CN111961061A - Novel dianhydride compound and preparation method and application thereof - Google Patents
Novel 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 R1、R2Independently of one another represent- (CH)2)‑、‑(CH2CH2)‑；R3、R4Identical or different, independently of one another, represent H or F. The novel dianhydride compound provided by the invention has a unique alicyclic structure and a fluorine-containing structure, and the polyimide film prepared by polymerizing the dianhydride compound and diamine realizes good optical characteristics that the light transmittance at 550nm is more than or equal to 85%, so that the defect of the traditional aromatic series is overcomeThe polyimide film has the defect of dark color, can be applied to the field of transparent polyimide films, and further has good prospect in the field of flexible display or photoelectricity. The preparation method provided by the invention is stable and efficient, the 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 high polymer containing an imide ring in the main chain, and is prepared by stepwise polymerizing a compound containing diamine and dianhydride; due to the specific imine ring and aromatic ring structures on the main chain of the PI and the conjugated effect thereof, the PI has the characteristics of excellent thermal stability, mechanical strength, dielectric property, low thermal expansion coefficient and the like, so that the PI 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 facilitates the intramolecular and intermolecular Charge Transfer Complex (CTC), affects the light transmittance of the PI film, and exhibits a brownish yellow color and poor light transmittance, which greatly limits the application of the PI film in the photoelectric field (e.g., optical waveguide materials in the optical communication field, flexible electrode materials in the flexible display field, optically transparent films of display substrates or cover plates, etc.). Meanwhile, with the recent development of the display device of the intelligent electronic device in the direction of being bendable, the development demand of the PI film with high transparency is particularly urgent to meet the requirement of flexible display of the electronic device.
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 sulfone group capable of realizing bending) or a structure (substituent group with large space volume) capable of destroying a plane conjugated structure in a main chain, an aliphatic structure (alicyclic or aliphatic structure), a fluorine-containing structure and the like are introduced to destroy the conjugated effect and symmetry of a molecular structure and reduce the charge transfer effect in molecules or among molecules so as to realize a good transparentization modification effect; it should be noted that the stronger the diamine or dianhydride with the stronger electron donating ability, the darker the color of the polyimide film material formed by polymerization; therefore, the selection of the monomer is particularly important, 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, which can effectively destroy the conjugated structure in the molecular structure of the PI film and weaken the charge transfer capability in the main structure by using the specific alicyclic structure; meanwhile, the introduction of the fluorine-containing group can further destroy the conjugated structure in the PI film molecular structure so as to realize good transparentization modification effect, and the method can be applied to the field of transparent polyimide films.
Disclosure of Invention
The first purpose of the invention is to provide a novel dianhydride compound, which has a structure shown in a formula I:
wherein R is1、R2Independently of one another represent- (CH)2) -or- (CH)2CH2) -; preferably R1、R2represents-CH2-；
R3、R4Identical or different, independently of one another, represent H or F; preferably R3、R4Simultaneously F or simultaneously H.
As the best mode for carrying out the invention, the novel dianhydride compound has a structure shown in a formula I-1 or I-2:
due to the unique alicyclic structure and fluorine-containing structure of the compound, Polyimide (PI) prepared from the compound can realize good optical characteristics, 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 fields of flexible display or photoelectricity.
The second objective of the present invention is to provide a method for preparing the above novel dianhydride compound, wherein the synthetic route is as follows:
the method specifically comprises the following steps:
(1) taking a compound I-a as a raw material, and carrying out addition reaction with a fluorine reagent to obtain a compound I-b;
(2) inserting the metal of the compound I-b into carbonyl group to obtain a compound I-c;
(3) dehydrating the compound I-c to obtain I-d.
Wherein, in the general formula I, the R1、R2Independently of one another represent- (CH)2) -or- (CH)2CH2)-；R3、R4Identical or different, independently of one another, represent H or F; preferably, in formula I, R is1、R2represents-CH2-；R3、R4While being H or R3、R4And is also F.
Preferably, the molar ratio of the compound I-a to the fluorine reagent in step (1) is 1.0: (1.0-10.0);
preferably, the fluorine reagent is selected from one of DAST, BAST, 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 the step (1) is-80-10 ℃, and preferably 0-10 ℃; the reaction pressure is not particularly limited.
Preferably, the step (2) is specifically: reacting an alcohol compound and carbon monoxide with the 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: 1-100, 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 a mixture of more than one of methanol, ethanol and isopropanol.
Preferably, the feeding 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 on carbon or palladium on alumina or the like, preferably palladium chloride or palladium on carbon.
Preferably, the feeding 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 one or a mixture of more than one of monovalent copper oxide, monovalent copper chloride, monovalent copper bromide, divalent copper oxide, divalent copper chloride and divalent copper bromide; one or more of bivalent cupric oxide, bivalent cupric chloride and bivalent cupric bromide is preferred; more preferably divalent copper chloride.
Preferably, the reaction in the step (2) is carried out in an organic solvent, and the mass ratio of the compound I-b to the organic solvent is 1: 1-100, preferably 1: 5-50;
the organic solvent is not particularly limited as long as it does not inhibit the reaction; for example, there may be mentioned 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 (e.g., 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, trifluoroacetic acid, etc.), aromatic hydrocarbons, 1, 4-dichlorobenzene, etc.), nitrated aromatic hydrocarbons (e.g., nitrobenzene, etc.), halogenated hydrocarbons (e.g., dichloromethane, chloroform, carbon tetrachloride, 1, 2-dichloroethane, etc.), carboxylic acid esters (e.g., ethyl acetate, propyl acetate, butyl acetate, etc.), nitriles (e.g., acetonitrile, propionitrile, benzonitrile, etc.), sulfoxides (e.g., dimethyl sulfoxide, etc.), sulfones (e.g., sulfolane, 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 organic solvents mentioned above may be used alone or in combination of one 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 ℃, and 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, sulfuric acid silica gel, zeolites, acidic alumina, and the like, and inorganic acids and organic sulfonic acids are preferably used, and organic sulfonic acids are more preferably used. These acids may be used alone or in combination of two or more.
Preferably, the organic solvent in step (3) is an organic acid solvent, and is selected from one or a mixture of more than one of toluene, xylene, trimethylbenzene, anisole, diphenyl ether, methyltetrahydrofuran, cyclohexane, n-hexane, methylcyclohexane, n-heptane, benzene, and n-octane; one or two of toluene and xylene are preferred;
preferably, the amount of the organic solvent is appropriately adjusted according to the uniformity and the stirring property of the reaction solution; the mass ratio of the compound I-c to the organic solvent is 1: 0.1-100, preferably 1: 1-10.
The details of each reaction are described by examples in the present invention, and those skilled in the art can change the solvent, the amount of charge, the reaction conditions, and the like, and after each reaction is completed, separation/purification of the reaction product and the like can be performed by a common method such as filtration, extraction, distillation, sublimation, recrystallization, column chromatography, and the like.
The starting materials I-a can be synthesized by methods known per se from the open commercial sources or from the literature.
Further, it is to be noted that, in the production method of the present invention, the solvent used in each step and the amount thereof, the separation and purification of the product, the dropping rate of the reactant, and the like, which are not particularly limited in part, are understood and grasped by those skilled in the art. In the present invention, the solvent is used in an amount of 5 to 15 times the amount of the reaction substance, unless otherwise specified, and the specific amount can be suitably adjusted depending on the amount of the reaction substrate and the size of the reaction flask selected; the dropping rate of the reactants is generally controlled in combination with a specific reaction rate. Based on the disclosure of the present invention, those skilled in the art can select any available technical solutions to implement the present invention according to practical situations.
The preparation method can stably and efficiently obtain the dianhydride compound.
The third object of the present invention is the use of any of the above described novel dianhydride compounds or any of the above described methods 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 a method for preparing a transparent polyimide film, which is prepared by polymerizing the novel dianhydride compound, the aliphatic or aromatic dianhydride compound, and the diamine compound.
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' -diaminodiphenylmethane (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 less than 85% under the wavelength of 550 nm.
The 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 novel dianhydride compounds, and the use of the transparent polyimide film produced by any one of the above methods in the optical field; preferably in flexible display devices and optically transparent films.
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 specific alicyclic structure of the dianhydride compound can effectively destroy the conjugated structure in the molecular structure of the PI film and weaken the charge transfer capability in the main structure; meanwhile, the conjugated structure in the PI film molecular structure can be further destroyed by introducing the fluorine-containing group, so that a good transparentization modification effect is realized, and the transparent polyimide film has the optical characteristic that the light transmittance is more than or equal to 85% under 550 nm; however, the application of the transparent polyimide film is not particularly limited, and the transparent polyimide film can be applied to the photoelectric field such as a flexible display device and an optical transparent film.
(2) The preparation method can stably and efficiently obtain the dianhydride compound, and has the advantages of easily obtained raw materials, simple preparation process and convenience for popularization.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The starting materials are commercially available from the open literature unless otherwise specified.
Hereinafter, the novel dianhydride compound of the present invention, the preparation method and the application thereof will be described in detail by examples. However, the present invention is not limited to the following examples.
Example 1
A novel dianhydride compound has 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 Compounds I-e
Adding I-a (836.244mg,3.48mmol) into a 250mL fluorinated three-necked bottle, dissolving in dichloromethane (150mL), cooling to-30 ℃ under nitrogen atmosphere, dropwise adding DAST (2.42g,13.92mmol), controlling the temperature from-30 ℃ to-35 ℃, naturally raising the temperature to room temperature, and stirring overnight. TLC monitored the reaction completion, the reaction solution was poured into a mixed solution of 50ml dichloromethane and 50ml saturated solution of ammonium dicarbonate and stirred for 15min, the layers were separated, the aqueous layer was extracted with dichloromethane (2X100mL), the organic layers were combined, washed once with 50ml saturated brine, dried over anhydrous sodium sulfate, filtered, and the solvent was removed under reduced pressure to give I-e as a yellow oil (847.58mg,85.76 percent).1H NMR(400MHz,CDCl36.06-6.12(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
Into a reaction vessel having a capacity of 1L, 364g of methanol, 62g of chloroform, 136g (1011mmol) of copper (II) chloride and 6g (33.7mmol) of palladium chloride were charged and stirred. The atmospheric gas in the system was replaced with carbon monoxide, and then the mixture was dissolved dropwise over 3 hours
A solution of (1) Compound I-e 19.12g (67.3mmol) in 178g of chloroform was reacted at 20-25 ℃ for 4 hours. Then, the atmosphere in the system was replaced with argon from carbon monoxide, and then the solvent was distilled off from the reaction mixture, and 621g of chloroform was added. The same operation was repeated twice. Insoluble matter was then removed from the resulting suspension of tea green color by filtration. The resulting solution was washed 3 times with 324g of a saturated aqueous sodium bicarbonate solution and then 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. Subsequently, purification was performed by silica gel chromatography (developing solvent; hexane: ethyl acetate: 10: 1 (volume ratio)) to obtain 26.62g (purity 99.1 pa%, yield 76% based on HPLC analysis) of 1,4,5, 8-dicanthracene-9, 10-tetrafluoro-2, 3,6, 7-tetracarboxymethyl ester (I-f) as a white solid.1H NMR(400MHz,CDCl3)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
6.19g (11.9mmol) of I-f, 26.3g of formic acid and 47mg (0.24mmol) of p-toluenesulfonic acid monohydrate were charged into a reaction vessel having a capacity of 100mL, 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 to distill off formic acid 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 a milky white solid. Then, recrystallization was performed using acetic anhydride and further using N, N' -dimethylacetamide to obtain 4.02g (purity 98.3% and yield 79% based on 1H-NMR analysis) of 1,4,5, 8-dimethanthracene-9, 10-tetrafluoro-2, 3,6, 7-dicarboxylic anhydride (I-1) as a white solid.
1H NMR(400MHz,CDCl3)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:
the synthetic route for the preparation of compound I-2 is shown below:
(1) synthesis of Compounds I-g
A reaction vessel having a capacity of 5L was charged with I-a100.5g (31.7mmol), 1.5L of methanol, and 1.5L of tetrahydrofuran. Then, 30.0g (60.3mmol) of sodium borohydride was added thereto at 5 ℃ for 1 hour, followed by reaction at 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, and 1.5L of ion-exchanged water was added to the obtained white solid, followed by stirring at 40 ℃ for 1 hour. Thereafter, the white solid was filtered, washed twice with 200mL of ion-exchanged water, washed twice with 100mL of ethyl acetate, and dried under vacuum to obtain 84.2g (purity 100% and yield 82% based on 1H-NMR analysis) of 1,4,4a,5,8,8a,9,9a,10,10 a-decahydro-1, 4: 5, 8-dimethanthracene-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 Compounds I-h
Adding I-g (850.26mg,3.48mmol) into a 250mL fluorinated three-necked bottle, dissolving in dichloromethane (150mL), cooling to-30 ℃ under nitrogen atmosphere, dropwise adding DAST (1.21g,7mmol), controlling the temperature from-30 ℃ to-35 ℃, naturally raising the temperature to room temperature, and stirring overnight. TLC monitored reaction completion, reaction solution poured into dichloromethane 50mL and saturated solution of ammonium bicarbonate 50mL composed of mixed solution stirring for 15min, liquid separation, aqueous layer extraction again dichloromethane (2X100mL), combined organic layer, 50mL saturated saline washing once, anhydrous sodium sulfate drying, filtering, decompression to remove solvent to obtain yellow oil (858.15mg,90percent) I-h.1HNMR (400MHz, 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 Compounds I-j
Into a reaction vessel having a capacity of 1L, 364g of methanol, 62g of chloroform, 136g (1011mmol) of copper (II) chloride and 6g (33.7mmol) of palladium chloride were charged and stirred. After replacing the atmosphere in the system with carbon monoxide, a solution of I-h16.711g (67.3mmol) dissolved in 178g of chloroform was added dropwise over 3 hours, and the reaction was carried out at 20 to 25 ℃ for 4 hours. Then, the atmosphere in the system was replaced with argon from carbon monoxide, and then the solvent was distilled off from the reaction mixture, and 621g of chloroform was added. The same operation was repeated twice. Insoluble matter was then removed from the resulting suspension of tea green color by filtration. The resulting solution was washed 3 times with 324g of a saturated aqueous sodium bicarbonate solution and then 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. Subsequently, purification was performed by silica gel chromatography (developing solvent; hexane: ethyl acetate: 10: 1 (volume ratio)) to obtain 24.45g (purity 99.1 pa%, yield 75% based on HPLC analysis) of 1,4,5, 8-dicanthracene-9, 10-difluoro-2, 3,6, 7-tetracarboxymethyl ester (I-j) as a white solid. 1H NMR (400MHz, CDCl3)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
A reaction vessel having a capacity of 100mL was charged with 5.76g (11.9mmol) of I-j, 26.3g of formic acid, and 47mg (0.24mmol) 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 to distill off formic acid 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 a milky white solid. Then, the resulting mixture was recrystallized from acetic anhydride and N, N' -dimethylacetamide to obtain 3.59g (98.3% purity and 77% yield based on 1H-NMR analysis) of 1,4,5, 8-dimethanthracene-9, 10-tetrafluoro-2, 3,6, 7-dicarboxylic anhydride (I-2) 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 evacuated in advance using nitrogen, after 30min 143.18g of N, N-dimethylacetamide (DMAc) was added, and 10.01g (50mmol) of 4, 4' -diaminodiphenyl ether (ODA) was charged and dissolved in DMAc, and stirred at 25 ℃ until completely dissolved, after 24h of removal of water by molecular sieves; then, 21.42g (50mmol) of the dianhydride compound (I-1) was gradually added thereto, and after stirring to be completely dissolved, the reaction was carried out for 12 hours while maintaining the temperature, thereby obtaining an 18 wt% polyimide acid solution.
After the reaction is finished, respectively adding acetic anhydride and isoquinoline with equimolar carboxylic acid groups, supplementing the DMAc with water and still preparing a solution with 18 wt%; stirring for 30min, heating to 60 deg.C, keeping the temperature for 3h, and cooling to room temperature; and coating the obtained polyimide acid solution on a glass substrate, drying the glass substrate on a hot plate at 120-150 ℃ for 40min, transferring the glass substrate into an oven, and performing heat treatment at 150 ℃/250 ℃/300 ℃/350 ℃ for 30min respectively to perform thermal imidization, thereby preparing the polyimide film. The obtained polyimide/glass laminate was immersed in water to conduct delamination, thereby obtaining a polyimide film having a thickness of about 25 μm.
Example 4
The reaction vessel was evacuated in advance using nitrogen, after 30min 134.98g of N, N-dimethylacetamide (DMAc) was added, and 10.01g (50mmol) of 4, 4' -diaminodiphenyl ether (ODA) was charged and dissolved in DMAc, and stirred at 25 ℃ until completely dissolved, after 24h of removal of water by molecular sieves; then, 19.62g (50mmol) of the dianhydride compound (I-2) was gradually added thereto, and after stirring to be completely dissolved, the reaction was carried out for 12 hours while maintaining the temperature, thereby obtaining an 18 wt% polyimide acid solution.
Then, a polyimide film having a thickness of 25 μm was prepared in the same manner as in example 3.
Example 5
The reaction vessel was evacuated in advance using nitrogen, after 30min 158.58g of N, N-dimethylacetamide (DMAc) was added, and 5.00g (25mmol) of 4, 4' -diaminodiphenyl ether (ODA) was charged and dissolved in DMAc, and stirred at 25 ℃ until completely dissolved, after 24h of removal of water by molecular sieves; then, 11.10g (25mmol) of 2, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride) (6FDA) was gradually added thereto, stirred until completely dissolved, and then reacted for 3 hours while maintaining the temperature; 8.00g (25mmol) of 2,2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl) (TFMB) was further added, and after stirring and reacting for 1 hour, 10.71g (25mmol) of the dianhydride compound (I-1) was added, and heat preservation was continued for 8 hours, thereby obtaining a 18 wt% polyimide acid solution.
Then, a polyimide film having a thickness of 25 μm was prepared in the same manner as in example 3.
Comparative example 1
The reaction vessel was evacuated in advance using nitrogen, after 30min 112.61g of N, N-dimethylacetamide (DMAc) was added, and 10.01g (50mmol) of 4, 4' -diaminodiphenyl ether (ODA) was charged and dissolved in DMAc, and stirred at 25 ℃ until completely dissolved, after 24h of removal of water by molecular sieves; then, 14.71g (50mmol) of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride (BPDA) was gradually added thereto, and after stirring to be completely dissolved, the mixture was reacted for 12 hours while maintaining the temperature, thereby obtaining an 18 wt% polyimide acid solution.
Then, a polyimide film having a thickness of 25 μm was prepared in the same manner as in example 3.
Comparative example 2
The reaction vessel was evacuated beforehand using nitrogen, after 30min 155.84g of N, N-dimethylacetamide (DMAc) were added (24 h earlier with molecular sieve for water removal), 8.00g (25mmol) of 2,2 ' -bis (trifluoromethyl) -4,4 ' -diaminobiphenyl) (TFMB) and 5.00g (25mmol) of 4,4 ' -diaminodiphenyl ether (ODA) were each charged and dissolved in DMAc and stirred at 25 ℃ until complete dissolution; then, 21.21g (50mmol) of 2, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride) (6FDA) was gradually added thereto, and after stirring to be completely dissolved, the mixture was reacted for 12 hours while maintaining the temperature, thereby obtaining an 18 wt% polyimide acid solution.
Then, a polyimide film having a thickness of 25 μm was prepared in the same manner as in example 3.
The properties of the polyimide films obtained in examples 3 to 5 and comparative examples 1 to 2 were measured by the methods described below, and the results are shown in Table 1.
(1) Coefficient of linear thermal expansion (CTE)
The thermal expansion coefficient of the polyimide film was measured according to the thermo-mechanical analysis method using a thermo-mechanical analyzer (TA Instrument, model Q400). The conditions for the measurement were as follows: test piece size: 20mm × 4mm, temperature: heating at a heating rate of 10 ℃/min to 50-250 ℃; loading: 10g (weight suspended from the test piece).
(2) Yellowness index
Measured according to the ASTM E313 standard using an ultraviolet spectrophotometer (Varian Corp., model Cary 100).
(3) Light transmittance
The visible light transmittance of the polyimide film was measured with an ultraviolet spectrophotometer (Varian corporation, model Cary 100).
(4) Glass transition temperature (Tg)
Measured with a scanning thermal differential analyser (TA instruments, model Q400). Atmosphere: under nitrogen atmosphere; temperature: the heating rate is 10 ℃/min; sample size: 5 x 5mm thickness.
TABLE 1 parameter Table of polyimide films produced in examples and comparative examples
As can be seen from the data in Table 1, when the novel dianhydride compounds, such as I-1 and I-2, are used for preparing polyimide, the light transmittance of the polyimide film can be effectively improved, and the optical characteristic that the light transmittance of the PI film at 550nm is more than or equal to 85 percent can be realized; the preparation method has the advantages of having a foundation for application in the field of transparent polyimide films and having good application prospects in the photoelectric fields of flexible display devices, optical transparent films and the like.
Although the present invention has been described with reference to the above embodiments, it should be understood that the scope of the present invention is defined by the appended claims.
Claims (10)
1. A novel dianhydride compound, characterized by having the structure shown in formula I:
wherein R is1、R2Independently of one another represent- (CH)2) -or- (CH)2CH2) -; preferably R1、R2All represent-CH2-；
R3、R4Identical or different, independently of one another, represent H or F; preferably R3、R4Simultaneously F or simultaneously H.
2. The novel dianhydride compound according to claim 1, having the structure according to formula I-1 or I-2:
3. a process for the preparation of a novel dianhydride compound according to any of the claims 1 or 2, characterized in that the synthesis scheme is as follows:
the method specifically comprises the following steps:
(1) taking a compound I-a as a raw material, and carrying out addition reaction with a fluorine reagent to obtain a compound I-b;
(2) inserting the metal of the compound I-b into 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; preferably DAST, and more preferably the molar ratio of the compound I-a to the fluorine reagent when the fluorine reagent is selected from DAST is 1.0: (1.5-5.0);
and/or, step (1) is carried out in an organic solvent, wherein the organic solvent is selected from one of dichloromethane or monofluorotrichloromethane, preferably dichloromethane;
and/or the reaction temperature in the step (1) is-80-10 ℃, and preferably 0-10 ℃.
5. The method according to any one of claims 3 or 4, wherein the step (2) is specifically: reacting an alcohol compound and carbon monoxide with the 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: 1-100, preferably 1: 5-50;
and/or the feeding molar ratio of the compound I-b to the palladium catalyst is 1: 0.001-1, preferably 1: 0.01-0.5;
and/or the feeding molar ratio of the compound I-b to the copper catalyst is 1: 1.0-50, preferably 1: 4.0-20;
and/or: 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;
and/or the copper catalyst is selected from one or a mixture of more than one of monovalent copper oxide, monovalent copper chloride, monovalent copper bromide, divalent copper oxide, divalent copper chloride and divalent copper bromide; one or more of bivalent cupric oxide, bivalent cupric chloride and bivalent cupric bromide is preferred; more preferably divalent copper chloride.
6. The method according to any one of claims 3 to 5, wherein the dehydration in the step (3) is: heating and stirring in an organic solvent in the presence of an acid catalyst;
the heating temperature is 50-130 ℃, and preferably 80-120 ℃;
the mass ratio of the compound I-c to the organic solvent is 1: 0.1-100, preferably 1: 1-10.
7. Use of a novel dianhydride compound according to claim 1 or 2 or of the process according to any of claims 3 to 6 for the preparation of transparent polyimide films.
8. A method for producing a transparent polyimide film, characterized in that it is produced by polymerizing the novel dianhydride compound according to claim 1 or 2, an aliphatic or aromatic dianhydride compound, and a diamine compound as raw materials.
9. The method according to claim 8, wherein the diamine compound is one or more selected from the group consisting of 4,4 '-diaminodiphenyl ether, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 4' -diaminodiphenylmethane, trans-1, 4-cyclohexanediamine, and 2,2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl.
10. Use of the novel dianhydride compound according to any of claims 1 or 2, the process according to any of claims 3 to 6, or the transparent polyimide film prepared by the process according to any of claims 8 or 9 in the field of optoelectronics;
preferably in flexible display devices and optically transparent films.
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| CN114057762B (en) * | 2021-11-30 | 2023-07-25 | 华中科技大学 | Rigid alicyclic ketone anhydride compound and preparation method and application thereof |
| CN116970276A (en) * | 2023-09-25 | 2023-10-31 | 北京八亿时空液晶科技股份有限公司 | Polyimide resin, photosensitive resin composition containing polyimide resin and photosensitive cured film |
| CN116970276B (en) * | 2023-09-25 | 2024-01-09 | 上海八亿时空先进材料有限公司 | Polyimide resin, photosensitive resin composition containing polyimide resin and photosensitive cured film |
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