CN110963985A - Preparation method of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride - Google Patents
Preparation method of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride Download PDFInfo
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- CN110963985A CN110963985A CN201911378527.7A CN201911378527A CN110963985A CN 110963985 A CN110963985 A CN 110963985A CN 201911378527 A CN201911378527 A CN 201911378527A CN 110963985 A CN110963985 A CN 110963985A
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- hexafluoroisopropylidene
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- 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
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Abstract
The invention discloses a preparation method of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride, which comprises the following steps: a) accurately weighing N-alkyl phthalimide and a catalyst, stirring and heating to 90-110 ℃ for dissolution; slowly dropwise adding hydrated hexafluoroacetone, heating to 100-130 ℃, stirring and reacting for 22-80h, and discharging to obtain 4,4- (hexafluoroisopropylidene) bis (N-alkyl phthalimide); b) carrying out alkaline hydrolysis and acidification to obtain hexafluoro-tetracid; c) dehydration gave 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride. According to the invention, hexafluoroacetone and specific N-alkylphthalimide are directly reacted under the action of a specific catalyst to prepare the hexafluorodianhydride, the step of oxidizing methyl in the traditional method is omitted, the use of metal oxides is avoided, the environmental pollution is low, the reaction is carried out at normal pressure, the high-pressure reaction is not required, the reaction risk is reduced, the purity of the prepared 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride is high, and the yield is up to more than 87%.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride (6 FDA).
Background
The fluorine-containing polyimide has excellent comprehensive performance and can be widely applied to the fields of aerospace, microelectronics, electronic and electric appliances, gas separation and the like. The structural properties of the fluorine-containing monomer ultimately affect the performance of the fluorine-containing polyimide. The fluorine-containing monomer has limited kinds, rigorous preparation conditions, complex process and high cost, and limits the popularization and application of the fluorine-containing polyimide. 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride (6 FDA) is the most widely used dianhydride monomer for synthesizing fluorine-containing polyimide, and the market demand of 6FDA is increased rapidly along with the rapid increase of the demand of the fields of microelectronics, OLED and the like for the fluorine-containing polyimide.
In general, the synthesis of 6FDA is carried out by Friedel-Crafts reaction of hexafluoroacetone with hydrogen on the benzene ring in the presence of a catalyst as described in U.S. Pat. No. 3,053, which is a direct synthesis of hexafluoroisopropyl xylene or its derivatives or diamines with hexafluoroisopropyl groups by condensation of 2 moles of aromatic hydrocarbon with fluoroketone in the presence of hydrofluoride or by condensation of 2 moles of aromatic amine with fluoroketone in the presence of aluminum chloride. Further, xylene (or mono toluene) methyl groups on both sides may be oxidized to obtain fluorine-containing dibenzoic acid and tetraphenylbenzoic acid, and tetraphenylbenzoic acid anhydride may be subjected to dehydration condensation to obtain acid anhydride. The reaction needs to use chromium trioxide or potassium permanganate or the like as a catalyst, the reaction process is complex, and the environmental pollution is great.
Disclosure of Invention
In order to solve the problems that in the prior art, hydrogen fluoride used as a catalyst is dangerous, and the environmental pollution is large due to the existence of a methyl oxidation step in the process for preparing 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride, the invention aims to provide a preparation method of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride, concentrated sulfuric acid, concentrated hydrochloric acid and the like are used as catalysts to replace hydrogen fluoride and carry out normal-pressure reaction, high-pressure reaction is not needed, the danger of the reaction is reduced, the methyl oxidation step in the traditional method is omitted, the use of metal oxides is avoided, and the environmental pollution is small; the prepared 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride has high purity and the yield is up to more than 70%.
The invention adopts the following technical scheme to realize the purpose of the invention:
a preparation method of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride comprises the following steps:
a) accurately weighing N-alkyl phthalimide and a catalyst, stirring and heating to 90-110 ℃ for dissolution; slowly dropwise adding hydrated hexafluoroacetone, heating to 100-130 ℃, stirring and reacting for 22-80h, and discharging to obtain 4,4- (hexafluoroisopropylidene) bis (N-alkyl phthalimide);
b) carrying out alkaline hydrolysis and acidification to obtain hexafluoro-tetracid;
c) dehydration gave 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride.
Wherein in the step a), the structural formula of the N-alkyl phthalimide is shown as
Wherein n = 0-8; is selected from one or more of N-methylphthalimide, N-ethylphthalimide, N-isopropylphthalimide, N-N-propylphthalimide and N-N-butylphthalimide.
Wherein, in the step a), the mass ratio of the N-alkyl phthalimide to the catalyst is (1-5) to (1-10).
Wherein in the step a), the molar ratio of the hydrated hexafluoroacetone to the N-alkylphthalimide is (1-1.5): 2.
wherein, in the step a), the catalyst is selected from concentrated sulfuric acid, concentrated hydrochloric acid, anhydrous aluminum trichloride, anhydrous ferric chloride and SnCl4、ZnCl2、H3PO4One or a mixture of several of them.
In the step b), the alkali adding hydrolysis is to add alkali NaOH or KOH into a reaction system for hydrolysis, wherein the molar ratio of the alkali to the hexafluorotetracid is (4-6): 1, heating to reflux for 3-20 h; the acidification is to drop into sulfuric acid or hydrochloric acid solution for further acidification, and the pH value is adjusted to be neutral.
Wherein, in the step c), the dehydration method can adopt acetic anhydride dehydration or high-temperature dehydration; wherein the molar ratio of acetic anhydride to hexafluorotetracid in the acetic anhydride dehydration is (5-10): 1; the high-temperature dehydration is heating dehydration at 200-280 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1) according to the invention, hexafluoroacetone and specific N-alkylphthalimide are adopted to directly react under the action of a specific catalyst, the step of methyl oxidation in the traditional method is omitted, the use of metal oxides is avoided, the environmental pollution is low, the reaction is carried out under normal pressure, the high-pressure reaction is not required, the reaction risk is reduced, the purity of the prepared 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride is high, and the yield is up to more than 87%.
2) The invention has simple production process and low reaction temperature, reduces the production cost and is suitable for large-scale batch production.
Detailed Description
The present invention is further illustrated by the following specific examples, which are, however, not intended to limit the scope of the invention.
The raw materials used in the examples of the present invention are all commercially available.
Various performance test standards or methods:
purity test method: HPLC test is adopted.
Example 1
A preparation method of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride comprises the following steps:
a) accurately weighing 37.8 g N-propyl phthalimide (0.2 mol), placing 40ml of concentrated sulfuric acid in a 500ml four-mouth bottle, stirring and heating to 100 ℃ for dissolution; slowly dropwise adding 22.0g of hexafluoroacetone trihydrate (0.1 mol), heating to 110 ℃, stirring while reacting for 24 hours, pouring into a large amount of water, filtering, neutralizing sulfuric acid, washing, and filtering to obtain 4,4- (hexafluoroisopropylidene) bis (N-propylphthalimide) powdery solid;
b) adding 160 g of 10% NaOH aqueous solution into the solid, refluxing for 18 hours at 95 ℃, hydrolyzing to obtain hexafluoro-tetra-acid sodium salt, adding dilute hydrochloric acid into the solution, adjusting the pH value to be neutral, and filtering to obtain hexafluoro-tetra-acid;
c) then 50ml of acetic anhydride is used for refluxing dehydration for 3h to obtain 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride. The purity and yield of the prepared 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride were measured as shown in table 1.
Example 2:
a preparation method of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride comprises the following steps:
a) accurately weighing 32.2 g N-methylphthalimide (0.2 mol), placing 60ml of concentrated sulfuric acid in a 500ml four-mouth bottle, stirring and heating to 110 ℃ for dissolution; slowly dropwise adding 33.0g of hexafluoroacetone trihydrate (0.15 mol), heating to 130 ℃, stirring for reaction for 60 hours, pouring into a large amount of water, filtering, neutralizing sulfuric acid, washing, and filtering to obtain 4,4- (hexafluoroisopropylidene) bis (N-methylphthalimide) powdery solid;
b) adding 100 g of aqueous solution of 20% NaOH into the solid, refluxing for 10 hours at 100 ℃, hydrolyzing to obtain sodium hexafluorotetraacetate, adding dilute sulfuric acid into the solution, adjusting the pH value to be neutral, and filtering to obtain hexafluorotetraacetate;
c) then heated and dehydrated for 1h at 280 ℃ to obtain 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride. The purity and yield of the prepared 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride were measured as shown in table 1.
Example 3:
a preparation method of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride comprises the following steps:
a) accurately weighing 40.6 g N-butylphthalimide (0.2 mol), placing 40ml of concentrated sulfuric acid in a 500ml four-mouth bottle, stirring and heating to 100 ℃ for dissolution; slowly dropwise adding 22.0g of diacetone hexafluoride (0.1 mol) dihydrate, then adding 5 g of anhydrous ferric chloride, heating to 100 ℃, stirring and reacting for 80h, then pouring into a large amount of water, filtering, neutralizing sulfuric acid, washing, and filtering to obtain 4,4- (hexafluoroisopropylidene) bis (N-butylphthalimide) powdery solid;
b) adding 135 g of 25% KOH aqueous solution into the solid, refluxing for 18 hours at 95 ℃, hydrolyzing to obtain hexafluoro-tetra-acid sodium salt, adding dilute hydrochloric acid into the solution, adjusting the pH value to be neutral, and filtering to obtain hexafluoro-tetra-acid;
c) and then dehydrated for 3 hours at 250 ℃ to obtain 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride. The purity and yield of the prepared 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride were measured as shown in table 1.
Comparative example 1:
a preparation method of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride comprises the following steps:
in step b), the solid is hydrolyzed at 200 ℃ under 5MPa for 3 hours by adding 133 g of aqueous solution of 15% NaOH, and the other steps are the same as in example 1. The purity and yield of the prepared 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride were measured as shown in table 1.
Comparative example 2:
a preparation method of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride comprises the following steps:
in step b), the solid is hydrolyzed under high pressure at 180 ℃ under 4MPa for 8 hours by adding 100 g of 25% NaOH aqueous solution, and the other steps are the same as in example 1. The purity and yield of the prepared 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride were measured as shown in table 1.
Comparative example 3:
adding 82 g (0.372 mol) of o-xylene 80g (0.754 mol) of hexafluoroacetone hydrate into a 500ml three-necked flask provided with a magnetic stirring pipe, a condensing pipe and a heating water carrying device, layering, stirring, heating the reaction solution to a reflux temperature to separate water in a water separator, continuously heating and refluxing until no water is separated out, wherein the reaction bottle is colorless and transparent and is a mixture of o-xylene and hexafluoroacetone, and a small amount of hexafluoroacetone trihydrate is separated out from a lower layer 15 g in the water separator; adding the obtained mixture of o-xylene and hexafluoroacetone hydrate into a 0.5L high-pressure kettle, adding 127 g of hydrofluoric acid, starting stirring, heating to 115 ℃ for reacting for 17 hours under the reaction pressure of 10.5atm, cooling after the reaction is finished, removing the pressure, purging with nitrogen for three times, absorbing tail gas with water and alkali, opening the kettle, stirring the reaction solution, pouring into ice water, separating out solids, and filtering to obtain yellow solids; adding 14.4 g of a mixed solvent of 4, 4' -hexafluoroisopropylidene-di-o-xylene and pyridine 200 ml/water 100ml into a 2000ml three-necked flask, heating to 100 ℃, adding potassium permanganate 38 g, reacting for 3 hours, and after the reaction is finished, dropwise adding a small amount of ethanol to remove unreacted potassium permanganate; filtering the mixture, evaporating pyridine from the filtrate, adjusting the pH value to 1, evaporating water to dryness, adding 320ml of acetone to dissolve organic matters, filtering insoluble matters, and evaporating the filtrate to dryness to obtain a crude product hexafluorotetracid; adding a mixed solvent of 4.8 g of hexafluorotetracid, 8ml of acetic anhydride and 8ml of xylene into a 150ml flask, reacting at the temperature of below 140 ℃ for 40 minutes, naturally cooling after the reaction is finished, filtering to obtain a crude product of 4,4 '- (hexafluoroisopropylidene) diphthalic anhydride, and sublimating and drying to obtain a 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride product. The purity and yield of the obtained product are shown in table 1.
TABLE 1
| Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Purity of% | 99.0 | 99.2 | 99.5 | 88 | 95 | 98 |
| Yield% | 87 | 88.8 | 89 | 72 | 78 | 79 |
Claims (7)
1. A preparation method of 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride is characterized by comprising the following steps:
a) accurately weighing N-alkyl phthalimide and a catalyst, stirring and heating to 90-110 ℃ for dissolution; slowly dropwise adding hydrated hexafluoroacetone, heating to 100-130 ℃, stirring and reacting for 22-80h, and discharging to obtain 4,4- (hexafluoroisopropylidene) bis (N-alkyl phthalimide);
b) carrying out alkaline hydrolysis and acidification to obtain hexafluoro-tetracid;
c) dehydration gave 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride.
2. The process for preparing 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride) as claimed in claim 1 or 2, wherein in step a), the N-alkylphthalimide has the formula
Wherein n = 0-8; preferably selected from N-methylphthalimide, N-ethylphthalimideOne or more of phthalimide, N-isopropyl phthalimide, N-N-propyl phthalimide and N-N-butyl phthalimide.
3. The method for preparing 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride as claimed in claim 1, wherein the mass ratio of N-alkylphthalimide to catalyst in step a) is (1-5) to (1-10).
4. The method for preparing 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride according to claim 1, wherein in step a), the molar ratio of the hydrated hexafluoroacetone to the N-alkylphthalimide is (1 to 1.5): 2.
5. the method for preparing 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride as claimed in claim 1, wherein in step a), the catalyst is selected from concentrated sulfuric acid, concentrated hydrochloric acid, anhydrous aluminum trichloride, anhydrous ferric chloride, SnCl4、ZnCl2、H3PO4One or a mixture of several of them.
6. The method for preparing 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride according to claim 1, wherein in step b), the alkali hydrolysis is performed by adding an alkali NaOH or KOH to the reaction system, wherein the molar ratio of the alkali to the hexafluorotetracid is (4-6): 1, heating to reflux for 3-20 h; the acidification is to drop into sulfuric acid or hydrochloric acid solution for further acidification, and the pH value is adjusted to be neutral.
7. The method for preparing 4, 4' - (hexafluoroisopropylidene) diphthalic anhydride as claimed in claim 1, wherein in step c), the dehydration method may be acetic anhydride dehydration or high temperature dehydration; wherein the molar ratio of acetic anhydride to hexafluorotetracid in the acetic anhydride dehydration is (5-10): 1; the high-temperature dehydration is heating dehydration at 200-280 ℃.
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