WO2020000968A1 - 一种刚性脂环含氟结构的二酐化合物及其制备方法与应用 - Google Patents

一种刚性脂环含氟结构的二酐化合物及其制备方法与应用 Download PDF

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WO2020000968A1
WO2020000968A1 PCT/CN2018/124730 CN2018124730W WO2020000968A1 WO 2020000968 A1 WO2020000968 A1 WO 2020000968A1 CN 2018124730 W CN2018124730 W CN 2018124730W WO 2020000968 A1 WO2020000968 A1 WO 2020000968A1
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bis
trifluoromethyl
dihydroanthracene
tetramethyl
reaction
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屠国力
李夫
王瑶
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Huazhong University of Science and Technology
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Huazhong University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • 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 technical field of new materials, and particularly relates to a novel rigid alicyclic fluorinated dianhydride compound and a synthesis method and application thereof.
  • the currently used flexible substrates are mainly engineering plastics such as polyethylene terephthalate (PET), polycarbonate (PC), and polyethylene naphthalate (PEN).
  • PET polyethylene terephthalate
  • PC polycarbonate
  • PEN polyethylene naphthalate
  • the above engineering plastics have high transmittance (> 85%), but all have one fatal disadvantage: poor heat resistance (Tg ⁇ 120 ° C) and poor solvent resistance.
  • Tg ⁇ 120 ° C poor heat resistance
  • solvent resistance solvent resistance
  • Traditional aromatic polyimide is prepared by copolymerizing aromatic dianhydride monomers with strong electron-withdrawing ability and diamine monomers with strong electron-donating ability.
  • the polymer main chain is tightly packed and there is a strong conjugate between the aromatic rings. Effect, which makes a strong charge transfer complex effect within and between the molecular chains of the polyimide.
  • the strong interchain interaction between the molecular chains not only imparts the above-mentioned excellent properties of PIs, but also leads to the defects of aromatic PIs, such as poor dissolvability and low optical transmittance, which affects the application of PIs in the display field.
  • HNTDA novel alicyclic dianhydride 2R, 5R, 7S, 10S-naphthalenetetracarboxylic dianhydride
  • polyimide is an aromatic dianhydride compound 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (sBPDA) or alicyclic dianhydride compound1,2 , 3,4-cyclobutane tetraacid dianhydride (CBDA) and aromatic diamine compounds as raw materials, prepared by a thermal imidization method.
  • sBPDA 4,4'-biphenyltetracarboxylic dianhydride
  • CBDA 3,4-cyclobutane tetraacid dianhydride
  • MBDA 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride
  • the glass transition temperature Tg of the polyimide film prepared by this method is less than 350 ° C.
  • 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride has a sp3 hybrid quaternary carbon structure.
  • This sp3 hybrid structure increases the degree of molecular distortion.
  • the steric hindrance effect imparted by the CF 3 group can well destroy the packing degree and packing density of the molecular chains, thereby reducing the interaction force within and between the molecular chains. Therefore, the formation of the polymer's charge transfer complex (CTC) has a great inhibitory effect. Therefore, the color of the relevant film can become very light, making the polyimide more suitable for some specific applications.
  • CTC charge transfer complex
  • the rigidity of the 6FDA molecule is weak, resulting in a large coefficient of linear thermal expansion (CTE) of the polyimide.
  • CTE linear thermal expansion
  • HPMDA 1,2,4,5-cyclohexanetetracarboxylic dianhydride
  • HPMDA-based polyimides show good thermal stability, weak oxidation resistance, and the most important disadvantage is that yellowing easily occurs at high temperatures.
  • an ideal substrate requires a glass transition temperature above 400 ° C and a CTE value below 20 ppm K -1 .
  • the present invention combines the advantages of 6FDA and HPMDA, and designs and synthesizes dianhydride 9,10-difluoro-9,10-bis (trifluoromethyl)-containing rigid semialicyclic, trifluoromethyl and fluorine atom substitution. 9,10-dihydroanthracene-2,3,6,7-tetracarboxylic dianhydride (8FDA).
  • the invention solves the technical problems of low glass transition temperature, high linear thermal expansion coefficient, and poor thermal stability of polymers containing dianhydride monomers in the prior art, and provides a rigid alicyclic fluorine-containing dianhydride compound and its Preparation method and application.
  • a rigid alicyclic fluorinated dianhydride compound is provided.
  • the structural formula of the compound is shown in Formula I:
  • R is F, Cl, CF 3 or
  • a method for preparing a rigid alicyclic fluorinated dianhydride compound including the following steps:
  • the reaction time is 0.5h to 5h and the reaction temperature is 25 ° C to 80 ° C, so that ((2,3,6,7- Trimethylsilyl on tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-9,10-diyl) bis (oxy)) bis (trimethylsilane)
  • the oxane is converted into a hydroxyl group to obtain 2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-9,10-diol;
  • step (2) After dissolving the 2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-9,10-diol obtained in step (2), ice bath Under the conditions, diethylaminosulfur trifluoride or bis (2-methoxyethyl) aminosulfur trifluoride is added dropwise, and the reaction is performed for 12 to 15 hours to obtain 9,10-difluoro-2,3,6, 7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene;
  • step (3) is the following technical scheme: 2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-9 obtained in step (2) After the 10-diol is dissolved, acetyl chloride is added, and the reaction is performed at 70 ° C-80 ° C for 8h-12h to obtain 9,10-dichloro-2,3,6,7-tetramethyl-9,10 -Bis (trifluoromethyl) -9,10-dihydroanthracene;
  • step (3) is the following technical scheme: 2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-9 obtained in step (2) After the 10-diol is dissolved, hydrogen halide and trifluorohalomethane are added and reacted for 15h-30h to obtain 2,3,6,7-tetramethyl-9,9 ', 10,10'-tetrakis (trifluoromethyl) Radical) -9,10-dihydroanthracene;
  • step (3) is the following technical scheme: 2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-9 obtained in step (2)
  • the first step is to add phosphorus tribromide, or hydrogen bromide and catalyst B, and react at 40 ° C-60 ° C for 12h-24h, so that the 2,3,6, The hydroxyl group on 7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-9,10-diol is converted into a bromine atom to obtain 9,10-dibromo-2, 3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene; in the second step add phenylmagnesium bromide and catalyst C, or add phenylboronic acid and catalyst D Under the condition of 75 °C -90 °C, reaction
  • the catalyst A in step (1) is cesium fluoride, tetrabutylammonium fluoride or tris (dimethylaminomethyl) fluorene difluorotrimethylammonium salt;
  • the catalyst B in step (3) is Concentrated sulfuric acid;
  • the catalyst C in step (3) is 1,3-bis (diphenylphosphinepropane) nickel dichloride, or a mixture of palladium acetate and triphenylphosphine;
  • the catalyst D in step (3) is A mixture of tetrakis (triphenylphosphine) palladium and potassium carbonate, or a mixture of palladium and potassium carbonate, or a mixture of sodium tetrachloropalladate and potassium carbonate;
  • the oxidizing agent in step (4) is potassium permanganate or three Chromium oxide.
  • the hydrogen halide in step (3) is hydrogen bromide, hydrogen iodide or hydrogen chloride; and the trifluorohalomethane is trifluorobromomethane, trifluoroiodomethane or trifluorochloromethane.
  • the ratio of the amounts of the 2,3,6,7-tetramethylanthracene-9,10-dione, trimethyl (trifluoromethyl) silane and the substance of the catalyst A in the step (1) is 1 : (2 to 3.5): (0.01 to 0.05).
  • the 2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-9,10-diol and di The ratio of the amount of ethylaminosulfur trifluoride or bis (2-methoxyethyl) aminosulfur trifluoride is 1: (2 to 3.5).
  • the ratio of the amount of bis (trifluoromethyl) -9,10-dihydroanthracene to the substance of the oxidant is 1: (10-12).
  • the application of the rigid alicyclic fluorinated dianhydride compound to the preparation of a polyimide material is provided.
  • a method for preparing a polyimide film including the following steps:
  • step (2) The polyamic acid solution obtained in step (1) is uniformly dispersed on the surface of the substrate, and the solvent in the polyamic acid solution is heated to volatilize; heating is continued to cause the polyamic acid to undergo a dehydration cyclization reaction to obtain polyimide membrane.
  • a polyimide film prepared by the method is provided.
  • the 1,4-cyclohexadiene half-alicyclic segment in the rigid alicyclic fluorinated dianhydride compound provided by the present invention can effectively destroy the degree of conjugation of the polymer chain and the effect of charge transfer complex It is effectively suppressed, and its optical performance is improved.
  • the steric effect of the fluorine-containing group and the alicyclic structure can increase the free volume (FFV) of the polymer segment, and improve the dissolution processing performance of the polyimide film based on the rigid alicyclic fluorine-containing dianhydride compound.
  • the rigid alicyclic structure can ensure the rigidity of the molecular chain and reduce the movement ability of the segment, thereby improving the glass transition temperature and thermal stability.
  • the rigid structure can reduce the linear thermal expansion coefficient of the polyimide based on the dianhydride compound containing a rigid alicyclic fluorine-containing structure according to the present invention. Therefore, it can be used to prepare a transparent high temperature and low linear thermal expansion coefficient polyimide film.
  • the dianhydride compound containing a rigid alicyclic fluorine-containing structure according to the present invention has a simple structure and has wide application value for the development of transparent polyimide films.
  • the rigid alicyclic fluorinated structure dianhydride of the present invention has rigid alicyclic and fluorinated structures, which can improve the light transmittance of the material, reduce the dielectric constant and water absorption of the material, and maintain good Thermal stability and dimensional stability, so it is suitable for preparing flexible transparent polyimide films.
  • the method for preparing a dianhydride compound having a rigid alicyclic fluorine-containing structure according to the present invention is simple, mild reaction conditions, convenient sources of reaction raw materials, low cost, fewer types of organic solvents used, and reduced environmental pollution.
  • the present invention integrates 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 1,2,4,5-cyclohexanetetracarboxylic dianhydride (HPMDA).
  • 6FDA 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride
  • HPMDA 1,2,4,5-cyclohexanetetracarboxylic dianhydride
  • Figure 1 (a) is the first step synthesized in Example 1 ((2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-9, NMR spectrum of 10-diyl) bis (oxy)) bis (trimethylsilane);
  • Figure 1 (b) is the first step ((2,3,6,7-tetramethyl) synthesized in Example 1 Carbon of 9-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-9,10-diyl) bis (oxy)) bis (trimethylsilane).
  • Figure 2 (a) is the 2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-9,10- Nuclear magnetic hydrogen spectrum of a diol
  • FIG. 2 (b) is the 2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10- Carbon spectrum of dihydroanthracene-9,10-diol.
  • Figure 3 (a) is the 9,10-difluoro-2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-bis synthesized in the third step of Example 1.
  • Nuclear magnetic hydrogen spectrum of hydroanthracene
  • Figure 3 (b) is 9,10-difluoro-2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) synthesized in the third step of Example 1.
  • Figure 4 (a) is the 9,10-difluoro-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-2,3,6,7-tetrasylate synthesized in the fourth step of Example 1 Nuclear magnetic hydrogen spectrum of formic acid;
  • Fig. 4 (b) is 9,10-difluoro-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-2 synthesized in the fourth step of Example 1.
  • Figure 5 (a) is the 9,10-difluoro-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-2,3,6,7-tetrasylate synthesized in the fifth step of Example 1 Nuclear magnetic hydrogen spectrum of carboxylic dianhydride;
  • Figure 5 (b) is 9,10-difluoro-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene synthesized in the fifth step of Example 1 Carbon spectrum of -2,3,6,7-tetracarboxylic dianhydride.
  • Figure 6 (a), Figure 6 (b), Figure 6 (c), Figure 6 (d) and Figure 6 (e) are the infrared spectra of the products of each step synthesized in the first step to the fifth step in Example 1 Illustration.
  • FIG. 7 (a) is a single crystal X-ray diffraction spatial structure product of the first step product of Example 1;
  • FIG. 7 (b) is a single crystal X-ray diffraction spatial structure product of the second step product of Example 1;
  • FIG. 7 (c) Is a single-crystal X-ray diffraction spatial structure diagram of the product of the third step in Example 1;
  • FIG. 8 is a structural formula of a compound 9,10-difluoro-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-2,3,6,7-tetracarboxylic dianhydride provided by the present invention .
  • FIG. 9 is a schematic diagram of the preparation process of compound 9,10-difluoro-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-2,3,6,7-tetracarboxylic dianhydride.
  • FIG. 10 is a DMA curve of a PI film.
  • FIG. 11 is a TGA curve of a PI film.
  • FIG. 12 is a transmittance curve of a PI film.
  • FIG. 13 is a TMA curve of a PI film.
  • Step 1 Suspend 2,3,6,7-tetramethylanthracene-9,10-dione (40.00g, 151.33 mmol, 1.00 equivalent) in THF (400 mL) at rt and add trimethyl (trifluoromethyl) ) Silane (49.21 mL, 332.93 mmol, 2.20 equivalents). The suspension was cooled to 0 ° C and CsF (459.74 mg, 3.03 mmol, 0.02 equivalents) was added. After stirring for 10 minutes, the reaction mixture was warmed to room temperature and stirred for 1.5 hours. The reaction mixture was filtered and the remaining yellow solid was rinsed with diethyl ether (25 mL).
  • Figure 1 (a) is the first step synthesized in Example 1 ((2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-9, NMR spectrum of 10-diyl) bis (oxy)) bis (trimethylsilane);
  • step 1 13 C NMR (150 MHz, CDCl 3 ) 137.56, 137.22, 131.04-130.69, 130.40, 125.87, 19.67, 2.19, 1.99-1.54. 19 F NMR (565 MHz, CDCl 3 ) ⁇ -78.39 (s, 6F), so the substance obtained in step 1 is (2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl)- 9,10-dihydroanthracene-9,10-diyl) bis (oxy)) bis (trimethylsilane)
  • Step 2 ((2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-9,10-diyl) bis (oxy) )
  • Figure 2 (a) is the 2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-9,10- Nuclear magnetic hydrogen spectrum of a diol
  • Step 3 Put 2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-9,10-diol (10g, 24.7mmol, 1.00 equivalent) ) Dissolved in 30mL of anhydrous THF, cooled to -78 °C under anhydrous and anaerobic conditions, and slowly added diethylaminosulfur trifluoride (DAST) (7.23mL, 54.4mmol, 2.20 equivalents), and the addition was completed After that, the reaction was continued for 12 hours. Point the plate to monitor the progress of the reaction. After the reaction was complete, excess DAST was quenched by the addition of sodium bicarbonate.
  • DAST diethylaminosulfur trifluoride
  • Figure 3 (a) is the 9,10-difluoro-2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-bis synthesized in the third step of Example 1.
  • Figure 3 (b) is the 9,10-difluoro-2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) synthesized in the third step of Example 1.
  • yl) -9,10-dihydro-anthracene carbon spectra; can be seen from FIG. 3, 1 H NMR, CDCl 3 ) ⁇ 7.68 (d, J 26.0Hz, 4H), 2.39 (s, 12H).
  • Step 4 Take 9,10-difluoro-2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene (5g, 12.2mmol, 1.00 equivalent) ) Is dissolved in 30 mL of a solvent having a volume ratio of 1: 1 of pyridine and water, and heated to reflux temperature. Weigh again (19.34 g, 0.122 mmol, 10.00 equivalents of potassium permanganate) and add to the reaction flask in portions within 1 hour. After the reaction was completed, suction filtration was performed while hot, and the filtrate was spin-dried.
  • the product was dissolved in hot water, acidified by adding concentrated hydrochloric acid, and filtered to obtain a tetraacid product. Acetic acid was recrystallized. The product was dried under vacuum to obtain 9,10-difluoro-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-2,3,6,7-tetracarboxylic acid with a yield of 85%; 1 H NMR (600 MHz, DMSO) ⁇ 13.98 (s, 1H), 8.53--7.94 (m, 1H).
  • Figure 4 (a) is the 9,10-difluoro-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-2,3,6,7-tetrasylate synthesized in the fourth step of Example 1
  • Nuclear magnetic hydrogen spectrum of formic acid
  • Fig. 4 (b) is 9,10-difluoro-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-2 synthesized in the fourth step of Example 1.
  • Step 5 Put 9,10-difluoro-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-2,3,6,7-tetracarboxylic acid (5g, 9.47mmol, 1.00 equivalent) Dissolve in 30 mL of acetic anhydride solvent and heat to reflux temperature. Reaction for 10 hours. Point the plate to monitor the progress of the reaction. After the reaction is completed, spin-dry and vacuum-dried to obtain 9,10-difluoro-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-2,3,6,7-tetracarboxylic dianhydride The yield is 85%.
  • Figure 8 is the compound 9,10-difluoro-9 prepared by the present invention, Structural formula of 10-bis (trifluoromethyl) -9,10-dihydroanthracene-2,3,6,7-tetracarboxylic dianhydride.
  • Figure 5 (a) is the 9,10-difluoro-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-2,3,6,7-tetrasylate synthesized in the fifth step of Example 1 Nuclear magnetic hydrogen spectrum of carboxylic dianhydride;
  • Figure 5 (b) is 9,10-difluoro-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene synthesized in the fifth step of Example 1 Carbon spectrum of -2,3,6,7-tetracarboxylic dianhydride; it can be seen from FIG. 5 that 1 H NMR (600 MHz, DMSO-d 6 ) ⁇ 8.83-8.63 (m, 4H).
  • Figure 6 (a), Figure 6 (b), Figure 6 (c), Figure 6 (d) and Figure 6 (e) are synthesized in step 1, step 2, step 3, step 4 and step 5 of this embodiment, respectively. Infrared spectrum of the product.
  • FIG. 7 (a) is a single crystal X-ray diffraction spatial structure product of the first step product of Example 1;
  • FIG. 7 (b) is a single crystal X-ray diffraction spatial structure product of the second step product of Example 1;
  • FIG. 7 (c) Is a single-crystal X-ray diffraction spatial structure diagram of the product of the third step in Example 1;
  • FIG. 7 (e) are single-crystal X-ray diffraction space structure diagrams of the product in the fifth step of Example 1 after sublimation
  • Figure 7 (f) is a single-crystal X-ray diffraction spatial structure diagram of the product obtained in the fifth step of Example 1 by recrystallization from toluene. It can be known from FIG. 7 that the corresponding products are obtained in each step.
  • a dianhydride compound containing a rigid alicyclic fluorine-containing structure 9,10-diphenyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-2,3,6,7-tetra The method for preparing carboxylic dianhydride comprises the following steps:
  • Steps 1 and 2 were performed according to the method in Example 1 to obtain 2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-9,10. -Diol.
  • Step 3 Put 2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-9,10-diol (200mg, 0.5mmol, 1 equivalent) ) Dissolved in 10 ml of anhydrous THF, stirred to dissolve, and then injected with PBr 3 (0.23 ml, 3.45 mg, 0.013 mmol, 0.026 equivalents), and protected from light, stirred at room temperature for 10-30 minutes, and then heated to 50 ° C, the reaction 24h, cool.
  • PBr 3 0.23 ml, 3.45 mg, 0.013 mmol, 0.026 equivalents
  • Step 4 Take 9,10-dibromo-2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene (40mg, 0.075mmol, 1 equivalent) ) Dissolved in 10 ml of anhydrous THF, 1,3-bis (diphenylphosphine propane) nickel dichloride (2.03 mg, 0.0038 mmol, 0.05 equivalent) was added, and then phenyl magnesium bromide (0.2 ml, 34 mg , 0.188 mmol, 2.5 equivalents), after reacting at room temperature for one hour, the temperature was raised to reflux temperature and refluxed for 20-24 h.
  • Step 5 Put 2,3,6,7-tetramethyl-9,10-diphenyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene (5g, 9.5mmol, 1.00 (Equivalent) was dissolved in 30 mL of a solvent having a volume ratio of 1: 1 of pyridine and water, and heated to reflux temperature. Weigh again (15.01 g, 95 mmol, 10.00 equivalents of potassium permanganate) and add to the reaction flask in portions within 1 hour. After the reaction was completed, suction filtration was performed while hot, and the filtrate was spin-dried.
  • the product was dissolved in hot water, acidified by adding concentrated hydrochloric acid, and filtered to obtain a tetraacid product. Acetic acid was recrystallized. The product was dried under vacuum to obtain 9,10-diphenyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-2,3,6,7-tetracarboxylic acid in a yield of 85%.
  • Step 6 Put 9,10-diphenyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-2,3,6,7-tetracarboxylic acid (5g, 7.76mmol, 1.00 equivalent) ) was dissolved in 30 mL of acetic anhydride solvent and heated to reflux temperature. Reaction for 10 hours. Point the plate to monitor the progress of the reaction. After the reaction is complete, spin-dry and vacuum-dried to obtain 9,10-diphenyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-2,3,6,7-tetracarboxylic acid di Anhydride, yield 85%.
  • a dianhydride compound containing a rigid alicyclic fluorine-containing structure 9,10-dichloro-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-2,3,6,7-tetracarboxylic acid The method for preparing acid dianhydride includes the following steps:
  • Steps 1 and 2 were performed according to the method in Example 1 to obtain 2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-9,10. -Diol.
  • Step 3 Put 2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-9,10-diol (200mg, 0.5mmol, 1 equivalent) ) was dissolved in 15 ml of toluene, and then acetyl chloride (98.125 mg, 1.25 mmol, 2.5 equivalents) was added, and the mixture was stirred at room temperature for 10 min, then heated to 75 ° C., and reacted for 8 h.
  • Step 4 Take 9,10-dichloro-2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene (5g, 11.3mmol, 1.00 equivalent) ) Is dissolved in 30 mL of a solvent having a volume ratio of 1: 1 of pyridine and water, and heated to reflux temperature. Weigh again (21.4 g, 135.6 mmol, 12.00 equivalents of potassium permanganate) and add to the reaction flask in portions within 1 hour. After the reaction was completed, suction filtration was performed while hot, and the filtrate was spin-dried.
  • the product was dissolved in hot water, acidified by adding concentrated hydrochloric acid, and filtered to obtain a tetraacid product. Acetic acid was recrystallized. The product was dried under vacuum to obtain 9,10-dichloro-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-2,3,6,7-tetracarboxylic acid in a yield of 85%.
  • Step 5 Put 9,10-dichloro-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-2,3,6,7-tetracarboxylic acid (5g, 8.9mmol, 1.00 equivalent) Dissolve in 30 mL of acetic anhydride solvent and heat to reflux temperature. Reaction for 10 hours. Point the plate to monitor the progress of the reaction. After complete reaction, spin-dry and vacuum-dried to obtain 9,10-dichloro-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-2,3,6,7-tetracarboxylic dianhydride The yield is 85%.
  • a dianhydride compound containing a rigid alicyclic fluorine-containing structure 9,9 ', 10,10'-tetrakis (trifluoromethyl) -9,10-dihydroanthracene-2,3,6,7-tetracarboxylic acid The method for preparing dianhydride includes the following steps:
  • Steps 1 and 2 were performed according to the method in Example 1 to obtain 2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-9,10. -Diol.
  • Step 3 Under the protection of nitrogen, 2,3,6,7-tetramethyl-9,10-bis (trifluoromethyl) -9,10-dihydroanthracene-9,10-diol (200mg, 0.5 mmol, 1 equivalent) was dissolved in 10 ml of THF, hydrogen iodide (0.17 ml, 190 mg, 1.5 mmol, 3 equivalents) was added, trifluoroiodomethane (293.85 mg, 1.5 mmol, 3 equivalents) was added, and the reaction was carried out at room temperature for 24 hours. Column separation gave 2,3,6,7-tetramethyl-9,9 ', 10,10'-tetrakis (trifluoromethyl) -9,10-dihydroanthracene.
  • Step 4 Put 2,3,6,7-tetramethyl-9,9 ', 10,10'-tetrakis (trifluoromethyl) -9,10-dihydroanthracene (5g, 9.84mmol, 1.00 equivalent) It was dissolved in 30 mL of a solvent having a volume ratio of 1: 1 of pyridine and water, and heated to reflux temperature. Weigh again (18.66 g, 118.08 mmol, 12.00 equivalents of potassium permanganate) and add to the reaction flask in portions within 1 hour. After the reaction was completed, suction filtration was performed while hot, and the filtrate was spin-dried.
  • the product was dissolved in hot water, acidified by adding concentrated hydrochloric acid, and filtered to obtain a tetraacid product. Acetic acid was recrystallized. The product was dried under vacuum to obtain 9,9 ', 10,10'-tetrakis (trifluoromethyl) -9,10-dihydroanthracene-2,3,6,7-tetracarboxylic acid in a yield of 85%.
  • Step 5 Dissolve 9,9 ', 10,10'-tetrakis (trifluoromethyl) -9,10-dihydroanthracene-2,3,6,7-tetracarboxylic acid (5g, 7.96mmol, 1.00 equivalent) In 30 mL of acetic anhydride solvent, heat to reflux temperature. Reaction for 10 hours. Point the plate to monitor the progress of the reaction. After the reaction is complete, spin-dry and vacuum dry to obtain 9,9 ', 10,10'-tetrakis (trifluoromethyl) -9,10-dihydroanthracene-2,3,6,7-tetracarboxylic dianhydride, Yield: 80%.
  • Step 1 Dissolve PPDA (3mmol) in a 50mL flask with an appropriate amount of dry NMP solvent, and then slowly add 8FDA, (3mmol) to the above-dissolved diamine solution at one time. The reaction was stirred at 25 ° C for 24 hours to obtain a polyamic acid (PAA) solution.
  • PAA polyamic acid
  • Step 2 Pour the polyamic acid solution on a piece of glass that has been cleaned with ITO glass, deionized water, and dry and clean the glass. Then, PAA is evenly dispersed on the glass surface by the casting method. Next, cast the PAA glass into an oven preheated to 80 ° C. Heating at 80 ° C for 2 hours to slowly release the solvent, and then heating up according to the following temperature program: heating at 100 ° C for 1 hour, 150 ° C for 1 hour, 200 ° C for 1 hour, 250 ° C for 1 hour, and 280 ° C for 1 hour. After the temperature of the oven is naturally cooled to room temperature, draw a line with a scalpel on the edge of the film, soak it in deionized water, and then peel it off the glass surface. A thermally imidized polyimide film was obtained.
  • the polyimide film obtained in Example 5 was used to evaluate the thermal and mechanical properties of the PI film by thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), and thermomechanical analysis (TMA).
  • TGA thermogravimetric analysis
  • DMA dynamic mechanical analysis
  • TMA thermomechanical analysis
  • Thermokinetic analysis (TGA) was performed with Perkin-Elmer TGA-2 under a nitrogen flow at a heating rate of 10 ° C / min.
  • DMA Q800V20.22Build 41 was used for dynamic mechanical analysis, and the tensile mode was used, and the frequency was 1Hz. Test the thermal expansion coefficient with TA Instrument Q400.
  • the nitrogen flow was 0.05N.
  • the heating rate is 5 ° C per minute.
  • FIG. 10 is a DMA curve of the PI film
  • FIG. 11 is a TGA curve of the PI film.
  • FIG. 12 is a transmittance curve of a PI film.
  • FIG. 13 is a TMA curve of a PI film.
  • the Tg value of the PI film based on the dianhydride compound (8FDA) of the rigid alicyclic fluorine-containing structure of the present invention is 414 ° C.
  • the Tg value of PI film based on 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) is 332 ° C. This is due to the rigid structure of the dianhydride compound (8FDA) monomer of the rigid alicyclic fluorine-containing structure of the present invention.
  • the T g value of polyimide is determined by the degree of rigidity of the molecular chain, the molecular interaction of CTC between the electron-withdrawing dianhydride residue and the electron-donating diamine residue.
  • FIG. 11 is a TGA curve of a PI film.
  • the 1% thermal decomposition temperature (T d1 ) and the carbon residue ratio of polyimide are in the range of 500-517 ° C. and 65-666%.
  • the PIs based on the rigid alicyclic fluorine-containing dianhydride compound (8FDA) of the present invention have higher PIs than the corresponding 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) film.
  • the rigid alicyclic fluorine-containing dianhydride compound (8FDA) -based polyimide of the present invention is a polysubstituted and rigid semialicyclic 1,4-cyclohexadiene, which has a molecular chain rigidity that is 4,4 '-(six Fluoroisopropylidene) diphthalic anhydride (6FDA) is strong, which enhances the degree of interaction and accumulation between chains and increases their heat resistance.
  • PPDA derived from a dianhydride compound (8FDA) having a rigid alicyclic fluorine-containing structure of the present invention shows a relatively low transmittance (T% ⁇ 30%) at 400 nm, as shown in FIG. 12 Show. From these test results, it can be seen that the PI-1 obtained by polymerizing the rigid alicyclic fluorine-containing dianhydride compound (8FDA) of the present invention and PPDA has excellent thermal stability and dimensional stability (T g is 414 ° C, CTE is 12 ppm K -1 ), T 450 is close to 80%.
  • FIG. 13 is a TMA curve of a PI film.
  • the CTE value of the PI film prepared by this method is 12 ppm K -1 .
  • the CTE value of the film based on the existing 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) is 47 ppm K -1 .
  • the film based on the rigid alicyclic fluorine-containing dianhydride compound (8FDA) of the present invention has a significantly lower CTE value Based on 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) film.

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Abstract

本发明提供了一种刚性脂环含氟结构的二酐化合物及其制备方法与应用，属于新材料技术领域。制备方法为第一步使2,3,6,7-四甲基蒽-9,10-二酮发生亲核加成反应，得到((2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二基)双(氧基))双(三甲基硅烷)；第二步使第一步产物上的三甲基硅氧烷转变成羟基；第三步使第二步产物上的羟基被F、Cl、CF 3或苯环取代，再通过氧化反应和脱水成酐，得到二酐化合物。本发明所述二酐化合物中具有刚性脂环结构和含氟基团，可提高玻璃化转变温度和热稳定性，降低线性热膨胀系数，在制备聚合物材料中可以提高材料的透光率，降低材料的介电常数和吸水率，保持良好的热稳定性与尺寸稳定性。

Description

一种刚性脂环含氟结构的二酐化合物及其制备方法与应用 技术领域
本发明属于新材料的技术领域，具体涉及一种新型刚性脂环含氟结构的二酐化合物及其合成方法与应用。
背景技术
近年来，随着显示行业更新换代的加速，大尺寸柔性有机发光二极管(OLED)的需求将成爆发式的增长，也带动了柔性基板的发展和需求。目前用的较多的柔性基板主要是：聚对苯二甲酸乙二酯(PET)，聚碳酸酯(PC)，聚萘二甲酸乙二醇酯(PEN)等工程塑料。以上几种工程塑料具有较高的透过率(＞85％)，但是均具有一个致命的缺点：耐热性能差(Tg＜120℃)，耐溶剂性较差。制备大尺寸柔性OLED有工序需要使用高温处理，显然上述几种工程塑料不能满足这一条件。因此，具有优异的耐热性能，耐溶剂性能的柔性透明聚酰亚胺薄膜(PI)成了理想的柔性OLED基板的最佳选择。
传统的芳香族聚酰亚胺由芳香族具有强吸电子能力的二酐单体与强给电子能力的二胺单体共聚制备，聚合物主链堆积紧密，芳环间存在很强的共轭作用，使得聚酰亚胺的分子链内和分子链间存在很强的电荷转移络合物效应。环间强的分子链间相互作用在赋予PIs上述优良性能的同时，也导致了芳香族PIs存在溶解加工性差、光学透过性低等缺陷，影响了PIs在显示领域的应用。
在题为“Colorless polyimides derived from 2R,5R,7S,10S-naphthanetetracarboxylic dianhydride”的文献中，作者合成了新型脂环族二酐2R，5R，7S，10S-萘四甲酸二酐(HNTDA)。他们发现，对比由氢化均苯四甲酸二酐HPMDA制备的PIs，基于HNTDA的PIs展示 出优异的热力学性能，同时，刚性稠环的萘四羧基二酰亚胺部分显著削弱了分子间和分子内相互作用，从而提高薄膜的光学性能，同时维持了良好的热稳定性。但是，薄膜的CTE值大于40ppm K -1，CTE值大，那么PI薄膜在受热时，会发生翘曲、开裂或者脱层，因此限制了PI薄膜的应用。
在题目“Flexible QLED and OPV based on transparent polyimide substrate with rigid alicyclic asymmetric isomer”的文献中，作者将含有刚性半脂环结构的茚满二胺引入到分子主链上，并与五种不同的商业化二酐聚合得到了一系列PIs。性能测试证明，引入这种刚性脂环结构，一方面有效地抑制了CTC效应的形成，提高了薄膜的光学透过率。另一方面，脂环结构直接与苯环相连，避免了传统全脂环结构耐热性差的问题。此外，将CPI-1作为柔性基底，制备了相应的OPV与QLED器件，表现出较好的器件效率。脂环结构对聚酰亚胺光学性能的改善效果还是非常明显的，但是打断共轭，削弱分子链间相互作用与CTC效应，引起了PIs的耐热性能的降低，这一点从上述报道的结构可以看出来。因此，仅仅通过引入脂环结构对聚酰亚胺进行改性还较难达到显示领域对柔性基板性能的要求。
在公开号为CN105131286A的中国专利中，聚酰亚胺是以芳香族二酐化合物3,3',4,4'-联苯四酸二酐(sBPDA)或脂环族二酐化合物1,2,3,4-环丁烷四酸二酐(CBDA)与芳香族二胺化合物为原料，通过热亚胺化方法制备的。通过调整sBPDA和CBDA或者1,3-二甲基-1,2,3,4-环丁烷四酸二酐(MCBDA)的比例，可以实现对所述的聚酰亚胺薄膜基板耐热稳定性和光学透明性的调控，但是该方法制备的聚酰亚胺薄膜玻璃化转变温度Tg小于350℃。
4,4'-(六氟异亚丙基)二邻苯二甲酸酐(6FDA)具有sp3杂化季碳结构，这种sp3杂化结构增加了分子扭曲的程度。此外，由CF 3基团赋予的空间位阻效应可以很好地破坏分子链的堆砌程度和堆砌密度，从而减少了分子链内和分子链间的相互作用力。因此，聚合物的电荷转移络合物(CTC) 的形成起到很大的抑制作用，因此，相关薄膜的颜色可以变得很浅，使得聚酰亚胺更适合于某些特定领域的应用。然而，6FDA分子的刚性较弱，导致聚酰亚胺的线性热膨胀系数(CTE)值很大。1,2,4,5-环己烷四羧酸二酐(HPMDA)作为脂族二酐单体可以显著降低CTC效应并改善PI透射率。然而，HPMDA分子的空间异构性会影响聚合反应的活性。另外，基于HPMDA的聚酰亚胺显示出良好的热稳定性，弱抗氧化能力，最重要的缺点是在高温下容易发生黄化现象。
在柔性显示领域，理想的基底需要其玻璃化转变温度高于400℃，CTE值低于20ppm K -1。本发明综合了6FDA和HPMDA的优点，设计并合成了含有刚性半脂环，三氟甲基和氟原子取代的二酐9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐(8FDA)。
发明内容
本发明解决了现有技术中含有二酐单体的聚合物玻璃化转变温度低、线性热膨胀系数高以及热稳定性差的技术问题，提供了一种刚性脂环含氟结构的二酐化合物及其制备方法与应用。
按照本发明的第一方面，提供了一种刚性脂环含氟结构的二酐化合物，该化合物的结构式如式Ⅰ所示：
Figure PCTCN2018124730-appb-000001
所述R为F、Cl、CF 3或
Figure PCTCN2018124730-appb-000002
按照本发明的另一方面，提供了一种刚性脂环含氟结构的二酐化合物的制备方法，包含以下步骤：
(1)向2,3,6,7-四甲基蒽-9,10-二酮溶液中加入三甲基(三氟甲基)硅烷或三乙基(三氟甲基)硅烷，冷却后，加入催化剂A，充分混匀后，将反应混合物升温至30℃～50℃，反应6h～24h，使2,3,6,7-四甲基蒽-9,10-二酮发生亲核加成反应，得到((2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二基)双(氧基))双(三甲基硅烷)；
(2)将步骤(1)得到的((2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二基)双(氧基))双(三甲基硅烷)溶解后置于酸性环境中，反应时间为0.5h～5h，反应温度为25℃～80℃，使((2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二基)双(氧基))双(三甲基硅烷)上的三甲基硅氧烷转变成羟基，得到2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二醇；
将步骤(2)得到的2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二醇溶解后，冰浴条件下，逐滴加入二乙胺基三氟化硫或双(2-甲氧基乙基)氨基三氟化硫，反应12h～15h，得到9,10-二氟-2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽；
或者步骤(3)为以下技术方案：将步骤(2)得到的2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二醇溶解后，加入乙酰氯，在70℃-80℃的条件下，反应8h-12h，得到9,10-二氯-2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽；
或者步骤(3)为以下技术方案：将步骤(2)得到的2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二醇溶解后，加入卤化氢和三氟卤甲烷，反应15h-30h，得到2,3,6,7-四甲基-9,9’,10,10’-四(三氟甲基)-9,10-二氢蒽；
或者步骤(3)为以下技术方案：将步骤(2)得到的2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二醇溶解后，第一步加入三溴化磷，或加入溴化氢和催化剂B，在40℃-60℃的条件下，反应12h-24h，使所述2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二醇上的羟基转变成溴原子， 得到9,10-二溴-2,3,6,7-四甲基-9,10-双(三氟甲基)-9,10-二氢蒽；第二步加入苯基溴化镁和催化剂C，或加入苯硼酸和催化剂D，在75℃-90℃条件下，反应8h-15h，使9,10-二溴-2,3,6,7-四甲基-9,10-双(三氟甲基)-9,10-二氢蒽上的溴原子被苯基取代，得到2,3,6,7,-四甲基-9,10-二苯基-9,10-双(三氟甲基)-9,10-二氢蒽；
(4)将步骤(3)得到的9,10-二氟-2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽、9,10-二氯-2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽、2,3,6,7-四甲基-9,9’,10,10’-四(三氟甲基)-9,10-二氢蒽或2,3,6,7,-四甲基-9,10-二苯基-9,10-双(三氟甲基)-9,10-二氢蒽溶解后，加入氧化剂，在90℃-110℃条件下，反应12h-15h后，抽滤，旋干滤液，产物溶解后并酸化，得到9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸、9,10-二氯-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸、9,9’,10,10’-四(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸或9,10-二苯基-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸；
(5)将步骤(4)得到的9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸、9,10-二氯-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸、9,9’,10,10’-四(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸或9,10-二苯基-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸脱水成酐，得到9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐、9,10-二氯-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐、9,9’,10,10’-四(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐或9,10-二苯基-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐。
优选地，步骤(1)所述催化剂A为氟化铯、四丁基氟化铵或三(二甲氨基甲基)锍二氟三甲基氨酸盐；步骤(3)所述催化剂B为浓硫酸；步骤(3)所述催化剂C为1,3-双(二苯基膦丙烷)二氯化镍，或者为醋酸钯和三苯基膦的混合物；步骤(3)所述催化剂D为四(三苯基膦)钯和碳酸钾 的混合物，或者为钯和碳酸钾的混合物，或者为四氯钯酸钠和碳酸钾的混合物；步骤(4)所述氧化剂为高锰酸钾或三氧化铬。
优选地，步骤(3)所述卤化氢为溴化氢、碘化氢或氯化氢；步骤(3)所述三氟卤甲烷为三氟溴甲烷、三氟碘甲烷或三氟氯甲烷。
优选地，步骤(1)所述2,3,6,7-四甲基蒽-9,10-二酮、三甲基(三氟甲基)硅烷与催化剂A的物质的量之比为1：(2～3.5)：(0.01～0.05)。
优选地，步骤(3)中所述2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二醇与二乙胺基三氟化硫，或者与双(2-甲氧基乙基)氨基三氟化硫的物质的量之比为1：(2～3.5)。
优选地，步骤(4)中所述9,10-二氟-2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽、9,10-二氯-2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽、2,3,6,7-四甲基-9,9’,10,10’-四(三氟甲基)-9,10-二氢蒽或2,3,6,7,-四甲基-9,10-二苯基-9,10-双(三氟甲基)-9,10-二氢蒽与氧化剂的物质的量之比为1：(10～12)。
按照本发明的另一方面，提供了所述的刚性脂环含氟结构的二酐化合物应用于制备聚酰亚胺材料的应用。
按照本发明的另一方面，提供了一种聚酰亚胺膜的制备方法，包含以下步骤：
(1)将二胺溶解后，加入所述的刚性脂环含氟结构的二酐化合物，在25℃～35℃条件下反应10h～30h，得到聚酰胺酸溶液；
(2)将步骤(1)得到的聚酰胺酸溶液均匀分散在基底表面，加热使聚酰胺酸溶液中的溶剂挥发；继续加热使所述聚酰胺酸发生脱水环化反应，得到聚酰亚胺膜。
按照本发明的另一方面，提供了由所述方法制备得到的聚酰亚胺膜。
总体而言，通过本发明所构思的以上技术方案与现有技术相比，主要具备以下的技术优点：
(1)本发明提供的刚性脂环含氟结构的二酐化合物中1,4-环己二烯这一半脂环链段可以有效地破坏聚合物链的共轭程度，电荷转移络合物效应得到有效地抑制，其光学性能随之提升。同时含氟基团和脂环结构的空间效应可以提高聚合物链段的自由体积(FFV)，提高基于刚性脂环含氟结构的二酐化合物的聚酰亚胺膜的溶解加工性能。此外，刚性脂环结构可以保证分子链的刚性，降低链段的运动能力，从而提高玻璃化转变温度和热稳定性。刚性结构可以降低基于本发明所述的含有刚性脂环含氟结构的二酐化合物的聚酰亚胺的线性热膨胀系数。因此能够用于制备透明耐高温低线性热膨胀系数的聚酰亚胺薄膜。本发明所述的含有刚性脂环含氟结构的二酐化合物结构简单，对透明聚酰亚胺薄膜的开发具有广泛应用价值。
(2)本发明的刚性脂环含氟结构二酐中具有刚性脂环和含氟结构，在制备聚合物材料中可以提高材料的透光率，降低材料的介电常数和吸水率，保持良好的热稳定性与尺寸稳定性，因此适用于制备柔性透明聚酰亚胺薄膜。
(3)本发明制备刚性脂环含氟结构的二酐化合物的方法简单，反应条件温和，反应原料来源方便，成本低，有机溶剂使用种类少，减少环境污染。
(4)本发明综合了4,4'-(六氟异亚丙基)二邻苯二甲酸酐(6FDA)和1,2,4,5-环己烷四羧酸二酐(HPMDA)的优点，合成了含有刚性半脂环，三氟甲基和氟原子取代的二酐9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐。该物质玻璃化转变温度高，线性热膨胀系数低，是制备聚酰亚胺膜的理想二酐单体材料。
附图说明
图1(a)是实施例1第一步合成的((2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二基)双(氧基))双(三甲基硅烷)的核磁氢谱图；图1(b)是实施例1第一步合成的((2,3,6,7-四甲基-9,10-二(三氟甲基) -9,10-二氢蒽-9,10-二基)双(氧基))双(三甲基硅烷)的碳谱图。
图2(a)是实施例1第二步合成的2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二醇的核磁氢谱图；图2(b)是实施例1第二步合成的2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二醇的碳谱图。
图3(a)是实施例1第三步合成的9,10-二氟-2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽的核磁氢谱图；图3(b)是实施例1第三步合成的9,10-二氟-2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽的碳谱图。
图4(a)是实施例1第四步合成的9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸的核磁氢谱图；图4(b)是实施例1第四步合成的9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸的碳谱图。
图5(a)是实施例1第五步合成的9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐的核磁氢谱图；图5(b)是实施例1第五步合成的9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐的碳谱图。
图6(a)、图6(b)、图6(c)、图6(d)和图6(e)分别是实施例1第一步到第五步合成的各步骤产物的的红外谱图。
图7(a)为实施例1第一步产物的单晶X射线衍射空间结构图；图7(b)为实施例1第二步产物的单晶X射线衍射空间结构图；图7(c)为实施例1第三步产物的单晶X射线衍射空间结构图；图7(d)和图7(e)为实施例1第五步产物升华后得到的单晶X射线衍射空间结构图；图7(f)为实施例1第五步产物在甲苯中重结晶得到的单晶X射线衍射空间结构图。
图8是本发明提供的化合物9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐的结构式。
图9为化合物9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐制备过程示意图。
图10为PI膜的DMA曲线。
图11为PI膜的TGA曲线。
图12为PI膜的透过率曲线。
图13为PI膜的TMA曲线。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以相互组合。
实施例1
一种含有刚性脂环含氟结构的二酐化合物9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐，简称为8FDA，制备过程示意图如图9所示。
步骤一：将2,3,6,7-四甲基蒽-9,10-二酮(40.00g,151.33mmol，1.00当量)悬浮于THF(400mL)在r.t.并加入三甲基(三氟甲基)硅烷(49.21mL，332.93mmol，2.20当量)。将悬浮液冷却至0℃，加入CsF(459.74mg，3.03mmol，0.02当量)。搅拌10分钟后，将反应混合物升温至室温，并搅拌持续1.5小时。过滤反应混合物，剩余的黄色固体用乙醚(25mL)冲洗。粗产物通过柱色谱分离(正戊烷至正戊烷/MTBE 15：1)上反应，得到化合物((2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二基)双(氧基))双(三甲基硅烷)(16.6g，30.27mmol，20％)为白色固体； 1H NMR(400MHz,CDCl3)δ7.67(s,1H),2.38(d,J＝3.3Hz,3H),-0.10(d,J＝15.5Hz,5H).
图1(a)是实施例1第一步合成的((2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二基)双(氧基))双(三甲基硅烷)的核磁氢谱图；图1(b)是实施例1第一步合成的((2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二基)双(氧基))双(三甲基硅烷)的碳谱图；由图1 可以得知， 1H NMR(600MHz,CDCl 3)δ7.67(s,4H),2.38(d,J＝3.3Hz,12H),-0.12(d,J＝14.4Hz,18H)。 13C NMR(150MHz,CDCl 3)137.56,137.22,131.04-130.69,130.40,125.87,19.67,2.19,1.99-1.54。 19F NMR(565MHz,CDCl 3)δ-78.39(s,6F)，因此步骤一得到的物质是(2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二基)双(氧基))双(三甲基硅烷)
步骤二：将((2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二基)双(氧基))双(三甲基硅烷)(双TMS)(20.00g，36.4mmol，1.00当量)单体溶于80mL THF中,加热至回流温度后，慢慢加入浓盐酸，立即变浑浊，继续加热反应3小时。监控反应进程，待其完全反应后，冷却至室温，抽滤，滤饼用水洗三次(30mL/次)，再用正己烷洗三次(30mL/次)。产物真空干燥。得到无色晶体2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二醇，产率95％； 1H NMR(400MHz,DMSO)δ7.68(d,J＝1.2Hz,1H),7.26(s,1H),2.31(s,3H).
图2(a)是实施例1第二步合成的2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二醇的核磁氢谱图；图2(b)是实施例1第二步合成的2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二醇的碳谱图；由图2可以得知， 1H NMR(600MHz,DMSO-d 6)δ7.69(d,J＝1.2Hz,4H),7.32(s,2H),2.32(s,12H)。 13C NMR(100MHz,DMSO-d 6)δ137.26(s),131.90(s),129.46(s),72.11(t,J＝26.6Hz),19.84(s)。 19F NMR(565MHz,DMSO-d 6)δ-76.69(s,6F)，因此步骤二得到的物质是2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二醇。
步骤三：将2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二醇(10g，24.7mmol，1.00当量)溶于30mL无水THF中，无水无氧条件下冷却至-78℃，慢慢滴加二乙胺基三氟化硫(DAST)(7.23mL，54.4mmol，2.20当量)，滴加完毕后继续反应12小时。点板监控反应进程。完全反应后，加入碳酸氢钠淬灭过量的DAST。淬灭完全后，然后将其过滤，滤液旋 干，柱分离。产物用正己烷重结晶。产物真空干燥。得到9,10-二氟-2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽，产率85％； 1H NMR(600MHz,CDCl3)δ7.68(d,J＝26.0Hz,1H),2.39(s,3H).
图3(a)是实施例1第三步合成的9,10-二氟-2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽的核磁氢谱图，图3(b)是实施例1第三步合成的9,10-二氟-2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽的碳谱图；由图3可以得知， 1H NMR,CDCl 3)δ7.68(d,J＝26.0Hz,4H),2.39(s,12H)。 13C NMR(100MHz,CDCl 3)δ139.87,139.61,129.18,128.90,127.44-126.52,19.90。 19F NMR(565MHz,CDCl 3)δ-77.80(d,2F),-77.98(m,4F),-157.55(m,2F)，因此步骤三得到的物质是9,10-二氟-2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽。
步骤四：将9,10-二氟-2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽(5g，12.2mmol，1.00当量)溶于30mL吡啶和水体积比1:1的溶剂中，加热至回流温度。再称量(19.34g，0.122mmol，10.00当量高锰酸钾)，在1小时内分批加入反应瓶中。反应结束后，趁热抽滤，旋干滤液。再用热水溶解产物，加入浓盐酸酸化，抽滤得到四酸产物。乙酸重结晶。产物真空干燥，得到9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸，产率85％； 1H NMR(600MHz,DMSO)δ13.98(s,1H),8.53–7.94(m,1H).
图4(a)是实施例1第四步合成的9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸的核磁氢谱图；图4(b)是实施例1第四步合成的9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸的碳谱图；由图4可以得知， 1H NMR(600MHz,DMSO-d 6)δ13.98(s,4H),8.53-7.94(m,4H)。 13C NMR(100MHz,DMSO-d 6)δ167.05,166.97,136.90,136.79-136.53,130.00,129.40。 19F NMR(565MHz,DMSO-d 6)δ-76.31(m,6F),-142.23(m,2F)，因此步骤四得到的物质是9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸。
步骤五：将9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸(5g，9.47mmol，1.00当量)溶于30mL乙酸酐溶剂中，加热至回流温度。反应10小时。点板监控反应进程。完全反应后，旋干，真空干燥得到9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐，产率85％。 1H NMR(600MHz,DMSO)δ8.83–8.63(m,1H),8.34(dd,J＝43.5,25.8Hz,1H).图8是本发明制备的化合物9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐的结构式。
图5(a)是实施例1第五步合成的9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐的核磁氢谱图；图5(b)是实施例1第五步合成的9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐的碳谱图；由图5可以得知， 1H NMR(600MHz,DMSO-d 6)δ8.83-8.63(m,4H)。 13C NMR(100MHz,DMSO-d 6)δ161.87,161.80,135.42,134.13,125.73,125.64。 19F NMR(565MHz,DMSO-d 6)δ-75.64(m,6F),-139.35(s,2F)，因此步骤五得到的物质是9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐。
图6(a)、图6(b)、图6(c)、图6(d)和图6(e)分别是本实施例步骤一、步骤二、步骤三、步骤四和步骤五合成的产物的红外谱图。
图7(a)为实施例1第一步产物的单晶X射线衍射空间结构图；图7(b)为实施例1第二步产物的单晶X射线衍射空间结构图；图7(c)为实施例1第三步产物的单晶X射线衍射空间结构图；图7(d)和图7(e)为实施例1第五步产物升华后得到的单晶X射线衍射空间结构图；图7(f)为实施例1第五步产物在甲苯中重结晶得到的单晶X射线衍射空间结构图。从图7中可以得知，各个步骤中得到的是相应的产物。
实施例2
一种含有刚性脂环含氟结构的二酐化合物9,10-二苯基-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐的制备方法，含有以下步骤：
步骤一和步骤二按照实施例1中的方法进行，得到2,3,6,7-四甲基-9,10-双(三氟甲基)-9,10-二氢蒽-9,10-二醇。
步骤三：将2,3,6,7-四甲基-9,10-双(三氟甲基)-9,10-二氢蒽-9,10-二醇(200mg，0.5mmol，1当量)溶于10ml无水THF中，搅拌使其溶解，再注射PBr 3(0.23ml，3.45mg，0.013mmol，0.026当量)，避光条件下，室温下搅拌10～30min后升温至50℃，反应24h，冷却。粗产物通过柱色谱分离(正戊烷至正戊烷/MTBE 15：1)上反应，得到化合物9,10-二溴-2,3,6,7-四甲基-9,10-双(三氟甲基)-9,10-二氢蒽。产率95％。
步骤四：将9,10-二溴-2,3,6,7-四甲基-9,10-双(三氟甲基)-9,10-二氢蒽(40mg，0.075mmol，1当量)溶于10ml无水THF中，加入1,3-双(二苯基膦丙烷)二氯化镍(2.03mg，0.0038mmol，0.05当量)，再滴加苯基溴化镁(0.2ml，34mg，0.188mmol，2.5当量)，在室温下反应一小时后，再升温到回流温度，回流20-24h。冷却至室温，用无水乙醚萃取，再通过柱色谱分离(正己烷)上反应，得到2,3,6,7-四甲基-9,10-二苯基-9,10-双(三氟甲基)-9,10-二氢蒽，产率50％。
步骤五：将2,3,6,7-四甲基-9,10-二苯基-9,10-双(三氟甲基)-9,10-二氢蒽(5g，9.5mmol，1.00当量)溶于30mL吡啶和水体积比1:1的溶剂中，加热至回流温度。再称量(15.01g，95mmol，10.00当量高锰酸钾)，在1小时内分批加入反应瓶中。反应结束后，趁热抽滤，旋干滤液。再用热水溶解产物，加入浓盐酸酸化，抽滤得到四酸产物。乙酸重结晶。产物真空干燥，得到9,10-二苯基-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸，产率85％。
步骤六：将9,10-二苯基-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸(5g，7.76mmol，1.00当量)溶于30mL乙酸酐溶剂中，加热至回流温度。反应10小时。点板监控反应进程。完全反应后，旋干，真空干燥得到9,10-二苯基-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐，产率 85％。
实施例3
一种含有刚性脂环含氟结构的二酐化合物9,10-二氯-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐的制备方法，包含以下步骤：
步骤一和步骤二按照实施例1中的方法进行，得到2,3,6,7-四甲基-9,10-双(三氟甲基)-9,10-二氢蒽-9,10-二醇。
步骤三：将2,3,6,7-四甲基-9,10-双(三氟甲基)-9,10-二氢蒽-9,10-二醇(200mg，0.5mmol，1当量)溶于15ml甲苯中，再加入乙酰氯(98.125mg，1.25mmol，2.5当量)，室温下搅拌10min，再升温至75℃，反应8h。冷却至室温，通过柱色谱分离得到产物9,10-二氯-2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽，产率65％。
步骤四：将9,10-二氯-2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽(5g，11.3mmol，1.00当量)溶于30mL吡啶和水体积比1:1的溶剂中，加热至回流温度。再称量(21.4g，135.6mmol，12.00当量高锰酸钾)，在1小时内分批加入反应瓶中。反应结束后，趁热抽滤，旋干滤液。再用热水溶解产物，加入浓盐酸酸化，抽滤得到四酸产物。乙酸重结晶。产物真空干燥，得到9,10-二氯-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸，产率85％。
步骤五：将9,10-二氯-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸(5g，8.9mmol，1.00当量)溶于30mL乙酸酐溶剂中，加热至回流温度。反应10小时。点板监控反应进程。完全反应后，旋干，真空干燥得到9,10-二氯-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐，产率85％。
实施例4
一种含有刚性脂环含氟结构的二酐化合物9,9’,10,10’-四(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐的制备方法，包含以下步骤：
步骤一和步骤二按照实施例1中的方法进行，得到2,3,6,7-四甲基-9,10- 双(三氟甲基)-9,10-二氢蒽-9,10-二醇。
步骤三：氮气保护下，将2,3,6,7-四甲基-9,10-双(三氟甲基)-9,10-二氢蒽-9,10-二醇(200mg，0.5mmol，1当量)溶于10mlTHF中，加入碘化氢(0.17ml，190mg，1.5mmol，3当量)，加入三氟碘甲烷(293.85mg，1.5mmol，3当量)，在室温下反应24h，通过柱分离，得到2,3,6,7-四甲基-9,9’,10，10’-四(三氟甲基)-9,10-二氢蒽。
步骤四：将2,3,6,7-四甲基-9,9’,10,10’-四(三氟甲基)-9,10-二氢蒽(5g，9.84mmol，1.00当量)溶于30mL吡啶和水体积比1:1的溶剂中，加热至回流温度。再称量(18.66g，118.08mmol，12.00当量高锰酸钾)，在1小时内分批加入反应瓶中。反应结束后，趁热抽滤，旋干滤液。再用热水溶解产物，加入浓盐酸酸化，抽滤得到四酸产物。乙酸重结晶。产物真空干燥，得到9,9’,10,10’-四(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸，产率85％。
步骤五：将9,9’,10,10’-四(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸(5g，7.96mmol，1.00当量)溶于30mL乙酸酐溶剂中，加热至回流温度。反应10小时。点板监控反应进程。完全反应后，旋干，真空干燥得到9，9’,10，10’-四(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐，产率80％。
实施例5
运用实施例1制备的二酐物质9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐来合成聚酰亚胺，包括以下步骤：
步骤一：将PPDA(3mmol)用适量的干燥的NMP溶剂，溶解于50mL烧瓶中的中，然后将8FDA，(3mmol)慢慢地，一次性加入到上述溶解了二胺的溶液中。将反应物在25℃条件下搅拌24小时，得到聚酰胺酸(PAA)溶液。
步骤二：将聚酰胺酸溶液倒在一块经过ITO玻璃清洗剂，去离子水彻底清洗，干燥的洁净的玻璃上面，然后利用流延法将PAA均匀的分散在玻璃表面。接下来将流延好的PAA玻璃至于预热到80℃的烘箱中。在80℃ 条件下加热2小时以缓慢释放溶剂，然后按照以下温度程序升温：在100℃下加热1小时，150℃加热1小时，200℃加热1小时，250℃加热1小时，280℃加热1小时。待烘箱温度自然冷却至室温后，在薄膜边缘用手术刀画一条线，将其放入去离子水中浸泡后，从玻璃表面剥离下来。得到热亚胺化的聚酰亚胺薄膜。
实施例6
将实施例5得到的聚酰亚胺薄膜通过热重分析(TGA)，动态机械分析(DMA)和热机械分析(TMA)评价PI膜的热性能和机械性能。用Perkin-Elmer TGA-2在氮气流下以10℃/分钟的加热速率进行热重分析(TGA)。用DMA Q800V20.22Build 41进行动态力学分析，使用拉伸模式，频率为1Hz。用TA Instrument Q400进行热膨胀系数的测试。氮气流0.05N。升温速率5℃每分钟。
测试结果如表1所示。图10为PI膜的DMA曲线；图11为PI膜的TGA曲线。图12为PI膜的透过率曲线。图13为PI膜的TMA曲线。
根据图10中的DMA曲线，基于本发明的刚性脂环含氟结构的二酐化合物(8FDA)的PI薄膜的Tg值为414℃。而基于4,4'-(六氟异亚丙基)二邻苯二甲酸酐(6FDA)的PI薄膜的Tg值为332℃。这归因于本发明的刚性脂环含氟结构的二酐化合物(8FDA)单体的刚性结构。聚酰亚胺的T g值由分子链的刚性程度，吸电子二酐残基和给电子二胺残基之间的CTC的分子相互作用共同决定。图11为PI薄膜的TGA曲线，聚酰亚胺的1％热分解温度(T d1)和残炭率的范围是500-517℃和65-66％。而基于本发明的刚性脂环含氟结构的二酐化合物(8FDA)的PIs具有比相应的4,4'-(六氟异亚丙基)二邻苯二甲酸酐(6FDA)膜更高的T d1值(分别为517℃和500℃)。本发明的刚性脂环含氟结构的二酐化合物(8FDA)基聚酰亚胺的多取代和刚性半脂环1,4-环己二烯，分子链的刚性较4,4'-(六氟异亚丙基)二邻苯二甲酸酐(6FDA)强，增强了链间的相互作用和积聚程度，增加了 它们的耐热性。与其他薄膜相比，来源于具有本发明的刚性脂环含氟结构的二酐化合物(8FDA)的PPDA的在400nm处显示出相当低的透射率(T％<30％)，如图12所示。由这些测试结果可知通过本发明的刚性脂环含氟结构的二酐化合物(8FDA)和PPDA聚合得到的PI-1具有优异的热稳定性和尺寸稳定性(T g为414℃，CTE为12ppm K -1)，T 450接近80％。图13为PI薄膜的TMA曲线，该方法制备的PI薄膜的CTE值为12ppm K -1。而目前已有的基于4,4'-(六氟异亚丙基)二邻苯二甲酸酐(6FDA)的薄膜的CTE值为47ppm K -1。与4,4'-(六氟异亚丙基)二邻苯二甲酸酐(6FDA)相比，基于本发明的刚性脂环含氟结构的二酐化合物(8FDA)的薄膜的CTE值明显低于基于4,4'-(六氟异亚丙基)二邻苯二甲酸酐(6FDA)的薄膜。这也可以归因于本发明的刚性脂环含氟结构的二酐化合物(8FDA)的更刚性的结构，可以增加链内取向，更强的分子间相互作用将抑制分子运动，并导致更低的CTE产生和更好的尺寸稳定性。
表1基于8FDA的PIs的热稳定性，机械性能和光学性能数据汇总表
Figure PCTCN2018124730-appb-000003
本领域的技术人员容易理解，以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种刚性脂环含氟结构的二酐化合物，其特征在于，该化合物的结构式如式Ⅰ所示：
    Figure PCTCN2018124730-appb-100001
    所述R为F、Cl、CF 3或
    Figure PCTCN2018124730-appb-100002
  2. 一种刚性脂环含氟结构的二酐化合物的制备方法，其特征在于，包含以下步骤：
    (1)向2,3,6,7-四甲基蒽-9,10-二酮溶液中加入三甲基(三氟甲基)硅烷或三乙基(三氟甲基)硅烷，冷却后，加入催化剂A，充分混匀后，将反应混合物升温至30℃～50℃，反应6h～24h，使2,3,6,7-四甲基蒽-9,10-二酮发生亲核加成反应，得到((2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二基)双(氧基))双(三甲基硅烷)；
    (2)将步骤(1)得到的((2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二基)双(氧基))双(三甲基硅烷)溶解后置于酸性环境中，反应时间为0.5h～5h，反应温度为25℃～80℃，使((2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二基)双(氧基))双(三甲基硅烷)上的三甲基硅氧烷转变成羟基，得到2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二醇；
    (3)将步骤(2)得到的2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二醇溶解后，冰浴条件下，逐滴加入二乙胺基三氟化硫或双(2-甲氧基乙基)氨基三氟化硫，反应12h～15h，得到9,10-二氟-2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽；
    或者步骤(3)为以下技术方案：将步骤(2)得到的2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二醇溶解后，加入乙酰氯，在70℃-80℃的条件下，反应8h-12h，得到9,10-二氯-2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽；
    或者步骤(3)为以下技术方案：将步骤(2)得到的2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二醇溶解后，加入卤化氢和三氟卤甲烷，反应15h-30h，得到2,3,6,7-四甲基-9,9’,10,10’-四(三氟甲基)-9,10-二氢蒽；
    或者步骤(3)为以下技术方案：将步骤(2)得到的2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二醇溶解后，第一步加入三溴化磷，或加入溴化氢和催化剂B，在40℃-60℃的条件下，反应12h-24h，使所述2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二醇上的羟基转变成溴原子，得到9,10-二溴-2,3,6,7-四甲基-9,10-双(三氟甲基)-9,10-二氢蒽；第二步加入苯基溴化镁和催化剂C，或加入苯硼酸和催化剂D，在75℃-90℃条件下，反应8h-15h，使9,10-二溴-2,3,6,7-四甲基-9,10-双(三氟甲基)-9,10-二氢蒽上的溴原子被苯基取代，得到2,3,6,7,-四甲基-9,10-二苯基-9,10-双(三氟甲基)-9,10-二氢蒽；
    (4)将步骤(3)得到的9,10-二氟-2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽、9,10-二氯-2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽、2,3,6,7-四甲基-9,9’,10,10’-四(三氟甲基)-9,10-二氢蒽或2,3,6,7,-四甲基-9,10-二苯基-9,10-双(三氟甲基)-9,10-二氢蒽溶解后，加入氧化剂，在90℃-110℃条件下，反应12h-15h后，抽滤，旋干滤液，产物溶解后并酸化，得到9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸、9,10-二氯-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸、9,9’,10,10’-四(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸或9,10-二苯基-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸；
    (5)将步骤(4)得到的9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽 -2,3,6,7-四甲酸、9,10-二氯-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸、9,9’,10,10’-四(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸或9,10-二苯基-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四甲酸脱水成酐，得到9,10-二氟-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐、9,10-二氯-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐、9,9’,10,10’-四(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐或9,10-二苯基-9,10-双(三氟甲基)-9,10-二氢蒽-2,3,6,7-四羧酸二酐。
  3. 如权利要求2所述的刚性脂环含氟结构的二酐化合物的制备方法，其特征在于，步骤(1)所述催化剂A为氟化铯、四丁基氟化铵或三(二甲氨基甲基)锍二氟三甲基氨酸盐；步骤(3)所述催化剂B为浓硫酸；步骤(3)所述催化剂C为1,3-双(二苯基膦丙烷)二氯化镍，或者为醋酸钯和三苯基膦的混合物；步骤(3)所述催化剂D为四(三苯基膦)钯和碳酸钾的混合物，或者为钯和碳酸钾的混合物，或者为四氯钯酸钠和碳酸钾的混合物；步骤(4)所述氧化剂为高锰酸钾或三氧化铬。
  4. 如权利要求2所述的刚性脂环含氟结构的二酐化合物的制备方法，其特征在于，步骤(3)所述卤化氢为溴化氢、碘化氢或氯化氢；步骤(3)所述三氟卤甲烷为三氟溴甲烷、三氟碘甲烷或三氟氯甲烷。
  5. 如权利要求2所述的刚性脂环含氟结构的二酐化合物的制备方法，其特征在于，步骤(1)所述2,3,6,7-四甲基蒽-9,10-二酮、三甲基(三氟甲基)硅烷与催化剂A的物质的量之比为1：(2～3.5)：(0.01～0.05)。
  6. 如权利要求2所述的刚性脂环含氟结构的二酐化合物的制备方法，其特征在于，步骤(3)中所述2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽-9,10-二醇与二乙胺基三氟化硫，或者与双(2-甲氧基乙基)氨基三氟化硫的物质的量之比为1：(2～3.5)。
  7. 如权利要求2所述的刚性脂环含氟结构的二酐化合物的制备方法，其特征在于，步骤(4)中所述9,10-二氟-2,3,6,7-四甲基-9,10-二(三氟甲基) -9,10-二氢蒽、9,10-二氯-2,3,6,7-四甲基-9,10-二(三氟甲基)-9,10-二氢蒽、2,3,6,7-四甲基-9,9’,10,10’-四(三氟甲基)-9,10-二氢蒽或2,3,6,7,-四甲基-9,10-二苯基-9,10-双(三氟甲基)-9,10-二氢蒽与氧化剂的物质的量之比为1：(10～12)。
  8. 如权利要求1所述的刚性脂环含氟结构的二酐化合物应用于制备聚酰亚胺材料的应用。
  9. 一种聚酰亚胺膜的制备方法，其特征在于，包含以下步骤：
    (1)将二胺溶解后，加入权利要求1所述的刚性脂环含氟结构的二酐化合物，在25℃～35℃条件下反应10h～30h，得到聚酰胺酸溶液；
    (2)将步骤(1)得到的聚酰胺酸溶液均匀分散在基底表面，加热使聚酰胺酸溶液中的溶剂挥发；继续加热使所述聚酰胺酸发生脱水环化反应，得到聚酰亚胺膜。
  10. 由权利要求9所述方法制备得到的聚酰亚胺膜。
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