CN113620916A - Preparation method of 4,4' - (hexafluoroisopropenyl) diphthalic anhydride - Google Patents
Preparation method of 4,4' - (hexafluoroisopropenyl) diphthalic anhydride Download PDFInfo
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- CN113620916A CN113620916A CN202110966024.2A CN202110966024A CN113620916A CN 113620916 A CN113620916 A CN 113620916A CN 202110966024 A CN202110966024 A CN 202110966024A CN 113620916 A CN113620916 A CN 113620916A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/34—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with ozone; by hydrolysis of ozonides
Abstract
The invention provides a preparation method of 4,4' - (hexafluoroisopropenyl) diphthalic anhydride, belonging to the technical field of organic synthesis. Mixing 4,4'- (hexafluoroisopropenyl) di-o-xylene, a catalyst and an organic solvent-water mixed solvent, introducing an ozone-air mixed gas, and carrying out an oxidation reaction under a normal pressure condition to obtain 4,4' - (hexafluoroisopropenyl) diphthalic acid; and (3) mixing the 4,4'- (hexafluoroisopropenyl) diphthalic acid with an acidic reagent for dehydration reaction to obtain 4,4' - (hexafluoroisopropenyl) diphthalic anhydride. According to the preparation method provided by the invention, ozone with strong oxidizing property is used as an oxidant, under the catalytic action of a catalyst, the oxidation of 4,4' - (hexafluoroisopropenyl) di-o-xylene can be rapidly realized under the conditions of normal pressure and low temperature, a byproduct for corroding equipment is not generated, the requirement on the equipment is low, and the preparation method is green and environment-friendly; moreover, the method is simple to operate, low in cost and suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of 4,4' - (hexafluoroisopropenyl) diphthalic anhydride.
Background
Compared with the common polyimide monomer material, the fluorine-containing polyimide monomer material has better chemical and thermal stability, light transmittance, lubricity and other properties, and has wide application in the fields of aviation, aerospace, electronic industry and the like. 4,4' - (hexafluoroisopropenyl) diphthalic anhydride (6-FDA) is the most widely used dianhydride monomer for the synthesis of fluorine-containing polyimides.
At present, the 6-FDA synthesis method mainly comprises the steps that 4,4'- (hexafluoroisopropenyl) di-o-xylene (6-FXP) is oxidized into 4,4' - (hexafluoroisopropenyl) diphthalic acid (6-FTA) under certain conditions, and the 6-FTA is subjected to dehydration reaction to generate the 6-FDA. Wherein, the oxidation method mainly comprises an oxygen oxidation method, a nitric acid oxidation method and a potassium permanganate oxidation method. Compared with nitric acid and potassium permanganate, the oxygen oxidation method is clean and pollution-free, and is widely applied. For example, Chinese patent CN201510427397.7 discloses that 6-FXP is oxidized to 6-FTA by using oxygen as an oxidant under the action of a metal ion catalyst I, a cocatalyst and a metal ion catalyst II, wherein the metal ion catalyst I and the metal ion catalyst II are both Co2+And Mn2+The metal ion and the cocatalyst are MBrx, and M is selected from H, NH4 and alkali metal. However, the above method needs to be carried out under high pressure (0.3 to 3.0MPa), and the reaction conditions are severe.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing 4,4' - (hexafluoroisopropenyl) diphthalic anhydride, which comprises reacting under normal pressure and under mild reaction conditions.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of 4,4' - (hexafluoroisopropenyl) diphthalic anhydride, which comprises the following steps:
mixing 4,4'- (hexafluoroisopropenyl) di-o-xylene, a catalyst and an organic solvent-water mixed solvent to obtain a mixed solution, introducing an ozone-air mixed gas into the mixed solution, and carrying out an oxidation reaction under the normal pressure condition to obtain 4,4' - (hexafluoroisopropenyl) diphthalic acid;
and (3) mixing the 4,4'- (hexafluoroisopropenyl) diphthalic acid with an acidic reagent for dehydration reaction to obtain 4,4' - (hexafluoroisopropenyl) diphthalic anhydride.
Preferably, the catalyst is a titanium-containing catalyst.
Preferably, the titanium-containing catalyst comprises one or more of a titanium-containing molecular sieve, amorphous silicon titanium and titanium dioxide.
Preferably, the mass of the catalyst is 1 to 10% of the mass of 4,4' - (hexafluoroisopropenyl) diorthoxylene.
Preferably, the organic solvent in the organic solvent-water mixed solvent comprises pyridine and/or toluene; the volume ratio of the organic solvent to the water in the organic solvent-water mixed solvent is 2-3: 1.
preferably, the volume concentration of ozone in the ozone-air mixed gas is 5-20%; the flow rate of the ozone-air mixed gas is 0.5-4.0L/min.
Preferably, the temperature of the oxidation reaction is 50-100 ℃, and the time is 3-4 h.
Preferably, the mass ratio of the 4,4' - (hexafluoroisopropenyl) diphthalic acid to the acidic reagent is 1: 3 to 5.
Preferably, the dehydration reaction temperature is 90-95 ℃ and the time is 0.5-3 h.
The invention provides a preparation method of 4,4' - (hexafluoroisopropenyl) diphthalic anhydride, which comprises the following steps: mixing 4,4'- (hexafluoroisopropenyl) di-o-xylene, a catalyst and an organic solvent-water mixed solvent to obtain a mixed solution, introducing an ozone-air mixed gas into the mixed solution, and carrying out an oxidation reaction under the normal pressure condition to obtain 4,4' - (hexafluoroisopropenyl) diphthalic acid; and (3) mixing the 4,4'- (hexafluoroisopropenyl) diphthalic acid with an acidic reagent for dehydration reaction to obtain 4,4' - (hexafluoroisopropenyl) diphthalic anhydride. According to the preparation method provided by the invention, ozone and air are used as oxidants, the ozone has strong oxidability which is stronger than oxygen, under the catalytic action of a catalyst, the oxidation of 4,4' - (hexafluoroisopropenyl) di-o-xylene can be rapidly realized under the conditions of normal pressure and low temperature, no by-product which corrodes equipment is generated in the oxidation reaction process, the requirements on corrosion resistance and high pressure resistance of the equipment are lower, and the preparation method is green and environment-friendly; moreover, the preparation method provided by the invention is simple to operate, low in production cost and suitable for industrial production.
Drawings
FIG. 1 is a hydrogen spectrum of 4,4' - (hexafluoroisopropenyl) diphthalic anhydride.
Detailed Description
The invention provides a preparation method of 4,4' - (hexafluoroisopropenyl) diphthalic anhydride, which comprises the following steps:
mixing 4,4'- (hexafluoroisopropenyl) di-o-xylene, a catalyst and an organic solvent-water mixed solvent to obtain a mixed solution, introducing an ozone-air mixed gas into the mixed solution, and carrying out an oxidation reaction under the normal pressure condition to obtain 4,4' - (hexafluoroisopropenyl) diphthalic acid;
and (3) mixing the 4,4'- (hexafluoroisopropenyl) diphthalic acid with an acidic reagent for dehydration reaction to obtain 4,4' - (hexafluoroisopropenyl) diphthalic anhydride.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
The method comprises the steps of mixing 4,4'- (hexafluoroisopropenyl) di-o-xylene, a catalyst and an organic solvent-water mixed solvent to obtain a mixed solution, introducing an ozone-air mixed gas into the mixed solution, and carrying out an oxidation reaction under a normal pressure condition to obtain 4,4' - (hexafluoroisopropenyl) diphthalic acid.
In the present invention, the organic solvent in the organic solvent-water mixed solvent preferably includes pyridine and/or toluene; the volume ratio of the organic solvent to water in the organic solvent-water mixed solvent is preferably 2-3: 1, more preferably 2.5: 1; the mass ratio of the 4,4' - (hexafluoroisopropenyl) di-o-xylene to the organic solvent-water mixed solvent is preferably 1.7-2.6: 1, more preferably 2 to 2.5: 1, more preferably 2.2: 1.
in the present invention, the catalyst is preferably a titanium-containing catalyst; the titanium-containing catalyst preferably comprises one or more of a titanium-containing molecular sieve, amorphous silicon titanium and titanium dioxide; the titanium-containing molecular sieve preferably comprises one or more of a titanium silicalite molecular sieve with an MFI structure, a titanium silicalite molecular sieve with a BEA structure and a titanium silicalite molecular sieve with an MWW structure; the mass of the catalyst is preferably 1 to 10%, more preferably 2 to 8%, and still more preferably 5 to 6% of the mass of 4,4' - (hexafluoroisopropenyl) diorthoxylene.
In the invention, the mixing temperature is preferably 50-100 ℃, more preferably 60-90 ℃, and further preferably 70-80 ℃; the mixing method is preferably stirring mixing, and the speed and time of stirring mixing are not particularly limited in the present invention, and the raw materials may be uniformly mixed.
In the invention, the volume concentration of ozone in the ozone-air mixed gas is preferably 5-20%, and more preferably 10-15%; the flow rate of the ozone-air mixed gas is preferably 0.5-4.0L/min, more preferably 1.0-3.0L/min, and even more preferably 2.0L/min.
In the invention, the temperature of the oxidation reaction is preferably 50-100 ℃, more preferably 60-90 ℃, and further preferably 70-80 ℃; the time of the oxidation reaction is preferably 3 to 4 hours, more preferably 3.2 to 3.8 hours, and further preferably 3.5 hours. In the present invention, the reaction occurring during the oxidation reaction is as follows:
after the oxidation reaction, the invention preferably further comprises the steps of carrying out solid-liquid separation on the system of the oxidation reaction, evaporating the obtained liquid component to remove the organic solvent, adjusting the pH value to 0.5-2 (more preferably 1-1.5), concentrating, and carrying out cooling crystallization on the obtained concentrated solution to obtain the 4,4' - (hexafluoroisopropenyl) diphthalic acid. The solid-liquid separation method is not particularly limited, and a solid-liquid separation method known to those skilled in the art, such as filtration, may be employed. In the invention, the acid used for adjusting the pH value preferably comprises one or more of hydrochloric acid, sulfuric acid and nitric acid. In the present invention, the concentration is preferably performed by distillation under reduced pressure; in the present invention, the conditions for the reduced pressure distillation are not particularly limited, and water may be removed. In the invention, the temperature reduction and crystallization are preferably carried out for 3-6 h, the temperature is reduced from 30 ℃ to 0-5 ℃, and then the temperature is kept for 0.5-1 h.
After 4,4' - (hexafluoroisopropenyl) diphthalic acid is obtained, the invention mixes the 4,4' - (hexafluoroisopropenyl) diphthalic acid with an acidic reagent for dehydration reaction to obtain 4,4' - (hexafluoroisopropenyl) diphthalic anhydride.
In the present invention, the acidic reagent preferably comprises an acid, preferably comprising sulfuric acid and/or phosphoric acid, and/or an acid anhydride, preferably comprising acetic anhydride. In the present invention, the mass ratio of the 4,4' - (hexafluoroisopropenyl) diphthalic acid to the acidic agent is preferably 1: 3-5, more preferably 1: 3.5 to 4.5, and preferably 1: 4.
in the invention, the dehydration reaction temperature is preferably 90-95 ℃, more preferably 91-94 ℃, and further preferably 92-93 ℃; the time of the dehydration reaction is preferably 0.5 to 3 hours, more preferably 1 to 2.5 hours, and further preferably 1.5 to 2 hours. In the present invention, the reactions occurring during the dehydration reaction are as follows:
after the dehydration reaction, the invention preferably further comprises cooling the system of the dehydration reaction to room temperature, carrying out solid-liquid separation, and drying the obtained solid component to obtain 4,4' - (hexafluoroisopropenyl) diphthalic anhydride. The solid-liquid separation method is not particularly limited, and a solid-liquid separation method known to those skilled in the art, such as filtration, may be employed. In the invention, the drying temperature is preferably 100-120 ℃, and more preferably 110 ℃; the drying time is preferably 8-12 h, and more preferably 10 h.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. 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 embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Adding 50g of 4,4'- (hexafluoroisopropenyl) di-o-xylene, 2g of titanium dioxide and 1050mL of pyridine/water mixed solvent into a reaction bottle, stirring and heating to 50 ℃, then introducing ozone/air mixed gas at the flow rate of 0.5L/min, carrying out oxidation reaction for 3h, filtering, distilling off pyridine in the obtained filtrate, adjusting the pH value to 1, carrying out reduced pressure distillation to remove water, cooling and crystallizing the obtained concentrated solution, and filtering to obtain a crude product of 4,4' - (hexafluoroisopropenyl) diphthalic acid (56.6g, the yield is 85.0%), wherein the volume ratio of pyridine to water in the pyridine/water mixed solvent is 2:1, and the volume concentration of ozone in the ozone/air mixed gas is 20%.
Adding 20g of 4,4'- (hexafluoroisopropenyl) diphthalic acid and 100g of acetic anhydride into a reaction bottle, dehydrating at 93 ℃ for 3h, cooling to 5-10 ℃, filtering, and drying the obtained solid product to obtain 4,4' - (hexafluoroisopropenyl) diphthalic anhydride (18.0g, the yield is 97%, and the purity is more than 99.5%).
The hydrogen spectrum of 4,4'- (hexafluoroisopropenyl) diphthalic anhydride is shown in FIG. 1, and it can be seen from FIG. 1 that 4,4' - (hexafluoroisopropenyl) diphthalic anhydride is obtained by the present invention.
Example 2
Adding 50g of 4,4'- (hexafluoroisopropenyl) di-o-xylene, 5g of titanium dioxide and 1050mL of pyridine/water mixed solvent into a reaction bottle, stirring and heating to 60 ℃, then introducing ozone/air mixed gas at the flow rate of 1L/min, carrying out oxidation reaction for 3h, filtering, distilling out pyridine in the obtained filtrate, adjusting the pH value to 1, carrying out reduced pressure distillation to remove water, cooling and crystallizing the obtained concentrated solution, and filtering to obtain a crude product of 4,4' - (hexafluoroisopropenyl) diphthalic acid (55.3g, the yield is 83.0%), wherein the volume ratio of pyridine to water in the pyridine/water mixed solvent is 2:1, and the volume concentration of ozone in the ozone/air mixed gas is 5%.
Adding 20g of 4,4'- (hexafluoroisopropenyl) diphthalic acid and 80g of acetic anhydride into a reaction bottle, dehydrating at 90 ℃ for 3h, cooling to 5-10 ℃, filtering, and drying the obtained solid product to obtain 4,4' - (hexafluoroisopropenyl) diphthalic anhydride (17.6g, the yield is 95%, and the purity is more than 99.5%).
Example 3
Adding 50g of 4,4'- (hexafluoroisopropenyl) di-o-xylene, 5g of titanium dioxide and 1050mL of pyridine/water mixed solvent into a reaction bottle, stirring and heating to 50 ℃, then introducing ozone/air mixed gas at the flow rate of 0.5L/min, carrying out oxidation reaction for 3h, filtering, distilling off pyridine in the obtained filtrate, adjusting the pH value to 1, carrying out reduced pressure distillation to remove water, cooling and crystallizing the obtained concentrated solution, and filtering to obtain a crude product of 4,4' - (hexafluoroisopropenyl) diphthalic acid (55.3g, the yield is 80.0%), wherein the volume ratio of pyridine to water in the pyridine/water mixed solvent is 2:1, and the volume concentration of ozone in the ozone/air mixed gas is 5%.
Adding 20g of 4,4'- (hexafluoroisopropenyl) diphthalic acid and 60g of acetic anhydride into a reaction bottle, dehydrating at 90 ℃ for 3h, cooling to 5-10 ℃, filtering, and drying the obtained solid product to obtain 4,4' - (hexafluoroisopropenyl) diphthalic anhydride (17.2g, the yield is 93%, and the purity is more than 99.5%).
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of 4,4' - (hexafluoroisopropenyl) diphthalic anhydride is characterized by comprising the following steps:
mixing 4,4'- (hexafluoroisopropenyl) di-o-xylene, a catalyst and an organic solvent-water mixed solvent to obtain a mixed solution, introducing an ozone-air mixed gas into the mixed solution, and carrying out an oxidation reaction under the normal pressure condition to obtain 4,4' - (hexafluoroisopropenyl) diphthalic acid;
and (3) mixing the 4,4'- (hexafluoroisopropenyl) diphthalic acid with an acidic reagent for dehydration reaction to obtain 4,4' - (hexafluoroisopropenyl) diphthalic anhydride.
2. The method of claim 1, wherein the catalyst is a titanium-containing catalyst.
3. The preparation method of claim 2, wherein the titanium-containing catalyst comprises one or more of a titanium-containing molecular sieve, amorphous silicon titanium and titanium dioxide.
4. The method according to claim 1, wherein the mass of the catalyst is 1 to 10% of the mass of 4,4' - (hexafluoroisopropenyl) diorthoxylene.
5. The production method according to claim 1, wherein the organic solvent in the organic solvent-water mixed solvent comprises pyridine and/or toluene; the volume ratio of the organic solvent to the water in the organic solvent-water mixed solvent is 2-3: 1.
6. the preparation method according to claim 1, wherein the volume concentration of ozone in the ozone-air mixed gas is 5-20%; the flow rate of the ozone-air mixed gas is 0.5-4.0L/min.
7. The method according to any one of claims 1 to 6, wherein the temperature of the oxidation reaction is 50 to 100 ℃ and the time is 3 to 4 hours.
8. The preparation method according to claim 1, wherein the mass ratio of the 4,4' - (hexafluoroisopropenyl) diphthalic acid to the acidic reagent is 1: 3 to 5.
9. The method according to claim 1 or 8, wherein the dehydration reaction is carried out at a temperature of 90 to 95 ℃ for 0.5 to 3 hours.
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| CN114315568A (en) * | 2021-12-30 | 2022-04-12 | 山东华夏神舟新材料有限公司 | 4,4' - (hexafluoroisopropylene) diphthalic acid and preparation method thereof |
| CN114874168A (en) * | 2022-05-12 | 2022-08-09 | 三明市海斯福化工有限责任公司 | 4,4' - (hexafluoroisopropenyl) diphthalic anhydride and preparation method thereof |
| CN115215824A (en) * | 2021-08-23 | 2022-10-21 | 河北海力香料股份有限公司 | Preparation method of 4,4' - (hexafluoroisopropenyl) diphthalic anhydride |
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Cited By (4)
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| CN115215824A (en) * | 2021-08-23 | 2022-10-21 | 河北海力香料股份有限公司 | Preparation method of 4,4' - (hexafluoroisopropenyl) diphthalic anhydride |
| CN114315568A (en) * | 2021-12-30 | 2022-04-12 | 山东华夏神舟新材料有限公司 | 4,4' - (hexafluoroisopropylene) diphthalic acid and preparation method thereof |
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