CN110963985B - Preparation method of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride - Google Patents
Preparation method of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride Download PDFInfo
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- CN110963985B CN110963985B CN201911378527.7A CN201911378527A CN110963985B CN 110963985 B CN110963985 B CN 110963985B CN 201911378527 A CN201911378527 A CN 201911378527A CN 110963985 B CN110963985 B CN 110963985B
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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
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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 ℃, reacting for 22-80h while stirring, 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 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 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 with the rapid increase of the demand of fluorine-containing polyimide in the fields of microelectronics, OLED and the like, the market demand of 6FDA is increased rapidly.
In general, the synthesis of 6FDA is carried out by Friedel-Crafts reaction of hexafluoroacetone with hydrogen on benzene ring in the presence of catalyst as described in U.S. Pat. No. 5, 3310573, which is a process for the synthesis of hexafluoroisopropylxylene or its derivatives or the direct synthesis of diamines with hexafluoroisopropyl group by condensation of 2 moles of aromatic hydrocarbon with fluoroketone in the presence of hydrofluoride or 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 hydrogen fluoride used as a catalyst in the process of preparing 4,4'- (hexafluoroisopropylidene) diphthalic anhydride in the prior art is dangerous, and the environmental pollution is large due to the existence of a methyl oxidation step, the invention aims to provide a preparation method of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride, which adopts concentrated sulfuric acid, concentrated hydrochloric acid and the like as catalysts to replace hydrogen fluoride and carry out normal-pressure reaction without high-pressure reaction, reduces the danger of the reaction, saves the methyl oxidation step in the traditional method, avoids the use of metal oxides and has small environmental pollution; and the prepared 4,4' - (hexafluoroisopropylidene) diphthalic anhydride has high purity and the yield reaches 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 ℃, reacting for 22-80h while stirring, 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; selected from N-methyl oOne or more of phthalimide, N-ethyl phthalimide, N-isopropyl phthalimide, N-N-propyl phthalimide and N-N-butyl phthalimide.
Wherein, in the step a), the mass ratio of the N-alkyl phthalimide to the catalyst is (1~5): (1-10).
Wherein in the step a), the molar ratio of the hydrated hexafluoroacetone to the N-alkylphthalimide is (1 to 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 SnCl 4 、ZnCl 2 、H 3 PO 4 One or a mixture of several of them.
Wherein, in the step b), the alkali hydrolysis is to add alkali NaOH or KOH into the reaction system for hydrolysis, wherein the molar ratio of the alkali to the hexafluorotetracid is (4~6): 1, heating to reflux for 3-20h; 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 to 10): 1; the high-temperature dehydration is carried out at the temperature of 200 to 280 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1) According to the invention, hexafluoroacetone and specific N-alkylphthalimide are directly reacted under the action of a specific catalyst, a methyl oxidation step 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 not intended to limit the scope of the invention.
The raw materials used in the examples of the present invention are all commercially available.
Each performance test standard or method:
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 of N-propyl phthalimide (0.2 mol), putting 40ml of concentrated sulfuric acid into 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 and reacting for 24 hours, then 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 10% of aqueous solution of NaHOH160 g into the solid, refluxing at 95 deg.C for 18 hr, hydrolyzing to obtain sodium hexafluorotetraacetate, adding dilute hydrochloric acid into the solution, adjusting pH to neutral, and filtering to obtain hexafluorotetraacetate;
c) Then 50ml of acetic anhydride is used for reflux dehydration for 3h to obtain 4,4' - (hexafluoroisopropylidene) diphthalic anhydride. The purity and yield of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride produced are 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 of 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) powder solid;
b) Adding 20% NaOH 100 g aqueous solution into the solid, refluxing at 100 deg.C for 10 hr, hydrolyzing to obtain sodium hexafluorotetraacetate, adding dilute sulfuric acid into the solution, adjusting pH to 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 4,4' - (hexafluoroisopropylidene) diphthalic anhydride produced are 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 of 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) powder solid;
b) Adding 25% KOH 135 g aqueous solution into the solid, refluxing at 95 deg.C for 18 hr, hydrolyzing to obtain sodium hexafluorotetraacetate, adding dilute hydrochloric acid into the solution, adjusting pH to neutral, and filtering to obtain hexafluorotetraacetate;
c) And then dehydrated for 3h at 250 ℃ to obtain 4,4' - (hexafluoroisopropylidene) diphthalic anhydride. The purity and yield of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride produced are shown in table 1.
Comparative example 1:
a preparation method of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride comprises the following steps:
in step b), the above solid was hydrolyzed at 5MPa for 3 hours at 200 ℃ by adding 15% NaHOH 133 g aqueous solution thereto, and the other steps were the same as in example 1. The purity and yield of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride produced are shown in table 1.
Comparative example 2:
a preparation method of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride comprises the following steps:
in step b), naOH 100 g of aqueous solution was added to the above solid at 25% by weight for hydrolysis at 4MPa 180 ℃ for 8 hours under high pressure, and the other steps were the same as in example 1. The purity and yield of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride produced are 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 bottle provided with a magnetic stirring pipe, a condensing pipe and a heating water carrier, 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 in 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 4,4' -hexafluoroisopropylidene-di-o-xylene and 100ml of pyridine/100 ml of water into a 2000ml three-necked bottle, heating to 100 ℃, adding 38 g of potassium permanganate, reacting for 3 hours, dropwise adding a small amount of ethanol after the reaction is finished, and removing 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; 4.8 g of hexafluoro-tetracid, 8ml of acetic anhydride and 8ml of xylene mixed solvent are added into a 150ml flask, the mixture reacts for 40 minutes at the temperature of 140 ℃, after the reaction is finished, the mixture is naturally cooled and filtered to obtain a crude product 4,4'- (hexafluoroisopropylidene) diphthalic anhydride, and the crude product is sublimed and dried 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% | 99.0 | 99.2 | 99.5 | 88 | 95 | 98 |
| Yield% | 87 | 88.8 | 89 | 72 | 78 | 79 |
Claims (3)
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 ℃, reacting for 22-80h while stirring, and discharging to obtain 4,4- (hexafluoroisopropylidene) bis (N-alkyl phthalimide);
b) Carrying out alkaline hydrolysis and acidification to obtain hexafluoro-tetracid;
c) Dehydrating to obtain 4,4' - (hexafluoroisopropylidene) diphthalic anhydride;
in the step a), the N-alkyl phthalimide is selected from one or more of N-methyl phthalimide, N-ethyl phthalimide, N-isopropyl phthalimide, N-N-propyl phthalimide and N-N-butyl phthalimide;
in the step a), the catalyst is selected from concentrated sulfuric acid, concentrated hydrochloric acid, anhydrous aluminum trichloride, anhydrous ferric chloride and SnCl 4 、ZnCl 2 、H 3 PO 4 One or a mixture of several of them;
in the step a), the mass ratio of the N-alkyl phthalimide to the catalyst is (1~5) to (1 to 10);
in the step b), the alkali-adding hydrolysis is to add alkali NaOH or KOH into the reaction system for hydrolysis, wherein the molar ratio of the alkali to the hexafluorotetracid is (4~6): 1, heating to reflux for 3-20h; the acidification is to drop into sulfuric acid or hydrochloric acid solution for further acidification, and the PH value is adjusted to be neutral.
2. The method for preparing 4,4' - (hexafluoroisopropylidene) diphthalic anhydride according to claim 1, wherein the molar ratio of the hydrated hexafluoroacetone to the N-alkylphthalimide in step a) is (1 to 1.5): 2.
3. the method for preparing 4,4' - (hexafluoroisopropylidene) diphthalic anhydride as claimed in claim 1, wherein in step c), said dehydration method may use acetic anhydride dehydration or high temperature dehydration; wherein the molar ratio of acetic anhydride to hexafluorotetracid in the acetic anhydride dehydration is (5 to 10): 1; the high-temperature dehydration is carried out at the temperature of 200 to 280 ℃.
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| CN101747158A (en) * | 2008-12-12 | 2010-06-23 | 南京理工大学 | One-step preparation method of bisphenol af |
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| US3310573A (en) * | 1963-06-17 | 1967-03-21 | Du Pont | Diaryl fluoro compounds |
| US4054584A (en) * | 1973-03-30 | 1977-10-18 | General Electric Company | Method for making bis(thioether anhydride)s |
| GB1477519A (en) * | 1974-07-02 | 1977-06-22 | Gen Electric | Anhydrides and imides |
| US6008374A (en) * | 1994-05-27 | 1999-12-28 | General Electric Company | Process for preparing bis (ether anhydrides) using alkylamine derived bisimides having low melting temperatures |
| CN101100416B (en) * | 2006-07-03 | 2011-02-16 | 中国科学院上海药物研究所 | Small molecule inhibitor for preventing Alzheimer's disease Abeta polypeptide from fiberizing and its preparation method, pharmaceutical composition and application |
| CN101696199B (en) * | 2009-11-06 | 2011-09-07 | 武邑新邑兴精细化工有限公司 | Preparation method of 4,4'-(Hexafluoroisopropylidene) diphthalic anhydride |
| CN106349200B (en) * | 2016-08-26 | 2019-03-08 | 山东华夏神舟新材料有限公司 | The synthetic method of 4,4 '-(hexafluoroisopropyli,ene) diphthalic anhydrides |
| US10059682B1 (en) * | 2016-09-30 | 2018-08-28 | The United States Of America As Represented By The Administrator Of National Aeronautics And Space Administration | Asymmetric dianhyrdrides and methods of making the same |
| CN109678826B (en) * | 2019-02-21 | 2023-03-14 | 浙江诺诚技术发展有限公司 | Method for preparing hexafluoro dianhydride under mild condition |
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| 上海市化学化工学会编.六氟丙酮水合物与苯酚及邻二甲苯的反应.《上海市化学化工学会1978年年会论文摘要选编》.上海市化学化工学会编,1980,(第1版),第62-63页. * |
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