WO2020211110A1 - 一种聚酰亚胺复合物、制备方法及其应用 - Google Patents

一种聚酰亚胺复合物、制备方法及其应用 Download PDF

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WO2020211110A1
WO2020211110A1 PCT/CN2019/084439 CN2019084439W WO2020211110A1 WO 2020211110 A1 WO2020211110 A1 WO 2020211110A1 CN 2019084439 W CN2019084439 W CN 2019084439W WO 2020211110 A1 WO2020211110 A1 WO 2020211110A1
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compound
polyamic acid
preparation
polyimide
polyimide composite
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汪亚民
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Wuhan China Star Optoelectronics Semiconductor Display Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0009—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Glucans, e.g. polydextrose, alternan, glycogen; (alpha-1,4)(alpha-1,6)-D-Glucans; (alpha-1,3)(alpha-1,4)-D-Glucans, e.g. isolichenan or nigeran; (alpha-1,4)-D-Glucans; (alpha-1,3)-D-Glucans, e.g. pseudonigeran; Derivatives thereof
    • C08B37/0012—Cyclodextrin [CD], e.g. cycle with 6 units (alpha), with 7 units (beta) and with 8 units (gamma), large-ring cyclodextrin or cycloamylose with 9 units or more; Derivatives thereof
    • C08B37/0015—Inclusion compounds, i.e. host-guest compounds, e.g. polyrotaxanes
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/01—Magnetic additives

Definitions

  • the present invention relates to the field of functional materials used in flat display panels, in particular, one of the functional polyimide (PI) materials.
  • PI functional polyimide
  • the electromagnetic wave absorption of the common detection material is calculated by the transmission line theory.
  • the electromagnetic radiation characteristic is within the range of -10dB, the electromagnetic radiation characteristic can be reduced to more than 90%, and when the absorption reaches -20dB, the material The electromagnetic radiation characteristics can be reduced to 99%, and when the absorption reaches -30dB, the electromagnetic radiation characteristics of the material can be reduced to 99.9%. This greatly reduces the electromagnetic wave pollution, and at the same time, people choose to shield more than 90% of the electromagnetic infection as an effective starting point, that is, it can reach -10dB and can be used as an electromagnetic wave absorbing material.
  • electromagnetic shielding materials are mainly made of composite polymer materials.
  • polymer materials As the matrix, metal oxides or particles are introduced to give the materials a better shielding effect.
  • the coating materials are often prone to force majeure damage, and the materials The damage itself will undoubtedly have a greater impact on the electromagnetic absorption performance, so the self-repairing properties of electromagnetic wave absorption materials are of far-reaching significance.
  • One aspect of the present invention is to provide a polyimide composite, which introduces Fe3O4 as the main body of the electromagnetic wave absorbing material, and then introduces the host and guest to give the material its own repair performance through the interaction between the two, so that it becomes A polyimide material with both electromagnetic shielding performance and self-repairing performance.
  • a polyimide compound with the general structural formula: PI/Fe3O4-( ⁇ -CD-Ada)x, where x 3 ⁇ 5.
  • the general structural formula of the polyamic acid is:
  • the raw materials used in the assembly Fe3O4-( ⁇ -CD-Ada)x include Fe3O4 and ⁇ -cyclodextrin.
  • One of the specific connection methods is that the Fe3O4 surface-OH in the raw material is connected to the cyclodextrin-COOH that has been carboxylated at position 6, but is not limited.
  • the raw materials used for the preparation of the polyamic acid include diamines: NH2-Ar-NH2, dianhydride, and sodium adamantate.
  • NH2-Ar-NH2 is one of the following five general structural formulas:
  • Ar a, b, c, d or e
  • the general structural formula adopted by the dianhydride includes one of the following two general structural formulas:
  • Another aspect of the present invention is to provide a method for preparing the polyimide composite according to the present invention, which includes the following steps:
  • Step S1 Preparation of host molecule: It is selected Fe3O4 particles to be grafted with ⁇ -cyclodextrin, and the obtained product is denoted as: compound A;
  • Step S2 Preparation of an assembly: adamantane is selected as the guest molecule and the compound A as the host molecule to form an assembly, wherein the obtained assembly is denoted as compound E;
  • Step S3 Preparation of a polyamic acid solution: the polyamic acid solution is prepared by selecting the diamine denoted as compound C, the dianhydride denoted as compound D, and sodium adamantate in a solvent, wherein the polyamic acid solution is obtained The polyamic acid in which the guest molecule is grafted with adamantane molecule is recorded as compound F;
  • Step S4 Preparation of the polyimide composite: it is to proportion the compound E and the compound F so that the Fe3O4 contained in the mixture of the two is in the range of 3%wt to 18%wt.
  • the molar ratio of the host molecule compound A to the guest molecule adamantane is (2 to 3): (1 to 3).
  • the selected compound C, the compound D, and sodium adamantate are fully dissolved and stirred in the N-methylpyrrolidone solvent, and the temperature is increased to 70 ⁇ At 90°C for 6-10 hours, the polyamic acid solution is obtained.
  • the selected molar ratio between the compound C and the compound D is in the range of 1.05-2.
  • another aspect of the present invention is to provide an application of the polyimide composite according to the present invention, which is used to form a polyimide film layer arranged on a glass substrate of a display panel .
  • Another aspect of the present invention is to provide a method for preparing the polyimide film layer on the display panel of the present invention using the polyimide composite of the present invention, including the following step:
  • polyimide composite according to the present invention which contains Fe3O4 in the range of 3% wt to 18% wt;
  • the stirring of the proportioned polyamic acid solution is performed at 0°C, and the stirring time is in the range of 24-96h.
  • the heating rate involved in the heating process is 4-8°C/min.
  • the constant temperature duration is in the range of 0.8 to 1.2 h.
  • the present invention relates to a polyimide composite, which imparts good electromagnetic shielding performance to the material itself by introducing magnetic particles Fe3O4, and the introduced guest molecules are through the interaction between the host molecules and the guest molecules. Endow the material itself with repairability, thus realizing a polyimide composite with both electromagnetic shielding performance and self-repairing performance.
  • the polyimide composite material involved in the present invention can be widely used in factories with electromagnetic radiation properties, such as OLED factories, semiconductor factories, etc.; it has a wide range of application prospects and market prospects.
  • Fig. 1 is a graph of the electromagnetic wave absorption performance of three PI coatings composed of three polyimide composites with different Fe3O4 contents according to the present invention
  • Fig. 2 is a super-depth pattern of the polyimide composite containing magnetic Fe3O4 particle filler before and after restoration.
  • the present invention relates to the structure of a polyimide composite and its preparation method, in order to avoid unnecessary repetitive descriptions and clearer descriptions, the preparation method will be mainly used for the preparation of the present invention.
  • the structure of the polyimide composite material is described in detail.
  • the method for preparing the polyimide compound of the present invention is prepared by a four-step method. Roughly:
  • the Fe3O4 particles are grafted with ⁇ -cyclodextrin to form functionalized particles and connect the carrier with repairing properties to form the main molecular structure;
  • the assembly is mixed with the polyamic acid solution in a proportion to obtain the polyimide composite of the present invention with electromagnetic shielding and self-repairing properties.
  • Step S1 Preparation of host molecule: specifically selecting Fe3O4 particles to be grafted with ⁇ -cyclodextrin, and the obtained product is denoted as compound A.
  • connection methods involved is that the Fe3O4 surface-OH bond in the raw material is connected to the cyclodextrin-COOH bond that has been carboxylated at position 6.
  • Step S3. Preparation of polyamic acid solution: specifically selecting 1-9mmol of diamine denoted as compound C: NH2-Ar-NH2, 1.1-9.9mmol of dianhydride denoted as compound D, and 1.1-9.9mmol of adamantanoic acid Sodium is fully dissolved and stirred in 10-40mL of N-methylpyrrolidone solvent. The temperature is raised to 80°C for 6-10h to form a polyamic acid solution for later use, which is referred to as compound F. Specifically, it can be called grafted diamond containing guest molecules Polyamic acid of alkane molecule.
  • NH2-Ar-NH2 uses one of the following five general structural formulas:
  • Ar a, b, c, d or e
  • the process of imidization of the polyamic acid is: the polyamic acid is stirred by itself to remove bubbles, and then goes through the H-VCD solvent removal process, and then uses the PI Curing method to raise the temperature stepwise to obtain the Compound F is the target polyimide.
  • the entire reaction process can be divided into two stages.
  • the first stage is:
  • the specific parameter condition range 40 ⁇ 90°C vacuum drying for 9 ⁇ 15 minutes, then the target product denoted as compound F as shown below will be obtained:
  • Step S4 Preparation of polyimide compound: it is to proportion the compound E and compound F so that the Fe3O4 contained in the mixture of the two is in the range of 3%wt to 18%wt, so that the invention relates to
  • the invention relates to a polyimide composite, which imparts good electromagnetic shielding performance to the material itself by introducing magnetic particles Fe3O4, and imparts the repairability of the material itself through the interaction between host and guest molecules when introducing guest molecules.
  • a polyimide composite with both electromagnetic shielding performance and self-repairing performance is realized.
  • another embodiment of the present invention provides an application of using the polyimide composite related to the present invention to form a PI layer of a display panel.
  • a specific method for preparing the PI layer involved is to distribute the compound E and compound F according to the mass ratio, and stir at 0°C for 24-96h to form a uniformly stirred polyamic acid solution, or directly The polyamic acid solution with a set ratio is provided.
  • the temperature was increased to 80°C at a heating rate of 4 ⁇ 8°C/min, and it was spin-coated on the glass substrate, and 70% of the solvent was removed by oven at 120°C, and then subjected to a constant temperature process of 400-450°C , Wherein the highest constant temperature is 450°C, and the constant temperature duration is 0.8-1.2h.
  • a PI layer composed of the polyimide composite involved in the present invention is obtained, which has both electromagnetic wave absorption performance and self-repair performance .
  • FIG. 1 illustrates a PI coating composed of three kinds of polyimide composites with different proportions of Fe3O4 particle fillers according to the present invention, and its electromagnetic wave absorption performance varies with frequency.
  • FIG. 2 illustrates the ultra-depth pattern of the polyimide composite material containing magnetic Fe3O4 particle fillers before and after restoration.
  • the scratches are obvious before the repair, and the scratches basically disappear after the repair, achieving the goal of achieving self-repair.
  • the polyimide composite material involved in the present invention can be widely used in factories with electromagnetic radiation properties, such as OLED factories, semiconductor factories, etc., so that it has broad application prospects and market prospects.

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Abstract

本发明提供了一种聚酰亚胺复合物，采用的结构通式为：PI/Fe3O4-(β-CD-Ada)x，其中x＝3～5。本发明的一个方面提供了一种聚酰亚胺复合物，其通过引入Fe3O4作为电磁波吸收材料的主体，在引入客体通过两者间的相互作用来赋予材料本身的修复性能，从而使得其成为一种既有电磁屏蔽效能又具有自修复性能的聚酰亚胺材料。

Description

一种聚酰亚胺复合物、制备方法及其应用 技术领域
本发明涉及平面显示面板中涉及使用的功能性材料领域，特别是，其中的一种功能性聚酰亚胺(PI)材料。
背景技术
已知，工业化的过程其实就是设备代替人工实现大批量生产的一个过程，随着电子通讯和电气工程设备逐步增加，我们生活的环境越开越受到电磁的污染，在工厂里面受到的影响更为明显，电磁辐射与干扰对人体的辐射受到较大的影响。
进一步的，随着电磁技术在受到广泛应用的同时，其也相应的带来了一些社会问题。例如，新型的四大污染已经变成水质污染、空气污染、噪音污染和电磁波污染。而在设备工厂，使用的涂层目前大多数是不具有防电磁污染的能力。
自1993年开始，业界开始对于电磁屏蔽涂层进行深入的研究(Bethune DS,Kiang CH,de Vries MS,et al.Cobalt-catalysed growth of carbon nanotubes with single atomic-layer walls.Nature 1993；363:605–6.)。
随着社会的发展，世界各国近年来都对此加大研发投入。而其中的一种常规的制备一种降低电磁污染的电磁波吸收涂层材料的方法，其为将所述电磁波的辐射控制在一定的范围内，或者是将其90％的辐射性能全部通过材料进行吸收掉。
通常的检测材料的电磁波吸收形成，通过传输线理论进行计算得知，在-10dB的范围内时，就可以将其电磁辐射特性减小到90％以上，而当吸收达到-20dB时，则材料的电磁辐射特性可以减小到99％，吸收达到-30dB时则材料的电磁辐射特性可以减小到99.9％。如此极大的降低了电磁波的污染，同时人们选择能屏蔽90％以上的电磁感染作 为有效起点，即能达到-10dB就可以作为电磁吸波材料使用。
目前电磁屏蔽材料主要是制备复合高分子材料为主，通过以高分子材料为基体，引入金属氧化物或颗粒等赋予材料较好的屏蔽效果，但是涂层材料往往容易产生不可抗力的破损，而材料本身的破损无疑会对电磁吸收性能产生较大的影响，所以电磁波吸收材料具有自修复性能具有深远意义。
技术问题
本发明的一个方面是提供一种聚酰亚胺复合物，其通过引入Fe3O4作为电磁波吸收材料的主体，再引入主客体通过两者间的相互作用来赋予材料本身的修复性能，从而使得其成为一种既有电磁屏蔽效能又具有自修复性能的聚酰亚胺材料。
技术解决方案
本发明采用的技术方案如下：
一种聚酰亚胺复合物，采用的结构通式为：PI/Fe3O4-(β-CD-Ada)x，其中x＝3～5。
进一步的，在不同实施方式中，其中本发明涉及的所述聚酰亚胺复合物采用的制备原料包括组装体Fe3O4-(β-CD-Ada)x与聚酰胺酸(polyamic acid，PAA)，其中x＝3～5。
进一步的，在不同实施方式中，其中所述聚酰胺酸的结构通式为：
Figure PCTCN2019084439-appb-000001
进一步的，在不同实施方式中，其中所述组装体Fe3O4-(β-CD-Ada)x采用的原料包括Fe3O4和β-环糊精。其中的一种具体连接方 式为原料中的所述Fe3O4表面-OH与6号位已经羧基化的环糊精-COOH连接形成，但不限于。
进一步的，在不同实施方式中，其中所述聚酰胺酸采用的制备原料包括二胺：NH2-Ar-NH2、二酸酐、金刚烷酸钠。
进一步的，在不同实施方式中，其中所述二胺：NH2-Ar-NH2采用的结构通式为以下5种结构通式中的一种：
Ar＝a、b、c、d或e；
其中a、b、c、d及e的结构式如下所示：
Figure PCTCN2019084439-appb-000002
进一步的，在不同实施方式中，其中所述二酸酐采用的结构通式包括以下2种结构通式中的一种：
Figure PCTCN2019084439-appb-000003
进一步的，本发明的又一方面是提供一种本发明涉及的所述聚酰亚胺复合物的制备方法，包括以下步骤：
步骤S1、制备主体分子：其为选用Fe3O4粒子接枝β-环糊精，获得的产物记为：化合物A；
步骤S2、制备组装体：其为选用金刚烷作为客体分子与所述作为主体分子的化合物A来形成组装体，其中获得的所述组装体记为 化合物E；
步骤S3、制备聚酰胺酸溶液：其为选用记为化合物C的二胺、记为化合物D的二酸酐以及金刚烷酸钠在溶剂中制备聚酰胺酸溶液，其中获得的所述聚酰胺酸溶液中含有客体分子接枝金刚烷分子的聚酰胺酸，并将其记为化合物F；
步骤S4、聚酰亚胺复合物的制备：其为配比所述化合物E和化合物F，使得两者混合物中含有的Fe3O4在3％wt～18％wt范围内。
进一步的，在不同实施方式中，在所述步骤S2中，其中所述主体分子化合物A与所述客体分子金刚烷的摩尔比为(2～3):(1～3)。
进一步的，在不同实施方式中，在所述步骤S3中，选用的所述化合物C、所述化合物D以及金刚烷酸钠是在N-甲基吡咯烷酮溶剂中充分溶解搅拌，并升温至70～90℃持续6-10h，进而获得所述聚酰胺酸溶液。
进一步的，在不同实施方式中，在所述步骤S3中，其中选用的所述化合物C和化合物D之间的摩尔比在1.05～2范围内。
进一步的，本发明的又一方面是提供一种本发明涉及的所述聚酰亚胺复合物的应用，其为用于构成设置在一种显示面板的玻璃基板上的聚酰亚胺膜层。
进一步的，本发明的又一方面是提供一种制备使用本发明涉及的所述聚酰亚胺复合物构成本发明涉及的所述显示面板上的聚酰亚胺膜层的制备方法，包括以下步骤：
提供本发明涉及的所述聚酰亚胺复合物，其中含有的Fe3O4在3％wt～18％wt范围内；
对其进行搅拌形成搅拌均匀的配比聚酰胺酸溶液，然后将温度升高到70～100℃，将其旋涂在一显示面板的玻璃基板上；
在110～130℃下除去涂布在所述玻璃基板上的所述聚酰胺酸溶液中50～70％的溶剂，然后对其升温并在400～450℃对其进行恒温制程，最终得到形成在所述玻璃基板上的聚酰亚胺膜层。
进一步的，在不同实施方式中，其中对所述配比聚酰胺酸溶液的搅拌是在0℃下进行的，其中搅拌时长在24-96h范围内。
进一步的，在不同实施方式中，其中升温过程中涉及的升温速率为4～8℃/min。
进一步的，在不同实施方式中，其中在所述恒温制程时，恒温时长在0.8～1.2h范围内。
有益效果
本发明涉及的一种聚酰亚胺复合物，其通过引入磁性粒子Fe3O4赋予材料本身良好的电磁屏蔽性能，在通过引入的客体分子通过所述主体分子和客体分子两者之间的相互作用来赋予材料本身的修复性，如此实现了一种既具有电磁屏蔽性能，又有自修复性能的聚酰亚胺复合物。
而对此，业界暂无关于既有电磁屏蔽作用，又有自修复性能的聚酰亚胺复合材料的研究成果的公开，相信未来这一块的应用会有更多的探索，而本发明则为这种探索提供了新颖的思路和一些解决方案。
进一步的，本发明涉及的这种聚酰亚胺复合物材料可以广泛应用于具有电磁辐射性质的工厂，例如，OLED工厂，半导体工厂等等；使其具有广泛的应用前景以及市场前景。
附图说明
为了更清楚地说明本发明实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本发明涉及的三种不同Fe3O4含量的聚酰亚胺复合物构成的3种PI涂层，其电磁波吸收性能随频率变化的曲线图；
图2为本发明涉及的含有磁性Fe3O4颗粒填充物的聚酰亚胺复合物在修复前、后的超景深图案。
本发明的实施方式
以下将结合附图和实施例，对本发明涉及的一种聚酰亚胺复合物、制备方法及其应用的技术方案作进一步的详细描述。
其中由于本发明涉及了一种聚酰亚胺复合物的结构及其制备方法，为了避免不必要的重复描述，以及更为清晰的说明，以下将以所述制备方法为主对本发明涉及的所述聚酰亚胺复合材料结构进行细节说明。
其中本发明涉及的一种制备本发明涉及的所述聚酰亚胺复合物的方法是通过四步法制备的。概略为：
首先，将Fe3O4粒子接枝β-环糊精，形成具有功能化的粒子与修复性能的载体连接，即形成主体分子结构；
其次，选择客体分子进行包合形成组装体；
然后，制备聚酰胺酸溶液；
最后，在将所述组装体与聚酰胺酸溶液配比混合，从而获得具有电磁屏蔽和自修复性能的本发明涉及的所述聚酰亚胺复合物。
以下将结合具体的参数细节对上述四个步骤进行详细的说明。
步骤S1、制备主体分子：具体为选用Fe3O4粒子接枝β-环糊精，获得的产物记为：化合物A。
其中涉及的一种具体连接方式为原料中的所述Fe3O4表面-OH键与6号位已经羧基化的环糊精-COOH键连接形成。
步骤S2、制备组装体：具体为选用1-3mmol金刚烷客体分子(常见的与β-环糊精包合的客体分子)与2-3mmol Fe3O4粒子接枝β-环糊精(化合物A)在常温下，搅拌24-96h，形成组装体Fe3O4-(β-CD-Ada)x，其中x＝3～5，记为化合物E；其中原料比例中的主体分子所述化合物A与客体分子金刚烷摩尔比优选为1:1。
步骤S3、制备聚酰胺酸溶液：具体为选用1-9mmol的记为化合物C的二胺：NH2-Ar-NH2、1.1-9.9mmol的记为化合物D的二酸酐以及1.1-9.9mmol金刚烷酸钠在10-40mL的N-甲基吡咯烷酮溶剂中充分溶解搅拌，升温至80℃持续6-10h，形成聚酰胺酸溶液备用，记为化合物F，具体可将其称为含有客体分子接枝金刚烷分子的聚酰胺酸。
其中涉及使用的所述二胺：NH2-Ar-NH2采用的结构通式为以下5种结构通式中的一种：
Ar＝a、b、c、d或e；
其中a、b、c、d及e的结构式如下所示：
Figure PCTCN2019084439-appb-000004
其中涉及使用的所述二酸酐采用的结构通式为以下2种结构通式中的一种：
Figure PCTCN2019084439-appb-000005
其中所述化合物F涉及的一种具体反应路线如下所示：
Figure PCTCN2019084439-appb-000006
其中所述聚酰胺酸进行亚胺化的过程为：聚酰胺酸自身搅拌除去气泡，然后再经过H-VCD除溶剂的过程，再使用PI Curing的方法进行阶梯式升温，从而得到所述记为化合物F的目标聚酰亚胺。
其中整个反应过程可以分为两个阶段，第一阶段形成的是：
Figure PCTCN2019084439-appb-000007
其是未经过搅拌除去气泡，可以记为聚酰胺酸溶液化合物F前驱体。
然后在对其进行下一步的H-VCD除溶剂的过程，具体参数条件范围为：40～90℃真空干燥9～15分钟，才会得到如下所示的记为化合物F的目标产物：
Figure PCTCN2019084439-appb-000008
步骤S4、聚酰亚胺复合物的制备：其为配比所述化合物E和化合物F，使得两者混合物中含有的Fe3O4在3％wt～18％wt范围内，如此，最终得到本发明涉及的所述聚酰亚胺复合物，其采用的结构通式可以表述为：PI/Fe3O4-(β-CD-Ada)x，其中x＝3～5。
本发明涉及的一种聚酰亚胺复合物，其通过引入磁性粒子Fe3O4赋予材料本身良好的电磁屏蔽性能，在引入客体分子通过主客体分子之间的相互作用来赋予材料本身的修复性，如此实现了一种既具有电磁屏蔽性能，又有自修复性能的聚酰亚胺复合物。
而对此，业界暂无关于既有电磁屏蔽作用，又有自修复性能的聚酰亚胺复合材料的研究成果的公开，相信未来这一块的应用会有更多的探索，而本发明则为这种探索提供了新颖的思路和一些解决方案。
进一步的，本发明的又一实施方式提供了一种将本发明涉及的所述聚酰亚胺复合物用于构成一种显示面板的PI层的应用。
其中涉及的一种具体PI层的制备方法为，按照质量比例来分配所述化合物E和化合物F，在0℃下进行搅拌24-96h，形成搅拌均匀的配比聚酰胺酸溶液，或者是直接提供设定配比的所述聚酰胺酸溶液。
然后，以4～8℃/min升温速率将温度升高到80℃，将其旋涂在玻璃基板上，在120℃下oven除去70％的溶剂，然后将其进行400～450℃的恒温制程，其中最高恒温温度为450℃，恒温时长为0.8～1.2h，最终得到由本发明涉及的所述聚酰亚胺复合物构成的一种PI层，其既具有电磁波吸收性能，又具有自修复性能。
进一步的，请参阅图1所示，其图示了由本发明涉及的三种不同配比含量Fe3O4颗粒填充物的聚酰亚胺复合物构成的PI涂层，其电磁波吸收性能随频率变化曲线。
由图中可以看出，当Fe3O4含量为5wt％时候，其吸收曲线相对较差，当含量提高到10％以上后，其电磁波吸收性能进一步加强，另 一方面考虑到相容性问题，不可以无限量的添加，优选控制在15wt％左右为佳。
进一步的，请参阅图2所示，其图示了本发明涉及的含有磁性Fe3O4颗粒填充物的聚酰亚胺复合物材料在修复前后的超景深图案。由图中所示，可以看到修复前划痕明显，而修复后划痕基本消失，达到了能够实现自身修复的目的。
本发明涉及的这种聚酰亚胺复合物材料可以广泛应用于具有电磁辐射性质的工厂，例如，OLED工厂，半导体工厂等等，使其具有广泛的应用前景以及市场前景。
本发明的技术范围不仅仅局限于上述说明中的内容，本领域技术人员可以在不脱离本发明技术思想的前提下，对上述实施例进行多种变形和修改，而这些变形和修改均应当属于本发明的范围内。

Claims (12)

  1. 一种聚酰亚胺复合物，采用的结构通式为：PI/Fe3O4-(β-CD-Ada)x，其中x＝3～5。
  2. 根据权利要求1所述的聚酰亚胺复合物，其采用的制备原料包括组装体Fe3O4-(β-CD-Ada)x与聚酰胺酸，其中x＝3～5。
  3. 根据权利要求2所述的聚酰亚胺复合物，其中所述聚酰胺酸的结构通式为：
    Figure PCTCN2019084439-appb-100001
  4. 根据权利要求2所述的聚酰亚胺复合物，其中所述聚酰胺酸采用的制备原料包括二胺：NH2-Ar-NH2、二酸酐和金刚烷酸钠。
  5. 根据权利要求4所述的聚酰亚胺复合物，其中所述二胺采用的结构通式为以下5种结构通式中的一种：
    Ar＝a、b、c、d或e；
    其中a、b、c、d及e的结构式如下所示：
    Figure PCTCN2019084439-appb-100002
  6. 根据权利要求4所述的聚酰亚胺复合物，其中所述二酸酐采用的结构通式为以下2种结构通式中的一种：
    Figure PCTCN2019084439-appb-100003
  7. 一种制备根据权利要求1所述的聚酰亚胺复合物的制备方法，包括以下步骤：
    步骤S1、制备主体分子：其为选用Fe3O4粒子接枝β-环糊精，获得的产物记为：化合物A；
    步骤S2、制备组装体：其为选用金刚烷作为客体分子与所述作为主体分子的化合物A来形成组装体，其中获得的所述组装体记为化合物E；
    步骤S3、制备聚酰胺酸溶液：其为选用记为化合物C的二胺：NH2-Ar-NH2、记为化合物D的二酸酐以及金刚烷酸钠在溶剂中制备聚酰胺酸溶液，其中获得的所述聚酰胺酸溶液中含有客体分子接枝金刚烷分子的聚酰胺酸，并将其记为化合物F；
    步骤S4、聚酰亚胺复合物的制备：其为配比所述化合物E和化合物F，使得两者混合物中含有的Fe3O4在3％wt～18％wt范围内。
  8. 一种根据权利要求7所述的制备方法，在所述步骤S2中，其中所述主体分子化合物A与所述客体分子金刚烷的摩尔比为(2～3):(1～3)。
  9. 一种根据权利要求7所述的制备方法，在所述步骤S3中，其中选用的所述化合物C、所述化合物D以及金刚烷酸钠是在N-甲基吡咯烷酮溶剂中充分溶解搅拌，并升温至70～90℃持续6-10h，进而获得所述聚酰胺酸溶液。
  10. 一种根据权利要求7所述的制备方法，在所述步骤S3中，其中选用的所述化合物C和所述化合物D之间的摩尔比在1.05～2范围内。
  11. 一种显示面板，其包括基板，其中所述基板上设置有聚酰亚胺膜层；其中所述聚酰亚胺膜层采用的材料包括根据权利要求1所述的聚酰亚胺复合物。
  12. 一种制备根据权利要求11所述显示面板的制备方法，包括以下步骤：
    提供根据权利要求1所述的聚酰亚胺复合物，其中含有的Fe3O4在3％wt～18％wt范围内；
    对其进行搅拌形成搅拌均匀的配比聚酰胺酸溶液，然后将温度升高到70～100℃，在将其旋涂在一显示面板的玻璃基板上；
    在110～130℃下除去涂布在所述玻璃基板上的所述聚酰胺酸溶液中50～70％的溶剂，然后在对其升温并在400～450℃对其进行恒温制程，最终得到形成在所述玻璃基板上的聚酰亚胺膜层。
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