阅读说明：本技术 一种制备3,3’，4,4’-联苯四甲酸二酐的方法 (Method for preparing 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride ) 是由 吴晓霞 于 2020-06-04 设计创作，主要内容包括：本发明公开了一种制备3,3’,4,4’-联苯四甲酸二酐的方法,包括以下步骤：1)偶联、酸析：以水为溶剂,氯代邻苯二甲酸单钠盐混合物在钯-铜炭负载催化剂的催化下,由肼类还原剂还原,发生脱氯偶联反应,得到3,3’,4,4’-联苯四甲酸,将过滤完催化剂后的滤液加入到稀硫酸中,降温结晶,得到3,3’,4,4’-联苯四甲酸粗品；2)精制：再用甲醇水溶液精制,得到3,3’,4,4’-联苯四甲酸精品；3)无水化：将3,3’,4,4’-联苯四甲酸精品加热脱水,得到3,3’,4,4’-联苯四甲酸二酐。本发明原料易得,采用钯-铜炭载催化剂,优选出了适宜的脱氯偶联还原剂硫酸肼,使氯代邻苯二甲酸钠盐混合物转化率达到100％；选用了适宜的溶剂体系,最后得到产物,含量大于99.7％,收率81～87％,金属离子小于2ppM。(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.)

1. A method for preparing 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride, which is characterized by comprising the following steps:

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%.

2. The process for producing 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein: the molar ratio of the chlorinated phthalic acid monosodium salt mixture to the hydrazine reducing agent is 1: 0.25-0.3.

3. The process for producing 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein: 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%.

4. The process for producing 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein: the hydrazine reducing agent is hydrazine hydrate, hydrazine hydrochloride or hydrazine sulfate.

5. The process according to claim 4 for producing 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride, wherein: the hydrazine reducing agent is hydrazine sulfate.

6. The process for producing 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein: the mass ratio of the chlorinated phthalic acid monosodium salt mixture to the palladium-copper carbon-supported catalyst is 1: 0.003-0.1.

7. The process for producing 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein: 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.

8. 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.

9. The process according to claim 8 for producing 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride, wherein: methanol aqueous solution according to mass ratio methanol: water 1: 1-4.

10. The process for producing 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein: the temperature for heating and dehydrating the 3,3 ', 4, 4' -biphenyl tetracarboxylic acid is 230-280 ℃.

Technical Field

The invention relates to a preparation method of a fine chemical organic material, in particular 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, a synthesis method disclosed in Japanese patent laid-open No. Sho 63-88155, in which dehalogenation coupling of 4-chlorophthalic acid is carried out using 5% palladium on charcoal as a catalyst and a polyhydric alcohol such as glycerol as a reducing agent, the conversion of 4-chlorophthalic acid is 99%, and the yield of 3,3 ', 4, 4' -biphenyltetracarboxylic acid is 65% at the maximum. 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 not acceptable. The domestic butyl bengxian 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 a 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' -biphenyl tetracarboxylic 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 scheme, 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 of 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.