CN111620769B - Method for preparing 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride - Google Patents
Method for preparing 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride Download PDFInfo
- Publication number
- CN111620769B CN111620769B CN202010501414.8A CN202010501414A CN111620769B CN 111620769 B CN111620769 B CN 111620769B CN 202010501414 A CN202010501414 A CN 202010501414A CN 111620769 B CN111620769 B CN 111620769B
- Authority
- CN
- China
- Prior art keywords
- biphenyl tetracarboxylic
- monosodium salt
- acid
- palladium
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, which comprises the following steps: 1) coupling and acid precipitation: using water as a solvent, reducing a chlorinated phthalic acid monosodium salt mixture by using a hydrazine reducing agent under the catalysis of a palladium-copper carbon supported catalyst to perform dechlorination coupling reaction to obtain 3,3 ', 4, 4' -biphenyl tetracarboxylic acid, adding a filtrate obtained after the catalyst is filtered into dilute sulfuric acid, and cooling and crystallizing to obtain a crude product of the 3,3 ', 4, 4' -biphenyl tetracarboxylic acid; 2) refining: refining with methanol water solution to obtain refined 3,3 ', 4, 4' -biphenyltetracarboxylic acid; 3) and (3) no hydration: heating and dehydrating the refined 3,3 ', 4, 4' -biphenyl tetracarboxylic acid to obtain the 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride. The raw materials are easy to obtain, and a palladium-copper carbon-supported catalyst is adopted to preferably select a proper dechlorination coupling reducing agent hydrazine sulfate so that the conversion rate of the chlorinated sodium phthalate salt mixture reaches 100 percent; and (3) selecting a proper solvent system to finally obtain a product, wherein the content of the product is more than 99.7%, the yield is 81-87%, and the metal ion content is less than 2 ppM.
Description
Technical Field
The invention relates to a preparation method of a fine chemical organic material, and particularly relates to a method for preparing 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride.
Background
The 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride can be obtained by the dehydration of 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, is an important monomer of polyimide, and can be polymerized with various amines to generate polyimide. Because of the rigid structure of the 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, the polyimide synthesized by using the 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride is super heat-resistant resin with the highest heat-resistant temperature so far, the stretched polyimide film and the copper foil have almost completely consistent thermal expansion coefficients, can be well combined with the copper foil under the conditions of high temperature and low temperature for a long time without peeling, and is widely applied to flexible circuit boards and super-high-power 5G signal transmitters. The polymer is polymerized with specific amines to prepare a transparent film for preparing a folding display screen, and the transparent film has the advantages of lightness, flexibility, thinness and no breakage when used as a hard cover; the novel LED display screen is scratch-resistant, transparent and heat-resistant, can be folded for dozens of thousands of times without folds, is used for foldable OLED display, can be used for wearable equipment, folding screen mobile phones, folding screen computers and the like, and is a basic material for recent hottest 5G science and technology and folding screen mobile phones. In addition, the composite material can be used for manufacturing heat-resistant photosensitive resin, optical filters, liquid crystal displays, cross-linking adhesives of conductors and semiconductors, and can also be used for lasers, lithium batteries and protective materials used in space.
Many documents have been reported on the synthesis of 3,3 ', 4, 4' -biphenyltetracarboxylic acid, and for example, in the synthesis method disclosed in Japanese patent application laid-open No. Sho 63-88155, the conversion of 4-chlorophthalic acid is 99% and the yield of 3,3 ', 4, 4' -biphenyltetracarboxylic acid is 65% at the maximum by dehalogenating 4-chlorophthalic acid using 5% palladium on charcoal as a catalyst and a polyhydric alcohol such as glycerin as a reducing agent. The conversion rate of the 4-chlorophthalic acid is only 99 percent but not 100 percent, which causes the residue of raw materials in 3,3 ', 4, 4' -biphenyl tetracarboxylic acid, leads to unqualified chloride ions of the final 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride product, limits the application of the 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride and can not be applied to the fields of high-grade flexible circuit boards, 5G materials and the like; in addition, the dosage of 5 percent Pd/C of the noble metal is 3.7 percent of that of 4-chlorophthalic acid, and the dosage is too large, so the production cost is unacceptable. Domestic Dingmenxian and the like adopt 4-chlorophthalic acid dimethyl ester as a raw material, and bis (triphenylphosphine) -nickel dichloride as a catalyst to carry out coupling reaction to prepare 3,3 ', 4, 4' -biphenyl tetracarboxylic acid; the method has the defects of difficult obtainment of raw materials and no industrialization.
Disclosure of Invention
In order to solve the technical problem of high production cost of 3,3 ', 4, 4' -biphenyltetracarboxylic acid and improve the product quality of the 3,3 ', 4, 4' -biphenyltetracarboxylic acid, the invention researches a dechlorination coupling catalyst and selects a proper reducing agent to obtain the method for preparing the 3,3 ', 4, 4' -biphenyltetracarboxylic acid, and the 3,3 ', 4, 4' -biphenyltetracarboxylic acid obtained by the method has good quality, low production cost, simple process and easy industrialization.
The invention provides the following technical scheme:
a method for preparing 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride comprising the steps of:
under the action of a palladium-copper carbon-supported catalyst, reducing a chlorinated phthalic acid monosodium salt mixture by using a hydrazine reducing agent to perform dechlorination coupling reaction, refining an obtained biphenyl tetracarboxylic acid crude product by using a methanol aqueous solution to obtain a white to off-white 3,3 ', 4, 4' -biphenyl tetracarboxylic acid refined product, and heating and dehydrating to obtain 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, wherein the yield is 81-87%, and the content is 99.7-99.95%.
In the technical scheme, the molar ratio of the chlorinated phthalic acid monosodium salt mixture to the hydrazine reducing agent is 1: 0.25-0.3.
In the technical scheme, furthermore, the mass percentage of the 4-chlorophthalic acid monosodium salt, the mass percentage of the 4, 5-dichlorophthalic acid monosodium salt, the mass percentage of the 3-chlorophthalic acid monosodium salt and the mass percentage of the phthalic acid monosodium salt in the chlorophthalic acid monosodium salt mixture are respectively 75-80%, 10-14%, 0.8-1.2% and 8-13%.
In the above technical solution, further, the hydrazine reducing agent is hydrazine hydrate, hydrazine hydrochloride or hydrazine sulfate. Preferably, the hydrazine-based reducing agent is hydrazine sulfate.
In the technical scheme, the mass ratio of the chlorinated phthalic acid monosodium salt mixture to the palladium-copper carbon-supported catalyst is 1: 0.003-0.1.
In the technical scheme, further, the preparation method of the palladium-copper carbon-supported catalyst comprises the steps of soaking 5% palladium carbon in a copper chloride aqueous solution, adjusting the pH value of the sodium hydroxide aqueous solution to 11, standing for 1-2 hours, stirring and heating, adding a sodium formate aqueous solution at the temperature of 80-100 ℃, carrying out heat preservation reaction for 8-12 hours, cooling to room temperature, filtering and washing to obtain the palladium-copper carbon-supported catalyst.
In the above technical scheme, further, the crude biphenyltetracarboxylic acid is added into a methanol aqueous solution, wherein the adding amount of the methanol aqueous solution is as follows: the mass ratio of the added chlorinated phthalic acid monosodium salt mixture to the methanol aqueous solution is 1: 8-12; after the feeding is finished, heating to 70-75 ℃, refluxing for 1-2h, cooling to 25-35 ℃, and filtering to obtain a white 3,3 ', 4, 4' -biphenyltetracarboxylic acid refined product.
In the above technical scheme, further, the methanol aqueous solution comprises methanol in a mass ratio of: water 1: 1-4.
In the technical scheme, the temperature for heating and dehydrating the 3,3 ', 4, 4' -biphenyl tetracarboxylic acid is 230-280 ℃.
Compared with the prior art, the invention has the beneficial effects that: the invention directly uses the mixture of the mono-sodium chlorophthalic acid, the mixture has simple industrial production and easily obtained raw materials; the unique palladium-copper carbon-supported catalyst for dechlorination coupling is prepared, and a proper dechlorination coupling reducing agent hydrazine sulfate is preferably selected, so that the conversion rate of the chlorinated sodium phthalate salt mixture reaches 100 percent, and the residue of the raw material in the product is avoided; a proper solvent system is selected, the methanol in the methanol aqueous solution ensures the solubility of the 3,3 ', 4, 4' -biphenyltetracarboxylic acid, organic impurities can be removed, and metal ions contained in the 3,3 ', 4, 4' -biphenyltetracarboxylic acid can be effectively removed by the water in the methanol aqueous solution; finally, white to off-white 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride is obtained, the content is more than 99.6%, the yield is 81-87%, and the metal ion content is less than 2 ppM.
Drawings
FIG. 1 is an experimental chromatogram of example 1.
FIG. 2 is an experimental chromatogram for example 2.
FIG. 3 is an experimental chromatogram of example 3.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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
Preparation of palladium-copper carbon-supported catalyst:
0.42g of solid CuCl is weighed2Dissolving the palladium-copper composite material in 100 ml of pure water, adding 20g of 5% palladium-carbon catalyst into the solution, heating to 80 ℃, adjusting the pH to 11 by using sodium hydroxide aqueous solution, standing for 1h, stirring and keeping the temperature, adding 8g of 10% sodium formate aqueous solution, keeping the temperature for 8h, cooling to room temperature, filtering, washing by using 260 ml of water, and draining to obtain the palladium-copper carbon-supported catalyst for later use.
Preparation of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride:
336.2ml of pure water and 59.3g of sodium hydroxide are put into a 1000ml four-mouth reaction bottle equipped with a peristaltic pump, a thermometer and a stirrer, stirred and dissolved, then 110g of a chlorinated phthalic acid monosodium salt mixture (4-chlorophthalic acid monosodium salt 75.1%, 4, 5-dichlorinated phthalic acid monosodium salt 10.3%, 3-chlorophthalic acid monosodium salt 0.80%, phthalic acid monosodium salt 13.5%) and 0.33g of palladium-copper carbon-supported catalyst are put into the reaction bottle, the temperature is raised to 70 ℃, the temperature is maintained, 80.5g of hydrazine sulfate aqueous solution with the mass concentration of 20% is pumped into the reaction bottle by the peristaltic pump, the time for use lasts 8h, the temperature is kept for 2h after the addition, the temperature is lowered to 40 ℃, and the palladium-copper carbon-supported catalyst is filtered. The filtrate was added dropwise to 550g of a 12% sulfuric acid solution, filtered, and washed with 300ml of pure water to obtain a crude product of 3,3 ', 4, 4' -biphenyltetracarboxylic acid. Putting the crude product into 880g of methanol water (50%) solution, heating to 70 ℃, refluxing for 2h, cooling to 25-35 ℃, filtering, washing with 300ml of pure water, and drying to obtain white 3,3 ', 4, 4' -biphenyltetracarboxylic acid refined product; heating refined 3,3 ', 4, 4' -biphenyl tetracarboxylic acid to 230 ℃ for heating and dehydrating, keeping the temperature for 12h, cooling, discharging to obtain white 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, wherein the yield is 81.3%, the content is 99.949% shown in the table I, and the metal ions are less than 2 ppM.
Watch 1
< Peak Table >
Detector A254 nm
| Peak number | Retention time | Area of | Height | Area% |
| 1 | 21.063 | 32003809 | 3991760 | 99.949 |
| 2 | 23.294 | 8775 | 1313 | 0.027 |
| 3 | 27.894 | 3234 | 422 | 0.010 |
| 4 | 28.275 | 1518 | 237 | 0.005 |
| 5 | 29.176 | 2896 | 470 | 0.009 |
| Total of | 32020233 | 3994202 | 100.000 |
Chromatogram 1 for each retention time.
Example 2
Preparation of palladium-copper carbon-supported catalyst:
0.42g of solid CuCl is weighed2Dissolving the palladium-copper composite material in 100 ml of pure water, adding 20g of 5% palladium-carbon catalyst into the solution, heating to 80 ℃, adjusting the pH to 11 by using sodium hydroxide aqueous solution, standing for 1.5h, stirring and keeping the temperature, adding 8g of 10% sodium formate aqueous solution, continuously preserving the temperature for 8h, cooling, filtering, washing by using 260 ml of water, and draining to obtain the palladium-copper carbon-supported catalyst for later use.
Preparation of 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride:
336.2ml of pure water and 59.3g of sodium hydroxide are put into a 1000ml four-mouth reaction bottle equipped with a peristaltic pump, a thermometer and a stirrer, stirred and dissolved, then 110g of a chlorinated phthalic acid monosodium salt mixture (4-chlorophthalic acid monosodium salt 79.6%, 4, 5-dichlorophthalic acid monosodium salt 11.1%, 3-chlorophthalic acid monosodium salt 0.99%, phthalic acid monosodium salt 8.1%) and 0.99g of palladium-copper carbon-supported catalyst are put into the reaction bottle, the temperature is raised to 80 ℃, the temperature is maintained, 88.5g of hydrazine sulfate aqueous solution with the mass concentration of 20% is pumped into the reaction bottle by the peristaltic pump, the time is 9 hours, the temperature is kept for 2 hours after the addition, the temperature is lowered to 40 ℃, and the palladium-copper carbon-supported catalyst is filtered. The filtrate was added dropwise to 550g of a 12% sulfuric acid solution, filtered, and washed with 300ml of pure water to obtain a crude product of 3, 3 ', 4, 4' -biphenyltetracarboxylic acid. Putting the crude product into 1100g of methanol-water (35%) solution, heating to 73 ℃, refluxing for 1h, cooling to 25-35 ℃, filtering, washing with 300ml of pure water, and drying to obtain white 3, 3 ', 4, 4' -biphenyltetracarboxylic acid refined product; heating the refined 3, 3 ', 4, 4' -biphenyl tetracarboxylic acid to 250 ℃ for heating and dehydrating, keeping the temperature for 10h, cooling, discharging to obtain white 3, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, wherein the yield is 83.5%, the content is 99.762% shown in the table II, and the metal ions are less than 2 ppM.
Watch 2
< Peak Table >
Detector A254 nm
| Peak number | Retention time | Area of | Height | Area% |
| 1 | 20.769 | 22696389 | 2570787 | 99.762 |
| 2 | 22.985 | 8366 | 1251 | 0.037 |
| 3 | 27.580 | 9535 | 1244 | 0.042 |
| 4 | 27.959 | 6265 | 725 | 0.028 |
| 5 | 28.848 | 19936 | 2727 | 0.088 |
| 6 | 29.433 | 8982 | 877 | 0.039 |
| 7 | 30.118 | 1087 | 151 | 0.005 |
| Total of | 22750559 | 2577762 | 100.000 |
Chromatogram 2 for each retention time.
Example 3
The preparation process of the palladium-copper carbon-supported catalyst comprises the following steps:
0.42g of solid CuCl is weighed2Dissolving the palladium-copper composite material in 100 ml of pure water, adding 20g of 5% palladium-carbon catalyst into the solution, heating to 100 ℃, adjusting the pH to 11 by using sodium hydroxide aqueous solution, standing for 1h, stirring and keeping the temperature, adding 8g of 10% sodium formate aqueous solution, continuously preserving the temperature for 12h, cooling, filtering, washing by using 260 ml of water, and draining to obtain the palladium-copper carbon-supported catalyst for later use.
Preparation of 3, 3 ', 4, 4' -biphenyltetracarboxylic dianhydride:
336.2ml of pure water and 59.3g of sodium hydroxide are put into a 1000ml four-mouth reaction bottle equipped with a peristaltic pump, a thermometer and a stirrer, stirred and dissolved, then 110g of a chlorinated phthalic acid monosodium salt mixture (76.6 percent of 4-chlorophthalic acid monosodium salt, 13.9 percent of 4, 5-dichlorophthalic acid monosodium salt, 1.20 percent of 3-chlorophthalic acid monosodium salt and 8.1 percent of phthalic acid monosodium salt) and 1.65g of palladium-copper carbon-supported catalyst are put into the reaction bottle, the temperature is raised to 90 ℃, the temperature is maintained, 96.5g of hydrazine sulfate aqueous solution with the mass concentration of 20 percent is pumped by the peristaltic pump, the time for use is 8 hours, the temperature is kept for 2 hours after the addition, the temperature is lowered to 40 ℃, and the palladium-copper carbon-supported catalyst is filtered. The filtrate was added dropwise to 550g of a 12% sulfuric acid solution, filtered, and washed with 300ml of pure water to obtain a crude product of 3, 3 ', 4, 4' -biphenyltetracarboxylic acid. Putting the crude product into 1320g methanol water (20%) solution, heating to 75 ℃, refluxing for 2h, cooling to 25-35 ℃, filtering, washing with 300ml pure water, and drying to obtain white 3, 3 ', 4, 4' -biphenyltetracarboxylic acid refined product; heating refined 3, 3 ', 4, 4' -biphenyl tetracarboxylic acid to 280 ℃ for heating and dehydrating, keeping the temperature for 12h, cooling, discharging to obtain white 3, 3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, wherein the yield is 87.1%, the content is 99.885% shown in table III, and the metal ions are less than 2 ppM.
Chromatogram for each retention time 2.
< Peak Table >
Detector A254 nm
| Number of peak | Retention time | Area of | Height | Area% |
| 1 | 21.063 | 30397762 | 3997212 | 99.885 |
| 2 | 23.302 | 13349 | 1706 | 0.044 |
| 3 | 27.894 | 4512 | 582 | 0.015 |
| 4 | 28.279 | 938 | 136 | 0.003 |
| 5 | 29.182 | 11991 | 1667 | 0.039 |
| 6 | 29.737 | 4104 | 549 | 0.013 |
| Total of | 30432657 | 4001852 | 100.000 |
Chromatogram 3 for each retention time.
Example 4 (comparative catalyst)
336.2ml of pure water and 59.3g of sodium hydroxide are put into a 1000ml four-mouth reaction bottle equipped with a peristaltic pump, a thermometer and a stirrer, stirred and dissolved, then 110g of a chlorinated phthalic acid monosodium salt mixture (78.3 percent of 4-chlorophthalic acid monosodium salt, 11.7 percent of 4, 5-dichloro phthalic acid monosodium salt, 1.1 percent of 3-chlorophthalic acid monosodium salt and 8.6 percent of phthalic acid monosodium salt) and 1.65g of 5 percent palladium carbon are put into the reaction bottle, the temperature is raised to 90 ℃, 104g of hydrazine sulfate aqueous solution with the mass concentration of 20 percent is pumped by the peristaltic pump at the keeping temperature, when the time is 8.5h, the sampling HPLC (high performance liquid chromatography) is used for control detection, the content of the 4, 5-dichloro phthalic acid monosodium salt is less than 0.5 percent, the reducing agent is stopped to be added, the temperature is kept for 2h, the temperature is lowered to 40 ℃, and the palladium-copper-carbon-carried catalyst is filtered. The filtrate is dripped into 400g of 20 percent hydrochloric acid solution, filtered and washed by 300ml of pure water to obtain the crude product of the 3,3 ', 4, 4' -biphenyl tetracarboxylic acid. Putting the crude product into 750ml of methanol water (50%) solution, heating to 75 ℃, refluxing for 2h, cooling to 25-35 ℃, filtering, washing with 300ml of pure water, and drying to obtain white 3,3 ', 4, 4' -biphenyltetracarboxylic acid refined product; heating the refined 3,3 ', 4, 4' -biphenyl tetracarboxylic acid to 260 ℃ for heating and dehydrating, keeping the temperature for 12 hours, cooling, discharging to obtain white 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, wherein the yield is 73.3%.
The method mainly comprises three steps of (1) coupling and acid precipitation: using water as a solvent, reducing a chlorinated phthalic acid monosodium salt mixture by using a hydrazine reducing agent under the catalysis of a palladium-copper carbon supported catalyst to perform a dechlorination coupling reaction to obtain 3,3 ', 4, 4' -biphenyl tetracarboxylic acid, reacting hydrogen chloride serving as another product with an alkali acid-binding agent to form a salt, adding the filtrate after the separation of the catalyst into dilute sulfuric acid after the reaction is finished, and performing cooling crystallization to obtain a 3,3 ', 4, 4' -biphenyl tetracarboxylic acid crude product; (2) refining: refining with methanol water solution to obtain refined 3,3 ', 4, 4' -biphenyl tetracarboxylic acid; (3) and (3) no hydration: heating and dehydrating the refined 3,3 ', 4, 4' -biphenyl tetracarboxylic acid to obtain the 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride.
For the selection of raw materials, considering that 4-chlorophthalic acid (monosodium salt) industrial products with the content of more than 98 percent are not easy to obtain and the production cost is high, the invention directly uses the mixture of the monosodium chlorophthalic acid, the industrial production of the mixture is simple, and the raw materials are easy to obtain; in addition, the monosodium salt adopted in the invention does not need to be refined, and the chlorinated phthalic acid monosodium salt mixture (the mass percentage of the 4-chlorinated phthalic acid monosodium salt is 75-80%, the mass percentage of the 4, 5-dichloro phthalic acid monosodium salt is 10-14%, the mass percentage of the 3-chlorinated phthalic acid monosodium salt is 0.8-1.2%, and the mass percentage of the phthalic acid monosodium salt is 8-13%) can be directly applied to the coupling reaction.
The invention discloses a method for preparing a palladium-copper carbon-supported catalyst for dechlorination coupling, which is characterized in that chloride such as 4-chlorophthalic acid (sodium salt) and the like can inevitably generate a dechlorinated uncoupled byproduct phthalic acid in a dechlorination coupling reaction, so that the yield of 3,3 ', 4, 4' -biphenyltetracarboxylic acid is reduced, and how to improve the selectivity of the 3,3 ', 4, 4' -biphenyltetracarboxylic acid is a research focus. The toxicity of 3-chlorophthalic acid to palladium is weakened, so that 4, 5-dichlorophthalic acid is reacted completely without residue.
The method preferably selects a proper dechlorination coupling reducing agent hydrazine sulfate, ensures that the conversion rate of the chlorinated sodium phthalate mixture reaches 100 percent, avoids the residue of raw materials in products, greatly increases the selectivity of dechlorination reaction for generating 3,3 ', 4, 4' -biphenyl tetracarboxylic acid, reduces the generation of dechlorination uncoupled products phthalic acid, and improves the yield of the 3,3 ', 4, 4' -biphenyl tetracarboxylic acid.
After the crude product of the 3,3 ', 4, 4' -biphenyltetracarboxylic acid is obtained, a proper solvent system is selected, and because the 3,3 ', 4, 4' -biphenyltetracarboxylic acid is difficult to dissolve in water, the methanol in the methanol aqueous solution ensures the solubility of the 3,3 ', 4, 4' -biphenyltetracarboxylic acid and can remove organic impurities, and the water in the methanol aqueous solution can effectively remove metal ions contained in the 3,3 ', 4, 4' -biphenyltetracarboxylic acid, so that the content of the refined product of the 3,3 ', 4, 4' -biphenyltetracarboxylic acid can meet the requirements of the subsequent production of 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride on purity and ion content only by one-time refining.
When the 3,3 ', 4, 4' -biphenyl tetracarboxylic acid is anhydrous, the dehydration of the 3,3 ', 4, 4' -biphenyl tetracarboxylic acid is ensured to be complete, the color of the obtained biphenyl tetracarboxylic dianhydride is prevented from being deepened due to overhigh temperature, and the white to off-white 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride is obtained after the dehydration of the technology, wherein the content is more than 99.7%, the yield is 81-87%, and the metal ion is less than 2 ppM.
The invention overcomes the defects of the prior art and has the outstanding advantages of unique method, simple process, easy operation, high yield, lower cost, higher production efficiency and economic benefit, and the like.
Claims (3)
1. A method for preparing 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, which is characterized by comprising the following steps:
reducing a chlorinated phthalic acid monosodium salt mixture by using a hydrazine reducing agent under the action of a palladium-copper carbon-supported catalyst, wherein the hydrazine reducing agent is hydrazine sulfate, performing dechlorination coupling reaction, refining an obtained biphenyl tetracarboxylic acid crude product by using a methanol aqueous solution to obtain a white to off-white 3,3 ', 4, 4' -biphenyl tetracarboxylic acid refined product, heating and dehydrating at the dehydration temperature of 230-280 ℃ to obtain 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, wherein the yield is 81-87%, and the content is 99.7-99.95%;
The preparation method of the palladium-copper carbon-supported catalyst comprises the steps of soaking 5% palladium carbon in a copper chloride aqueous solution, adjusting the pH value of the copper chloride aqueous solution to 11, standing for 1-2h, stirring and heating, adding a sodium formate aqueous solution at 80-100 ℃, carrying out heat preservation reaction for 8-12 h, cooling to room temperature, filtering and washing to obtain the palladium-copper carbon-supported catalyst;
the molar ratio of the chlorinated phthalic acid monosodium salt mixture to the hydrazine reducing agent is 1: 0.25-0.3;
in the chlorinated phthalic acid monosodium salt mixture, the mass percentage of 4-chlorophthalic acid monosodium salt is 75-80%, the mass percentage of 4, 5-dichlorinated phthalic acid monosodium salt is 10-14%, the mass percentage of 3-chlorophthalic acid monosodium salt is 0.8-1.2%, and the mass percentage of phthalic acid monosodium salt is 8-13%;
the mass ratio of the chlorinated phthalic acid monosodium salt mixture to the palladium-copper carbon-supported catalyst is 1: 0.003-0.1.
2. The process for producing 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein: putting the biphenyl tetracarboxylic acid crude product into a methanol aqueous solution, wherein the adding amount of the methanol aqueous solution is as follows: the mass ratio of the added chlorinated phthalic acid monosodium salt mixture to the methanol aqueous solution is =1: 8-12; after the feeding is finished, heating to 70-75 ℃, refluxing for 1-2h, cooling to 25-35 ℃, and filtering to obtain a white 3,3 ', 4, 4' -biphenyltetracarboxylic acid refined product.
3. The process according to claim 2 for producing 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride, characterized in that: methanol aqueous solution according to mass ratio methanol: water = 1: 1-4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010501414.8A CN111620769B (en) | 2020-06-04 | 2020-06-04 | Method for preparing 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010501414.8A CN111620769B (en) | 2020-06-04 | 2020-06-04 | Method for preparing 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111620769A CN111620769A (en) | 2020-09-04 |
| CN111620769B true CN111620769B (en) | 2022-06-28 |
Family
ID=72269090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010501414.8A Active CN111620769B (en) | 2020-06-04 | 2020-06-04 | Method for preparing 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111620769B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114853705A (en) * | 2022-04-24 | 2022-08-05 | 河北海力香料股份有限公司 | Method for preparing chlorophthalic anhydride by recovering 4-chlorophthalic acid monosodium salt reaction mother liquor |
| CN115010601B (en) * | 2022-08-03 | 2022-11-22 | 河北海力香料股份有限公司 | Method for treating 3,3',4,4' -biphenyl tetracarboxylic acid production wastewater |
| CN115805070A (en) * | 2022-10-09 | 2023-03-17 | 天津大学 | Preparation method of 3,3',4,4' -biphenyl tetracarboxylic dianhydride, catalyst and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944419A (en) * | 2006-10-26 | 2007-04-11 | 上海固创化工新材料有限公司 | Process for synthesizing bibenzene tetracarboxylic dianhydride |
| CN101607894A (en) * | 2009-07-15 | 2009-12-23 | 石家庄海力精化有限责任公司 | A kind of preparation 3,3 ＇, the method for 4,4 ＇-bibenzene tetracarboxylic |
| CN103191730A (en) * | 2013-03-29 | 2013-07-10 | 浙江工业大学 | High-selectivity iridium carbon catalyst as well as preparation and application thereof |
| CN106034401A (en) * | 2013-09-04 | 2016-10-19 | 塔明克公司 | Improved process for the reductive amination and selective hydrogenation of substrates containing a selected halogen |
| CN110563678A (en) * | 2019-10-15 | 2019-12-13 | 上海固创化工新材料有限公司 | Preparation method of 3,3',4,4' -biphenyl tetracarboxylic dianhydride |
-
2020
- 2020-06-04 CN CN202010501414.8A patent/CN111620769B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1944419A (en) * | 2006-10-26 | 2007-04-11 | 上海固创化工新材料有限公司 | Process for synthesizing bibenzene tetracarboxylic dianhydride |
| CN101607894A (en) * | 2009-07-15 | 2009-12-23 | 石家庄海力精化有限责任公司 | A kind of preparation 3,3 ＇, the method for 4,4 ＇-bibenzene tetracarboxylic |
| CN103191730A (en) * | 2013-03-29 | 2013-07-10 | 浙江工业大学 | High-selectivity iridium carbon catalyst as well as preparation and application thereof |
| CN106034401A (en) * | 2013-09-04 | 2016-10-19 | 塔明克公司 | Improved process for the reductive amination and selective hydrogenation of substrates containing a selected halogen |
| CN110563678A (en) * | 2019-10-15 | 2019-12-13 | 上海固创化工新材料有限公司 | Preparation method of 3,3',4,4' -biphenyl tetracarboxylic dianhydride |
Non-Patent Citations (6)
| Title |
|---|
| "Pd/CNF催化脱卤偶联合成3，3"，4，4"-联苯四甲酸二酐的研究";孙培生;《中国优秀硕士学位论文全文数据库》;20090515(第05期);B016-36 * |
| 3,3’,4,4’-联苯四甲酸二酐的合成;张波等;《化学工业与工程技术》;20040430(第02期);30-34 * |
| 3,3’,4,4’-联苯四甲酸合成中偶联工艺的研究;李永真等;《绝缘材料》;20111020(第05期);24-26 * |
| 3,3′,4,4′-联苯四甲酸二酐的合成工艺;谢开林等;《化工学报》;20050930(第09期);1805-1808 * |
| 李效军等.3,3',4,4'-联苯四甲酸二酐的合成.《河北工业大学学报》.2007,(第01期), * |
| 联苯四酸二酐几种异构体的合成方法;宋颉等;《绝缘材料》;20051020(第05期);52-56 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111620769A (en) | 2020-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111620769B (en) | Method for preparing 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride | |
| CN101659647B (en) | Method for preparing diphenyl tetracarboxylic dianhydride | |
| CN101481366B (en) | Preparation of 2,3,3',4'-biphenyl-tetracarboxylic acid dianhydride and derivatives thereof | |
| CN102531925B (en) | Method for preparing high-purity 1-aminoanthraquinone through catalytic hydrogenation | |
| CN112142570B (en) | Preparation method of p-hydroxybiphenyl diphenol | |
| CN101607894B (en) | Preparation method of 3,3',4,4'-tetra carboxylic acid biphenyl | |
| CN110862310A (en) | Synthesis method of cyclopropyl methyl ketone | |
| CN103539662B (en) | Preparation and recovery method of 2-methyl-5-iodobenzoic acid | |
| KR101002061B1 (en) | Process for preparing 4-aminomethylbenzoic acid | |
| CN115504870B (en) | Preparation method and application of 4-methoxy-2-naphthol | |
| CN105541637A (en) | Preparation method of 2,2'-bis-trifluoromethyl-4,4'-diaminodiphenyl | |
| CN101492381B (en) | Method of preparing 2,2-di(3-amino-4-hydroxyl phenyl) hexafluoroacetore | |
| CN113816858B (en) | Preparation method of trans-1, 2-diaminomethylcyclobutane and hydrochloride thereof | |
| CN112679342A (en) | Preparation method of trans, trans-4, 4' -dicyclohexyl dicarboxylic acid | |
| WO2023151157A1 (en) | Chemical intermediate and preparation method | |
| CN114230540A (en) | Method for synthesizing alpha-BPDA | |
| CN107935971A (en) | It is a kind of（S）The preparation method of 3 hydroxyl tetrahydrofurans | |
| CN106380455A (en) | Synthetic method and application of vortioxetine hydrobromide | |
| CN112574148A (en) | Preparation method of 4,4'- (4,4' -isopropylidenediphenoxy) bis (phthalic anhydride) | |
| CN111116319A (en) | Synthesis and refining method of high-purity 1, 6-dihydroxynaphthalene | |
| JP4796366B2 (en) | Bis (glycidyloxy) decalin | |
| CN113548948B (en) | Preparation method of methyl octabromoether | |
| CN112209841B (en) | Synthesis method of terbutaline and application of terbutaline in preparation of terbutaline sulfate | |
| CN114478413B (en) | Preparation method and application of 2- (2 ' -hydroxy-3 ' -methallyl-5 ' -methylphenyl) benzotriazole | |
| CN115745782B (en) | Preparation method and production method of phthalic acid derivative |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230403 Address after: 050000, 200 meters east of the intersection of Industrial Street and Huahua North Road in the Circular Chemical Industry Park of Shijiazhuang City, Hebei Province Patentee after: Hebei Dongli New Material Co.,Ltd. Address before: 226407 No.10, Huanghai 4th Road, Rudong Coastal Economic Development Zone, Nantong City, Jiangsu Province Patentee before: NANTONG HUISHUN CHEMICAL Co.,Ltd. |