A preparation method of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride

Abstract

The invention provides a preparation method of 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, comprising the following steps: S1: adding fluorenone and indane into a reaction bottle, adding acid in batches, and heating in stages; S2: after the reaction in step S1 is completed, post-processing is performed to obtain 9,9-bis(2,3-dihydro-1H-inden-5-yl)-9H-fluorene; S3: oxidizing the 9,9-bis(2,3-dihydro-1H-inden-5-yl)-9H-fluorene and nitric acid in an ionic liquid under heating conditions to obtain white solid 9,9-bis(3,4-dicarboxyphenyl)fluorene by reaction; S4: adding a deionized xylene solution to the 9,9-bis(3,4-dicarboxyphenyl)fluorene in step S3, and post-processing is performed to obtain 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride. The method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride of the present invention has the advantages of short reaction time, simple operation, high yield, high purity of finished product, and recyclable solvent.

Description

Technical Field

[0001] The invention belongs to the technical field of catalyst preparation, and in particular relates to a method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride. Background Art

[0002] 9,9-Bis(3,4-dicarboxyphenyl)fluorene dianhydride is a polyimide dianhydride monomer. It can be polymerized with diamine to produce polyimide film, which can be applied to flexible circuit boards, substrates, display touch panels, solar cell linings, etc. used in electronic devices such as computers and mobile phones.

[0003] Nowadays, microelectronic devices are getting smaller and smaller, and the density of wiring on chips is getting higher and higher, which requires materials with lower dielectric constants. It is inferred from the Claslius-Mosott equation that the introduction of structural units with low molar polarizability and large molar volume can effectively reduce the dielectric constant. Therefore, the introduction of large side groups in the dianhydride structure can interrupt the conjugation structure to destroy the coplanarity between the aromatic rings, thereby reducing the interchain interaction and effectively reducing the dielectric constant. In addition, the introduction of macromolecular side chains can also improve the solubility of polyimide in organic solvents.

[0004] At present, patent US05061809 reports a method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride, which is divided into three steps:

[0005] Step 1: 9-fluorenone was used as a raw material and o-xylene was reacted at 120°C for 2 days under nitrogen protection and in the presence of trifluoromethanesulfonic acid, then neutralized with sodium bicarbonate, decolorized with activated carbon in ethyl acetate, dried and concentrated with magnesium sulfate to obtain a dark yellow powder, which was refined with ethyl acetate and ethanol to obtain a brown solid with a yield of 66%. Chromatographic detection showed that some raw materials were not completely reacted and fluorescent impurities were generated.

[0006] Secondly, a method for preparing tetramethylfluorene from phosphorus pentoxide and polyphosphoric acid is also disclosed.

[0007] Step 2: Under nitrogen protection, with the catalysis of cobalt acetate tetrahydrate, manganese acetate tetrahydrate, sodium and propionic acid, 0.2-0.5 L / min of air is blown in, and the mixture is vigorously stirred at 132° C. for 2 days to obtain the tetraacid.

[0008] Step 3: The tetraacid is heated at 150°C for one day under a pressure of 0.5 torr to obtain the dianhydride.

[0009] In the above method, only the first step clearly defines the reaction yield, and the other steps are only mentioned, from which it can be inferred that the yield may not be high; secondly, the reaction time of each step of the method is 1-2 days. Summary of the invention

[0010] In view of this, the present invention aims to provide a method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride, which uses the characteristics of containing large groups in its structure to reduce the dielectric constant and improve the solubility.

[0011] A method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride comprises the following two reaction steps:

[0012] (1) Add fluorenone, indane and half of the acid to a reaction flask. After the first stage of heating for 2 hours, add the remaining acid, and then heat for 5 hours in the second stage. After the reaction is completed, cool to 80°C and filter the acid. The filtrate is decompressed to recover part of the indane (which can be applied), and the remainder is cooled to 0°C to precipitate a solid, which is filtered, rinsed with a 5% carbonic acid aqueous solution, rinsed with a small amount of ethanol, and vacuum dried to obtain 9,9-bis(2,3-dihydro-1H-inden-5-yl)-9H-fluorene.

[0013] (2) 9,9-bis(2,3-dihydro-1H-inden-5-yl)-9H-fluorene and nitric acid are oxidized in an ionic liquid under heating conditions. After 2-5 hours of complete reaction of the raw materials, the reaction solution is poured into water to precipitate a solid, which is filtered and washed with deionized water for 8-12 times to obtain a white solid 9,9-bis(3,4-dicarboxyphenyl)fluorene. The solid is directly added to a deionized o-xylene solution without drying, and the temperature is raised to reflux for reaction for 3 hours until no water is separated. The temperature is lowered to 0°C, and the mixture is filtered after stirring for 2 hours. The filtrate is used to recover xylene (which can be applied). The filter cake is slurried twice with methyl tert-butyl ether, filtered, and the filtrate is used to recover methyl tert-butyl ether (which can be applied). The filter cake is vacuum dried to obtain 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride.

[0014] The above reaction route is:

[0015]

[0016] Furthermore, in step 1, the acid can be: perfluorosulfonic acid resin, sulfonic acid resin, p-toluenesulfonic acid, trifluoromethanesulfonic acid, sulfuric acid, sulfonic acid, trifluoroacetic acid, disulfonic acid, etc., preferably perfluorosulfonic acid resin.

[0017] Furthermore, in step 1, the temperature is raised to 40-60°C, preferably 50°C, in the first stage of the reaction component, and to 150-180°C, preferably 170°C in the second stage.

[0018] Furthermore, in step 1, the molar ratio of fluorenone to indane is: 1:(2-8); preferably: 1:5; the mass ratio of fluorenone to perfluorosulfonic acid resin is 1:(1-4), preferably 1:2.

[0019] Furthermore, in step 2, the ionic liquid used can be: ethyl imidazole nitrate, butyl imidazole nitrate, 1-ethyl-3-methyl imidazole nitrate, 1,3-dimethyl imidazole nitrate, 1-propyl-3-methyl imidazole nitrate and other nitrate ionic liquids; preferably ethyl imidazole nitrate.

[0020] Furthermore, in step 2, the mass fraction of nitric acid used is 2%-50%, preferably 15%. The mass ratio of 9,9-bis(2,3-dihydro-1H-inden-5-yl)-9H-fluorene to nitric acid is: 1:(5-20), preferably 1:10.

[0021] Furthermore, in step 2, the nitric acid oxidation reaction temperature is 60-100°C, preferably 80°C.

[0022] Furthermore, in step 2, the mass of xylene added is 1-5 times, preferably 3 times, of (2,3-dihydro-1H-inden-5-yl)-9H-fluorene; the amount of methyl tert-butyl ether added is 0.5-3 times, preferably 1 time.

[0023] To achieve the above object, the technical solution of the present invention is achieved as follows:

[0024] Compared with the prior art, the preparation method of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride described in the present invention has the following beneficial effects:

[0025] The preparation method of the present invention has the advantages of short reaction time, simple operation, high yield, high purity of finished product, and the solvent used can be recycled and reused. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The accompanying drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the accompanying drawings:

[0027] Figure 1 This is a liquid chromatogram of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride described in Example 1 of the present invention. DETAILED DESCRIPTION

[0028] Unless otherwise defined, the technical terms used in the following examples have the same meanings as those generally understood by those skilled in the art. The test reagents used in the following examples are all conventional biochemical reagents unless otherwise specified; the experimental methods are all conventional methods unless otherwise specified.

[0029] The present invention will be described in detail below with reference to the embodiments and the accompanying drawings.

[0030] Example 1

[0031] 18g of fluorenone, 59g of indane and 18g of perfluorosulfonic acid resin were added to the reaction bottle, heated to 50°C for 2 hours, and then 18g of perfluorosulfonic acid resin was added and heated to 170°C for 5 hours. After the reaction was completed, the temperature was lowered to 80°C and the perfluorosulfonic acid resin was filtered. The filtrate was decompressed to recover part of the indane (which can be applied), and the residue was cooled to 0°C and stirred for 3 hours, filtered, rinsed twice with 100 ml of 5% carbonic acid aqueous solution, rinsed with a small amount of ethanol, and vacuum dried to obtain 35.7g of 9,9-bis(2,3-dihydro-1H-inden-5-yl)-9H-fluorene, a light yellow solid, with a yield of 89.58%.

[0032] Add 35g 9,9-bis(2,3-dihydro-1H-inden-5-yl)-9H-fluorene and 350g 15% nitric acid to 80g ethylimidazole nitrate ionic liquid, heat to 80℃ and react for 3h. After the raw materials react completely, pour the reaction solution into ice water, stir to precipitate white solid, stir for 2h and filter, wash the filter cake with deionized water 10 times to obtain white solid 9,9-bis(3,4-dicarboxyphenyl)fluorene, directly add it to 105g deionized o-xylene solution, heat to reflux and separate water for 3h, cool to 0℃ when no water is separated, stir for 2h and filter, recover xylene from the filtrate (can be applied). The filter cake was added with 35 g of methyl tert-butyl ether and slurried twice, filtered, and the filtrate was used to recover methyl tert-butyl ether (can be applied), and the filter cake was vacuum dried to obtain 31.9 g of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride, a white powder, with a yield of 92.43% and a liquid content of 99.86% (see attached Figure 1 ), and the viscosity of polymerization with ODA reaches above 100.

[0033] Example 2

[0034] 18g of fluorenone, 94g of indane and 36g of perfluorosulfonic acid resin were added to the reaction bottle, heated to 50℃ for 2h, then 36g of perfluorosulfonic acid resin was added, and the temperature was raised to 170℃ for 4h. After the reaction was completed, the temperature was lowered to 80℃, and the perfluorosulfonic acid resin was filtered. The filtrate was decompressed to recover part of the indane (which can be applied), and the residue was cooled to 0℃ and stirred for 2h, filtered, rinsed twice with 100ml of 5% carbonic acid aqueous solution, rinsed with a small amount of ethanol, and vacuum dried to obtain 35.9g of 9,9-bis(2,3-dihydro-1H-inden-5-yl)-9H-fluorene, a light yellow solid, with a yield of 90.09%.

[0035] Add 35g 9,9-bis(2,3-dihydro-1H-inden-5-yl)-9H-fluorene and 700g 15% nitric acid to 180g ethylimidazole nitrate ionic liquid, heat to 80℃ and react for 3h. After the raw materials react completely, pour the reaction solution into ice water and stir to precipitate white solid. After stirring for 2h, filter and wash the filter cake with deionized water 10 times to obtain white solid 9,9-bis(3,4-dicarboxyphenyl)fluorene, directly add it to 150g deionized o-xylene solution, heat to reflux and separate water for 3h, cool to 0℃ when no water is separated, stir for 2h and filter, and recover xylene in the filtrate (can be applied). 35 g of methyl tert-butyl ether was added to the filter cake and the mixture was slurried twice. The mixture was filtered and the methyl tert-butyl ether was recovered from the filtrate (which can be applied). The filter cake was vacuum dried to obtain 29.6 g of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride as a white powder with a yield of 85.77% and a liquid content of 99.72%.

[0036] Example 3

[0037] 18g of fluorenone, 35g of indane and 30g of trifluoromethanesulfonic acid were added to a reaction bottle, and the temperature was raised to 100°C for reaction. After 2h of reaction, impurities tended to increase, so the reaction was stopped and the solvent was evaporated under reduced pressure. The residue was added to ice water, cooled to 0°C and stirred for 3 hours, filtered, rinsed three times with 160 ml of 5% carbonic acid aqueous solution, rinsed with a small amount of ethanol, and vacuum dried to obtain 22.5g of 9,9-bis(2,3-dihydro-1H-inden-5-yl)-9H-fluorene as a yellow solid with a yield of 56.46%.

[0038] 22g 9,9-bis(2,3-dihydro-1H-inden-5-yl)-9H-fluorene and 420g 15% nitric acid were added to 44g ethylimidazole nitrate ionic liquid, and the mixture was heated to 90°C for reaction for 3h. After the reaction of the raw materials was complete, the reaction solution was poured into ice water, and a white solid was precipitated under stirring. The mixture was stirred for 1h and then filtered. The filter cake was washed 10 times with deionized water to obtain a white solid 9,9-bis(3,4-dicarboxyphenyl)fluorene, which was directly added to a deionized o-xylene solution of 66g. The mixture was heated to reflux for 2h, cooled to 0°C for filtration, and xylene was recovered from the filtrate (can be applied). 20 g of methyl tert-butyl ether was added to the filter cake and the mixture was slurried twice, filtered, and the methyl tert-butyl ether was recovered from the filtrate (which can be applied). The filter cake was vacuum dried to obtain 20.5 g of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride as a white powder with a yield of 81.03% and a liquid content of 98.25%.

[0039] Example 4

[0040] 18g of fluorenone, 94g of indane and 72g of perfluorosulfonic acid resin were added to the reaction bottle at one time. After the temperature was raised to 50℃ for reaction for 2h, the temperature was raised to 170℃ for reaction for 10h. The color of the reaction solution became darker and the reaction was stopped. The temperature was lowered to 80℃ and the perfluorosulfonic acid resin was filtered. The filtrate was decompressed to recover part of the indane (which can be applied), the residue was cooled to 0℃ and stirred for 3 hours, filtered, rinsed twice with 200ml of 5% carbonic acid aqueous solution, rinsed with a small amount of ethanol, and vacuum dried to obtain 26.2g of 9,9-bis(2,3-dihydro-1H-inden-5-yl)-9H-fluorene, a light yellow solid, with a yield of 65.74%.

[0041] Add 26g 9,9-bis(2,3-dihydro-1H-inden-5-yl)-9H-fluorene and 390g 15% nitric acid to 104g ethylimidazole nitrate ionic liquid, heat to 80°C and react for 3h. After the raw materials react completely, pour the reaction solution into ice water and stir to precipitate a white solid. Stir for 2h and filter. Wash the filter cake 10 times with deionized water to obtain a white solid 9,9-bis(3,4-dicarboxyphenyl)fluorene. Add it directly to 200g deionized o-xylene solution, heat to reflux and separate water until no water is separated, cool to 0°C, stir for 2h and filter. Recover xylene from the filtrate (can be applied). 30 g of methyl tert-butyl ether was added to the filter cake and the mixture was slurried twice, filtered, and the methyl tert-butyl ether was recovered from the filtrate (which can be applied). The filter cake was vacuum dried to obtain 30 g of 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride as a white powder with a yield of 86.93% and a liquid content of 99.72%.

Claims

1. A method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride, characterized in that: The steps include: S1: Add fluorenone and indane into a reaction flask, add acid in portions, and raise the temperature in stages; S2: After the reaction in step S1 is completed, the temperature is lowered and the acid is filtered, the remaining material is cooled and a solid is precipitated, the solid is filtered, and washed with a carbonic acid aqueous solution and ethanol, and vacuum dried to obtain 9,9-bis(2,3-dihydro-1H-inden-5-yl)-9H-fluorene; S3: 9,9-bis(2,3-dihydro-1H-inden-5-yl)-9H-fluorene and nitric acid in step S2 are oxidized in an ionic liquid under heating conditions. After the reaction is complete, the reaction solution is poured into water, precipitated, fixed, filtered, and rinsed with deionized water for multiple times to obtain a white solid 9,9-bis(3,4-dicarboxyphenyl)fluorene; S4: adding a deionized xylene solution to the 9,9-bis(3,4-dicarboxyphenyl)fluorene in step S3, heating to reflux reaction until no water is precipitated, cooling, stirring and filtering, beating the filter cake with methyl tert-butyl ether for multiple times, and vacuum drying the filter cake to obtain 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride; In step S1, the acid is added twice, the acid is added for the first time, and the first stage is heated for reaction for 2 hours, the acid is added for the second time, and then the second stage is heated for reaction for 5 hours; In the first stage, the temperature rises to 40-60°C; The second stage is heating to 150-180℃; The ionic liquid in step S3 is a nitrate ionic liquid; The acid in step S1 is one of perfluorosulfonic acid resin, sulfonic acid resin, p-toluenesulfonic acid, trifluoromethanesulfonic acid, sulfuric acid, sulfonic acid, trifluoroacetic acid or disulfonic acid.

2. The method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride according to claim 1, characterized in that: The first stage is to heat up to 50°C.

3. The method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride according to claim 1, characterized in that: The second stage is heating up to 170°C.

4. The method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride according to claim 1, characterized in that: The amount of acid added was the same twice.

5. The method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride according to claim 1, characterized in that: The acid is perfluorosulfonic acid resin.

6. The method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride according to claim 5, characterized in that: The molar ratio of fluorenone to indane in step S1 is 1:(2-8); the mass ratio of fluorenone to perfluorosulfonic acid resin is 1:(1-4).

7. A method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride according to claim 1 or 6, characterized in that: The molar ratio of fluorenone to indane in step S1 is 1:

5.

8. The method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride according to claim 6, characterized in that: The mass ratio of fluorenone to perfluorosulfonic acid resin is 1:

2.

9. The method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride according to claim 1, characterized in that: After the reaction in step S2 is completed, the temperature is lowered to 80°C, the acid is filtered, and the filtrate is decompressed to recover part of the indane. The residue is cooled to 0°C, the solid is precipitated, filtered, rinsed with 5% carbonic acid aqueous solution, rinsed with a small amount of ethanol, and vacuum dried to obtain 9,9-bis(2,3-dihydro-1H-indene-5-yl)-9H-fluorene.

10. The method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride according to claim 1, characterized in that: The oxidation time under heating conditions in step S3 is 2-5 hours; In step S3, the deionized water is rinsed 8-12 times; The nitrate ionic liquid is one of ethyl imidazole nitrate, butyl imidazole nitrate, 1-ethyl-3-methyl imidazole nitrate, 1,3-dimethyl imidazole nitrate, and 1-propyl-3-methyl imidazole nitrate.

11. A method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride according to claim 1 or 10, characterized in that: The ionic liquid is ethyl imidazolium nitrate.

12. The method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride according to claim 1, characterized in that: In step S3, the mass fraction of nitric acid used is 2%-50%, and the mass ratio of 9,9-bis(2,3-dihydro-1H-inden-5-yl)-9H-fluorene to nitric acid is: 1:(5-20).

13. A method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride according to claim 1 or 12, characterized in that: In step S3, the mass fraction of nitric acid used is 15%.

14. A method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride according to claim 1 or 12, characterized in that: The mass ratio of 9,9-bis(2,3-dihydro-1H-inden-5-yl)-9H-fluorene to nitric acid is 1:

10.

15. The method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride according to claim 1, characterized in that: In step S3, the reaction temperature of nitric acid in the ionic liquid under heating conditions is 60-100°C.

16. A method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride according to claim 1 or 15, characterized in that: In step S3, the reaction temperature of nitric acid in the ionic liquid under heating conditions is 80°C.

17. The method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride according to claim 1, characterized in that: In step S4, the temperature is raised to reflux reaction for 3 hours until no water is separated, the temperature is lowered to 0°C, and the mixture is stirred for 2 hours and filtered to recover xylene from the filtrate; the filter cake is slurried twice with methyl tert-butyl ether, filtered, methyl tert-butyl ether is recovered from the filtrate, and the filter cake is vacuum dried to obtain 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride.

18. The method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride according to claim 1, characterized in that: In step S4, the mass of xylene added is 1-5 times that of (2,3-dihydro-1H-inden-5-yl)-9H-fluorene, and the mass of methyl tert-butyl ether added is 0.5-3 times that of (2,3-dihydro-1H-inden-5-yl)-9H-fluorene.

19. A method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride according to claim 1 or 18, characterized in that: The mass of xylene added in step S4 is 3 times that of (2,3-dihydro-1H-inden-5-yl)-9H-fluorene.

20. The method for preparing 9,9-bis(3,4-dicarboxyphenyl)fluorene anhydride according to claim 1 or 18, characterized in that: The added mass of methyl tert-butyl ether is 1 times that of (2,3-dihydro-1H-inden-5-yl)-9H-fluorene.

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