CN112724111A - Method for preparing ODPA - Google Patents
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- CN112724111A CN112724111A CN202011617227.2A CN202011617227A CN112724111A CN 112724111 A CN112724111 A CN 112724111A CN 202011617227 A CN202011617227 A CN 202011617227A CN 112724111 A CN112724111 A CN 112724111A
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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
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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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, obtaining oxo-bis- (N-methylphthalimide) through condensation, then obtaining ODPA after hydrolytic acidification, recrystallization purification and dehydration; the condensation step comprises: with KF/Al2O3The 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 into the rest liquid2O3And (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
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 PI, the demand of the industry increases, and especially the explosive demand of PI films brought by the large-scale application of OLEDs on smartphones increases year by year for the basic monomers ODPA. 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 hydrolytic 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.
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 reported in J.org.chem.,1977,3431-2CO3、NaNO2And 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, after the reaction is finished, the reaction liquid is poured into a large amount of dilute hydrochloric acid to separate out solids, and the yield is 60-78%. However, the reaction in the report only uses a plurality of grams of oxo-bis- (N-methyl phthalimide) as a raw material, and uses a large amount of solvent, so that the yield of the condensation product is between 60 and 78 percent. 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 dosage and cannot be recycled, and the reaction needs to pour the reaction liquid into a large amount of dilute hydrochloric acid after the reaction is finished to precipitate solids, so that 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, and 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 crucial 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, 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/Al2O3Taking 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 product2O3Solid 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, 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 KF aqueous solution and adding Al2O3Mixing with ethanol, dripping KF aqueous solution under ultrasonic stirring, aging, removing solvent, drying, and roasting to obtain KF/Al2O3A solid base catalyst; the preferred mass of ethanol is Al2O31.5-4 times of the mass, the aging time is more than 1 hour, more than 50 percent of the solvent is removed by distillation, the drying temperature 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 4-7: 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 stage2O3The using amount of the solid base catalyst is 5-30 wt%, preferably 10-20 wt% of the raw material N-methyl-4-nitrophthalimide, and the KF/Al is obtained by the second-stage reaction2O3The solid base catalyst is used in an amount of 8 to 35 wt%, preferably 12 to c, based on the weight of the raw material25wt％。
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 the 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 the 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 filtration while hot.
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 of the first stage is 4-10 hours, preferably 6-8 hours, and the reaction time of the second stage is 5-20 hours, preferably 8-12 hours.
In the invention, the temperature of the reflux water separation reaction is different due to different solvent ratios in the mixed solvent, but is mostly 150-160 ℃.
The invention has at least the following beneficial effects:
1. the invention provides a method for synthesizing ODPA and a key intermediate oxo-bis- (N-methyl phthalimide) 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 more than or equal to 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%, the content of more than or equal to 93.0% 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 using singlesOr the composite 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 the 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 used2O3The solid base catalyst has catalytic performance not affected by the content of water impurity in the material and solvent, so that 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 invention, only a small amount of water (about 0.5-2 times of 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 weighed2O3And 80.0g of ethanol are added into a three-mouth 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, the KF/Al with the mass fraction of 30 percent is 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 percent2O3A catalyst.
150.0g of 150.0g 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 added2O3And (3) stirring the catalyst, heating until reflux water diversion is carried out, wherein the reaction temperature of the reflux water diversion is 150-160 ℃, and reacting for 6.0 h. 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), which was 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 added2O3Stirring the catalyst, heating to reflux and divide water, wherein the reaction temperature of the reflux and the division 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; the reaction solution was cooled to room temperature, 100.0g of purified water was added, and a yellowish brown solid, i.e., a condensation product oxybis- (N-methylphthalimide), was precipitated by filtration, and was 34.6g, with a content of 95.1%, after drying. The overall yield of the condensation reaction was 82.8% (molar yield, the same applies below).
Catalyst regeneration: catalyst KF/Al obtained by twice filtration2O3Adding 100.0g of ethanol, heating and refluxing for 8.0h, filtering, and drying for the next batch of reaction.
Example 2
150.0g of 150.0g N-methyl-4-nitrophthalimide, 600.0g of DMF and 100.0g of toluene were charged in a 1L jacketed reactor, and 15.0g of recovered KF/Al was added2O3The catalyst (the catalyst obtained in the catalyst regeneration step in example 1) was stirred, heated to reflux and separated from water, and reacted for 8.0 h. 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), which was dried to 67.9g and contained 98.2%.
The filtrate was reintroduced into the jacketed reactor and 20.0g of the recovered filtrate was addedKF/Al2O3Stirring 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: putting the filtrate obtained by filtering when the second part of condensation product is separated in the embodiments 1 and 2 into a jacket reactor, and heating and dividing water in a reflux water dividing device, wherein 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 654.7g of a DMF/toluene mixed solution, DMF: the mass ratio of toluene is 6.7: 1, the amount of high-boiling and viscous organic matter was 27.9 g.
Comparative example 1
150.0g of 150.0g 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 as described in example 1 above was added2O3And (3) stirring the catalyst, heating until reflux water diversion is carried out, wherein the reaction temperature of the reflux water diversion is 150-160 ℃, and reacting for 18.0 h. 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. Method for preparing ODPAThe ODPA is 3,3 ', 4, 4' -diphenyl ether dianhydride, and the method comprises the steps of firstly condensing N-methyl-4-nitrophthalimide serving as a raw material to obtain oxo-bis- (N-methylphthalimide), and then hydrolyzing, acidifying, recrystallizing, purifying and dehydrating to obtain 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/Al2O3Taking 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 product2O3Solid 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.
2. The method of 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 after the solid-liquid separation of the second part of the 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 of claim 1The method is characterized in that the content of KF in the catalyst is 25-40 wt%, and the preparation method of the catalyst comprises the following steps: preparing KF aqueous solution and adding Al2O3Mixing with ethanol, dripping KF aqueous solution under ultrasonic stirring, aging, removing solvent, drying, and roasting to obtain KF/Al2O3A solid base catalyst; the preferred mass of ethanol is Al2O31.5-4 times of the mass, the aging time is more than 1 hour, more than 50 percent of the solvent is removed by distillation, the drying temperature is 60-120 ℃, the roasting temperature is 300-400 ℃, and the roasting time is 6-10 hours.
5. The method of claim 1, wherein the catalyst regeneration method is heating reflux washing in an organic solvent, and the organic solvent comprises 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 3-8 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 stage2O3The using amount of the solid base catalyst is 5-30 wt%, preferably 10-20 wt% of the raw material N-methyl-4-nitrophthalimide, and the KF/Al is obtained by the second-stage reaction2O3The using amount of the solid base catalyst is 8-35 wt% of the raw materials, and preferably 12-25 wt%.
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 of the first stage is 4-10 hours, preferably 6-8 hours, and the reaction time of the second stage is 5-20 hours, preferably 8-12 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550102A (en) * | 2009-05-07 | 2009-10-07 | 西北农林科技大学 | Method for preparing di-(N-methyl phthalimide) ether |
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| CN101550102A (en) * | 2009-05-07 | 2009-10-07 | 西北农林科技大学 | Method for preparing di-(N-methyl phthalimide) ether |
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