CN111961061B - Dianhydride compound and preparation method and application thereof - Google Patents
Dianhydride compound and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of high polymer materials, in particular to the technical field of colorless transparent polyimide films, and specifically relates to a novel dianhydride compound and a preparation method and application thereof. The novel dianhydride compound has a structure shown as a formula I, wherein R 1 、R 2 Independent of each other, represent- (CH) 2 )‑、‑(CH 2 CH 2 )‑；R 3 、R 4 Identical or different, independently of one another, H or F. The novel dianhydride compound provided by the invention has the advantages that the polyimide film prepared by polymerization of the novel dianhydride compound and diamine realizes good optical characteristics that the light transmittance at 550nm is more than or equal to 85 percent due to the unique alicyclic structure and fluorine-containing structure, overcomes the defect of deep color of the traditional aromatic polyimide film, can be applied to the field of transparent polyimide films, and further has good application prospect in the field of flexible display or photoelectricity. The preparation method provided by the invention is stable and efficient, raw materials are easy to obtain, the preparation process is simple, and the popularization of the dianhydride compound is facilitated.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to the technical field of colorless transparent polyimide films. In particular to a novel dianhydride compound and a preparation method and application thereof.
Background
Polyimide (PI) is a polymer with imine ring on the main chain, and is prepared by gradually polymerizing compounds with diamine and dianhydride; because of the special imine ring and aromatic ring structure on the PI main chain and the conjugation effect thereof, the polyimide has the characteristics of excellent thermal stability, mechanical strength, dielectric property, low thermal expansion coefficient and the like, and is widely applied to the fields of aerospace, microelectronics, mechanical engineering, petrochemical industry, liquid crystal and the like.
However, the specific aromatic ring conjugated structure in the PI structure promotes intramolecular and intermolecular Charge Transfer Complexes (CTCs), affects the light transmittance of the PI film, and exhibits brown yellow color and poor light transmittance, thus greatly limiting the application of the PI film in the photoelectric field (such as optical waveguide materials in the optical communication field and flexible electrode materials in the flexible display field, optical transparent films of display substrates or cover plates, and the like). Meanwhile, with the development of intelligent electronic equipment display devices in recent years in the bendable direction, the development requirement for high-transparency PI films is particularly urgent in order to meet the requirement of flexible display of the electronic equipment.
In order to realize good transparency of the PI film, the PI film is usually realized by designing a PI molecular structure; for example, a group (ether bond or sulfonyl group capable of realizing bending) or a structure (substituent with large space volume) capable of destroying a plane conjugated structure in a main chain is introduced, an aliphatic structure (alicyclic or aliphatic structure) and a fluorine-containing structure are introduced, so that the conjugation effect and symmetry of a molecular structure are destroyed, the load transfer effect in molecules or among molecules is reduced, and a good transparentization modification effect is realized; it should be noted that the more electron donating diamine or the more electron withdrawing dianhydride, the darker the color of the polyimide film formed by polymerization; therefore, it is particularly important for the selection of the monomer, and the improvement of the transparency of the PI film can be realized by selecting one or more modes.
Based on the above, the invention provides a novel dianhydride compound, and the unique alicyclic structure of the dianhydride compound can not only effectively destroy the conjugated structure in the PI film molecular structure, but also weaken the charge transfer capability in the main structure; meanwhile, the conjugated structure in the molecular structure of the PI film can be further destroyed by introducing fluorine-containing groups, so that a good transparentization modification effect is realized, and the method can be applied to the field of transparent polyimide films.
Disclosure of Invention
A first object of the present invention is to provide a novel dianhydride compound having a structure represented by formula I:
wherein R is 1 、R 2 Independent of each other, represent- (CH) 2 ) -or- (CH) 2 CH 2 ) -; preferably R 1 、R 2 represents-CH 2 -；
R 3 、R 4 Identical or different, independently of one another, H or F; preferably R 3 、R 4 Simultaneously F or simultaneously H.
As a preferred embodiment of the present invention, the novel dianhydride compound has a structure as shown in formula I-1 or I-2:
the Polyimide (PI) prepared by the compound can realize good optical characteristics due to the unique alicyclic structure and fluorine-containing structure, overcomes the defect of dark color of the traditional aromatic polyimide film, can be applied to the field of transparent polyimide films, and further has good application prospect in the field of flexible display or photoelectricity.
A second object of the present invention is to provide a process for producing the novel dianhydride compound, which comprises the following steps:
the method specifically comprises the following steps:
(1) The compound I-a is taken as a raw material, and is subjected to an addition reaction with a fluorine reagent to obtain a compound I-b;
(2) Inserting a metal catalyst of the compound I-b into a carbonyl group to obtain a compound I-c;
(3) Dehydrating the compound I-c to obtain I-d.
Wherein in formula I, the R 1 、R 2 Independent of each other, represent- (CH) 2 ) -or- (CH) 2 CH 2 )-；R 3 、R 4 Identical or different, independently of one another, H or F; preferably, in formula I, the R 1 、R 2 represents-CH 2 -；R 3 、R 4 At the same time H or R 3 、R 4 And F.
Preferably, the molar ratio of compound I-a to the fluorogenic reagent in step (1) is 1.0: (1.0 to 10.0);
preferably, the fluorine reagent is selected from one of DAST, BAST and sulfur tetrafluoride, preferably DAST, and when the fluorine reagent is selected from DAST, the molar ratio of the compound I-a to the fluorine reagent is more preferably 1.0: (1.5-5.0).
Preferably, step (1) is generally carried out in an organic solvent selected from one of dichloromethane or monofluorotrichloromethane, preferably dichloromethane.
Preferably, the reaction temperature in step (1) is from-80 to 10 ℃, preferably from 0 to 10 ℃; the reaction pressure is not particularly limited.
Preferably, the step (2) specifically comprises: reacting an alcohol compound and carbon monoxide with a compound I-b in the presence of a palladium catalyst and a copper catalyst; the feeding mass ratio of the compound I-b to the alcohol compound is 1:1 to 100, preferably 1:5 to 50.
The alcohol compound is selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, amyl alcohol, methoxyethanol, ethoxyethanol, ethylene glycol and triethylene glycol; preferably one or more of methanol, ethanol, n-propanol and isopropanol; more preferably one or more of methanol, ethanol, and isopropanol.
Preferably, the molar ratio of the compound I-b to the palladium catalyst in the step (2) is 1:0.001-1, preferably 1:0.01-0.5;
the palladium catalyst used in the step (2) is not particularly limited as long as it contains palladium, and examples thereof include palladium halides such as palladium chloride and palladium bromide; palladium organic acid salts such as palladium acetate and palladium oxalate; palladium inorganic acid salts such as palladium nitrate and palladium sulfate; palladium carbon or palladium alumina, etc. having palladium supported on a carrier such as carbon or alumina, palladium chloride or palladium carbon is preferably used.
Preferably, the molar ratio of the compound I-b to the copper catalyst in the step (2) is 1:1.0-50, preferably 1:4.0-20;
the copper catalyst is selected from one or more than one of monovalent copper oxide, monovalent copper chloride, monovalent copper bromide, divalent copper oxide, divalent copper chloride and divalent copper bromide; preferably one or more of bivalent copper oxide, bivalent copper chloride and bivalent copper bromide; more preferably divalent copper chloride.
Preferably, the reaction of step (2) is carried out in an organic solvent, the mass ratio of said compound I-b to said organic solvent being from 1:1 to 100, preferably from 1:5 to 50;
the organic solvent is not particularly limited as long as it does not inhibit the reaction; examples thereof include aliphatic carboxylic acids (e.g., formic acid, acetic acid, propionic acid, trifluoroacetic acid, etc.), organic sulfonic acids (e.g., methanesulfonic acid, trifluoromethanesulfonic acid, etc.), ketones (e.g., acetone, butanone, cyclohexanone, etc.), aliphatic hydrocarbons (e.g., N-pentane, N-hexane, N-heptane, cyclohexane, etc.), amides (e.g., N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, etc.), ureas (N, N' -dimethylimidazolidinone, etc.), ethers (e.g., diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, 1, 2-methylenedioxybenzene, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, etc.), halogenated aromatic hydrocarbons (e.g., chlorobenzene, 1, 2-dichlorobenzene, 1, 3-dichlorobenzene, 1, 4-dichlorobenzene, etc.), nitroaromatic hydrocarbons (e.g., nitrobenzene, etc.), halogenated hydrocarbons (e.g., dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, etc.), carboxylic acids (e.g., ethyl acetate, propyl acetate, butyl acetate, sulfoxides, etc.), sulfoxides (e.g., sulfoxides, etc.), nitrites (e.g., methyl sulfones, etc.), sulfoxides (e.g., sulfoxides, etc.), etc. Aliphatic hydrocarbons, aromatic hydrocarbons, halogenated hydrocarbons and halogenated aromatic hydrocarbons are preferably used. These organic solvents may be used alone or in combination of two or more. The above organic solvents may be used alone or in combination of two or more.
Preferably, the dehydration in step (3) is: heating and stirring in an organic solvent in the presence of an acid catalyst, wherein the heating temperature is 50-130 ℃, preferably 80-120 ℃;
the acid catalyst is not particularly limited, and examples thereof include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, chlorosulfuric acid, and nitric acid; organic sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid; halogenated carboxylic acids such as chloroacetic acid and trifluoroacetic acid, ion exchange resins, silica gel sulfate, zeolite, and acidic alumina, and the like are preferably used as the inorganic acids and organic sulfonic acids, and more preferably as the organic sulfonic acids. These acids may be used alone or in combination of two or more.
Preferably, the organic solvent in the step (3) is an organic acid solvent, which is selected from one or more of toluene, xylene, trimethylbenzene, anisole, diphenyl ether, methyltetrahydrofuran, cyclohexane, n-hexane, methylcyclohexane, n-heptane, benzene and n-octane; preferably toluene, xylene or both;
preferably, the amount of the organic solvent is appropriately adjusted according to the uniformity and the stirring property of the reaction liquid; the mass ratio of the compound I-c to the organic solvent is 1:0.1-100, preferably 1:1-10.
The present invention will be described in detail with reference to examples, and those skilled in the art can change the solvent, the amount of the solvent to be fed, the reaction conditions, etc., and after completion of each reaction, the reaction product may be separated and purified by a usual method such as filtration, extraction, distillation, sublimation, recrystallization, column chromatography, etc.
The starting materials I-a can be synthesized by methods known per se from the open commercial route or literature.
In addition, it is to be noted that in the production method of the present invention, the solvent and the amount thereof, the separation and purification of the product, the dropping rate of the reactant, etc. used in each step are not particularly limited in part and are understood and grasped by those skilled in the art. In the present invention, unless specifically described otherwise, the volume amount of the solvent is generally 5 to 15 times the mass of the reactants, and the specific amount can be appropriately adjusted according to the amount of the reaction substrate and the size of the selected reaction flask; the drop rate of reactants is typically controlled in combination with specific reaction rates, etc. Based on the disclosure of the present invention, a person skilled in the art may select any available technical scheme according to the actual situation to implement the present invention.
The preparation method can stably and efficiently obtain the dianhydride compound.
A third object of the present invention is the use of any of the novel dianhydride compounds described above or any of the methods described above for the preparation of transparent polyimide films.
The invention provides application of the novel dianhydride compound in the field of transparent polyimide films.
The fourth object of the present invention is to provide a method for producing a transparent polyimide film, which is produced by polymerizing the novel dianhydride compound, aliphatic or aromatic dianhydride compound, and diamine compound as raw materials.
Preferably, the diamine compound is selected from one or more of 4,4 '-diaminodiphenyl ether (ODA), p-phenylenediamine (p-PDA), m-phenylenediamine (m-PDA), o-phenylenediamine (o-PDA), 4' -diaminodiphenyl Methane (MDA), trans-1, 4-cyclohexanediamine (t-DACH), 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl (TFMB).
The light transmittance of the transparent polyimide film obtained by the method is not lower than 85% at 550 nm.
A fifth object of the present invention is to provide any one of the above novel dianhydride compounds, any one of the above methods for producing a novel dianhydride compound, and the use of the transparent polyimide film produced by any one of the above methods in the optical field; applications in flexible display devices and optically transparent films are preferred.
The invention has the following beneficial effects:
(1) The dianhydride compound provided by the invention can be used in the field of transparent polyimide films, and the unique alicyclic structure of the dianhydride compound can not only effectively destroy the conjugated structure in the molecular structure of the PI film, but also weaken the charge transfer capability in the main structure; meanwhile, the conjugated structure in the molecular structure of the PI film can be further destroyed by introducing fluorine-containing groups, so that a good transparentization modification effect is realized, and the transparent polyimide film has the optical characteristic that the light transmittance at 550nm is more than or equal to 85 percent; however, the application of the transparent polyimide film is not particularly limited, and the transparent polyimide film can be applied to the photoelectric fields such as flexible display devices and optical transparent films.
(2) The preparation method can stably and efficiently obtain the dianhydride compound, has the advantages of easily available raw materials and simple preparation process, and is convenient for popularization of the dianhydride compound.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
The starting materials are available from published commercial sources unless otherwise specified.
The novel dianhydride compound of the present invention, and the preparation method and application thereof are specifically described below by way of examples. The present invention is not limited to the following examples.
Example 1
A novel dianhydride compound having the structural formula:
the synthetic route for the preparation of compound I-1 is shown below:
the method comprises the following specific steps:
(1) Synthesis of Compound I-e
A250 mL three-necked flask was charged with I-a (836.244 mg,3.48 mmol) dissolved in methylene chloride (150 mL), cooled to-30℃under nitrogen, DAST (2.42 g,13.92 mmol) was added dropwise thereto at-30℃to-35℃and the mixture was naturally warmed to room temperature after completion of the dropwise addition, followed by stirring overnight. TLC monitored completion of the reaction, pouring the reaction solution into a mixed solution composed of 50ml of methylene chloride and 50ml of saturated solution of ammonium dicarbonate, stirring for 15min, separating the solution, extracting the aqueous layer with methylene chloride (2X 100 ml), combining the organic layers, washing once with 50ml of saturated brine, drying over anhydrous sodium sulfate, filtering, and removing the solvent under reduced pressure to give yellow oil (847.58 mg,85.76 percent) I-e. 1 H NMR(400MHz,CDCl 3 6.06-6.12(m,4H),2.83-2.90(m,4H),2.00-2.02(m,4H),1.91–1.99(m,4H),1.19-1.26(m,2H).
Cl-MS(m/z)；285(M+1)
(2) Synthesis of Compounds I-f
To a reaction vessel having a capacity of 1L, 364g of methanol, 62g of chloroform, 136g (1011 mmol) of copper (II) chloride and 6g (33.7 mmol) of palladium chloride were added and stirred. After the atmosphere gas in the system was replaced with carbon monoxide, the mixture was dissolved by dropwise addition over 3 hours
A solution of 19.12g (67.3 mmol) of compound I-e of (1) in 178g of chloroform was reacted at 20-25℃for 4 hours. Then, the atmosphere in the system was changed from carbon monoxide to argon, and then the solvent was distilled off from the reaction mixture, and 621g of chloroform was added. The same operation was repeated twice. Insoluble material was then removed from the resulting dark green suspension by filtration. The resulting solution was washed 3 times with 324g of saturated aqueous sodium hydrogencarbonate solution and 3 times with 324g of purified water, and then 2.7g of anhydrous magnesium sulfate and 2.7g of activated carbon were added to the organic layer and stirred. Then, the solution was filtered and concentrated under reduced pressure to obtain 51g of a white solid. Then, purification was performed by silica gel chromatography (developing solvent; hexane: ethyl acetate=10:1 (volume ratio)) to obtain 26.62g (purity 99.1pa, yield 76% based on HPLC analysis) of 1,4,5, 8-dimethylbridged anthracene-9, 10-tetrafluoro-2, 3,6, 7-tetracarboxylic methyl ester (I-f) as a white solid. 1 H NMR(400MHz,CDCl 3 )3.67(S,12H),3.11-3.15(dd,4H),2.21-2.27(m,4H),1.81–1.94(m,4H),1.76-1.80(m,2H).1.52-1.57(m,2H).
Cl-MS(m/z)；521(M+1)
(3) Synthesis of Compound I-1
A100 mL-volume reaction vessel was charged with 6.19g (11.9 mmol) of I-f, 26.3g of formic acid, and 47mg (0.24 mmol) of p-toluenesulfonic acid monohydrate, and reacted at 98℃for 30 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and 30g of toluene was added to the concentrate. This operation was repeated 6 times, and the formic acid was distilled off almost completely. The resulting suspension was filtered, and the resulting solid was washed with 30g of toluene and dried under vacuum at 80℃to give 4.0g of milky solid. Thereafter, the mixture was recrystallized from acetic anhydride and then N, N' -dimethylacetamide to obtain 4.02g of 1,4,5, 8-dimethylanthracene-9, 10-tetrafluoro-2, 3,6, 7-dianhydride (I-1) as a white solid (purity: 98.3% based on 1H-NMR analysis, yield: 79%).
1 H NMR(400MHz,CDCl 3 )3.14-3.18(dd,4H),2.19-2.25(m,4H),1.88–2.0(m,4H),1.75-1.80(m,2H).0.90-0.95(m,2H).
Cl-MS(m/z)；429(M+1)
Example 2
The structural formula of the compound is as follows:
the synthetic route for the preparation of compound I-2 is shown below:
(1) Synthesis of Compound I-g
To a reaction vessel having a capacity of 5L, 100.5g (31.7 mmol) of I-a, 1.5L of methanol and 1.5L of tetrahydrofuran were charged. Then, 30.0g (60.3 mmol) of sodium borohydride was added at a temperature of 5℃for 1 hour, followed by a reaction at a temperature of 5 to 10℃for 7 hours. Then, 1L of a saturated aqueous ammonium chloride solution was added dropwise at a temperature of 5℃and then the temperature was raised to 25 ℃. The white solid precipitated in the reaction solution was filtered, and the solvent was distilled off under reduced pressure. The precipitated white solid was filtered, 1.5L of ion-exchanged water was added to the obtained white solid, and the mixture was stirred at 40℃for 1 hour. After that, the white solid was filtered, washed twice with 200mL of ion-exchanged water, washed twice with 100mL of ethyl acetate, and vacuum-dried to obtain 84.2g (purity 100% based on 1H-NMR analysis, yield 82%) of 1, 4a,5, 8a, 9a,10 a-decahydro-1, 4:5, 8-dimethanoanthracene-9, 10-diol (I-g) as a white solid.
1H-NMR(DMS0-d6,σ(ppm))；0.99(d,J＝7.8Hz,1H),1.16(d,J＝7.8Hz,1H),1.26-1.34(m,2H),1.52-1.62(m,2H),2.34-2.42(m,2H),2.77(s,2H),2.85(s,2H),2.91(brs,2H),4.26(s,1H),4.28(s,1H),6.04(t,J＝1.8Hz,2H),6.09(t,J1.8Hz,2H)
Cl-MS(m/z):245(M+1)
(2) Synthesis of Compound I-h
A250 mL three-necked flask was charged with I-g (850.26 mg,3.48 mmol) dissolved in methylene chloride (150 mL), cooled to-30deg.C under nitrogen report, DAST (1.21 g,7 mmol) was added dropwise at-30deg.C to-35deg.C, and the mixture was naturally warmed to room temperature after completion and stirred overnight. TLC monitored completion of the reaction, pouring the reaction solution into a mixed solution composed of 50ml of methylene chloride and 50ml of saturated solution of ammonium dicarbonate, stirring for 15min, separating the aqueous layer, extracting with methylene chloride (2X 100 ml), combining the organic layers, washing once with 50ml of saturated saline, drying over anhydrous sodium sulfate, filtering, and removing the solvent under reduced pressure to give yellow oil (858.15 mg,90 percent) I-h.1HNMR (400 MHz, CDCl36.15-6.10 (m, 4H), 4.10-4.12 (m, 1H), 4.00-4.03 (m, 1H), 2.83-2.88 (m, 4H), 2.00-2.02 (m, 4H), 1.81-1.93 (m, 6H), 1.17-1.22 (m, 2H).
Cl-MS(m/z)；249(M+1)
(3) Synthesis of Compound I-j
To a reaction vessel having a capacity of 1L, 364g of methanol, 62g of chloroform, 136g (1011 mmol) of copper (II) chloride and 6g (33.7 mmol) of palladium chloride were added and stirred. After the atmosphere gas in the system was replaced with carbon monoxide, a solution of I-h16.711g (67.3 mmol) dissolved in 178g of chloroform was added dropwise over 3 hours, and the mixture was reacted at 20 to 25℃for 4 hours. Then, the atmosphere in the system was changed from carbon monoxide to argon, and then the solvent was distilled off from the reaction mixture, and 621g of chloroform was added. The same operation was repeated twice. Insoluble material was then removed from the resulting dark green suspension by filtration. The resulting solution was washed 3 times with 324g of saturated aqueous sodium hydrogencarbonate solution and 3 times with 324g of purified water, and then 2.7g of anhydrous magnesium sulfate and 2.7g of activated carbon were added to the organic layer and stirred. Then, the solution was filtered and concentrated under reduced pressure to obtain 51g of a white solid. Then, purification was performed by silica gel chromatography (developing solvent; hexane: ethyl acetate=10:1 (volume ratio)) to obtain 24.45g (purity 99.1pa, yield 75% based on HPLC analysis) of 1,4,5, 8-dimethylbridged anthracene-9, 10-difluoro-2, 3,6, 7-tetracarboxylic methyl ester (I-j) as a white solid. 1H NMR (400 MHz, CDCl 3) 4.13-4.16 (t, 1H) 4.00-4.07 (t, 1H), 3.67 (S, 12H), 2.95-2.99 (dd, 4H), 2.21-2.27 (m, 4H), 1.76-1.86 (m, 4H), 1.68-1.74 (m, 2H) 1.47-1.52 (m, 2H).
Cl-MS(m/z)；485(M+1)
(4) Synthesis of Compound I-2
A100 mL-volume reaction vessel was charged with 5.76g (11.9 mmol) of I-j, 26.3g of formic acid, and 47mg (0.24 mmol) of p-toluenesulfonic acid monohydrate, and reacted at a temperature of 98℃for 30 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and 30g of toluene was added to the concentrate. This operation was repeated 6 times, and the formic acid was distilled off almost completely. The resulting suspension was filtered, and the resulting solid was washed with 30g of toluene and dried under vacuum at 80℃to give 4.0g of milky solid. Thereafter, the mixture was recrystallized from acetic anhydride and then N, N' -dimethylacetamide to obtain 3.59g of 1,4,5, 8-dimethylanthracene-9, 10-tetrafluoro-2, 3,6, 7-dianhydride (I-2) (purity 98.3% by 1H-NMR analysis, yield 77%) as a white solid.
1H NMR(400MHz,CDCl3)4.12-4.15(t，1H)4.03-4.05(t，1H)3.13-3.15(dd,4H),2.18-2.24(m,4H),1.76–1.86(m,4H),1.66-1.71(m,2H).0.87-0.92(m,2H).
Cl-MS(m/z)；393(M+1)
Example 3
The reaction vessel was purged with nitrogen beforehand, after 30min 143.18g of N, N-dimethylacetamide (DMAc, 24h ahead of time with molecular sieves) were added, 10.01g (50 mmol) of 4,4' -diaminodiphenyl ether (ODA) was then charged and dissolved in DMAc and stirred at 25℃until completely dissolved; 21.42g (50 mmol) of the dianhydride compound (I-1) was gradually added thereto, and after stirring until complete dissolution, the reaction was continued for 12 hours with heat preservation, thereby obtaining an 18wt% polyimide acid solution.
After the reaction is finished, acetic anhydride and isoquinoline with equimolar carboxylic acid groups are respectively added, and DMAc with water is added, so that 18 weight percent solution is still prepared; stirring for 30min, heating to 60 ℃, continuously preserving heat for 3h, and cooling to room temperature for standby; coating the obtained polyimide acid solution on a glass substrate, drying for 40min at 120-150 ℃ on a hot plate, transferring into an oven, and respectively carrying out heat treatment for 30min at 150 ℃/250 ℃/300 ℃/350 ℃ for thermal imidization to obtain the polyimide film. The prepared polyimide/glass laminate was immersed in water to be layered, thereby obtaining a polyimide film having a thickness of about 25 μm.
Example 4
The reaction vessel was purged with nitrogen beforehand, after 30min 134.98g of N, N-dimethylacetamide (DMAc, 24h ahead of water with molecular sieves) was added, 10.01g (50 mmol) of 4,4' -diaminodiphenyl ether (ODA) was then charged and dissolved in DMAc and stirred at 25℃until completely dissolved; 19.62g (50 mmol) of the dianhydride compound (I-2) was gradually added thereto, and after stirring until complete dissolution, the reaction was continued for 12 hours with heat preservation, thereby obtaining an 18wt% polyimide acid solution.
Then, a polyimide film 25 μm thick was prepared in the same manner as in example 3.
Example 5
The reaction vessel was purged with nitrogen in advance, after 30min 158.58g of N, N-dimethylacetamide (DMAc, 24h in advance with molecular sieves for water removal) were added, and 5.00g (25 mmol) of 4,4' -diaminodiphenyl ether (ODA) was charged and dissolved in DMAc, stirred at 25℃until completely dissolved; then, 11.10g (25 mmol) of 2,2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride) (6 FDA) was gradually added, and after stirring until completely dissolved, the reaction was carried out for 3 hours with heat preservation; 8.00g (25 mmol) of 2,2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl) (TFMB) was further added, and after stirring for 1 hour, 10.71g (25 mmol) of dianhydride compound (I-1) was added thereto, and the reaction was continued for 8 hours, thereby obtaining an 18wt% polyimide acid solution.
Then, a polyimide film 25 μm thick was prepared in the same manner as in example 3.
Comparative example 1
The reaction vessel was purged with nitrogen beforehand, after 30min, 112.61g of N, N-dimethylacetamide (DMAc, 24h ahead of time with molecular sieves) was added, and 10.01g (50 mmol) of 4,4' -diaminodiphenyl ether (ODA) was charged and dissolved in DMAc, stirred at 25℃until completely dissolved; 14.71g (50 mmol) of 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) was further added gradually, and after stirring until completely dissolved, the reaction was continued for 12 hours with heat preservation, thereby obtaining an 18wt% polyimide acid solution.
Then, a polyimide film 25 μm thick was prepared in the same manner as in example 3.
Comparative example 2
The reaction vessel was purged beforehand with nitrogen, after 30min 155.84g of N, N-dimethylacetamide (DMAc, 24h in advance of water removal by molecular sieves) were added, and 8.00g (25 mmol) of 2,2' -bis (trifluoromethyl) -4,4' -diaminobiphenyl) (TFMB) and 5.00g (25 mmol) of 4,4' -diaminodiphenyl ether (ODA) were each charged and dissolved in DMAc, followed by stirring at 25℃until complete dissolution; 21.21g (50 mmol) of 2,2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride) (6 FDA) was further gradually added thereto, and after stirring until complete dissolution, the reaction was continued for 12 hours with heat preservation, thereby obtaining an 18wt% polyimide acid solution.
Then, a polyimide film 25 μm thick was prepared in the same manner as in example 3.
The polyimide films obtained in examples 3 to 5 and comparative examples 1 to 2 were measured for properties by the methods described below, and the results are summarized in table 1.
(1) Coefficient of linear thermal expansion (CTE)
According to the thermo-mechanical analysis method, the thermal expansion coefficient of the polyimide film was measured using a thermo-mechanical analyzer (TA Instrument company, model Q400). The conditions of measurement are as follows: test piece size: 20mm x 4mm, temperature: heating to 50-250 ℃ at a heating rate of 10 ℃/min; load is as follows: 10g (weight hung from the test piece).
(2) Yellowness index
Measured according to ASTM E313 using an ultraviolet spectrophotometer (Varian Co., model Cary 100).
(3) Transmittance of light
The visible light transmittance of the polyimide film was measured by an ultraviolet spectrophotometer (Varian corporation, model Cary 100).
(4) Glass transition temperature (Tg)
Measured using a scanning thermal differential analyzer (TA Instrument Co., model Q400). Atmosphere: under nitrogen atmosphere; temperature: heating at a rate of 10deg.C/min; sample size: 5 x 5mm thickness.
Table 1 parameter tables for polyimide films prepared in examples and comparative examples
As can be seen from the data in Table 1, the novel dianhydride compounds, such as I-1 and I-2, can effectively improve the light transmittance of the polyimide film when being used for preparing polyimide, and can realize the optical characteristic that the light transmittance of the PI film at 550nm is more than or equal to 85%; the polyimide film has the basis of application in the field of transparent polyimide films, and has good application prospect in the photoelectric fields such as flexible display devices, optical transparent films and the like.
Although the invention has been described with reference to the above embodiments, it should be understood that the invention is not limited thereto, but may be modified or substituted with other modifications and equivalents within the spirit and scope of the invention as defined by the appended claims.
Claims (15)
1. A dianhydride compound having a structure represented by formula I:
wherein R is 1 、R 2 Is- (CH) 2 )-；
R 3 、R 4 Identical or different, independently of one another, H or F.
2. The dianhydride compound of claim 1 having a structure represented by formula I-1 or I-2:
3. the process for producing a dianhydride compound as claimed in claim 1 or 2, characterized in that the synthetic route is as follows:
the method specifically comprises the following steps:
(1) The compound I-a is taken as a raw material, and is subjected to an addition reaction with a fluorine reagent to obtain a compound I-b;
(2) Inserting a metal catalyst of the compound I-b into a carbonyl group to obtain a compound I-c;
(3) Dehydrating the compound I-c to obtain I-d.
4. The method according to claim 3, wherein the molar ratio of the compound I-a to the fluorine reagent is 1.0:1.0 to 10.0;
and/or the fluorine reagent is selected from one of DAST, BAST and sulfur tetrafluoride;
and/or, step (1) is carried out in an organic solvent selected from one of dichloromethane or fluorotrichloromethane;
and/or the reaction temperature of the step (1) is-80-10 ℃.
5. The method according to claim 4, wherein the fluorine reagent is selected from DAST, and the molar ratio of the compound I-a to the fluorine reagent is 1.0: (1.5-5.0);
and/or, step (1) is performed in an organic solvent selected from dichloromethane;
and/or the reaction temperature of the step (1) is 0-10 ℃.
6. The method according to any one of claims 3 to 5, wherein the step (2) is specifically: reacting an alcohol compound and carbon monoxide with a compound I-b in the presence of a palladium catalyst and a copper catalyst;
and/or the feeding mass ratio of the compound I-b to the alcohol compound is 1:1 to 100;
and/or the feeding mole ratio of the compound I-b to the palladium catalyst is 1:0.001-1;
and/or the feeding mole ratio of the compound I-b to the copper catalyst is 1:1.0-50;
the alcohol compound is selected from one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, amyl alcohol, methoxyethanol, ethoxyethanol, ethylene glycol and triethylene glycol; the copper catalyst is selected from one or more than one of bivalent copper oxide, bivalent copper chloride and bivalent copper bromide.
7. The preparation method according to claim 6, wherein the mass ratio of the compound I-b to the alcohol compound is 1:5 to 50 percent;
and/or the feeding mole ratio of the compound I-b to the palladium catalyst is 1:0.01-0.5;
and/or the feeding mole ratio of the compound I-b to the copper catalyst is 1:4.0-20;
the alcohol compound is selected from one or more of methanol, ethanol, n-propanol and isopropanol;
the copper catalyst is selected from divalent copper chloride.
8. The method according to claim 7, wherein the alcohol compound is one or a mixture of more than one selected from the group consisting of methanol, ethanol and isopropanol.
9. The method of any one of claims 3-5, wherein the dewatering of step (3) is: heating and stirring in an organic solvent in the presence of an acid catalyst;
the heating temperature is 50-130 ℃;
the mass ratio of the compound I-c to the organic solvent is 1:0.1-100.
10. The method of claim 9, wherein the heating temperature is 80-120 ℃;
the mass ratio of the compound I-c to the organic solvent is 1:1-10.
11. Use of the dianhydride compound according to claim 1 or 2 for producing a transparent polyimide film.
12. A method for preparing a transparent polyimide film, characterized in that the transparent polyimide film is prepared by taking the dianhydride compound, the aliphatic or aromatic dianhydride compound and the diamine compound as raw materials through polymerization reaction.
13. The method according to claim 12, wherein the diamine compound is selected from one or more of 4,4 '-diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 4' -diaminodiphenyl methane, trans-1, 4-cyclohexanediamine, 2 '-bis (trifluoromethyl) -4,4' -diaminobiphenyl.
14. Use of the dianhydride compound according to claim 1 or 2, the transparent polyimide film produced by the method according to any one of claims 12 or 13 in the photovoltaic field.
15. The use according to claim 14, in flexible display devices and optically transparent films.
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