the degree of polymerization, and n is a natural number.
  • n is a natural number of 1 to 1000.
  • n is a natural number from 100 to 1000.
  • it may be 200, 300, 400, 500, 600, 700, 800 or 900, and the like.
  • the modified polyimide film provided by the second aspect of the invention is obtained by the method of the first aspect of the invention, and the modified polyimide film has better high temperature resistance characteristics and exhibits superiority without Color transparency and flexibility, visible light transmittance, can be used as a substrate material for transparent flexible display technology.
  • a cyclic aliphatic dianhydride monomer represented by the formula (I) is copolymerized with a fluorine-containing aromatic diamine monomer represented by the formula (II) to obtain a reaction liquid containing a polyamic acid, and then subjected to a unique heat.
  • the modified polyimide film is obtained by the imidization process and the stripping process. The method is simple and convenient, the reaction degree is controllable, the product purity is high, the solvent residue is small, and the film surface of the modified polyimide film is smooth and flat.
  • CTC intramolecular or intermolecular charge transfer complex
  • a method for preparing a colorless transparent flexible polyimide film comprising the steps of:
  • the chemical structure of the modified polyimide film obtained in this embodiment is The degree of polymerization n in this embodiment is 1000. In other embodiments, n may also be other positive integers such as 250, 450, 600; the ultraviolet absorption cutoff wavelength of the obtained modified polyimide film is 330 nm at 420 nm. The transmission rate is 88%.
  • a method for preparing a modified polyimide film comprising the steps of:
  • Diaminodiphenyl ether was dissolved in 250 mL of N-methyl-2-pyrrolidone (NMP), added to the reaction vessel, and thoroughly stirred under a nitrogen atmosphere to control the temperature at 20 ° C. After 6 h of reaction, a polyamic acid was obtained. Solution.
  • the glass substrate was baked at 60 ° C for 8 min in a vacuum environment to evaporate and withdraw the solvent NMP.
  • the chemical structure of the modified polyimide film obtained in this embodiment is The degree of polymerization n in this example was 800; the obtained modified polyimide film had an ultraviolet absorption cutoff wavelength of 313 nm and a transmittance of 91% at 420 nm.
  • a method for preparing a modified polyimide film comprising the steps of:
  • the chemical structure of the modified polyimide film obtained in this embodiment is The degree of polymerization n in this example was 350; the obtained modified polyimide film had an ultraviolet absorption cutoff wavelength of 302 nm and a transmittance of 90% at 420 nm.
  • a method for preparing a colorless transparent flexible polyimide film comprising the steps of:
  • the glass substrate was baked at 70 ° C for 10 min in a vacuum environment to evaporate and withdraw the solvent.
  • the temperature was raised from 120 ° C to 380 ° C at a heating rate of 8 ° C / min under a nitrogen atmosphere, and the film was cured for 40 min, and then cooled to room temperature by circulating cooling water.
  • n 500; the film has an ultraviolet absorption cutoff wavelength of 301 nm and a transmittance of 92% at 420 nm.

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

可用于无色透明柔性显示技术的改性聚酰亚胺薄膜及其制备方法，该改性聚酰亚胺的材料具有如式（III）的结构式，其中，式（A）选自式（B）、式（C）、式（D）、式（E）和式（F）中的一种；-R 2-选自式（G）、式（H）、式（J）和式（K）中的一种；n为聚合度，n为自然数。所得薄膜具有良好的耐热性，优异的无色透明性和柔性。

Description

一种改性聚酰亚胺薄膜及其制备方法
本申请要求于2017年03月23日提交中国专利局、申请号为2017101795349、发明名称为“一种改性聚酰亚胺薄膜及其制备方法”的中国专利申请的优先权，上述在先申请的内容以引入的方式并入本文本中。
技术领域
本发明涉及透明柔性显示技术领域，特别涉及一种改性聚酰亚胺薄膜及其制备方法。
背景技术
随着现代光电技术的快速发展，显示技术领域正朝着更轻、更薄、更柔、更透明的方向发展。聚合物材料制成的薄膜基板具有质轻、柔性、透明、综合性能优异等特点，可以很好地满足显示技术的要求。
目前已报导的用于柔性基板最具发展前景的高分子材料是聚酰亚胺(polyimide，PI)。聚酰亚胺具有优异的耐热性、耐辐射性能、耐化学性、电绝缘性、机械性能等性能，但传统的商用PI薄膜为棕黄色，这主要是由于大分子主链中交替的二酐残基的吸电子作用和二胺残基的给电子作用而产生的强烈分子内与分子间电荷转移络合物(Charge Transfer Complex，CTC)的光谱吸收，极大限制了其在透明柔性显示技术方面的应用。因此要获得无色透明的聚酰亚胺类材料，就必须对其进行改性，以减弱或消除CTC的影响。
发明内容
有鉴于此，本发明将脂肪族二酐单体与含氟二胺单体共聚，制备改性聚酰亚胺薄膜，在保持良好耐热性的同时，改善其柔性和无色透明性、可见光透过率，能够作为透明柔性显示技术的基板材料。
第一方面，本发明提供了一种改性聚酰亚胺薄膜的制备方法，包括以下步骤：
(1)取如下式(Ⅰ)所示的脂肪族二酐与式(Ⅱ)所示的含氟芳香二胺溶解在非质子极性溶剂中，在氮气保护下进行共聚反应2～10h，得到反应液；
Figure PCTCN2017082048-appb-000001
其中，
Figure PCTCN2017082048-appb-000002
选自
Figure PCTCN2017082048-appb-000003
Figure PCTCN2017082048-appb-000004
中的一种；-R2-选自-O-、
Figure PCTCN2017082048-appb-000005
Figure PCTCN2017082048-appb-000006
中的一种；
(2)在氮气气氛下，将所述反应液涂覆在洁净光滑的玻璃基板上；并在真空环境下于50～120℃下烘烤成膜；
(3)在氮气气氛下，将步骤(2)所得薄膜从80～120℃开始进行升温固化，待冷却至室温，从所述玻璃基板上剥离脱膜，得到改性聚酰亚胺薄膜。
其中，步骤(1)中，所述共聚反应的温度为10～40℃。优选为15～30℃。
其中，步骤(1)中，所述非质子极性溶剂选自N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMAc)、N-甲基-2-吡咯烷酮(NMP)、二甲基亚砜(DMSO)中的一种或多种。
其中，步骤(1)中，所述脂肪族二酐与所述含氟芳香二胺的摩尔比为1:(0.95～1.05)。优选地，所述脂肪族二酐与所述含氟芳香二胺的摩尔比为1:1。
优选地，步骤(2)中，在将所述反应液涂覆在玻璃基板之前，还包括：对所述反应液进行抽真空脱泡处理12～24h。所述真空脱泡处理是在搅拌情况下进行，脱泡可以便于后续在玻璃基板上形成平整、无气泡的薄膜表面。
优选地，步骤(2)中，涂覆到玻璃基板上形成的涂覆厚度为50～200μm。
其中，步骤(2)中，所述烘烤的时间为4～10min。烘烤的目的是为了将反应液中的溶剂挥发掉，在真空条件下边烘边抽可以使挥发的溶剂不因冷却至室温而滴落在薄膜表面；之后在步骤(3)进行升温固化时，溶剂已基本不存在，故只需在氮气下高温固化即可，无需再抽气。
优选地，步骤(2)中，所述烘烤成膜的温度为90～115℃。
优选地，步骤(3)中，所述薄膜升温固化的开始温度为90～115℃。本申请中，在升温固化时，先将带氮气保护的烘箱等实验设备加热至升温固化的起始温度(例如90、100或110℃)，然后将步骤(2)所得薄膜置于这样温度的烘箱中，按预设程序开始进行升温固化。
优选地，步骤(3)中，所述升温固化的方式为热风式加热和红外线加热中的一种。
优选地，步骤(3)中，所述固化温度为360～450℃，固化时间为10～60min。
本发明中选择360～450℃作为固化温度，一来，在该温度下固化时薄膜的 质量损失较少，二来，在该温度下进行固化，进一步强化了改性PI薄膜的耐高温性能，基于后续所得改性聚酰亚胺主要用于柔性薄膜基板的制造，其工艺高达400℃左右，耐高温的改性PI薄膜更有利于应用。
优选地，步骤(3)中，所述固化的升温速率为10～20℃/min。
其中，在将步骤(2)所得薄膜从80～120℃开始进行升温固化之前，还包括：先将步骤(2)所得薄膜在120℃保温15～30min。这样保温可以进一步保证残余的溶剂可以彻底挥发干净。
优选地，步骤(3)中，所述剥离脱膜的方式为激光剥离、机械剥离。具体地，所述机械剥离为手动撕除。
本发明中，步骤(1)中，所得反应液中含有聚酰胺酸，其结构式如下所示：
Figure PCTCN2017082048-appb-000007
n为聚合度，n为自然数。
进一步地，n为1～1000的自然数。优选地，n为100～1000的自然数。例如可以是200、300、400、500、600、700、800或900等。
本发明中，步骤(3)中，升温固化后所得改性聚酰亚胺薄膜的化学结构式如下式(Ⅲ)所示：
Figure PCTCN2017082048-appb-000008
其中，
Figure PCTCN2017082048-appb-000009
选自
Figure PCTCN2017082048-appb-000010
Figure PCTCN2017082048-appb-000011
中的一种；-R2-选自-O-、
Figure PCTCN2017082048-appb-000012
和
Figure PCTCN2017082048-appb-000013
中的一种；n为聚合度，n为自然数。
进一步地，n为1～1000的自然数。
本发明第一方面提供的改性聚酰亚胺薄膜的制备方法，先将式(Ⅰ)所示的环状脂肪族二酐单体与式(Ⅱ)所示的含氟芳香二胺单体共聚，得到含聚酰胺酸的反应液，再经独特的热酰亚胺化工艺(先于50～120℃真空烘烤、再从80～120℃开始的升温固化)、剥离过程得到改性聚酰亚胺薄膜。其反应历程如下：
Figure PCTCN2017082048-appb-000014
其中，脂肪族二酐中使用脂环结构替代通常的芳香环结构，能有效打断最终产物聚酰亚胺分子内的共轭作用，减小CTC形成的几率，提高其材料的无色透明性并表现出较优异的柔性。含氟芳香二胺单体分子中引入三氟甲基基团(-CF3)和带醚键(-O-)的基团R2，其具有强吸电子特性，也能减小终产物聚酰亚胺的分子间共轭作用，有效抑制CTC的形成，明显改善聚酰亚胺薄膜的无色透明性并提高其溶解性和热稳定性。这使得本发明得到的聚酰亚胺膜既具有较好的耐高温特性，又表现出较优异的无色透明性和柔性、可见光透过率等。该备方法简便易行，反应程度可控，改性聚酰亚胺薄膜的膜面光滑平整，溶剂残留少，纯度高，可实现工业化生产。
第二方面，本发明提供了一种改性聚酰亚胺薄膜，所述改性聚酰亚胺薄膜的材质的化学结构式如下式(Ⅲ)所示：
Figure PCTCN2017082048-appb-000015
其中，
Figure PCTCN2017082048-appb-000016
选自
Figure PCTCN2017082048-appb-000017
Figure PCTCN2017082048-appb-000018
中的一种；-R2-选自-O-、
Figure PCTCN2017082048-appb-000019
和
Figure PCTCN2017082048-appb-000020
中的一种；n为聚合度，n为自然数。
进一步地，n为1～1000的自然数。
优选地，n为100～1000的自然数。例如可以是200、300、400、500、600、700、800或900等。
本发明第二方面提供的改性聚酰亚胺薄膜采用本发明第一方面所述的方法制得，该改性聚酰亚胺薄膜具有较好的耐高温特性，又表现出较优异的无色透明性和柔性、可见光透过率，能够作为透明柔性显示技术的基板材料。
本发明的有益效果包括以下几个方面：
1)先将式(Ⅰ)所示的环状脂肪族二酐单体与式(Ⅱ)所示的含氟芳香二胺单体共聚，得到含聚酰胺酸的反应液，再经独特的热酰亚胺化工艺、剥离过程得到改性聚酰亚胺薄膜，该方法简便易行，反应程度可控，产物纯度高、溶剂残留少，改性聚酰亚胺薄膜的膜面光滑平整，可工业化生产；
2)所述改性聚酰亚胺薄膜的材质中，脂环结构、带有醚键、三氟甲基的 芳香结构，能有效消除改性聚酰亚胺的分子内或分子间电荷转移络合物(CTC)的形成，提高该材料的无色透明性、溶解性和热稳定性，表现出较好的柔性。
本发明的优点将会在下面的说明书中部分阐明，一部分根据说明书是显而易见的，或者可以通过本发明实施例的实施而获知。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
一种无色透明柔性聚酰亚胺膜的制备方法，包括以下步骤：
1)在室温下，将0.01mol的1,2,3,4-环丁烷四甲酸二酐(CBDA)与0.01mol的2,2'-双三氟甲基-4,4'-二氨基二苯醚(TFODA)溶解于250mL的N-甲基-2-吡咯烷酮(NMP)中，加入到反应釜中，在氮气气氛保护下充分搅拌，控制温度为30℃，反应6h后，得到聚酰胺酸溶液。
2)将聚酰胺酸溶液进行抽真空脱泡处理后，在氮气气氛下，将其涂覆于洁净光滑的玻璃基板上，控制涂覆厚度为150μm。
3)在真空环境下，将上述玻璃基板置于50℃下烘烤10min，使溶剂NMP挥发并抽离出去。
4)在氮气气氛下，先在120℃保温30min后，之后以10℃/min的升温速 率从120℃升温至400℃，使薄膜固化30min，再经循环冷却水冷却至室温。
5)使用激光剥离技术将薄膜从玻璃基板上剥离，得到无色透明状的改性聚酰亚胺薄膜，还具有一定柔性。
本实施例所得改性聚酰亚胺薄膜的化学结构式为
Figure PCTCN2017082048-appb-000021
本实施例中的聚合度n为1000，在其他实施例中，n还可为250、450、600等其他正整数；所得改性聚酰亚胺薄膜的紫外吸收截止波长为330nm，在420nm处透过率为88％。
实施例2
一种改性聚酰亚胺膜的制备方法，包括以下步骤：
1)在室温下，将0.01mol的2,3,5,6-双环[2.2.1]庚烷四甲酸二酐与0.01mol的2,2'-双三氟甲基-4,4'-二氨基二苯醚溶解于250mL的N-甲基-2-吡咯烷酮(NMP)中，加入到反应釜中，在氮气气氛保护下充分搅拌，控制温度为20℃，反应6h后，得到聚酰胺酸溶液。
2)将聚酰胺酸溶液进行抽真空脱泡处理后，在氮气气氛下，将其涂覆于洁净光滑的玻璃基板上，控制涂覆厚度为100μm。
3)在真空环境下，将上述玻璃基板置于60℃下烘烤8min，使溶剂NMP挥发并抽离出去。
4)在氮气气氛下，先在120℃保温20min后，之后以20℃/min的升温速率从120℃升温至450℃，使薄膜固化45min，再经循环冷却水冷却至室温。
5)使用激光剥离技术将薄膜从玻璃基板上剥离，得到无色透明状的改性 聚酰亚胺薄膜，且具有一定柔性。
本实施例所得改性聚酰亚胺薄膜的化学结构式为
Figure PCTCN2017082048-appb-000022
本实施例中的聚合度n为800；所得改性聚酰亚胺薄膜的紫外吸收截止波长为313nm，在420nm处透过率为91％。
实施例3
一种改性聚酰亚胺膜的制备方法，包括以下步骤：
1)在室温下，将0.01mol的2,3,5,6-双环[2.2.1]庚烷四甲酸二酐与0.0095mol的1,4-双(4-氨基-2-三氟甲基苯氧基)苯溶解于250mL的N-甲基-2-吡咯烷酮(NMP)中，加入到反应釜中，在氮气气氛保护下充分搅拌，控制温度30℃，反应6h后，得到聚酰胺酸溶液(PAA)。
2)将聚酰胺酸溶液进行抽真空脱泡处理后，在氮气气氛下，将其涂覆于洁净光滑的玻璃基板上，控制涂覆厚度为50μm。
3)在真空环境下，将上述玻璃基板置于70℃下烘烤4min，使溶剂NMP挥发并抽离出去。
4)在氮气气氛下，先在120℃保温15min后，之后以15℃/min的升温速率从120℃升温至380℃，使薄膜固化60min，再经循环冷却水冷却至室温。
5)使用激光剥离技术将薄膜从玻璃基板上剥离，得到无色透明状的改性聚酰亚胺薄膜，且具有一定柔性。
本实施例所得改性聚酰亚胺薄膜的化学结构式为
Figure PCTCN2017082048-appb-000023
本实施例中的聚合度n为350；所得改性聚酰亚胺薄膜的紫外吸收截止波长为302nm，在420nm处透过率为90％。
实施例4
一种无色透明柔性聚酰亚胺膜的制备方法，包括以下步骤：
1)在室温下，将1mol的1,2,4,5-环己烷四羧酸二酐与1.05mol的2,2-双[4-(4-氨基-2三氟甲基苯氧基)苯基]丙烷溶解于25mL的二甲基甲酰胺(DMF)中，加入到三口瓶中，在氮气气氛保护下充分搅拌，控制温度为20℃，反应4h后，得到聚酰胺酸溶液。
2)将聚酰胺酸溶液进行抽真空脱泡处理后，在氮气气氛下，将其涂覆于洁净光滑的玻璃基板上，控制涂覆厚度为60μm。
3)在真空环境下，将上述玻璃基板置于70℃下烘烤10min，使溶剂挥发并抽离出去。
4)在氮气气氛下，以8℃/min的升温速率从120℃升温至380℃，使薄膜固化40min，再经循环冷却水冷却至室温。
5)使用激光剥离技术将薄膜从玻璃基板上剥离，得到无色透明状的改性聚酰亚胺薄膜，还具有一定柔性。
本实施例所得改性聚酰亚胺薄膜的化学结构式如下所示：
Figure PCTCN2017082048-appb-000024
其中n为500；该薄膜的紫外吸收截止波长为301nm，在420nm处透过率为92％。
需要说明的是，根据上述说明书的揭示和和阐述，本发明所属领域的技术人员还可以对上述实施方式进行变更和修改。因此，本发明并不局限于上面揭示和描述的具体实施方式，对本发明的一些等同修改和变更也应当在本发明的权利要求的保护范围之内。此外，尽管本说明书中使用了一些特定的术语，但这些术语只是为了方便说明，并不对本发明构成任何限制。

Claims (15)

  1. 一种改性聚酰亚胺薄膜的制备方法，其中，包括以下步骤
    (1)取如下式(Ⅰ)所示的脂肪族二酐与式(Ⅱ)所示的含氟芳香二胺溶解在非质子极性溶剂中，在氮气保护下进行共聚反应2～10h，得到反应液；
    Figure PCTCN2017082048-appb-100001
    其中，
    Figure PCTCN2017082048-appb-100002
    选自
    Figure PCTCN2017082048-appb-100003
    Figure PCTCN2017082048-appb-100004
    中的一种；-R2-选自-O-、
    Figure PCTCN2017082048-appb-100005
    Figure PCTCN2017082048-appb-100006
    中的一种；
    (2)在氮气气氛下，将所述反应液涂覆在洁净光滑的玻璃基板上；并在真空环境下于50～120℃下烘烤成膜；
    (3)在氮气气氛下，将步骤(2)所得薄膜从80～120℃开始进行升温固化，待冷却至室温，从所述玻璃基板上剥离脱膜，得到改性聚酰亚胺薄膜。
  2. 如权利要求1所述的制备方法，其中，步骤(1)中，所述共聚反应的温度为10～40℃。
  3. 如权利要求1所述的制备方法，其中，步骤(2)中，在将所述反应液涂覆在玻璃基板之前，还包括：对所述反应液进行抽真空脱泡处理12～24h。
  4. 如权利要求1所述的制备方法，其中，步骤(2)中，所述反应液涂覆到玻璃基板上形成的涂覆厚度为50～200μm。
  5. 如权利要求1所述的制备方法，其中，步骤(2)中，所述烘烤的时间为4～10min。
  6. 如权利要求1所述的制备方法，其中，步骤(2)中，所述烘烤成膜的温度为90～115℃。
  7. 如权利要求1所述的制备方法，其中，步骤(3)中，所述固化温度为360～450℃，固化时间为10～60min。
  8. 如权利要求1所述的制备方法，其中，步骤(3)中，所述固化时的升温速率为10～20℃/min。
  9. 如权利要求1所述的制备方法，其中，步骤(3)中，在将步骤(2)所得薄膜从80～120℃开始进行升温固化之前，还包括：先将步骤(2)所得薄膜在120℃保温15～30min。
  10. 如权利要求1所述的制备方法，其中，步骤(3)中，所述薄膜升温固化的开始温度为90～115℃。
  11. 如权利要求1所述的制备方法，其中，所述共聚反应的温度为15～30℃。
  12. 如权利要求1所述的制备方法，其中，步骤(1)中，所述脂肪族二酐与所述含氟芳香二胺的摩尔比为1:(0.95～1.05)。
  13. 如权利要求1所述的制备方法，其中，所述非质子极性溶剂选自N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮和二甲基亚砜中的一种或多种。
  14. 一种改性聚酰亚胺薄膜，其中，所述改性聚酰亚胺薄膜的材质的化学 结构式如下式(Ⅲ)所示：
    Figure PCTCN2017082048-appb-100007
    其中，
    Figure PCTCN2017082048-appb-100008
    选自
    Figure PCTCN2017082048-appb-100009
    Figure PCTCN2017082048-appb-100010
    中的一种；-R2-选自-O-、
    Figure PCTCN2017082048-appb-100011
    Figure PCTCN2017082048-appb-100012
    中的一种；n为聚合度，n为自然数。
  15. 如权利要求14所述的改性聚酰亚胺薄膜，其中，n为1～1000的自然数。
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