CN112724111B - Method for preparing ODPA - Google Patents

Method for preparing ODPA Download PDF

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CN112724111B
CN112724111B CN202011617227.2A CN202011617227A CN112724111B CN 112724111 B CN112724111 B CN 112724111B CN 202011617227 A CN202011617227 A CN 202011617227A CN 112724111 B CN112724111 B CN 112724111B
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洪俊杰
范占成
王群
周君
陈科宇
方彦中
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Zhejiang Qinghe New Material Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B01J27/12—Fluorides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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Abstract

The invention provides a method for preparing ODPA, which comprises the steps of firstly using N-methyl-4-nitrophthalimide as a raw material, and obtaining oxo through condensationHydrolyzing and acidifying the bis- (N-methylphthalimide), recrystallizing and purifying, and dehydrating to obtain ODPA; the condensation step comprises: by KF/Al 2 O 3 The solid base catalyst is a catalyst, a first-stage reaction is carried out under the conditions of a mixed solvent and the reaction temperature of more than 120 ℃, after the reaction is finished, the catalyst is removed by solid-liquid separation while the reaction is hot at the temperature of more than 80 ℃, and the separated liquid is cooled to separate out a condensation product to obtain a first part of condensation product; adding new KF/Al to the residual liquid 2 O 3 And (3) a solid alkali catalyst is used for carrying out a second-stage reaction, after the reaction is finished, the liquid from which the catalyst is removed is cooled, and water is added to separate out a condensation product, so that a second part of condensation product is obtained. The invention provides a preparation method of ODPA with high yield and less three wastes.

Description

Method for preparing ODPA
Technical Field
The invention belongs to the field of fine chemical engineering and chemical synthesis, and particularly relates to a method for preparing ODPA.
Background
3,3',4,4' -diphenyl ether dianhydride (ODPA) is an important monomer for producing polyimide polymer materials (PI). The polyimide product has wide application in the fields of aerospace, motor lapping, automobile industry, mechanical industry, light industry and electrical appliance industry, precision machinery industry, electronic industry and the like. With the increase of the types of PIs, the demand of the industry increases, especially the explosive demand of PI films brought by the large-scale application of OLEDs on smart phones, and the demand for basic monomers of ODPAs also increases year by year. Some problems which are easy to solve or even neglect in the conventional small-batch production of ODPA are highlighted in the process of large-scale continuous production, especially the problem of environmental protection.
The main synthesis methods of ODPA are two (see formula 1): firstly, N-methyl-4-nitrophthalimide I is taken as a raw material, oxo-bis- (N-methylphthalimide) II is obtained through condensation, and ODPA is obtained through hydrolysis acidification, recrystallization purification and dehydration; the other one is 4-chlorophthalic anhydride as raw material, which is condensed, hydrolyzed, purified and dehydrated to obtain the product. The first method has longer steps, more three wastes and low yield; the second method is relatively simple and convenient, has less three wastes and high atom utilization rate, but the 4-chlorophthalic anhydride which is used as the raw material is synthesized by a chlorination process, and can generate two products which are difficult to separate, namely 3-chlorophthalic anhydride and 4-chlorophthalic anhydride, so that the high-purity 4-chlorophthalic anhydride can not be easily obtained in a large batch; meanwhile, a phase transfer catalyst is often used in the route of the chlorophthalic anhydride, and the residue of the phase transfer catalyst in the finished product ODPA is difficult to completely remove, so that the subsequent polymerization reaction is greatly influenced. Therefore, the prior industry adopts the first route with more defects, easily obtained raw materials and stable product quality.
Figure BDA0002872766650000011
The bottleneck of the route using N-methyl-4-nitrophthalimide as a raw material is the condensation reaction in the first step, the yield is low, the three wastes are more, and the reaction is unstable. The first reports of condensation reactions to oxo-bis- (N-methylphthalimide) are described in J.org.chem.,1977,3431-3434 as K 2 CO 3 、NaNO 2 And single or composite alkali metal salts such as KF and the like are used as catalysts, and are subjected to reflux reaction in aprotic polar solvents such as DMAc (N, N-dimethylacetamide), NMP (N-methylpyrrolidone), DMF (N, N-dimethylformamide) and the like, the reaction time is usually 18 hours, and after the reaction is finished, the reaction liquid is poured into a large amount of diluted hydrochloric acid to separate out solids, and the yield is between 60 and 78 percent. However, the reaction in this report uses only a few grams of oxybis- (N-methylphthalimide) as a starting material and uses a large amount of solvent so that the yield of the condensation product is between 60 and 78%. On the other hand, if the reaction is amplified and the solvent capacity is reduced, the yield of the condensation product is only about 50%. The catalyst in the reaction is large in amount and cannot be recycled, and the reaction needs to pour a large amount of reaction liquid into the reaction solution after the reaction is finishedSolid is separated out from the dilute hydrochloric acid, so the three-waste discharge amount is large. Since no water-carrying agent is used in the reaction, the condensation reaction may be unstable due to unstable water content in the raw material or solvent. Therefore, further improvements to this method are needed.
The subsequent research includes replacing catalyst alkali metal salt with acetate, replacing solvent with DMAc/water carrying agent system, or adopting mixed alkali metal salt system as catalyst, and the post-treatment includes distilling most of solvent after reaction, adding purified water, pulping and filtering to obtain condensation product. However, these methods have a limited yield increase in the condensation step, and the process flow is not much different from the original flow, and still generates much waste water.
In addition, in the first route of formula 1, although the subsequent hydrolysis, acidification, recrystallization purification, dehydration processes are complicated, the operation is simple, but the purity and color of the condensation product oxybis- (N-methylphthalimide) obtained in the first step of the route affect the quality of the final ODPA.
Therefore, the step of reaction for obtaining the oxo-bis- (N-methyl phthalimide) by condensation by taking the N-methyl-4-nitrophthalimide as the raw material is very important in the synthesis process of ODPA, and if the first step of condensation reaction can be environment-friendly, the whole process route can be industrialized on a large scale.
Therefore, there is a need in the art for a new method for preparing oxybis- (N-methylphthalimide), and for a new method for the synthesis of ODPA.
Disclosure of Invention
The invention provides a method for preparing ODPA, wherein the ODPA is 3,3', 4' -diphenyl ether dianhydride, and the method comprises the steps of firstly using N-methyl-4-nitrophthalimide as a raw material, obtaining oxo-bis- (N-methylphthalimide) through condensation, then obtaining ODPA through hydrolytic acidification, recrystallization purification and dehydration; the step of obtaining the oxo-bis- (N-methylphthalimide) by condensation by using the N-methyl-4-nitrophthalimide as a raw material comprises the following steps: first KF/Al 2 O 3 Solid base catalysisTaking a catalyst as a solvent, taking a mixed solvent containing an aprotic polar solvent and a water-carrying agent as a solvent, carrying out a first-stage reaction at a reaction temperature of more than 120 ℃, after the first-stage reaction is finished, carrying out solid-liquid separation to remove the catalyst at a temperature of more than 80 ℃ when the catalyst is hot, cooling the separated liquid to separate out a condensation product of oxybis- (N-methylphthalimide), and carrying out solid-liquid separation to obtain a first part of condensation product of oxybis- (N-methylphthalimide); adding new KF/Al into the liquid after solid-liquid separation to obtain condensation product 2 O 3 Solid alkali catalyst, the second stage reaction is carried out under the condition that the reaction temperature is more than 120 ℃, after the second stage reaction is finished, the catalyst is removed by solid-liquid separation when the reaction is hot at the temperature of more than 80 ℃, the separated liquid is cooled and water is added to separate out condensation product oxybis- (N-methyl phthalimide), and then the second part of condensation product oxybis- (N-methyl phthalimide) is obtained by solid-liquid separation.
In a specific embodiment, the first stage and the second stage of reaction are carried out in a reflux water separation device, and water is separated from the mixed solvent in time during the reaction.
In the present invention, the water separated from the reflux water separator may be derived from the raw material or the solvent, or may be water generated by some side reactions.
In a specific embodiment, the liquid after the solid-liquid separation of the second part of the condensation product is separated from water in a reflux water separator, and the remaining liquid is distilled under reduced pressure to obtain a mixed solvent, and the obtained mixed solvent is repeatedly used in the condensation reaction.
In a specific embodiment, the KF content in the catalyst is 25-40 wt%, and the preparation method of the catalyst comprises the following steps: preparing aqueous KF solution and adding Al 2 O 3 Mixing with ethanol, dripping KF aqueous solution under ultrasonic stirring, aging, removing solvent, drying, and roasting to obtain KF/Al 2 O 3 A solid base catalyst; the preferred mass of ethanol is Al 2 O 3 1.5-4 times of the mass, aging for more than 1 hour, and distilling to remove 50% of the waterThe drying temperature of the solvent is 60-120 ℃, the roasting temperature is 300-400 ℃, and the roasting time is 6-10 hours.
In a specific embodiment, the catalyst regeneration method is heating reflux washing in an organic solvent, wherein the organic solvent comprises one or more of ethanol, methanol, acetone and tetrahydrofuran.
In a specific embodiment, the aprotic polar solvent is one or more of DMAc, NMP and DMF, the water-carrying agent is toluene or xylene, and the mass ratio of the amount of the aprotic polar solvent to the amount of the water-carrying agent is 4 to 7:1, and the dosage of the mixed solvent is 3-8 times of the mass of the raw material N-methyl-4-nitrophthalimide.
In a specific embodiment, the KF/Al is reacted in the first stage 2 O 3 The solid alkali catalyst is used in 5-30 wt%, preferably 10-20 wt% of N-methyl-4-nitrophthalimide as material, and the KF/Al is the second stage reaction 2 O 3 The solid base catalyst is used in an amount of 8 to 35wt%, preferably 12 to 25wt%, based on the raw material.
In a specific embodiment, after the first-stage reaction is completed, the liquid obtained after removing the catalyst by solid-liquid separation is cooled to room temperature to precipitate a condensation product, and after the second-stage reaction is completed, the liquid obtained after removing the catalyst by solid-liquid separation is cooled to room temperature and water is added to precipitate a condensation product.
In a specific embodiment, the solid-liquid separation and removal of the catalyst after the end of the first-stage reaction and after the end of the second-stage reaction are both carried out by hot filtration.
In a specific embodiment, the temperature of the reflux water diversion reaction of the first stage reaction and the second stage reaction is 150-160 ℃; the reaction time in the first stage is 4 to 10 hours, preferably 6 to 8 hours, and the reaction time in the second stage is 5 to 20 hours, preferably 8 to 12 hours.
In the invention, the temperature of the reflux water separation reaction is different but is mostly 150-160 ℃ because the solvent proportion in the mixed solvent is different.
The invention has at least the following beneficial effects:
1. the invention provides a method for synthesizing ODPA and a key intermediate oxybis- (N-methylphthalimide) thereof, which has high yield and less three wastes. Specifically, the yield of the first partial condensation product oxo-bis- (N-methyl phthalimide) obtained by the first-stage reaction is 45.0-55.0%, the content is not less than 98.5%, and the color is light yellow; the second part of condensation product oxo-bis- (N-methyl phthalimide) obtained by the second stage reaction has the yield of 30-40 percent, the content of more than or equal to 93.0 percent and the color of yellow brown. And the total yield of the condensation product obtained by the two-stage reaction reaches 80.0-85.0%. In addition, the liquid obtained after the solid-liquid separation of the second part of condensation product is separated from water in a reflux water-separating device, and then the mixed solvent is obtained through reduced pressure distillation, and the obtained mixed solvent is repeatedly used in the condensation reaction. Therefore, the three wastes in the invention only contain a small amount of organic impurities with high boiling point and sticky state and a small amount of water in the reflux water-dividing device, and the method is green and environment-friendly.
2. In the prior art, single or compound alkali metal salt is used as a catalyst, the catalyst is dissolved in a mixed solvent, and the catalytic performance of the catalyst is easily influenced by the content of moisture impurities in raw materials and the solvent, so that the effect of condensation reaction is influenced. That is, the difference in solubility of the prior art alkali metal salt catalysts in mixed solvent systems can lead to instability of the condensation reaction. In the present invention, a water-insoluble catalyst, i.e., KF/Al, is used 2 O 3 The solid base catalyst has catalytic performance not affected by the water impurity content in the material and solvent, and thus the condensation reaction of the present invention has high stability.
3. In the prior art, the method adds water and pulp after evaporating the solvent, and generates a large amount of high-salt high-COD wastewater which is difficult to treat. Specifically, in the prior art, after the condensation reaction is finished, a large amount of water (about 20 times the mass of the condensation product) is added to dissolve the alkali metal salt catalyst used in the condensation reaction, and the condensation product is insoluble in water and then separated by solid-liquid separation. Therefore, a large amount of high-salt high-COD wastewater which is difficult to treat is generated in the reaction. In the present invention, only a small amount of water (about 0.5-2 times the mass of the condensation product) is added in the second stage of the reaction to promote the crystallization of the condensation product. Therefore, the method is green and environment-friendly.
4. Experiments prove that the method of the invention has no amplification effect in further pilot plant test and industrial production, namely, the method can still keep the excellent characteristics of high yield of condensation products and green and environment-friendly process after amplification.
5. In the method of the invention, the activity of the regenerated catalyst is not substantially reduced.
Detailed Description
Example 1
Preparing a catalyst: 40.0g of Al is weighed 2 O 3 And 80.0g of ethanol are added into a three-necked bottle, stirred and ultrasonically treated, then 60.0mL of 0.2g/mL KF aqueous solution is slowly dripped, ultrasonically aged for 3.0h after the addition is finished, the solvent is removed by rotary evaporation, baked for 8.0h at 80 ℃ and baked for 8.0h at 350 ℃ to obtain 51.2g of KF/Al with the mass fraction of 30 percent 2 O 3 A catalyst.
150.0g of N-methyl-4-nitrophthalimide, 600.0g of DMF and 100.0g of toluene were charged in a 1L jacketed reactor, and 15.0g of KF/Al obtained above was added 2 O 3 The catalyst is stirred and heated until the reflux water diversion is carried out, the reaction temperature of the reflux water diversion is 150-160 ℃, and the reaction lasts for 6.0h. Reducing the temperature to 80-90 ℃, discharging the reaction liquid from the bottom of the jacket reactor, and removing the catalyst by heat filtration; the reaction solution was cooled to room temperature and filtered to obtain a pale yellow solid, i.e., a condensation product oxybis- (N-methylphthalimide), 69.3g after drying, with a content of 98.7%.
The filtrate was again charged into a jacketed reactor, and 20.0g of KF/Al prepared as described above was added 2 O 3 Stirring the catalyst, heating to reflux and divide water, wherein the reaction temperature of the reflux and the division of water is 150-160 ℃, continuing to react for 8.0h, reducing the temperature to 80-90 ℃, discharging the reaction liquid from the bottom of the jacketed reactor, and thermally filtering to remove the catalyst; cooling the reaction solution to room temperature, adding 100.0g of purified water, and filtering to separate out yellowish-brown solid, namely condensation productOxo-bis- (N-methylphthalimide), 34.6g after oven drying, content 95.1%. The overall yield of the condensation reaction was 82.8% (molar yield, the same applies below).
Catalyst regeneration: catalyst KF/Al obtained by twice filtration 2 O 3 Adding 100.0g of ethanol, heating and refluxing for 8.0h, filtering, and drying for the next batch of reaction.
Example 2
150.0g of N-methyl-4-nitrophthalimide, 600.0g of DMF and 100.0g of toluene were charged into a 1 liter jacketed reactor, and 15.0g of recovered KF/Al was added 2 O 3 The catalyst (the catalyst obtained in the catalyst regeneration step in example 1) was stirred, heated to reflux and separated from water, and reacted for 8.0h. Reducing the temperature to 80-90 ℃, discharging the reaction liquid from the bottom of the jacket reactor, and removing the catalyst by heat filtration; the reaction solution was cooled to room temperature and filtered to obtain a pale yellow solid, i.e., a condensation product oxybis- (N-methylphthalimide), 67.9g after drying, with a content of 98.2%.
The filtrate was again charged into the jacketed reactor, and 20.0g of recovered KF/Al was added 2 O 3 Stirring and heating a catalyst (the catalyst obtained in the catalyst regeneration step in the embodiment 1) until the reflux water diversion reaction temperature is 150-160 ℃, continuing the reaction for 12.0 hours, reducing the temperature to 80-90 ℃, discharging the reaction liquid from the bottom of the jacket reactor, and thermally filtering to remove the catalyst; the reaction solution was cooled to room temperature, 100.0g of purified water was added, and a yellowish brown solid, which was a condensation product oxybis- (N-methylphthalimide), was precipitated by filtration, and after drying, it was 35.6g, with a content of 94.7%. The total yield of the condensation reaction was 82.1%.
Recovering the mixed solvent: when the second part of condensation product is separated in the embodiment 1 and the embodiment 2, the filtrate obtained by filtration is put into a jacket reactor, and is heated and divided in a reflux water dividing device, and the reaction temperature of the reflux water dividing is 150-160 ℃ until no water is separated; the organic solvent was then recovered by distillation under reduced pressure to give a DMF/toluene mixed solution of 654.7g, DMF: the mass ratio of toluene is 6.7:1, the amount of high-boiling and viscous organic matter was 27.9g.
Comparative example 1
150.0g of N-methyl-4-nitrophthalimide, 600.0g of DMF and 100.0g of toluene were charged in a 1L jacketed reactor, and 35.0g of KF/Al prepared in example 1 above was added 2 O 3 The catalyst is stirred and heated until the reflux water diversion is carried out, the reaction temperature of the reflux water diversion is 150-160 ℃, and the reaction lasts 18.0h. Reducing the temperature to 80-90 ℃, discharging the reaction liquid from the bottom of the jacket reactor, and removing the catalyst by heat filtration; the reaction solution was cooled to room temperature and filtered to obtain a yellow-brown solid, i.e., a condensation product oxybis- (N-methylphthalimide), 97.1g, 92.2% in content after drying, and the yield of the condensation reaction was 73.2%.
The above examples are only for clearly illustrating the technical solutions of the present invention, and are not intended to limit the embodiments of the present invention. Any other changes or modifications of the equivalent technical features without changing the basic idea and essence of the present invention shall fall within the protection scope of the claims of the present invention.

Claims (10)

1. A method for preparing ODPA, said ODPA is 3,3', 4' -diphenyl ether dianhydride, said method comprises taking N-methyl-4-nitro phthalimide as raw materials, get oxo bis- (N-methyl phthalimide) through condensation, hydrolyze and acidify, recrystallize and purify, dehydrate and get ODPA; the step of obtaining the oxo-bis- (N-methylphthalimide) by condensation by using the N-methyl-4-nitrophthalimide as a raw material comprises the following steps: first KF/Al 2 O 3 Taking a solid base catalyst as a catalyst, taking a mixed solvent containing an aprotic polar solvent and a water-carrying agent as a solvent, carrying out a first-stage reaction at a reaction temperature of more than 120 ℃, carrying out solid-liquid separation to remove the catalyst while the mixed solvent is hot at a temperature of more than 80 ℃ after the first-stage reaction is finished, cooling the separated liquid to separate out a condensation product oxybis- (N-methylphthalimide), and carrying out solid-liquid separation to obtain a first part of condensation product oxybis- (N-methylphthalimide); adding new KF/Al into the liquid after solid-liquid separation to obtain condensation product 2 O 3 Solid base catalyst at reaction temperature over 120 deg.cAfter the second stage reaction, the catalyst is removed by solid-liquid separation while the reaction is hot at the temperature of more than 80 ℃, the separated liquid is cooled and water is added to separate out the condensation product oxybis- (N-methylphthalimide), and then the second part of condensation product oxybis- (N-methylphthalimide) is obtained by solid-liquid separation.
2. The method according to claim 1, wherein the first stage and the second stage are carried out in a reflux water separation device, and water is separated from the mixed solvent in time during the reaction.
3. The process according to claim 1, wherein the liquid obtained by solid-liquid separation of the second partial condensation product is subjected to water separation in a reflux water separator, and the remaining liquid is subjected to distillation under reduced pressure to obtain a mixed solvent, and the obtained mixed solvent is repeatedly used in the condensation reaction.
4. The method according to claim 1, wherein the KF content in the catalyst is 25 to 40wt%, and the method for preparing the catalyst comprises the following steps: preparing aqueous KF solution and adding Al 2 O 3 Mixing with ethanol, dripping KF water solution under ultrasonic stirring, aging, removing solvent, drying and roasting to obtain KF/Al 2 O 3 A solid base catalyst; and the mass of the ethanol is Al 2 O 3 1.5 to 4 times of the mass, aging for more than 1 hour, removing more than 50 percent of the solvent by distillation, drying at 60 to 120 ℃, baking at 300 to 400 ℃ and baking for 6 to 10 hours.
5. The method of claim 1, wherein the catalyst regeneration method comprises heating and refluxing in an organic solvent selected from one or more of ethanol, methanol, acetone and tetrahydrofuran.
6. The method according to claim 1, wherein the aprotic polar solvent is one or more of DMAc, NMP and DMF, the water-carrying agent is toluene or xylene, and the mass ratio of the dosage of the aprotic polar solvent to the dosage of the water-carrying agent is 4-7: 1, and the dosage of the mixed solvent is 3 to 8 times of the mass of the raw material N-methyl-4-nitrophthalimide.
7. The method of claim 1, wherein the KF/Al is reacted in the first stage 2 O 3 The usage amount of the solid base catalyst is 10 to 20wt% of the raw material N-methyl-4-nitrophthalimide, and the KF/Al is obtained through a second-stage reaction 2 O 3 The using amount of the solid base catalyst is 12 to 25wt% of the raw materials.
8. The process according to claim 1, wherein after the first-stage reaction, the liquid obtained after removing the catalyst by solid-liquid separation is cooled to room temperature to precipitate the condensation product, and after the second-stage reaction, the liquid obtained after removing the catalyst by solid-liquid separation is cooled to room temperature and the condensation product is precipitated by adding water.
9. The process according to claim 1, wherein the solid-liquid separation is carried out to remove the catalyst after the completion of the first-stage reaction and after the completion of the second-stage reaction by filtration while the reaction mixture is still hot.
10. The method according to any one of claims 1 to 9, wherein the reflux water diversion reaction temperature of the first stage reaction and the second stage reaction is 150 to 160 ℃; the reaction time in the first stage is 6 to 8 hours, and the reaction time in the second stage is 8 to 12 hours.
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