CN111303183A - Synthetic method of tetracarboxylic dianhydride with fluorinated rigid structure - Google Patents
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Abstract
The invention provides a synthetic method of tetracarboxylic dianhydride with a fluorinated rigid structure, which adopts trifluoromethanesulfonic acid, trifluoroacetic acid and/or sulfuric acid to replace hydrofluoric acid as a catalyst to realize the conversion of 3, 4-dimethylphenol or 3, 3', 4, 4' -tetramethyldiphenyl ether to xanthene tetracarboxylic dianhydride.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a synthesis method of tetracarboxylic dianhydride with a fluorinated rigid structure.
Background
The tetracarboxylic dianhydride with a fluorinated rigid structure can be directly used for preparing high-performance polymers as a monomer, and particularly has wide application in the synthesis of polyimide.
In the synthesis of such tetracarboxylic dianhydrides, U.S. patent publication No. 5051520 (published 24.9.1991) relates to the addition condensation reaction of 3, 4-dimethylphenol or 3, 3', 4, 4' -tetramethyldiphenyl ether with a fluoroketone-containing compound under the presence of an acid catalyst, but the acid catalyst used therein is hydrofluoric acid. Hydrofluoric acid (HF) is an aqueous solution of hydrogen fluoride gas, a colorless, fuming corrosive liquid, and has a strong pungent odor. Has extremely strong corrosivity, and can strongly corrode metal, glass and objects containing silicon. The hydrogen fluoride and the aqueous solution thereof are toxic and are easy to deform bones and teeth, and the hydrofluoric acid can be absorbed by mucous membranes, respiratory tracts and gastrointestinal tracts through the skin to cause burn which is difficult to cure.
How to improve the traditional preparation method, the hydrofluoric acid used in the synthesis process is replaced by a safe and low-toxic catalyst, so that the controllability of the reaction and the yield of the target product are improved, which is of great significance to the technical personnel in the field.
Disclosure of Invention
Based on the technical problems existing in the background technology, the invention provides a synthesis method of tetracarboxylic dianhydride with a fluorinated rigid structure, wherein the conversion of 3, 4-dimethylphenol or 3, 3', 4, 4' -tetramethyldiphenyl ether to xanthene tetracarboxylic dianhydride is realized by adopting trifluoromethanesulfonic acid, trifluoroacetic acid and/or sulfuric acid instead of hydrofluoric acid as a catalyst, and the whole synthesis method has the advantages of high efficiency, safety and controllability.
The invention provides a synthetic method of tetracarboxylic dianhydride with a fluorinated rigid structure, which comprises the following steps:
s1, carrying out addition condensation reaction on 3, 4-dimethylphenol or 3, 3', 4, 4' -tetramethyldiphenyl ether and a fluorine-containing ketone compound under the condition of a strong acid catalyst to obtain a tetramethylxanthene derivative;
s2, carrying out methyl oxidation reaction on the tetramethyl xanthene derivative to obtain a xanthene tetracarboxylic acid derivative;
s3, carrying out carboxyl dehydration condensation reaction on the xanthene tetracarboxylic acid derivative to obtain the xanthene tetracarboxylic dianhydride derivative, namely the tetracarboxylic dianhydride with the fluorinated rigid structure;
wherein, the strong acid catalyst in the step S1 is trifluoromethanesulfonic acid, trifluoroacetic acid and/or sulfuric acid.
The synthetic route of the synthetic method of the tetracarboxylic dianhydride with the fluorinated rigid structure is as follows:
preferably, in step S1, the structural formula of the tetramethylxanthene derivative is as follows:
in step S2, the structural formula of the xanthene tetracarboxylic acid derivative is shown below:
in step S3, the structural formula of the xanthene tetracarboxylic dianhydride derivative is as follows:
preferably, the structural formula of the fluorine-containing ketone compound is as follows:
R1-CO-R2
preferably, the fluoroketone compound is 1, 1, 1-trifluoroacetone, hexafluoroacetone, 2, 2, 2-trifluoroacetophenone, 4- (trifluoroacetyl) toluene, 4- (trifluoroacetyl) trifluoromethylbenzene or pentafluoroethyl phenyl ketone.
Preferably, R1Is any one of the following groups:
R2is any one of the following groups:
-CH3-CF3-CF2CF3-CF2CF2CF3
preferably, in step S1, the addition condensation reaction is carried out at a reaction temperature of 10-30 ℃ for a reaction time of 20-24 h.
Preferably, in step S2, the oxidizing agent for methyl oxidation is KMnO4Preferably, it is further providedThe reaction temperature for methyl oxidation reaction is 90-110 ℃, and the reaction time is 48-56 h.
Preferably, in step S3, the dehydrating agent for performing the carboxyl dehydrating condensation reaction is acetic anhydride, and the reaction temperature for performing the carboxyl dehydrating condensation reaction is preferably 130-150 ℃ and the reaction time is 24-30 h.
Preferably, the method for synthesizing tetracarboxylic dianhydride with a fluorinated rigid structure specifically comprises the following steps:
s1, dissolving a fluorine-containing ketone compound in an organic solvent, adding 3, 4-dimethylphenol or 3, 3', 4, 4' -tetramethyldiphenyl ether under the conditions of inert gas protection and ice bath, adding a strong acid catalyst, reacting for 20-24 hours at 10-30 ℃ under the stirring condition, pouring the reaction liquid into deionized water to obtain a solid, filtering, washing and drying to obtain a tetramethylxanthene derivative;
s2, adding the tetramethyl xanthene derivative obtained in the S1 into a mixed solvent of pyridine and water, heating to 90-110 ℃, and adding KMnO4Stirring for reaction for 48-56h, filtering to obtain filtrate, acidifying the filtrate and precipitating solid, filtering, washing and drying to obtain xanthene tetracarboxylic acid derivative;
s3, adding the xanthene tetracarboxylic acid derivative obtained in the step S2 into acetic anhydride, heating to 130-150 ℃, stirring for reaction for 48-56h, performing suction filtration, and drying to obtain the xanthene tetracarboxylic dianhydride derivative, namely the tetracarboxylic dianhydride with the fluorinated rigid structure.
The invention further provides polyimide which is obtained by polymerizing tetracarboxylic dianhydride monomers and diamine monomers, wherein at least one of the tetracarboxylic dianhydride monomers is the tetracarboxylic dianhydride with the fluorinated rigid structure synthesized by the synthesis method.
In the invention, the conversion of 3, 4-dimethylphenol or 3, 3', 4, 4' -tetramethyldiphenyl ether to xanthene tetracarboxylic dianhydride is realized by adopting trifluoromethanesulfonic acid, trifluoroacetic acid and/or sulfuric acid instead of hydrofluoric acid as a catalyst, and the whole synthesis method has the advantages of high efficiency, safety and controllability.
Drawings
FIG. 1 is a hydrogen spectrum of 9-methyl-9- (trifluoromethyl) -2, 3, 6, 7-tetramethylxanthene;
FIG. 2 is a hydrogen spectrum of 9-methyl-9- (trifluoromethyl) -2, 3, 6, 7-xanthenetetracarboxylic acid;
FIG. 3 is a hydrogen spectrum of 9-methyl-9- (trifluoromethyl) -2, 3, 6, 7-xanthenetetracarboxylic dianhydride.
Detailed Description
Hereinafter, the technical solution of the present invention will be described in detail by specific examples, but these examples should be explicitly proposed for illustration, but should not be construed as limiting the scope of the present invention.
Example 1
A tetracarboxylic dianhydride with a fluorinated rigid structure has the following structural formula:
the synthesis method of the tetracarboxylic dianhydride shown in the structural formula comprises the following steps:
s1, under the conditions of nitrogen atmosphere and ice bath, adding 30g of 1, 1, 1-trifluoroacetone (0.268mol) into 350mL of dichloromethane, stirring until the solution is completely dissolved, adding 66g of 3, 4-dimethylphenol (0.536mol) and 40g of trifluoromethanesulfonic acid (0.268mol), stirring until the solution is completely dissolved, reacting for 24 hours at room temperature, slowly pouring the reaction solution into deionized water after the reaction is finished, extracting an organic phase, carrying out rotary evaporation to obtain a solid, and carrying out vacuum drying overnight to obtain 38g of 9-methyl-9- (trifluoromethyl) -2, 3, 6, 7-tetramethylxanthene (yield: 44%), wherein a hydrogen spectrum of the hydrogen spectrum is shown in figure 1;
s2, 20g of 9-methyl-9- (trifluoromethyl) -2, 3, 6, 7-tetramethylxanthene (0.062mol) was added to a mixture of pyridine: to a mixed solvent of water (v: v ═ 2:1), 45g of KMnO was added slowly and in portions with stirring4(0.285mol), heating to 90 ℃, keeping the temperature for reaction for 2 days, adding isopropanol after the reaction is finished, quenching, carrying out suction filtration, adding concentrated hydrochloric acid into the filtrate for acidification, filtering to obtain white solid powder, and drying in vacuum overnight to obtain 18g of 9-methyl-9- (trifluoromethyl) -2, 3The hydrogen spectrum of 6, 7-xanthenetetracarboxylic acid (yield: 65%) is shown in FIG. 2;
s3, adding the 9-methyl-9- (trifluoromethyl) -2, 3, 6, 7-xanthenetetracarboxylic acid obtained in S2 into 50mL of acetic anhydride, heating to 140 ℃, carrying out reflux reaction for 24h, precipitating white crystals after the reaction is finished, carrying out suction filtration, vacuum drying, and carrying out dehydration condensation to obtain 9-methyl-9- (trifluoromethyl) -2, 3, 6, 7-xanthenetetracarboxylic dianhydride, namely the tetracarboxylic dianhydride shown in the structural formula, wherein a hydrogen spectrum of the tetracarboxylic dianhydride is shown in figure 3.
Example 2
A tetracarboxylic dianhydride with a fluorinated rigid structure has the following structural formula:
the synthesis method of the tetracarboxylic dianhydride shown in the structural formula comprises the following steps:
s1, under the conditions of nitrogen atmosphere and ice bath, adding 30g of hexafluoroacetone (0.181mol) into 350mL of dichloromethane, stirring until the hexafluoroacetone is completely dissolved, adding 44g of 3, 4-dimethylphenol (0.362mol) and 28g of trifluoromethanesulfonic acid (0.181mol), stirring until the hexafluoroacetone is completely dissolved, reacting for 24 hours at room temperature, slowly pouring the reaction solution into deionized water after the reaction is finished, extracting an organic phase, carrying out rotary evaporation to obtain a solid, and carrying out vacuum drying overnight to obtain 24g of 9-bis (trifluoromethyl) -2, 3, 6, 7-tetramethylxanthene (yield: 36%);
s2, 20g of 9-bis (trifluoromethyl) -2, 3, 6, 7-tetramethylxanthene (0.053mol) were added to a solution of pyridine: to a mixed solvent of water (v: v ═ 2:1), 45g of KMnO was added slowly and in portions with stirring4(0.285mol), heating to 90 ℃, keeping the temperature for reaction for 2 days, adding isopropanol for quenching after the reaction is finished, carrying out suction filtration, adding concentrated hydrochloric acid into the filtrate for acidification, filtering to obtain white solid powder, and carrying out vacuum drying overnight to obtain 20g of 9-bis (trifluoromethyl) -2, 3, 6, 7-xanthenetetracarboxylic acid (yield: 76%);
s3, adding the 9-bis (trifluoromethyl) -2, 3, 6, 7-xanthenetetracarboxylic acid obtained in S2 into 50mL of acetic anhydride, heating to 140 ℃, carrying out reflux reaction for 24h, precipitating white crystals after the reaction is finished, carrying out suction filtration, drying in vacuum, and carrying out dehydration condensation to obtain 9-bis (trifluoromethyl) -2, 3, 6, 7-xanthenetetracarboxylic dianhydride, namely the tetracarboxylic dianhydride shown in the structural formula.
Example 3
A tetracarboxylic dianhydride with a fluorinated rigid structure has the following structural formula:
the synthesis method of the tetracarboxylic dianhydride shown in the structural formula comprises the following steps:
s1, under the conditions of nitrogen atmosphere and ice bath, adding 30g of 2, 2, 2-trifluoro acetophenone (0.172mol) into 350mL of dichloromethane, stirring until the mixture is completely dissolved, adding 42g of 3, 4-dimethylphenol (0.344mol) and 20g of trifluoroacetic acid (0.172mol), stirring until the mixture is completely dissolved, reacting for 24 hours at room temperature, slowly pouring the reaction liquid into deionized water after the reaction is finished, extracting an organic phase, carrying out rotary evaporation to obtain a solid, and carrying out vacuum drying overnight to obtain 43g of 9-phenyl-9- (trifluoromethyl) -2, 3, 6, 7-tetramethyl xanthene (yield: 64%);
s2, 20g of 9-phenyl-9- (trifluoromethyl) -2, 3, 6, 7-tetramethylxanthene (0.053mol) was added to a solution of pyridine: to a mixed solvent of water (v: v ═ 2:1), 45g of KMnO was added slowly and in portions with stirring4(0.285mol), heating to 90 ℃, keeping the temperature for 2 days for reaction, adding isopropanol for quenching after the reaction is finished, carrying out suction filtration, adding concentrated hydrochloric acid into the filtrate for acidification, filtering to obtain white solid powder, and carrying out vacuum drying overnight to obtain 22g of 9-phenyl-9- (trifluoromethyl) -2, 3, 6, 7-xanthenetetracarboxylic acid (yield: 82%);
s3, adding the 9-phenyl-9- (trifluoromethyl) -2, 3, 6, 7-xanthenetetracarboxylic acid obtained in S2 into 50mL of acetic anhydride, heating to 140 ℃, carrying out reflux reaction for 24h, precipitating white crystals after the reaction is finished, carrying out suction filtration, vacuum drying, and carrying out dehydration condensation to obtain 9-phenyl-9- (trifluoromethyl) -2, 3, 6, 7-xanthenetetracarboxylic dianhydride, namely the tetracarboxylic dianhydride shown in the structural formula.
Example 4
A tetracarboxylic dianhydride with a fluorinated rigid structure has the following structural formula:
the synthesis method of the tetracarboxylic dianhydride shown in the structural formula comprises the following steps:
s1, under the conditions of nitrogen atmosphere and ice bath, adding 30g of 4- (trifluoroacetyl) toluene (0.159mol) into 350mL of dichloromethane, stirring until the mixture is completely dissolved, adding 39g of 3, 4-dimethylphenol (0.318mol) and 19g of trifluoroacetic acid (0.159mol), stirring until the mixture is completely dissolved, reacting for 24 hours at room temperature, slowly pouring the reaction liquid into deionized water after the reaction is finished, extracting an organic phase, carrying out rotary evaporation to obtain a solid, and drying overnight under vacuum to obtain 39g of 9- (p-tolyl) -9- (trifluoromethyl) -2, 3, 6, 7-tetramethylxanthene (yield: 61%);
s2, 20g of 9- (p-tolyl) -9- (trifluoromethyl) -2, 3, 6, 7-tetramethylxanthene (0.051mol) were added to a reaction mixture of pyridine: to a mixed solvent of water (v: v ═ 2:1), 45g of KMnO was added slowly and in portions with stirring4(0.285mol), heating to 90 ℃, keeping the temperature for 2 days, adding isopropanol for quenching after the reaction is finished, carrying out suction filtration, adding concentrated hydrochloric acid into the filtrate for acidification, filtering to obtain white solid powder, and carrying out vacuum drying overnight to obtain 21g of 9- (p-tolyl) -9- (trifluoromethyl) -2, 3, 6, 7-xanthenetetracarboxylic acid (yield: 80%);
s3, adding the 9- (p-tolyl) -9- (trifluoromethyl) -2, 3, 6, 7-xanthenetetracarboxylic acid obtained in S2 into 50mL of acetic anhydride, heating to 140 ℃, carrying out reflux reaction for 24h, precipitating white crystals after the reaction is finished, carrying out suction filtration, vacuum drying, and carrying out dehydration condensation to obtain 9- (p-tolyl) -9- (trifluoromethyl) -2, 3, 6, 7-xanthenetetracarboxylic dianhydride, namely the tetracarboxylic dianhydride shown in the structural formula.
Example 5
A tetracarboxylic dianhydride with a fluorinated rigid structure has the following structural formula:
the synthesis method of the tetracarboxylic dianhydride shown in the structural formula comprises the following steps:
s1, under the conditions of nitrogen atmosphere and ice bath, adding 30g of 4- (trifluoroacetyl) trifluoromethylbenzene (0.124mol) into 350mL of dichloromethane, stirring until the mixture is completely dissolved, adding 29g of 3, 3', 4, 4' -tetramethyldiphenyl ether (0.124mol) and 13g of sulfuric acid (0.124mol), stirring until the mixture is completely dissolved, reacting for 20 hours at 30 ℃, slowly pouring the reaction liquid into deionized water after the reaction is finished, extracting an organic phase, carrying out rotary evaporation to obtain a solid, and carrying out vacuum drying overnight to obtain 32g of 9- (4- (trifluoromethyl) phenyl) -9- (trifluoromethyl) -2, 3, 6, 7-tetramethylxanthene (yield: 57%);
s2, 20g of 9- (4- (trifluoromethyl) phenyl) -9- (trifluoromethyl) -2, 3, 6, 7-tetramethylxanthene (0.045mol) were added to a solution of pyridine: to a mixed solvent of water (v: v ═ 2:1), 45g of KMnO was added slowly and in portions with stirring4(0.285mol), heating to 110 ℃, then preserving heat for reaction for 56h, adding isopropanol after the reaction is finished, quenching, carrying out suction filtration, adding concentrated hydrochloric acid into the filtrate for acidification, filtering to obtain white solid powder, and carrying out vacuum drying overnight to obtain 19g of 9- (4- (trifluoromethyl) phenyl) -9- (trifluoromethyl) -2, 3, 6, 7-xanthenetetracarboxylic acid (yield: 74%);
s3, adding the 9- (4- (trifluoromethyl) phenyl) -9- (trifluoromethyl) -2, 3, 6, 7-xanthenetetracarboxylic acid obtained in S2 into 50mL of acetic anhydride, heating to 130 ℃, carrying out reflux reaction for 30h, precipitating white crystals after the reaction is finished, carrying out suction filtration, drying in vacuum, and carrying out dehydration condensation to obtain 9- (4- (trifluoromethyl) phenyl) -9- (trifluoromethyl) -2, 3, 6, 7-xanthenetetracarboxylic dianhydride, namely the tetracarboxylic dianhydride shown in the structural formula.
Example 6
A tetracarboxylic dianhydride with a fluorinated rigid structure has the following structural formula:
the synthesis method of the tetracarboxylic dianhydride shown in the structural formula comprises the following steps:
s1, under the conditions of nitrogen atmosphere and ice bath, adding 30g of pentafluoroethyl phenyl ketone (0.134mol) into 350mL of dichloromethane, stirring until the mixture is completely dissolved, adding 31g of 3, 3', 4, 4' -tetramethyl diphenyl ether (0.134mol) and 14g of sulfuric acid (0.134mol) into the mixture, stirring until the mixture is completely dissolved, reacting for 24 hours at 10 ℃, slowly pouring the reaction liquid into deionized water after the reaction is finished, extracting an organic phase, carrying out rotary evaporation to obtain a solid, and carrying out vacuum drying overnight to obtain 35g of 9-phenyl-9- (pentafluoroethyl) -2, 3, 6, 7-tetramethyl xanthene (yield: 60%);
s2, 20g of 9-phenyl-9- (pentafluoroethyl) -2, 3, 6, 7-tetramethylxanthene (0.047mol) was added to a solution of pyridine: to a mixed solvent of water (v: v ═ 2:1), 45g of KMnO was added slowly and in portions with stirring4(0.285mol), heating to 100 ℃, then preserving heat for reacting for 2 days, adding isopropanol after the reaction is finished to quench, filtering, adding hydrochloric acid into filtrate for acidification, filtering to obtain white solid powder, and drying overnight in vacuum to obtain 21g of 9 phenyl-9- (pentafluoroethyl) -2, 3, 6, 7-xanthenetetracarboxylic acid (yield: 78%);
s3, adding the 9-phenyl-9- (pentafluoroethyl) -2, 3, 6, 7-xanthenetetracarboxylic acid obtained in S2 into 50mL of acetic anhydride, heating to 150 ℃, carrying out reflux reaction for 24h, precipitating white crystals after the reaction is finished, carrying out suction filtration, vacuum drying, and carrying out dehydration condensation to obtain 9-phenyl-9- (pentafluoroethyl) -2, 3, 6, 7-xanthenetetracarboxylic dianhydride, namely the tetracarboxylic dianhydride shown in the structural formula.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (9)
1. A synthetic method of tetracarboxylic dianhydride with a fluorinated rigid structure is characterized by comprising the following steps:
s1, carrying out addition condensation reaction on 3, 4-dimethylphenol or 3, 3', 4, 4' -tetramethyldiphenyl ether and a fluorine-containing ketone compound under the condition of a strong acid catalyst to obtain a tetramethylxanthene derivative;
s2, carrying out methyl oxidation reaction on the tetramethyl xanthene derivative to obtain a xanthene tetracarboxylic acid derivative;
s3, carrying out carboxyl dehydration condensation reaction on the xanthene tetracarboxylic acid derivative to obtain the xanthene tetracarboxylic dianhydride derivative, namely the tetracarboxylic dianhydride with the fluorinated rigid structure;
wherein, the strong acid catalyst in the step S1 is trifluoromethanesulfonic acid, trifluoroacetic acid and/or sulfuric acid.
2. The method for synthesizing a tetracarboxylic dianhydride with a fluorinated rigid structure according to claim 1, wherein,
in step S1, the structural formula of the tetramethylxanthene derivative is shown below:
in step S2, the structural formula of the xanthene tetracarboxylic acid derivative is shown below:
in step S3, the structural formula of the xanthene tetracarboxylic dianhydride derivative is as follows:
3. a method for synthesizing a tetracarboxylic dianhydride with a fluorinated rigid structure according to claim 1 or 2, wherein the structural formula of the fluoroketone-containing compound is as follows:
R1-CO-R2
preferably, the fluoroketone compound is 1, 1, 1-trifluoroacetone, hexafluoroacetone, 2, 2, 2-trifluoroacetophenone, 4- (trifluoroacetyl) toluene, 4- (trifluoroacetyl) trifluoromethylbenzene or pentafluoroethyl phenyl ketone.
4. The method for synthesizing a tetracarboxylic dianhydride with a fluorinated rigid structure according to claim 2 or 3, wherein,
R1is any one of the following groups:
R2is any one of the following groups:
-CH3-CF3-CF2CF3-CF2CF2CF3
5. a method for synthesizing a tetracarboxylic dianhydride with a fluorinated rigid structure according to any one of claims 1 to 4, wherein the step S1 is carried out at a reaction temperature of 10 to 30 ℃ and a reaction time of 20 to 24 hours.
6. A method for synthesizing a tetracarboxylic dianhydride with a fluorinated rigid structure according to any one of claims 1 to 5, wherein the oxidizing agent for the methyl oxidation reaction in step S2 is KMnO4Preferably, the methyl oxidation is carried out at a reaction temperature of 90-110 ℃ for a reaction time of 48-56 h.
7. A method for synthesizing tetracarboxylic dianhydride with fluorinated rigid structure according to any of claims 1 to 6, wherein the dehydrating agent for the dehydration condensation reaction of carboxyl group in step S3 is acetic anhydride, preferably the reaction temperature for the dehydration condensation reaction of carboxyl group is 130-150 ℃ and the reaction time is 24-30 h.
8. A method for synthesizing a tetracarboxylic dianhydride with a fluorinated rigid structure according to any one of claims 1 to 7, comprising the following steps:
s1, dissolving a fluorine-containing ketone compound in an organic solvent, adding 3, 4-dimethylphenol or 3, 3', 4, 4' -tetramethyldiphenyl ether under the conditions of inert gas protection and ice bath, adding a strong acid catalyst, reacting for 20-24 hours at 10-30 ℃ under the stirring condition, pouring the reaction liquid into deionized water to obtain a solid, filtering, washing and drying to obtain a tetramethylxanthene derivative;
s2, adding the tetramethyl xanthene derivative obtained in the S1 into a mixed solvent of pyridine and water, heating to 90-110 ℃, and adding KMnO4Stirring for reaction for 48-56h, filtering to obtain filtrate, acidifying the filtrate and precipitating solid, filtering, washing and drying to obtain xanthene tetracarboxylic acid derivative;
s3, adding the xanthene tetracarboxylic acid derivative obtained in the step S2 into acetic anhydride, heating to 130-150 ℃, stirring for reaction for 48-56h, performing suction filtration, and drying to obtain the xanthene tetracarboxylic dianhydride derivative, namely the tetracarboxylic dianhydride with the fluorinated rigid structure.
9. A polyimide obtained by polymerizing a tetracarboxylic dianhydride monomer and a diamine monomer, wherein at least one of the tetracarboxylic dianhydride monomers is a tetracarboxylic dianhydride having a fluorinated rigid structure synthesized by the synthesis method according to any one of claims 1 to 8.
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| CN113912620A (en) * | 2020-12-24 | 2022-01-11 | 常州市阳光药业有限公司 | Preparation method of 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride |
| CN114133403A (en) * | 2021-11-03 | 2022-03-04 | 常州市阳光药业有限公司 | Synthesis method of 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride |
| CN115746013A (en) * | 2022-09-27 | 2023-03-07 | 南京大学 | Preparation method and application of benzo-heterocycle dianhydride derivatives |
| CN116003429A (en) * | 2022-12-28 | 2023-04-25 | 陕西泰合利华工业有限公司 | Preparation method of 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride |
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| WO2019195148A1 (en) * | 2018-04-06 | 2019-10-10 | E. I. Du Pont De Nemours And Company | Polymers for use in electronic devices |
| CN108948035A (en) * | 2018-06-25 | 2018-12-07 | 华中科技大学 | A kind of dianhydride compound and the preparation method and application thereof of the rigidity alicyclic ring containing fluorine structure |
| CN110317339A (en) * | 2019-07-31 | 2019-10-11 | 武汉柔显科技股份有限公司 | Polyimide precursor, Kapton and the display device including the film |
| CN110540645A (en) * | 2019-09-12 | 2019-12-06 | 深圳市华星光电半导体显示技术有限公司 | Prepolymer of polymer dispersed liquid crystal, polymer dispersed liquid crystal composition and display panel |
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| CN113912620A (en) * | 2020-12-24 | 2022-01-11 | 常州市阳光药业有限公司 | Preparation method of 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride |
| CN114133403A (en) * | 2021-11-03 | 2022-03-04 | 常州市阳光药业有限公司 | Synthesis method of 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride |
| CN115746013A (en) * | 2022-09-27 | 2023-03-07 | 南京大学 | Preparation method and application of benzo-heterocycle dianhydride derivatives |
| CN116003429A (en) * | 2022-12-28 | 2023-04-25 | 陕西泰合利华工业有限公司 | Preparation method of 9, 9-bis (trifluoromethyl) -2,3,6, 7-xanthene tetracarboxylic dianhydride |
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