CN110452251B - Dianhydride compound and preparation method and application thereof - Google Patents

Dianhydride compound and preparation method and application thereof Download PDF

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CN110452251B
CN110452251B CN201910822805.7A CN201910822805A CN110452251B CN 110452251 B CN110452251 B CN 110452251B CN 201910822805 A CN201910822805 A CN 201910822805A CN 110452251 B CN110452251 B CN 110452251B
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dianhydride
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邓师勇
姜坤
张海威
戴雄
黄明义
游维涛
高立龙
程友文
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Shanghai 800 million spacetime Advanced Material Co.,Ltd.
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Beijing Bayi Space LCD Technology Co Ltd
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Abstract

The invention relates to a dianhydride compound and a preparation method and application thereof, wherein the dianhydride compound effectively destroys a conjugated structure in a PI film molecular structure by a specific full alicyclic or semi-alicyclic structure, and simultaneously weakens the charge transfer capacity in a main structure so as to realize a good transparentization modification effect. The light transmittance of the transparent polyimide film to light waves with the wavelength of 550mm is more than or equal to 85 percent. The application of the transparent polyimide film is not particularly limited, and the transparent polyimide film can be applied to the photoelectric fields of flexible transparent display substrates, optical transparent films, optical communication materials, solar cell substrates and the like. 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.

Description

Dianhydride compound and preparation method and application thereof
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a 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 the PI is widely applied to the fields of aerospace, microelectronics, mechanical engineering, petrochemical industry, liquid crystal display and the like.
With the development of the photoelectric field, on the basis of keeping the original good thermal property and mechanical property, higher requirements are put forward on the optical property of polyimide, and the unique aromatic ring conjugated structure in the traditional polyimide structure leads to the formation of intramolecular and intermolecular Charge Transfer Complexes (CTC), thereby greatly influencing the light transmission of the PI film, presenting brownish yellow and poor light transmission and limiting the development of the PI film in the photoelectric field. 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; the improvement of the transparency of the PI film is often achieved by selecting one or more of the above-mentioned means.
The present invention has been made in view of the above circumstances.
Disclosure of Invention
In order to solve the above problems in the prior art, a first object of the present invention is to provide a dianhydride compound, wherein the structural general formula of the dianhydride compound is shown as formula (I):
Figure BDA0002188069160000021
wherein, X1、X2And X3Identical or different, R1、R2And R3The same or different, n is an integer of 0 to 12;
saidX1Is CmR1S atom, N atom or O atom, m ═ 1 to 12 integer;
said X2Is CmR1S atom, N atom or O atom, m ═ 1 to 12 integer;
said X3Is CmR1S atom, N atom or O atom, m ═ 1 to 12 integer;
said R1、R2And R3Independently represents any one of hydrogen, deuterium, halogen, alkyl or alkoxy containing 1 to 12 carbon atoms, alkanyl or alkoxyalkenyl containing 2 to 12 carbon atoms, alkynyl containing 2 to 12 carbon atoms, cycloalkyl or cycloalkenyl containing 3 to 12 carbon atoms, aryl or aryloxy containing 6 to 12 carbon atoms, alkylthio oxy containing 1 to 12 carbon atoms, arylthio oxy containing 6 to 12 carbon atoms, alkylamino containing 1 to 12 carbon atoms, arylamino containing 6 to 12 carbon atoms, aryl containing 6 to 12 carbon atoms, heteroaryl containing 2 to 12 carbon atoms and having a heteroatom O, N or S, alkylsilyl containing 1 to 12 carbon atoms, and arylsilyl containing 6 to 12 carbon atoms; wherein H in said alkyl, alkoxy, alkanyl, alkoxyalkenyl, alkynyl, cycloalkyl, cycloalkenyl may be substituted by F, one or more non-adjacent-CH2-may each be independently substituted by-O-, -N-, -S-, and the O and S atoms are not directly attached to each other;
preferably, R1、R2And R3Identical or different, R1、R2And R3Independently represents any one of hydrogen, deuterium, F, alkyl or alkoxy with 1-6 carbon atoms, alkyl alkenyl or alkoxy alkenyl with 2-6 carbon atoms, alkynyl with 2-6 carbon atoms, cycloalkyl or cycloalkenyl with 3-12 carbon atoms and aryl or aryloxy with 6-12 carbon atoms; wherein H in said alkyl, alkoxy, alkanyl, alkoxyalkenyl, alkynyl, cycloalkyl, cycloalkenyl may be substituted by F, one or more non-adjacent-CH2-may each independently be substituted by-O-, but with the proviso that the O atoms are not directly attached to each other;
more preferably, m is an integer of 1 to 6, and n is 0 or 1.
Further, the dianhydride compound is any one of the following structures:
Figure BDA0002188069160000031
Figure BDA0002188069160000041
the second object of the invention provides a preparation method of the dianhydride compound, and the synthesis route of the dianhydride is as follows:
Figure BDA0002188069160000042
the preparation method comprises the following steps:
(1) taking a compound A-1 as a raw material, and obtaining a diamine compound A-2 through a Mannich reaction;
(2) deaminating the compound A-2 to obtain a diene compound A-3;
(3) carrying out a retaining ring reaction on the compound A-3 and cyclopentadiene to obtain a bicyclohexene compound A-4;
(4) performing carbonyl insertion and oxidation reaction on the compound A-4 under the action of a catalyst to obtain a compound A-5;
(5) and (3) carrying out hydrolysis and dehydration reaction on the compound A-5 to obtain a compound A-6, namely the dianhydride compound.
Further, in the step (1), the compound A-1 is reacted with an amine salt of a secondary amine and a formaldehyde derivative to obtain a compound A-2, preferably, the amine salt of the secondary amine is a hydrochloride, a sulfate or an acetate of the secondary amine, the molar ratio of the compound A-2 to the amine salt of the secondary amine is 1:2-10, the molar ratio of the compound A-1 to the formaldehyde derivative is 1:2-10, and more preferably, the molar ratio of the compound A-1 to the formaldehyde derivative is 1: 1.5-5.0;
further, the reaction conditions in the step (1) are as follows: heating and reacting for 0.5-10 hours under inert atmosphere, wherein the heating temperature is 30-180 ℃, preferably 85-95 ℃;
the reaction is carried out in an organic solvent, wherein the organic solvent is one of tetrahydrofuran, methanol, ethanol, isopropanol, butanol, acetonitrile, methyl cellosolve, ethyl cellosolve, ethylene glycol, propylene glycol monomethyl ether, propylene glycol, dichloromethane and fluorotrichloromethane, and is preferably isopropanol.
Further, the molar ratio of the compound A-3 to the cyclopentadiene in the step (3) is 1:2-10, preferably 1:2.5, the reaction is carried out under an inert atmosphere, and the reaction is carried out in a water bath at the temperature of 120-125 ℃ for 0.5-10 hours, preferably in a water bath at the temperature of 85-95 ℃.
Further, the step (4) of reacting the alcohol compound, carbon monoxide and the compound a-4 in the presence of a palladium catalyst and a copper catalyst;
the mass ratio of the compound A-4 to the alcohol compound is 1:1-100, preferably 1: 5-50;
the alcohol compound is selected from one or a mixture of 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.
The molar ratio of the compound A-4 to the palladium catalyst is 1:0.001-1, preferably 1: 0.01-0.5;
the palladium catalyst to be used is not particularly limited as long as it contains palladium. For example, 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.
The molar ratio of the compound A-4 to the copper catalyst is 1:1-50, preferably 1: 4-20.
The copper catalyst is selected from one or a mixture of more of monovalent copper oxide, monovalent copper chloride, monovalent copper bromide, divalent copper oxide, divalent copper chloride and divalent copper bromide; one or a mixture of more of bivalent copper oxide, bivalent copper chloride and bivalent copper bromide is preferred; more preferably divalent copper chloride.
Further, in the step (5), the dehydration reaction is carried out by heating in an organic solvent under the action of an acid catalyst, wherein the heating temperature is 50-130 ℃, the preferred heating temperature is 80-120 ℃, and the mass ratio of the compound A-5 to the organic solvent is 1:0.1-100, and the preferred mass ratio is 1: 1-10.
The organic solvent in the step (5) is the same as the organic solvent in the step (1). The acid is one or more of inorganic acid, organic sulfonic acid, halogenated carboxylic acid, ion exchange resin, sulfuric acid silica gel, zeolite and acidic alumina, the inorganic acid is one or more of hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, chlorosulfuric acid and nitric acid, the organic sulfonic acid is one or more of methanesulfonic acid, benzenesulfonic acid and p-toluenesulfonic acid, preferably, the acid is inorganic acid or organic sulfonic acid, and more preferably, the acid is organic sulfonic acid.
The present invention will be described in detail with reference to examples. The solvent, the amount of charge, the reaction conditions, etc. can be varied by those skilled in the art. After the completion of each reaction, the reaction product can be isolated and purified by a common method such as filtration, extraction, distillation, sublimation, recrystallization, column chromatography, or the like.
The starting material A-1 in the present invention can be synthesized by publicly available commercial methods or methods known per se in 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. According to the invention, except for specific description, the volume dosage of the solvent is generally 5-15 times of the mass of the reactant, and the specific dosage can be properly adjusted according to the dosage of the reaction substrate and the size of the selected reaction bottle; 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 purpose of the invention is to provide an application of the dianhydride compound or the dianhydride compound prepared by the preparation method in the field of transparent polyimide films.
Further, the transparent polyimide film is prepared from the dianhydride compound and the aliphatic or aromatic diamine compound.
The diamine compound described in the present invention 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), and 2,2 '-bis (trifluoromethyl) -4, 4' -diaminobiphenyl) (TFMB).
Compared with the prior art, the invention has the beneficial effects that:
(1) the dianhydride compound provided by the invention can be used in the field of transparent polyimide films, and the specific full alicyclic or semi-alicyclic structure of the dianhydride compound can effectively destroy the conjugated structure in the PI film molecular structure, and simultaneously weaken the charge transfer capability in the main structure, so as to realize good transparentization modification effect. The light transmittance of the transparent polyimide film to light waves with the wavelength of 550mm is more than or equal to 85 percent. The application of the transparent polyimide film is not particularly limited, and the transparent polyimide film can be applied to the photoelectric fields of flexible transparent display substrates, optical transparent films, optical communication materials, solar cell substrates and the like.
(2) The preparation method can stably and efficiently obtain the dianhydride compound, the raw materials are easy to obtain, the preparation process is simple, the yield of the target compound is high, and the popularization of the dianhydride compound is facilitated.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the examples given herein without any inventive step, are within the scope of the present invention.
The hydrochloride formed during the synthesis of compound A-2 of the present invention is unstable in the heated state and is easily deaminated to form diene, resulting in compound A-3, and therefore the synthesis of compounds A-2 and A-3 is described as a one-step reaction in the examples below.
Example 1
The dianhydride compound A1-6 of this example has the following structural formula:
Figure BDA0002188069160000081
the synthesis route of the dianhydride compound of this example is as follows:
Figure BDA0002188069160000082
the preparation method comprises the following steps:
(1) synthesis of Compound A1-2 and Compound A1-3
Adding 24.0g of 50% aqueous dimethylamine solution into a 250ml three-neck flask, dropwise adding 33.2g of 30% aqueous hydrochloric acid solution under ice-cooling conditions, stirring and reacting for 1 hour to obtain dimethylamine hydrochloride, slowly adding 9.9g of paraformaldehyde and 15.0g of the compound A1-1 into the three-neck flask, heating to 85-90 ℃ under the protection of nitrogen, reacting for 3 hours to obtain a reaction solution, using the reaction solution for synthesizing the compound A1-4, carrying out conventional aftertreatment, and carrying out HPLC analysis to obtain the compound A1-1 with the conversion rate of 99.3%.
(2) Synthesis of Compound A1-4
The temperature of the reaction liquid is reduced to 50 ℃, 80ml of methyl cellosolve, 3.8g of dimethylamine aqueous solution with the mass fraction of 50 percent, 25.4g of cyclopentadiene and nitrogen protection are slowly added, the temperature is increased to 115 ℃ and 120 ℃, the reaction is carried out for 1.5h at the temperature, and the mixed liquid is cooled to the room temperature (25 ℃). After conventional post-treatment, the product was purified by chromatography, eluted with n-hexane, and distilled by short path to give 22.8g of a colorless oily liquid (A1-4), 98% by GC, and 71% yield.
(3) Synthesis of Compound A1-5
Adding 50ml of methanol, 10ml of chloroform, 0.5g of copper (II) chloride and 0.8g of palladium chloride into a reaction flask, stirring, replacing carbon monoxide by three times, dropwise adding a mixture of 20g of compound A1-4 and 50ml of chloroform at the temperature of 20-25 ℃, finishing dropping within about 3 hours, continuing the reaction for 4 hours at the temperature, replacing nitrogen by three times, evaporating the solvent, performing conventional aftertreatment, and purifying by silica gel chromatography (hexane: ethyl acetate is 10: 1) to obtain 26.3g of a white solid compound A1-5, LC: 99.4% and yield 73%.
(4) Synthesis of Compound A1-6
Adding 1-525.0 g of A, 20.5g of formic acid and 25.0mg of p-toluenesulfonic acid monohydrate into a reaction bottle, reacting at 98 ℃ for 20 hours, distilling to remove formic acid after the reaction is finished, filtering, leaching a filter cake with toluene, recrystallizing the obtained crude product with acetic anhydride, and recrystallizing with N 'N' -dimethylacetamide to obtain white solid A1-616.9 g, LC: 99.5% and yield 82%.
Example 2
The dianhydride compound A2-6 of this example has the following structural formula:
Figure BDA0002188069160000091
the synthesis route of the dianhydride compound of this example is as follows:
Figure BDA0002188069160000101
the preparation method comprises the following steps:
(1) synthesis of Compound A2-2 and Compound A2-3
A hydrochloric acid salt of dimethylamine was prepared by adding 48.0g of a 50% aqueous dimethylamine solution in a 250ml three-necked flask, dropwise adding 66.5g of a 30% aqueous hydrochloric acid solution under ice-cooling, and reacting the mixture under stirring for 1 hour. And (2) slowly adding 19.8g of paraformaldehyde and 35.8g of the compound A2-1 into the three-neck flask, heating to 80-90 ℃ under the protection of nitrogen, reacting for 3 hours, carrying out conventional post-treatment, carrying out HPLC analysis to obtain a reaction solution with the compound A2-1 conversion rate of 99.1%, and directly feeding the reaction solution into the next step.
(2) Synthesis of Compound A2-4
The temperature of the reaction liquid is reduced to 50 ℃, 100ml of methyl cellosolve, 7.2g of dimethylamine aqueous solution with the mass fraction of 50 percent, 50.8g of cyclopentadiene and nitrogen protection are slowly added, the temperature is increased to 110-120 ℃, the reaction is carried out for 2.0h at the temperature, and the mixed liquid is cooled to the room temperature (25 ℃). After conventional post-treatment, the product was purified by chromatography, eluted with n-hexane, and distilled by short path to obtain 51.2g of a colorless oily liquid (A2-4), GC: 96%, yield: 75.5%.
(3) Synthesis of Compound A2-5
Adding 200ml of methanol, 20ml of chloroform, 0.6g of copper (II) chloride and 0.7g of palladium chloride into a reaction flask, stirring, replacing carbon monoxide by three times, dropwise adding a mixture of 50.5g of compound A2-4 and 100ml of chloroform at the temperature of 20-25 ℃, completing dropwise addition within about 3 hours, controlling the temperature to continue the reaction for 4 hours, replacing nitrogen by three times, evaporating the solvent, carrying out conventional aftertreatment, and purifying by silica gel chromatography (hexane: ethyl acetate: 10: 1) to obtain 2-563.8 g of a white solid compound A, LC: 99.6%, yield: 71.6 percent.
(4) Synthesis of Compound A2-6
Adding 2-563.5 g of compound A, 240ml of formic acid and 32mg of p-toluenesulfonic acid monohydrate into a reaction bottle, reacting at 100 ℃ for 22 hours, distilling to remove formic acid after the reaction is finished, filtering, leaching a filter cake with toluene, recrystallizing the obtained crude product with acetic anhydride, and recrystallizing with N 'N' -dimethylacetamide to obtain 2-641.8 g of white solid compound A, LC: 99.4%, yield: 79.4 percent. GC-MS (m/z); 452.50(M +), elemental analysis: 69.01 for C, 6.24 for H and 24.75 for O.
Example 3
The dianhydride compound A3-6 of this example has the following structural formula:
Figure BDA0002188069160000111
the dianhydride prepared in this example was prepared in the same manner as in example 1, with the experimental parameters and conditions being adjusted conventionally, and the dianhydride compound prepared in this example was analyzed by GC-MS (m/z); 438.47(M +), elemental analysis: 68.48, 5.98 percent of H and 25.52 percent of O.
Example 4
The dianhydride compound A4-6 of this example has the following structural formula:
Figure BDA0002188069160000112
the dianhydride prepared in this example was prepared in the same manner as in example 1, with the experimental parameters and conditions being adjusted conventionally, and the dianhydride compound prepared in this example was analyzed by GC-MS (m/z); 424.44(M +), elemental analysis: 67.91 for C, 5.72 for H and 26.39 for O.
The following is the application of the dianhydride compound prepared by the invention in preparing the polyimide film, and the specific preparation method of the polyimide film is as follows:
example 5
The reaction vessel was evacuated in advance using nitrogen, after 30min 127.74g N, N-dimethylacetamide (DMAc) was added (24 h earlier with molecular sieve for water removal), 10.01g (50mmol) of 4, 4' -diaminodiphenyl ether (ODA) was charged and dissolved in DMAc and stirred at 25 ℃ until completely dissolved; then, 21.92g (50mmol) of a dianhydride compound (dianhydride compound A1-6 prepared in example 1) was gradually added thereto, and after stirring to be completely dissolved, the reaction was carried out for 72 hours while maintaining the temperature, thereby obtaining a 20 wt% polyimide acid solution.
After the reaction is finished, adding acetic anhydride and isoquinoline with the same mole of carboxylic acid groups respectively, supplementing the dehydrated DMAc, and adjusting to be 15-18 wt% solution; the obtained polyimide acid solution was coated on a glass substrate, pre-dried and transferred to a needle plate, and then transferred to an oven, and heat-treated at 150 ℃/250 ℃/300 ℃/350 ℃ for 30min, respectively, to perform thermal imidization, thereby obtaining a polyimide film having a thickness of about 25 μm.
Example 6
The reaction vessel was evacuated in advance using nitrogen, after 30min 130.55g N, N-dimethylacetamide (DMAc) was added (24 h earlier with molecular sieve for water removal), 10.01g (50mmol) of 4, 4' -diaminodiphenyl ether (ODA) was charged and dissolved in DMAc and stirred at 25 ℃ until completely dissolved; then, 22.62g (50mmol) of dianhydride compound (dianhydride compound A2-6 prepared in example 2) was gradually added thereto, and after stirring to be completely dissolved, the reaction was carried out for 72 hours while maintaining the temperature, thereby obtaining a 20 wt% polyimide acid solution.
Then, a polyimide film having a thickness of 25 μm was prepared in the same manner as in example 5.
Example 7
The reaction vessel was evacuated in advance using nitrogen, after 30min 127.74g N, N-dimethylacetamide (DMAc) was added (24 h earlier with molecular sieve for water removal), 10.01g (50mmol) of 4, 4' -diaminodiphenyl ether (ODA) was charged and dissolved in DMAc and stirred at 25 ℃ until completely dissolved; then, 21.92g (50mmol) of a dianhydride compound (dianhydride compound A3-6 prepared in example 3) was gradually added thereto, and after stirring to be completely dissolved, the reaction was carried out for 72 hours while maintaining the temperature, thereby obtaining a 20 wt% polyimide acid solution.
Then, a polyimide film having a thickness of 25 μm was prepared in the same manner as in example 5.
Example 8
The reaction vessel was evacuated in advance using nitrogen, after 30min 124.94g N, N-dimethylacetamide (DMAc) was added (24 h earlier with molecular sieve for water removal), 10.01g (50mmol) of 4, 4' -diaminodiphenyl ether (ODA) was charged and dissolved in DMAc and stirred at 25 ℃ until completely dissolved; then, 21.22g (50mmol) of dianhydride compound (dianhydride compound A4-6 prepared in example 4) was gradually added thereto, and after stirring to be completely dissolved, the reaction was carried out for 72 hours while maintaining the temperature, thereby obtaining a 20 wt% polyimide acid solution.
Then, a polyimide film having a thickness of 25 μm was prepared in the same manner as in example 5.
Comparative example 1
The reaction vessel was evacuated in advance using nitrogen, after 30min 98.89g N, N-dimethylacetamide (DMAc, with molecular sieve removal of water 24h in advance) was added, 10.01g (50mmol) of 4, 4' -diaminodiphenyl ether (ODA) was charged and dissolved in DMAc and stirred at 25 ℃ until completely dissolved; 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 72 hours while maintaining the temperature, thereby obtaining a 20 wt% polyimide acid solution.
Then, a polyimide film having a thickness of 25 μm was prepared in the same manner as in example 5.
Comparative example 2
The reaction vessel was evacuated beforehand using nitrogen, after 30min 140.90g N, N-dimethylacetamide (DMAc) was added (24 h beforehand 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 charged and dissolved in DMAc, respectively, and stirred at 25 ℃ until complete dissolution; then, 22.21g (50mmol) of 2, 2' -bis (3, 4-dicarboxylic acid) hexafluoropropane dianhydride) (6FDA) was gradually added thereto, and after stirring to be completely dissolved, the reaction was carried out for 72 hours while maintaining the temperature, thereby obtaining a 20 wt% polyimide acid solution.
Then, a polyimide film having a thickness of 25 μm was prepared in the same manner as in example 5.
Test example 1
The polyimide films prepared in examples 5 to 8 and comparative examples 1 to 2 were respectively subjected to the following property analyses, 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: 16mm × 4mm, atmosphere: under nitrogen atmosphere; temperature: the heating rate is 10 ℃/min, and the scanning range is 50-250 ℃; the stretching force is 0.05N, and the value range is 50-200 ℃.
(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 5 ℃/min; tensile force is 0.05N; sample size: 16mm 4mm.
TABLE 1
Figure BDA0002188069160000141
As can be seen from Table 1, the light transmittance of the polyimide films prepared in examples 5 to 8 is much higher than that of comparative example 1 (conventional polyimide formulation), indicating that the dianhydride prepared in the present invention has significant optical properties when used to prepare polyimide films.
Therefore, when the dianhydride compound prepared by the invention is 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 the position of 550mm is more than or equal to 85% can be realized; meanwhile, the heat resistance is better; 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.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (15)

1. A dianhydride compound, characterized in that the dianhydride compound is any one of the following structures:
Figure FDA0002956284820000011
2. a method for preparing dianhydride compound according to claim 1, wherein the dianhydride is synthesized by the following route:
Figure FDA0002956284820000021
the preparation method comprises the following steps:
(1) performing Mannich reaction on the compound A-1, amine salt of secondary amine and formaldehyde derivative to obtain a diamine compound A-2;
(2) deaminating the compound A-2 to obtain a diene compound A-3;
(3) carrying out a retaining ring reaction on the compound A-3 and cyclopentadiene to obtain a bicyclohexene compound A-4;
(4) performing carbonyl insertion and oxidation reaction on the compound A-4 under the action of a catalyst to obtain a compound A-5;
(5) and (3) carrying out hydrolysis and dehydration reaction on the compound A-5 to obtain a compound A-6, namely the dianhydride compound.
3. The process for producing a dianhydride compound according to claim 2, wherein the amine salt of the secondary amine is a hydrochloride, a sulfate or an acetate of the secondary amine, the molar ratio of the compound a-2 to the amine salt of the secondary amine is 1:2 to 10, and the molar ratio of the compound a-1 to the formaldehyde derivative is 1:2 to 10.
4. The method for producing a dianhydride compound according to claim 2, wherein the molar ratio of the compound a-1 to the formaldehyde derivative is 1: 1.5-5.0.
5. The method for producing a dianhydride compound according to claim 2, wherein the reaction conditions in step (1) are: heating and reacting for 0.5-10 hours under inert atmosphere, wherein the heating temperature is 30-180 ℃;
the reaction is carried out in an organic solvent, and the organic solvent is one of tetrahydrofuran, methanol, ethanol, isopropanol, butanol, acetonitrile, methyl cellosolve, ethyl cellosolve, ethylene glycol, propylene glycol monomethyl ether, propylene glycol, dichloromethane and fluorotrichloromethane.
6. The method for producing a dianhydride compound according to claim 5, wherein the heating temperature is 85 to 95 ℃.
7. The method for producing a dianhydride compound according to claim 5, wherein the organic solvent is isopropyl alcohol.
8. The method for producing a dianhydride compound according to claim 2, wherein the molar ratio of the compound A-3 to the cyclopentadiene in the step (3) is 1:2-10, the reaction is carried out under an inert atmosphere, and the reaction is carried out in a water bath at 120 ℃ and 125 ℃ for 0.5-10 hours.
9. The method for producing a dianhydride compound according to claim 8, wherein the molar ratio of the compound A-3 to the cyclopentadiene in the step (3) is 1: 2.5.
10. The method for producing a dianhydride compound according to claim 2, wherein the step (4) comprises reacting an alcohol compound, carbon monoxide and the compound a-4 in the presence of a palladium catalyst and a copper catalyst;
the mass ratio of the compound A-4 to the alcohol compound is 1: 1-100;
the molar ratio of the compound A-4 to the palladium catalyst is 1: 0.001-1;
the molar ratio of the compound A-4 to the copper catalyst is 1: 1-50.
11. The method for producing a dianhydride compound according to claim 10,
the mass ratio of the compound A-4 to the alcohol compound is 1: 5-50;
the molar ratio of the compound A-4 to the palladium catalyst is 1: 0.01-0.5;
the molar ratio of the compound A-4 to the copper catalyst is 1: 4-20.
12. The method for producing a dianhydride compound according to claim 2, wherein in the step (5), the dehydration reaction is carried out by heating in an organic solvent under an acid catalyst at a temperature of 50 to 130 ℃ in a mass ratio of the compound A-5 to the organic solvent of 1:0.1 to 100.
13. The method for producing a dianhydride compound according to claim 12, wherein the heating temperature is 80 to 120 ℃ and the mass ratio of the compound a-5 to the organic solvent is 1:1 to 10.
14. Use of a dianhydride compound according to claim 1 or prepared according to the preparation method of any one of claims 2 to 13 in the field of transparent polyimide films.
15. The use according to claim 14, wherein the transparent polyimide film is prepared from the dianhydride compound, the aliphatic or aromatic diamine compound.
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