WO2023029341A1 - 一种无色透明聚酰亚胺树脂薄膜及其制备方法 - Google Patents

一种无色透明聚酰亚胺树脂薄膜及其制备方法 Download PDF

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WO2023029341A1
WO2023029341A1 PCT/CN2022/070497 CN2022070497W WO2023029341A1 WO 2023029341 A1 WO2023029341 A1 WO 2023029341A1 CN 2022070497 W CN2022070497 W CN 2022070497W WO 2023029341 A1 WO2023029341 A1 WO 2023029341A1
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bis
aminophenoxy
trifluoromethyl
benzene
anhydride
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English (en)
French (fr)
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于克波
虞鑫海
武海朋
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山东中柔新材料有限公司
虞鑫海
东华大学
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Publication of WO2023029341A1 publication Critical patent/WO2023029341A1/zh

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    • 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
    • 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
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • 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
    • C08G73/12—Unsaturated polyimide precursors
    • C08G73/123—Unsaturated polyimide precursors the unsaturated precursors comprising halogen-containing substituents
    • 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
    • C08G73/12—Unsaturated polyimide precursors
    • C08G73/124—Unsaturated polyimide precursors the unsaturated precursors containing oxygen in the form of ether bonds in the main chain
    • 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

Definitions

  • the invention belongs to the field of polymer films, in particular to a colorless and transparent polyimide resin film and a preparation method thereof.
  • Polyimide is a class of polymers with excellent comprehensive properties. It has excellent heat resistance, low temperature resistance, solvent resistance, self-lubrication and flame retardancy. At the same time, it also has very good mechanical properties and Dielectric properties.
  • Cisokia hydroxyl group discloses a preparation method of polyimide powder containing phenolic hydroxyl group, which is mainly characterized in that: aromatic diamine compound containing phenolic hydroxyl group or a mixture of aromatic diamine containing phenolic hydroxyl group and other diamines and Aromatic dibasic anhydrides are reacted in a strong polar aprotic organic solvent under nitrogen protection at 0°C to 30°C for 3 to 12 hours to obtain a transparent and viscous polyhydroxyamic acid solution, followed by azeotropic dehydration agent, heating and heating, in the temperature range of 120°C to 160°C, reflux azeotropic dehydration imidization reaction for 5 to 18 hours, cool to room temperature, filter, wash, and vacuum dry to obtain polyimide powder containing phenolic hydroxyl groups.
  • U.S. Patent US5147966 discloses a kind of preparation method of polyimide powder, and its main feature is: use diglyme (diglyme) as solvent, make 3,4'-diaminodiphenyl ether (34ODA) and 3 , 3', 4, 4'-tetracarboxylic acid diphenyl ether dianhydride (ODPA) and phthalic anhydride (PA) react at room temperature, after obtaining polyamic acid solution, add N-methyl-2-pyrrolidone ( NMP), triethylamine (TEA) and acetic anhydride (Ac2O) carry out chemical imidization reaction, add water precipitation, filter, wash with water, dry, obtain polyimide powder.
  • diglyme diglyme
  • 34ODA 3,4'-diaminodiphenyl ether
  • ODPA 3,4'-diaminodiphenyl ether
  • PA phthalic anhydride
  • NMP N-methyl-2-pyrroli
  • Japanese patent JP H05-0175175A discloses the molecular structure and preparation method of colorless transparent polyimide, and its main feature is: 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride and polyimide
  • the ether-type diamine reacts to obtain fluorine-containing polyamic acid, and then obtains colorless and transparent polyimide through chemical imidization or thermal imidization.
  • NTT Corporation of Japan also uses 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride monomer, which is expensive and has low reactivity, to combine with pyromellitic dianhydride or 3,3'-bis( Trifluoromethyl)-4,4'-diaminobiphenyl has been developed as a polyimide film material with better light transmittance in the visible light range.
  • Liu Jingang et al [Preparation and Performance Research of Colorless Transparent High Temperature Polyimide Film, Functional Materials, 2006, 9 (37): 1496-1499] disclosed the molecular structure and properties of visible light transparent polyimide film.
  • the preparation method is mainly characterized in that two kinds of biphenyl dianhydride monomers, 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) with symmetrical structure and s-BPDA with asymmetric structure are respectively used.
  • s-BPDA 3,3',4,4'-biphenyltetracarboxylic dianhydride
  • a-BPDA 2,3,3',4'-Biphenyltetracarboxylic dianhydride
  • TFDAB fluorinated aromatic diamine 1,4-bis(4'-amino-2'-trifluoromethylphenoxy)
  • PI-1(s-BPDA/TFDAB) and PI-2(a-BPDA/TFDAB) were prepared by two-step polycondensation of biphenyl (TFDAB).
  • TFDAB biphenyl
  • the technical problem to be solved by the present invention is to provide a colorless transparent polyimide resin film and its preparation method, the resin film has excellent dimensional stability, low water absorption and excellent electrical properties, mechanical properties and heat resistance property; the source of reaction raw materials is convenient, the cost is low, and it is convenient for further popularization and application.
  • the invention provides a colorless and transparent polyimide resin film, the general formula of molecular structure is:
  • p is an integer not less than 1
  • q is an integer not less than 0
  • p and q are independent of each other, and the range of p+q is 20-500
  • -Ar1- is a divalent residue of monoanhydride
  • -Q1- is the divalent residue of aromatic dibasic anhydride
  • -Q1- is the divalent residue of aromatic diether quadrature primary amine
  • -Ar1- is preferably:
  • -Q1- is preferably:
  • -Q2- is preferably:
  • the monoanhydride is selected from maleic anhydride, phthalic anhydride, 4-fluorophthalic anhydride, tetrafluorophthalic anhydride, nadic anhydride, methylnadic anhydride, methyltetrahydrophthalic anhydride , tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride or one or more of them.
  • the aromatic dianhydride is selected from 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)benzene base] propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]hexafluoropropane dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy ) diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)biphenyl Dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 3,3',4, 4'-tetracarboxydiphenyl ether dianhydride,
  • the aromatic diether quaternary primary amine is selected from 1,4-bis(2,4-diaminophenoxy)benzene, 1,3-bis(2,4-diaminophenoxy)benzene, 4, 4'-bis(2,4-diaminophenoxy)biphenyl, 4,4'-bis(2,4-diaminophenoxy)diphenylsulfone, 4,4'-bis(2,4- Diaminophenoxy)diphenylsulfide, 4,4'-bis(2,4-diaminophenoxy)diphenylmethane, 4,4'-bis(2,4-diaminophenoxy)bis Phenyl ether, 2,2-bis[4-(2,4-diaminophenoxy)phenyl]propane, 2,2-bis[4-(2,4-diaminophenoxy)phenyl]hexa Fluoropropane, 2,5-bis(2,4-diaminophenoxy)tolu
  • the aromatic dibasic primary amine is selected from m-phenylenediamine, p-phenylenediamine, o-methyl-p-phenylenediamine, 2,4,6-trimethyl-m-phenylenediamine, 4,4'-diaminodiamine Phenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'- Diaminodiphenylmethane, 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane , 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetraethy
  • the present invention also provides a kind of preparation method of colorless transparent polyimide resin film, comprising:
  • the polymerization reaction is carried out at a temperature range of 0°C-5°C to prepare Obtain a colorless and transparent homogeneous viscous polyamic acid solution; adjust the viscosity, cast to form a film, heat up under the action of a dehydrating agent and a catalyst to carry out chemical imidization, remove the organic solvent and dehydrating agent, and remove the film by heat Stretching and winding to obtain a colorless and transparent polyimide resin film.
  • the molar ratio of the aromatic dibasic primary amine to the aromatic diether primary quaternary amine is 1:0.1-10; the molar ratio of the monoanhydride to the aromatic diether tetrabasic primary amine is 2:1; the aromatic dianhydride The number of moles is equal to the sum of the number of moles of the aromatic diether tetra-primary amine and the aromatic di-primary amine.
  • the reaction temperature of the monoanhydride and the aromatic diether tetravalent primary amine is 0° C. to 5° C., and the reaction time is 0.5 hours to 2 hours.
  • the reaction temperature of the aromatic dibasic anhydride and the aromatic primary amine is 0° C. to 5° C., and the reaction time is 1 hour to 5 hours.
  • the highly polar aprotic organic solvent is selected from N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, di One or more of methyl sulfoxide; the mass ratio of the strong polar aprotic organic solvent to the total reactant is 3-9:1, wherein the quality of the total reactant refers to the aromatic diether quaternary primary The sum of the masses of amines, aromatic dibasic primary amines, monoanhydrides and aromatic dianhydrides.
  • the dehydrating agent is selected from one or more of acetic anhydride, trifluoroacetic anhydride, propionic anhydride; the catalyst is selected from triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trialkyl
  • the catalyst is selected from triethylamine, trimethylamine, tripropylamine, tributylamine, tripentylamine, trialkyl
  • the temperature range of the chemical imidization is 60°C-130°C.
  • the temperature range for removing the solvent and the dehydrating agent is 150°C-250°C.
  • the temperature range of the release heat stretching is 280°C-350°C
  • Reaction equation of the present invention is as follows:
  • the present invention has excellent dimensional stability, low water absorption and excellent electrical properties, mechanical properties and heat resistance;
  • reaction conditions of the synthetic resin solution of the present invention are mild, simple to operate, the reaction process is carried out under normal pressure, does not involve and does not produce corrosive substances, has no special requirements for equipment, and has less investment, which is conducive to reducing production costs;
  • the organic solvent used in the present invention has few types, is convenient to recycle, can be recycled repeatedly, has few wastes, and is environmentally friendly;
  • the molecular weight of resin of the present invention is easy to control, and molecular structure is also easy to adjust, is conducive to preparing the polyimide product of ideal performance;
  • the used resin synthesis process equipment and film-forming equipment are all general-purpose, and the existing complete set of equipment for producing polyimide film can be utilized to implement the present invention, which is very conducive to the industrialization of products.
  • the film of the present invention has better visible light transmittance and is closer to colorless and transparent.
  • Test instrument differential scanning calorimeter
  • Sample preparation and testing method The samples were analyzed by differential scanning calorimetry. Weigh 5-8 mg of sample into the crucible, and test it in the temperature range of 40-300 °C. It needs to be protected by nitrogen gas, and the heating rate is 10 °C/min.
  • Test equipment Instron 3365 universal tensile machine
  • Rm is the tensile strength (MPa)
  • F is the spline load (N)
  • a is the width of the spline (mm)
  • d is the thickness of the spline (mm).
  • the elongation at break ( ⁇ ) can be calculated from the following formula:
  • ⁇ is the elongation at break (%)
  • La is the initial length of the spline (cm)
  • Lb is the length (cm) of the spline when it breaks.
  • Test instrument UV visible spectrophotometer
  • Sample preparation and test method select a film of about 15 ⁇ m, and use a UV-visible spectrophotometer to test the optical properties, using air as a control, and the wavelength scanning range is 200-1100 nm.
  • Composition of 0.01:1 pyridine and acetic anhydride heat up, chemical imidization in the temperature range of 60°C-130°C, devolatilization in the temperature range of 150°C-250°C (removal of volatiles such as solvents and dehydrating agents) , solvent recovery can be reused, stripping, thermal stretching in the temperature range of 280°C-350°C, and winding to obtain a colorless, transparent and tough polyimide film with a glass transition temperature of 223°C and a tensile strength of 127.5 MPa, the elongation at break is 45.8%, and the maximum visible light transmittance is 97.3%.
  • solvent recovery can be reused, film removal, thermal stretching in the temperature range of 280°C-350°C, and winding to obtain a colorless, transparent and tough polyimide film.
  • the glass transition temperature is 285.4°C
  • the tensile strength is 154.3MPa
  • the elongation at break is 24.1%
  • the maximum visible light transmittance is 93.2%.

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Abstract

本发明涉及一种无色透明聚酰亚胺树脂薄膜及其制备方法，分子结构通式为（I）。本发明具有优异的尺寸稳定性、低的吸水率以及优异的电气性能、力学性能和耐热性；反应原料来源方便，成本较低，便于进一步推广应用。

Description

一种无色透明聚酰亚胺树脂薄膜及其制备方法 技术领域
本发明属于聚合物薄膜领域，特别涉及一种无色透明聚酰亚胺树脂薄膜及其制备方法。
背景技术
聚酰亚胺是一类综合性能非常优异的聚合物，具有非常优良的耐热性、耐低温性、耐溶剂性、自润滑性以及阻燃等特性，同时，也具有非常优良的力学性能和介电性能。
中国专利CN1927908A公开了一种含酚羟基聚酰亚胺粉末的制备方法，其主要特征在于：含酚羟基芳香族二元胺化合物或含酚羟基芳香族二元胺与其它二元胺的混合物和芳香族二元酐在强极性非质子有机溶剂中，氮气保护下，于0℃～30℃下反应3～12小时后，得到透明粘稠的聚羟基酰胺酸溶液，随后，加入共沸脱水剂，加热升温，于120℃～160℃的温度范围内，回流共沸脱水亚胺化反应5～18小时，冷却至室温，过滤，洗涤，真空干燥，得到含酚羟基聚酰亚胺粉末。
美国专利US5147966公开了一种聚酰亚胺粉末的制备方法，其主要特征在于：以二甘醇二甲醚(diglyme)为溶剂，使3，4’-二氨基二苯醚(34ODA)与3，3’，4，4’-四甲酸二苯醚二酐(ODPA)和邻苯二甲酸酐(PA)在室温下反应，得到聚酰胺酸溶液后，加入N-甲基-2-吡咯烷酮(NMP)、三乙胺(TEA)和乙酸酐(Ac2O)进行化学亚胺化反应，加水沉析、过滤、水洗、干燥，得到聚酰亚胺粉末。
日本专利JP H05-0175175A公开了无色透明聚酰亚胺的分子结构及其制备方法，其主要特征在于：2，2-双(3，4-二羧基苯基)六氟丙烷二酐与多种醚型二胺反应得到含氟聚酰胺酸，随后通过化学亚胺化或热亚胺化得到无色透明的聚酰亚胺。
日本NTT公司也是利用价格昂贵、反应活性低下的2,2-双(3,4-二羧基苯基)六氟丙烷二酐单体，与均苯四甲酸二酐或3,3'-二(三氟甲基)-4,4'-二氨基联苯开发得到了在可见光范围内光透过率较好的聚酰亚胺薄膜材料。
Chul Ha Ju等(Synthesis and Characterization of Colorless Polyimide Nanocomposite Films,Journal of Applied Polymer Science,2007,106:4192-4201)公开了无色聚酰亚胺纳米杂化复合膜的制备方法，其主要特征在于：2，2-双(3，4-二羧基苯基)六氟丙烷二酐与2,2'-双(三氟甲基)联苯二胺反应制得前驱体聚合物，再与无机(如云母等)纳米粒子杂化，制得到无色聚酰亚胺纳米杂化复合膜。
刘金刚等人【无色透明耐高温聚酰亚胺薄膜的制备与性能研究，功能材料，2006，9 (37)：1496-1499】公开了可见光透过性聚酰亚胺薄膜的分子结构及其制备方法，其主要特征在于：分别采用两种联苯型二酐单体,对称结构的3,3’,4,4’-联苯四甲酸二酐(s-BPDA)以及不对称结构的2,3,3’,4’-联苯四甲酸二酐(a-BPDA)与含氟芳香族二胺1,4-双(4’-氨基-2’-三氟甲基苯氧基)联苯(TFDAB)通过两步缩聚法制备了两种聚酰亚胺材料PI-1(s-BPDA/TFDAB)与PI-2(a-BPDA/TFDAB)。研究结果表明,不对称结构可以显著增加PI薄膜在可见光区的透明性，25μm厚的PI-2薄膜在450nm处的透光率达到93％。
但是，不对称结构的2,3,3’,4’-联苯四甲酸二酐(a-BPDA)单体来源困难，薄膜的透光率仍然偏低。
虞鑫海等人对用于制备高可见光透过性的聚酰亚胺单体做了大量的研究开发工作：
(1)【新型聚酰亚胺特种单体的合成及其表征，绝缘材料通讯，1999，32(5)：1-4】公开了1,3-双(3-氨基苯氧基)苯的制备方法；
(2)【3,3'-二氨基二苯醚的合成及其聚酰亚胺，绝缘材料，2001，34(4)：13-16】公开了3,3'-二氨基二苯醚的制备方法；
(3)【含氟聚酰亚胺特种弹体的合成及其表征，化工新型材料，2003，31(10)：24-27，31】公开了2,2-双[4-(4-氨基苯氧基)苯基]六氟丙烷的制备方法；
(4)【4,4'-双(4-氨基苯氧基)二苯硫醚及其聚酰亚胺的合成与性能研究，绝缘材料，2008，41(5)：10-14】公开了4,4'-双(4-氨基苯氧基)二苯硫醚的制备方法。
刘金刚等人【高折射率高透明性半脂环聚酰亚胺的合成与性能，高分子学报，2008，(5)：460-465】公开了含脂环聚酰亚胺薄膜的分子结构及其制备方法，其主要特征在于：采用脂环二酐单体2,3,5-三羧基环戊烷基乙酸二酐(TCAAH)分别与两种含硫芳香族二胺单体,4,4′-双(4-氨基苯硫基)二苯硫醚(3SDA)与2,7-双(4-氨基苯硫基)噻蒽(APTT)通过两步法制备了两种半脂环聚酰亚胺(PI).制备的PI薄膜在可见光波长范围内(400～700nm)具有优良的透明性,400nm处的透过率超过85％。但是，其原料来源困难，价格昂贵，难以规模生产。
发明内容
本发明所要解决的技术问题是提供一种无色透明聚酰亚胺树脂薄膜及其制备方法，该树脂薄膜具有优异的尺寸稳定性、低的吸水率以及优异的电气性能、力学性能和耐热性；反应原料来源方便，成本较低，便于进一步推广应用。
本发明提供了一种无色透明聚酰亚胺树脂薄膜，分子结构通式为：
Figure PCTCN2022070497-appb-000001
其中p为不少于1的整数，q为不小于0的整数，p、q相互独立，p+q的范围为20-500；-Ar1-为单酐的二价残基；
Figure PCTCN2022070497-appb-000002
为芳香族二元酐的四价残基；-Q1-为芳香族二醚四元伯胺的二价残基；-Q2-为芳香族二元伯胺的二价残基。
-Ar1-优选为：
Figure PCTCN2022070497-appb-000003
-Q1-优选为：
Figure PCTCN2022070497-appb-000004
-Q2-优选为：
Figure PCTCN2022070497-appb-000005
Figure PCTCN2022070497-appb-000006
Figure PCTCN2022070497-appb-000007
Figure PCTCN2022070497-appb-000008
Figure PCTCN2022070497-appb-000009
Figure PCTCN2022070497-appb-000010
Figure PCTCN2022070497-appb-000011
Figure PCTCN2022070497-appb-000012
Figure PCTCN2022070497-appb-000013
所述单酐选自马来酸酐、邻苯二甲酸酐、4-氟代邻苯二甲酸酐、四氟代邻苯二甲酸酐、 纳迪克酸酐、甲基纳迪克酸酐、甲基四氢苯酐、四氢苯酐、六氢苯酐、甲基六氢苯酐中的一种或几种。
所述芳香族二元酐选自2,2-双(3,4-二羧基苯基)六氟丙烷二酐、2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酐、2,2-双[4-(3,4-二羧基苯氧基)苯基]六氟丙烷二酐、4,4'-双(3,4-二羧基苯氧基)二苯硫醚二酐、4,4'-双(3,4-二羧基苯氧基)二苯砜二酐、4,4'-双(3,4-二羧基苯氧基)联苯二酐、1,4-双(3,4-二羧基苯氧基)苯二酐、1,3-双(3,4-二羧基苯氧基)苯二酐、3,3',4,4'-四羧基二苯醚二酐、3,3',4,4'-四羧基二苯甲酮二酐、3,3',4,4'-四羧基联苯二酐、均苯四甲酸二酐中的一种或几种。
所述芳香族二醚四元伯胺选自1,4-双(2,4-二氨基苯氧基)苯、1,3-双(2,4-二氨基苯氧基)苯、4,4’-双(2,4-二氨基苯氧基)联苯、4,4’-双(2,4-二氨基苯氧基)二苯砜、4,4’-双(2,4-二氨基苯氧基)二苯硫醚、4,4’-双(2,4-二氨基苯氧基)二苯甲烷、4,4’-双(2,4-二氨基苯氧基)二苯醚、2,2-双[4-(2,4-二氨基苯氧基)苯基]丙烷、2,2-双[4-(2,4-二氨基苯氧基)苯基]六氟丙烷、2,5-双(2,4-二氨基苯氧基)甲苯、2,5-双(2,4-二氨基苯氧基)特丁基苯、2,5-二叔丁基-1,4-双(2,4-二氨基苯氧基)苯、4,4'-双(2,4-二氨基苯氧基)二苯甲酮中的一种或几种。
所述芳香族二元伯胺选自间苯二胺、对苯二胺、邻甲基对苯二胺、2,4,6-三甲基间苯二胺、4,4’-二氨基二苯醚、3,4’-二氨基二苯醚、3,3’-二氨基二苯醚、4,4’-二氨基二苯甲烷、3,3’-二甲基-4,4’-二氨基二苯甲烷、3,3’-二乙基-4,4’-二氨基二苯甲烷、3,3’,5,5’-四甲基-4,4’-二氨基二苯甲烷、3,3’,5,5’-四乙基-4,4’-二氨基二苯甲烷、3,3’-二甲基-5,5’-二乙基-4,4’-二氨基二苯甲烷、4,4’-二氨基二苯甲酮、3,3’-二氨基二苯甲酮、4,4’-二氨基二苯砜、3,3’-二氨基二苯砜、3,3’,5,5’-四甲基-4,4’-二氨基二苯砜、4,4’-二氨基联苯、3,3’,5,5’-四甲基-4,4’-二氨基联苯、2,2’-二(三氟甲基)-4,4’-二氨基联苯、4,4’-二氨基二苯硫醚、3,4’-二氨基二苯硫醚、3,3’-二氨基二苯硫醚、2,2-双(4-氨基苯基)丙烷、2,2-双(4-氨基苯基)六氟丙烷、1,4-双(4-氨基苯氧基)苯、1,4-双(3-氨基苯氧基)苯、1,3-双(4-氨基苯氧基)苯、1,3-双(3-氨基苯氧基)苯、2,5-双(4-氨基苯氧基)甲苯、2,5-双(3-氨基苯氧基)甲苯、2,5-双(4-氨基苯氧基)特丁基苯、2,5-双(3-氨基苯氧基)特丁基苯、2,5-二叔丁基-1,4-双(4-氨基苯氧基)苯、2,5-二叔丁基-1,4-双(3-氨基苯氧基)苯、2,2-双[4-(4-氨基苯氧基)苯基]丙烷、2,2-双[4-(3-氨基苯氧基)苯基]丙烷、2,2-双[4-(4-氨基苯氧基)苯基]六氟丙烷、2,2-双[4-(3-氨基苯氧基)苯基]六氟丙烷、4,4’-双(4-氨基苯氧基)二苯甲酮、4,4’-双(3-氨基苯氧基)二苯甲酮、4,4’-双(4-氨基苯氧基)联苯、4,4’-双(3-氨基苯氧基)联苯、4,4’-双(4-氨基苯氧基)二苯砜、4,4’-双(3-氨基苯氧基)二苯砜、4,4'-双(4-氨基苯氧基)-3,3',5,5'-四甲基二苯砜、4,4'-双(3-氨基 苯氧基)-3,3',5,5'-四甲基二苯砜、4,4’-双(4-氨基苯氧基)二苯醚、4,4’-双(3-氨基苯氧基)二苯醚、4,4’-双(4-氨基苯氧基)二苯甲烷、4,4’-双(3-氨基苯氧基)二苯甲烷、4,4’-双(4-氨基苯氧基)二苯硫醚、4,4’-双(3-氨基苯氧基)二苯硫醚、1,4-双(2-三氟甲基-4-氨基苯氧基)苯、1,4-双(3-三氟甲基-4-氨基苯氧基)苯、1,3-双(2-三氟甲基-4-氨基苯氧基)苯、1,3-双(3-三氟甲基-4-氨基苯氧基)苯、2,2-双[4-(2-三氟甲基-4-氨基苯氧基)苯基]丙烷、2,2-双[4-(3-三氟甲基-4-氨基苯氧基)苯基]丙烷、2,2-双[4-(2-三氟甲基-4-氨基苯氧基)苯基]六氟丙烷、2,2-双[4-(3-三氟甲基-4-氨基苯氧基)苯基]六氟丙烷、2,5-双(2-三氟甲基-4-氨基苯氧基)甲苯、2,5-双(3-三氟甲基-4-氨基苯氧基)甲苯、2,5-双(2-三氟甲基-4-氨基苯氧基)叔丁基苯、2,5-双(3-三氟甲基-4-氨基苯氧基)叔丁基苯、2,5-二叔丁基-1,4-双(2-三氟甲基-4-氨基苯氧基)苯、2,5-二叔丁基-1,4-双(3-三氟甲基-4-氨基苯氧基)苯、4,4'-双(2-三氟甲基-4-氨基苯氧基)二苯砜、4,4'-双(3-三氟甲基-4-氨基苯氧基)二苯砜、4,4'-双(2-三氟甲基-4-氨基苯氧基)-3,3',5,5'-四甲基二苯砜、4,4'-双(3-三氟甲基-4-氨基苯氧基)-3,3',5,5'-四甲基二苯砜、4,4'-双(2-三氟甲基-4-氨基苯氧基)联苯、4,4'-双(3-三氟甲基-4-氨基苯氧基)联苯、4,4'-双(2-三氟甲基-4-氨基苯氧基)-3,3',5,5'-四甲基联苯、4,4'-双(3-三氟甲基-4-氨基苯氧基)-3,3',5,5'-四甲基联苯、4,4'-双(2-三氟甲基-4-氨基苯氧基)二苯醚、4,4'-双(3-三氟甲基-4-氨基苯氧基)二苯醚中的一种或几种。
本发明还提供了一种无色透明聚酰亚胺树脂薄膜的制备方法，包括：
采用芳香族二醚四元伯胺、芳香族二元伯胺、单酐以及芳香族二酐，在强极性非质子有机溶剂体系中，于0℃-5℃温度范围内进行聚合反应，制得无色透明的均相粘稠状聚酰胺酸溶液；调节粘度，流延成膜，在脱水剂与催化剂的作用下加热升温进行化学亚胺化，脱除有机溶剂与脱水剂，脱膜热拉伸，收卷，获得无色透明聚酰亚胺树脂薄膜。
所述芳香族二元伯胺与芳香族二醚四元伯胺的摩尔比为1:0.1-10；单酐与芳香族二醚四元伯胺的摩尔比为2:1；芳香族二酐的摩尔数等于芳香族二醚四元伯胺与芳香族二元伯胺的摩尔数之和。
所述单酐与芳香族二醚四元伯胺的反应温度为0℃～5℃，反应时间为0.5小时～2小时。
所述芳香族二元酐与芳香族伯胺的反应温度为0℃～5℃，反应时间为1小时～5小时。
所述强极性非质子有机溶剂选自N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、二甲基亚砜中的一种或几种；所述强极性非质子有机溶剂与总反应物的质量比为3-9:1，其中总反应物的质量是指芳香族二醚四元伯胺、芳香族二元 伯胺、单酐和芳香族二酐的质量之和。
所述脱水剂选自乙酸酐、三氟乙酸酐、丙酸酐中的一种或几种；所述催化剂选自三乙胺、三甲胺、三丙胺、三丁胺、三戊胺、三烷基胺、烷基吡啶、联吡啶、烷基联吡啶、吡啶、甲基吡啶、二甲基吡啶、喹啉、异喹啉中的一种或几种；所述催化剂与脱水剂的摩尔比为0.01-0.2:1。
所述化学亚胺化的温度范围为60℃-130℃。
所述脱除溶剂与脱水剂的温度范围为150℃-250℃。
所述脱膜热拉伸的温度范围为280℃-350℃
本发明的反应方程式如下：
Figure PCTCN2022070497-appb-000014
有益效果
(1)本发明具有优异的尺寸稳定性、低的吸水率以及优异的电气性能、力学性能和耐热性；
(2)本发明合成树脂溶液的反应条件温和，操作简单，反应过程在常压下进行，不涉及也不产生腐蚀性物质，对设备无特殊要求，投资少，有利于降低生产成本；
(3)本发明有机溶剂使用种类少，而且回收方便，可反复循环再用，三废少，对环境友好；
(4)本发明树脂的分子量容易控制，分子结构也容易调整，有利于制备理想性能的聚酰 亚胺产品；
(5)合成聚酰亚胺树脂的反应原料来源方便，成本较低，便于进一步推广应用。
(6)所用的树脂合成工艺设备以及成膜设备均为通用型，完全可以利用现有的生产聚酰亚胺薄膜的成套设备来实施本发明，非常有利于产品的产业化。
(7)相比于支化聚酰亚胺薄膜，本发明薄膜具备更优异的可见光透过率，更贴近于无色透明。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
测试方法：
1.玻璃化转变温度
(1)测试仪器：差示扫描量热仪
(2)制样及测试方法：利用差示扫描量热仪对样品进行分析。称量5～8mg样品放入坩埚中，在40-300℃温度范围内进行测试，需要通入氮气保护，升温速率为10℃/min。
2.力学性能测试
(1)测试仪器：Instron 3365万能拉伸机
(2)制样及测试方法：将薄膜裁剪成1cmx5cm的长条，在10mm/min的拉伸速度下对薄膜进行拉伸测试。每种薄膜取五个样品，最后结果取五个样品力学性能的平均值。拉伸强度(Rm)可通过下式计算：
Figure PCTCN2022070497-appb-000015
式中，Rm为拉伸强度(MPa)，F为样条载荷(N)，a为样条的宽度(mm)，d为样条的厚度(mm)。
断裂伸长率(σ)可以从下式计算：
Figure PCTCN2022070497-appb-000016
式中，σ为断裂伸长率(％)，La是样条的初始长度(cm)，Lb是样条断裂时的长度(cm)。
3.可见光透过率
(1)测试仪器：紫外可见分光光度计
(2)制样及测试方法：选取15μm左右的薄膜，使用紫外可见分光光度计进行光学性能测试，以空气为对照，波长扫描范围200～1100nm。
实施例1
将548.0克(1.0摩尔)的2,2-双[4-(2,4-二氨基苯氧基)苯基]六氟丙烷和4850克N,N-二甲基乙酰胺加入反应釜中，室温下搅拌，完全溶解后，冰水浴冷却至0℃，加入440.0克(2.0摩尔)四氟邻苯二甲酸酐，于0℃-5℃温度范围内搅拌反应，呈均相溶液后，继续反应0.5小时，加入54.7克(0.1摩尔)2,2-双[4-(2-三氟甲基-4-氨基苯氧基)苯基]丙烷，搅拌，完全溶解后，冰水浴冷却至0℃，加入572.0克(1.1摩尔)2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酐，于0℃-5℃温度范围内搅拌，完全溶解后，维持反应5小时，获得无色透明的均相粘稠状溶液，过滤，除去机械杂质，调节粘度，在流延机上流延成预定厚度的薄膜，进入化学亚胺化浴，浴液由摩尔比为0.01:1的吡啶与乙酸酐组成，加热升温，于60℃-130℃温度范围内化学亚胺化，于150℃-250℃温度范围内脱挥(即脱除溶剂和脱水剂等挥发物)，溶剂回收可再利用，脱膜，于280℃-350℃温度范围内热拉伸，收卷，获得无色透明坚韧的聚酰亚胺薄膜，玻璃化转变温度为223℃，抗拉强度为127.5MPa，断裂伸长率45.8％，最大可见光透过率97.3％。
实施例2
将548.0克(1.0摩尔)的2,2-双[4-(2,4-二氨基苯氧基)苯基]六氟丙烷和16千克N,N-二甲基甲酰胺加入反应釜中，室温下搅拌，完全溶解后，冰水浴冷却至0℃，加入332.0克(2.0摩尔)4-氟邻苯二甲酸酐，于0℃-5℃温度范围内搅拌反应，呈均相溶液后，继续反应2小时，记作A组分。
将440.5克(1.0摩尔)的2,2-双[4-(2,4-二氨基苯氧基)苯基]丙烷和16千克N,N-二甲基甲酰胺加入反应釜中，室温下搅拌，完全溶解后，冰水浴冷却至0℃，加入196.0克(2.0摩尔)马来酸酐，于0℃-5℃温度范围内搅拌反应，呈均相溶液后，继续反应2小时，记作B组分。
将A组分与B组分混合，搅拌均匀后，加入800.0克(2.0摩尔)的4,4'-双(4-氨基苯氧基)二苯硫醚，搅拌，完全溶解后，冰水浴冷却至0℃，加入1240.0克(4.0摩尔) 3,3',4,4'-四甲酸二苯醚二酐粉末，于0℃-5℃温度范围内搅拌，完全溶解后，维持反应1小时，获得无色透明的均相粘稠状溶液，过滤，除去机械杂质，调节粘度，在流延机上流延成预定厚度的薄膜，进入化学亚胺化浴，浴液由摩尔比为0.2:1的三乙胺与乙酸酐组成，加热升温，于60℃-130℃温度范围内化学亚胺化，于150℃-250℃温度范围内脱挥(即脱除溶剂和脱水剂等挥发物)，溶剂回收可再利用，脱膜，于280℃-350℃温度范围内热拉伸，收卷，获得无色透明坚韧的聚酰亚胺薄膜，玻璃化转变温度为276.7℃，抗拉强度为142.7MPa，断裂伸长率37.6％，最大可见光透过率96.5％。
实施例3
将322.4克(1.0摩尔)的1,3-双(2,4-二氨基苯氧基)苯、20千克N-甲基-2-吡咯烷酮和20千克N,N-二甲基乙酰胺加入反应釜中，室温下搅拌，完全溶解后，冰水浴冷却至0℃，加入220.0克(1.0摩尔)四氟邻苯二甲酸酐和98.0克(1.0摩尔)马来酸酐，于0℃-5℃温度范围内搅拌反应，呈均相溶液后，继续反应1.5小时，加入547.0克(1.0摩尔)2,2-双[4-(2-三氟甲基-4-氨基苯氧基)苯基]丙烷、292.0克(1.0摩尔)1,3-双(4-氨基苯氧基)苯、400.0克(1.0摩尔)4,4'-双(4-氨基苯氧基)二苯硫醚、320.0克(1.0摩尔)2,2’-二(三氟甲基)-4,4’-二氨基联苯和2004克(6.0摩尔)2,2-双(4-氨基苯基)六氟丙烷，搅拌，完全溶解后，冰水浴冷却至0℃，加入520.0克(1.0摩尔)2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酐、2790克(9.0摩尔)3,3',4,4'-四甲酸二苯醚二酐和444.0克(1.0摩尔)，于0℃-5℃温度范围内搅拌，完全溶解后，维持反应4小时，获得无色透明的均相粘稠状溶液，过滤，除去机械杂质，调节粘度，在流延机上流延成预定厚度的薄膜，进入化学亚胺化浴，浴液由摩尔比为0.1:1的二甲基吡啶-吡啶混合催化剂(二甲基吡啶与吡啶的摩尔比为1:1)与乙酸酐组成，加热升温，于60℃-130℃温度范围内化学亚胺化，于150℃-250℃温度范围内脱挥(即脱除溶剂和脱水剂等挥发物)，溶剂回收可再利用，脱膜，于280℃-350℃温度范围内热拉伸，收卷，获得无色透明坚韧的聚酰亚胺薄膜，玻璃化转变温度为285.4℃，抗拉强度为154.3MPa，断裂伸长率24.1％，最大可见光透过率93.2％。

Claims (10)

  1. 一种无色透明聚酰亚胺树脂薄膜，其特征在于：分子结构通式为：
    Figure PCTCN2022070497-appb-100001
    其中p为不少于1的整数，q为不小于0的整数，p、q相互独立，p+q的范围为20-500；-Ar1-为单酐的二价残基；
    Figure PCTCN2022070497-appb-100002
    为芳香族二元酐的四价残基；-Q1-为芳香族二醚四元伯胺的二价残基；-Q2-为芳香族二元伯胺的二价残基。
  2. 根据权利要求1所述的树脂薄膜，其特征在于：所述单酐选自马来酸酐、邻苯二甲酸酐、4-氟代邻苯二甲酸酐、四氟代邻苯二甲酸酐、纳迪克酸酐、甲基纳迪克酸酐、甲基四氢苯酐、四氢苯酐、六氢苯酐、甲基六氢苯酐中的一种或几种。
  3. 根据权利要求1所述的树脂薄膜，其特征在于：所述芳香族二元酐选自2,2-双(3,4-二羧基苯基)六氟丙烷二酐、2,2-双[4-(3,4-二羧基苯氧基)苯基]丙烷二酐、2,2-双[4-(3,4-二羧基苯氧基)苯基]六氟丙烷二酐、4,4'-双(3,4-二羧基苯氧基)二苯硫醚二酐、4,4'-双(3,4-二羧基苯氧基)二苯砜二酐、4,4'-双(3,4-二羧基苯氧基)联苯二酐、1,4-双(3,4-二羧基苯氧基)苯二酐、1,3-双(3,4-二羧基苯氧基)苯二酐、3,3',4,4'-四羧基二苯醚二酐、3,3',4,4'-四羧基二苯甲酮二酐、3,3',4,4'-四羧基联苯二酐、均苯四甲酸二酐中的一种或几种。
  4. 根据权利要求1所述的树脂薄膜，其特征在于：所述芳香族二醚四元伯胺选自1,4-双(2,4-二氨基苯氧基)苯、1,3-双(2,4-二氨基苯氧基)苯、4,4’-双(2,4-二氨基苯氧基)联苯、4,4’-双(2,4-二氨基苯氧基)二苯砜、4,4’-双(2,4-二氨基苯氧基)二苯硫醚、4,4’-双(2,4-二氨基苯氧基)二苯甲烷、4,4’-双(2,4-二氨基苯氧基)二苯醚、2,2-双[4-(2,4-二氨基苯氧基)苯基]丙烷、2,2-双[4-(2,4-二氨基苯氧基)苯基]六氟丙烷、2,5-双(2,4-二氨基苯氧基)甲苯、2,5-双(2,4-二氨基苯氧基)特丁基苯、2,5-二叔丁基-1,4-双(2,4-二氨基苯氧基)苯、4,4'-双(2,4-二氨基苯氧基)二苯甲酮中的一种或几种。
  5. 根据权利要求1所述的树脂薄膜，其特征在于：所述芳香族二元伯胺选自间苯二胺、对苯二胺、邻甲基对苯二胺、2,4,6-三甲基间苯二胺、4,4’-二氨基二苯醚、3,4’-二氨基二苯醚、3,3’-二氨基二苯醚、4,4’-二氨基二苯甲烷、3,3’-二甲基-4,4’-二氨基二苯甲烷、3,3’-二乙基-4,4’-二氨基二苯甲烷、3,3’,5,5’-四甲基-4,4’-二氨基二苯甲烷、3,3’,5,5’-四乙基-4,4’-二氨基二苯甲烷、3,3’-二甲基-5,5’-二乙基-4,4’-二氨基二苯甲烷、4,4’-二氨基二苯甲酮、3,3’-二氨基二苯甲酮、4,4’-二氨基二苯砜、3,3’-二氨基二苯砜、3,3’,5,5’-四甲基-4,4’-二氨基二苯砜、 4,4’-二氨基联苯、3,3’,5,5’-四甲基-4,4’-二氨基联苯、2,2’-二(三氟甲基)-4,4’-二氨基联苯、4,4’-二氨基二苯硫醚、3,4’-二氨基二苯硫醚、3,3’-二氨基二苯硫醚、2,2-双(4-氨基苯基)丙烷、2,2-双(4-氨基苯基)六氟丙烷、1,4-双(4-氨基苯氧基)苯、1,4-双(3-氨基苯氧基)苯、1,3-双(4-氨基苯氧基)苯、1,3-双(3-氨基苯氧基)苯、2,5-双(4-氨基苯氧基)甲苯、2,5-双(3-氨基苯氧基)甲苯、2,5-双(4-氨基苯氧基)特丁基苯、2,5-双(3-氨基苯氧基)特丁基苯、2,5-二叔丁基-1,4-双(4-氨基苯氧基)苯、2,5-二叔丁基-1,4-双(3-氨基苯氧基)苯、2,2-双[4-(4-氨基苯氧基)苯基]丙烷、2,2-双[4-(3-氨基苯氧基)苯基]丙烷、2,2-双[4-(4-氨基苯氧基)苯基]六氟丙烷、2,2-双[4-(3-氨基苯氧基)苯基]六氟丙烷、4,4’-双(4-氨基苯氧基)二苯甲酮、4,4’-双(3-氨基苯氧基)二苯甲酮、4,4’-双(4-氨基苯氧基)联苯、4,4’-双(3-氨基苯氧基)联苯、4,4’-双(4-氨基苯氧基)二苯砜、4,4’-双(3-氨基苯氧基)二苯砜、4,4'-双(4-氨基苯氧基)-3,3',5,5'-四甲基二苯砜、4,4'-双(3-氨基苯氧基)-3,3',5,5'-四甲基二苯砜、4,4’-双(4-氨基苯氧基)二苯醚、4,4’-双(3-氨基苯氧基)二苯醚、4,4’-双(4-氨基苯氧基)二苯甲烷、4,4’-双(3-氨基苯氧基)二苯甲烷、4,4’-双(4-氨基苯氧基)二苯硫醚、4,4’-双(3-氨基苯氧基)二苯硫醚、1,4-双(2-三氟甲基-4-氨基苯氧基)苯、1,4-双(3-三氟甲基-4-氨基苯氧基)苯、1,3-双(2-三氟甲基-4-氨基苯氧基)苯、1,3-双(3-三氟甲基-4-氨基苯氧基)苯、2,2-双[4-(2-三氟甲基-4-氨基苯氧基)苯基]丙烷、2,2-双[4-(3-三氟甲基-4-氨基苯氧基)苯基]丙烷、2,2-双[4-(2-三氟甲基-4-氨基苯氧基)苯基]六氟丙烷、2,2-双[4-(3-三氟甲基-4-氨基苯氧基)苯基]六氟丙烷、2,5-双(2-三氟甲基-4-氨基苯氧基)甲苯、2,5-双(3-三氟甲基-4-氨基苯氧基)甲苯、2,5-双(2-三氟甲基-4-氨基苯氧基)叔丁基苯、2,5-双(3-三氟甲基-4-氨基苯氧基)叔丁基苯、2,5-二叔丁基-1,4-双(2-三氟甲基-4-氨基苯氧基)苯、2,5-二叔丁基-1,4-双(3-三氟甲基-4-氨基苯氧基)苯、4,4'-双(2-三氟甲基-4-氨基苯氧基)二苯砜、4,4'-双(3-三氟甲基-4-氨基苯氧基)二苯砜、4,4'-双(2-三氟甲基-4-氨基苯氧基)-3,3',5,5'-四甲基二苯砜、4,4'-双(3-三氟甲基-4-氨基苯氧基)-3,3',5,5'-四甲基二苯砜、4,4'-双(2-三氟甲基-4-氨基苯氧基)联苯、4,4'-双(3-三氟甲基-4-氨基苯氧基)联苯、4,4'-双(2-三氟甲基-4-氨基苯氧基)-3,3',5,5'-四甲基联苯、4,4'-双(3-三氟甲基-4-氨基苯氧基)-3,3',5,5'-四甲基联苯、4,4'-双(2-三氟甲基-4-氨基苯氧基)二苯醚、4,4'-双(3-三氟甲基-4-氨基苯氧基)二苯醚中的一种或几种。
  6. 一种如权利要求1-5任一所述的无色透明聚酰亚胺树脂薄膜的制备方法，包括：
    采用芳香族二醚四元伯胺、芳香族二元伯胺、单酐以及芳香族二酐，在强极性非质子有机溶剂体系中，于0℃-5℃温度范围内进行聚合反应，制得无色透明的均相粘稠状聚酰 胺酸溶液；调节粘度，流延成膜，在脱水剂与催化剂的作用下加热升温进行化学亚胺化，脱除有机溶剂与脱水剂，脱膜热拉伸，收卷，获得无色透明聚酰亚胺树脂薄膜。
  7. 根据权利要求6所述的制备方法，其特征在于：所述芳香族二元伯胺与芳香族二醚四元伯胺的摩尔比为1:0.1-10；单酐与芳香族二醚四元伯胺的摩尔比为2:1；芳香族二酐的摩尔数等于芳香族二醚四元伯胺与芳香族二元伯胺的摩尔数之和。
  8. 根据权利要求6所述的制备方法，其特征在于：所述强极性非质子有机溶剂选自N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮、N-乙基-2-吡咯烷酮、二甲基亚砜中的一种或几种；所述强极性非质子有机溶剂与总反应物的质量比为3-9:1，其中总反应物的质量是指芳香族二醚四元伯胺、芳香族二元伯胺、单酐和芳香族二酐的质量之和。
  9. 根据权利要求6所述的制备方法，其特征在于：所述脱水剂选自乙酸酐、三氟乙酸酐、丙酸酐中的一种或几种；所述催化剂选自三乙胺、三甲胺、三丙胺、三丁胺、三戊胺、三烷基胺、烷基吡啶、联吡啶、烷基联吡啶、吡啶、甲基吡啶、二甲基吡啶、喹啉、异喹啉中的一种或几种；所述催化剂与脱水剂的摩尔比为0.01-0.2:1。
  10. 根据权利要求6所述的制备方法，其特征在于：所述化学亚胺化的温度范围为60℃-130℃。
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