Preparation method of 1, 2, 3, 4-butane tetracarboxylic dianhydride

Abstract

The invention discloses a preparation method of 1, 2, 3, 4-butane tetracarboxylic dianhydride, which comprises the following steps: adding alkali into an organic solvent under shielding gas, adding dimethyl 2-cyanosuccinate and maleic anhydride, carrying out heat preservation reaction, adding acid after the reaction is finished, carrying out reaction, and carrying out post-treatment to obtain the 1, 2, 3, 4-butane tetracarboxylic dianhydride. The preparation method is novel, raw materials are easy to obtain, the selectivity is good, the total preparation cost is low, the yield is high, and the preparation method is suitable for industrial production.

Description

Technical Field

[0001] The invention belongs to the technical field of organic chemical synthesis, and in particular relates to a method for preparing 1,2,3,4-butanetetracarboxylic dianhydride. Background Art

[0002] 1,2,3,4-Butanetetracarboxylic dianhydride (BDA) and its precursor, 1,2,3,4-butanetetracarboxylic acid (BTCA), are both high-value-added fine chemical intermediates and important raw materials in many fields. BTCA is widely used in formaldehyde-free durable press finishes. Fabrics treated with BTCA exhibit high drying self-leveling properties, wrinkle resistance, low yellowing, and low toxicity. BDA is the primary monomer in the synthesis of polyimides. Polyimide (PI) materials offer numerous advantages, including high-temperature resistance, radiation resistance, and mechanical strength. They are used in films, foams, coatings, fibers, and photoresists. PI films, with continuous operating temperatures up to 250°C and short-term operating temperatures up to 450°C, are widely used in aerospace, marine, atomic energy, and electronics industries. PI materials prepared from BDA and other diamine monomers exhibit excellent mechanical properties, outstanding heat resistance, excellent light transmittance, excellent chemical corrosion resistance, high radiation resistance, low thermal expansion coefficient, and superior dielectric properties. They are widely used in electrical insulation materials, photosensitive materials, liquid crystal display alignment film materials, and microelectronics. Therefore, the efficient and simple synthesis of 1,2,3,4-butanetetracarboxylic dianhydride through molecular design has high theoretical significance and practical application value.

[0003] The structural formula of 1,2,3,4-butanetetracarboxylic dianhydride is as follows: .

[0004] Currently, the synthesis of 1,2,3,4-butanetetracarboxylic dianhydride primarily involves a Diels-Alder reaction between maleic anhydride and 1,3-butadiene to produce tetrahydrophthalic anhydride, followed by oxidation with ozone or nitric acid to produce 1,2,3,4-butanetetracarboxylic acid. Finally, acetic anhydride is dehydrated to produce the anhydride. This method involves a long reaction process, and the second oxidation step, involving ozone or nitric acid, is highly hazardous. Furthermore, the conversion of acetic anhydride to anhydride produces a large amount of waste acid, making it difficult to apply to industrial production. Summary of the Invention

[0005] In view of this, the present invention aims to provide a method for preparing 1,2,3,4-butanetetracarboxylic dianhydride to solve at least one technical problem in the background technology.

[0006] To achieve the above object, the technical solution of the present invention is achieved as follows: A method for preparing 1,2,3,4-butanetetracarboxylic dianhydride, comprising the following steps: adding a base to an organic solvent under protective gas, adding dimethyl 2-cyanosuccinate and maleic anhydride, carrying out a heat-insulating reaction, adding an acid after the reaction is completed, and performing a post-treatment to obtain 1,2,3,4-butanetetracarboxylic dianhydride; The structural formula of 1,2,3,4-butanetetracarboxylic dianhydride is .

[0007] Furthermore, the molar ratio of maleic anhydride, dimethyl 2-cyanosuccinate and the base is 1.0:(1.1-3.0):(1.1-3.0).

[0008] Furthermore, the temperature of the heat preservation reaction is 5-15°C.

[0009] Furthermore, the insulation reaction time is 4-6 h.

[0010] Furthermore, the base includes one or more of sodium methoxide, potassium tert-butoxide, sodium tert-butoxide, sodium ethoxide, potassium ethoxide, sodium hydride, and potassium hydride.

[0011] Furthermore, the acid includes one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, hydroiodic acid, and hydrobromic acid. Preferably, the acid concentration is 8-12%.

[0012] Furthermore, the temperature for the reaction when the acid is added is 85-95° C., and the reaction time is 1.5-2.5 h.

[0013] Furthermore, the organic solvent includes methanol, ethanol, tetrahydrofuran, ethylene glycol dimethyl ether, dioxane, N,N -dimethylformamide, N,N - one or more of dimethylacetamide.

[0014] Furthermore, the protective atmosphere is a nitrogen atmosphere.

[0015] Furthermore, post-treatment includes cooling, filtering, washing with water, and vacuum drying to obtain the compound 1,2,3,4-butanetetracarboxylic dianhydride represented by formula I.

[0016] Compared with the prior art, the method for preparing 1,2,3,4-butanetetracarboxylic dianhydride of the present invention has the following advantages: The invention uses maleic anhydride and dimethyl 2-cyanosuccinate as main raw materials, performs a base-catalyzed addition reaction, hydrolyzes, and vacuum-dries and dehydrates to anhydride to obtain 1,2,3,4-butanetetracarboxylic dianhydride. The main raw materials are cheap and readily available, the reaction steps are simple and safe, the preparation method is easy to implement, the reaction selectivity is higher, the side reactions are less, and the reaction yield is high. Therefore, the preparation method of the invention is novel, the raw materials are readily available, the selectivity is good, the overall preparation cost is low, the yield is high, and the method is suitable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] The accompanying drawings, which constitute part of the present invention, are provided to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are provided to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings: Figure 1 This is an HPLC chart of 1,2,3,4-butanetetracarboxylic dianhydride described in Example 1 of the present invention. DETAILED DESCRIPTION

[0018] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features in the embodiments may be combined with each other.

[0019] The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with embodiments.

[0020] The synthetic route of 1,2,3,4-butanetetracarboxylic dianhydride is as follows: ; Example 1: A method for preparing 1,2,3,4-butanetetracarboxylic dianhydride comprises the following steps: Step (1): The molar ratio of maleic anhydride to dimethyl 2-cyanosuccinate was 1.0:1.1. Under nitrogen protection, 500 mL of methanol and sodium methoxide (60.6 g, 1.1 eq) were added to a 2 L four-necked flask. Dimethyl 2-cyanosuccinate (192.0 g, 1.1 eq) was added dropwise with stirring. The temperature was controlled at 0-10°C and the addition was completed in about 1 hour. Maleic anhydride (100 g, 1.0 eq) was then added. The temperature was maintained at 10°C and stirred for 5 hours. After the reaction was completed as determined by GC, 500 mL of 10% hydrochloric acid was added, the mixture was heated to 90°C and reacted for 2 hours, the temperature was lowered, the mixture was filtered, the mixture was washed with water, and vacuum dried at 200°C for 24 hours to obtain 190.5 g of 1,2,3,4-butanetetracarboxylic dianhydride, a compound of formula II, with a yield of 94.3%.

[0021] Its H NMR spectrum Figure 1 As shown: 1H NMR (600MHz, CD3CN, δppm): 2.99-3.03 (m, 2H), 3.21-3.26 (m, 2H), 3.74-3.76 (m, 2H). In the above reaction, in order to complete the reaction of the substrate maleic anhydride, dimethyl 2-cyanosuccinate and sodium methoxide are in excess, so as to complete the reaction of the raw materials to the greatest extent.

[0022] Example 2: A method for preparing 1,2,3,4-butanetetracarboxylic dianhydride comprises the following steps: Step (1): The molar ratio of maleic anhydride to dimethyl 2-cyanosuccinate is 1.0:1.5. Under nitrogen protection, 500 mL of ethanol and sodium ethoxide (104.1 g, 1.5 eq) are added to a 2 L four-necked flask. Dimethyl 2-cyanosuccinate (261.8 g, 1.5 eq) is added dropwise with stirring. The temperature is controlled at 0-10°C and the addition is completed in about 1 hour. Maleic anhydride (100 g, 1.0 eq) is then added and the temperature is maintained at 10°C with stirring for 5 hours. After the reaction is completed as determined by GC, 500 mL of 10% sulfuric acid is added, the mixture is heated to 90°C for 2 hours, the temperature is lowered, the mixture is filtered, the mixture is washed with water, and vacuum dried at 200°C for 24 hours to obtain 193.2 g of 1,2,3,4-butanetetracarboxylic dianhydride, a compound of formula II, with a yield of 95.6%.

[0023] Example 3: A method for preparing 1,2,3,4-butanetetracarboxylic dianhydride comprises the following steps: Step (1): The molar ratio of maleic anhydride to dimethyl 2-cyanosuccinate is 1.0:2.0. Under nitrogen protection, 500 mL of tetrahydrofuran and sodium tert-butoxide (196.0 g, 2.0 eq) are added to a 2 L four-necked flask. Dimethyl 2-cyanosuccinate (349.1 g, 2.0 eq) is added dropwise with stirring. The temperature is controlled at 0-10°C and the addition is completed in about 1 hour. Maleic anhydride (100 g, 1.0 eq) is then added and the temperature is maintained at 10°C with stirring for 5 hours. After the reaction is completed as determined by GC, 500 mL of 10% perchloric acid is added, the mixture is heated to 90°C for 2 hours, the temperature is lowered, the mixture is filtered, washed with water, and vacuum dried at 200°C for 24 hours to obtain 199.6 g of 1,2,3,4-butanetetracarboxylic dianhydride, a compound of formula II, with a yield of 98.8%.

[0024] Example 4: A method for preparing 1,2,3,4-butanetetracarboxylic dianhydride comprises the following steps: Step (1): The molar ratio of maleic anhydride to dimethyl 2-cyanobutanedioate is 1.0:2.5. Under nitrogen protection, 500 mL of ethylene glycol dimethyl ether and potassium tert-butoxide (286.1 g, 2.5 eq) are added to a 2 L four-necked flask. Dimethyl 2-cyanobutanedioate (436.3 g, 2.5 eq) is added dropwise with stirring. The temperature is controlled at 0-10°C and the addition is completed in about 1 hour. Maleic anhydride (100 g, 1.0 eq) is then added and the temperature is maintained at 10°C with stirring for 5 hours. After the reaction is completed as determined by GC, 500 mL of 10% hydrochloric acid is added, the mixture is heated to 90°C for 2 hours, the temperature is lowered, the mixture is filtered, the mixture is washed with water, and vacuum dried at 200°C for 24 hours to obtain 197.0 g of 1,2,3,4-butanetetracarboxylic dianhydride, a compound of formula II, with a yield of 97.5%.

[0025] Example 5: A method for preparing 1,2,3,4-butanetetracarboxylic dianhydride comprises the following steps: Step (1): The molar ratio of maleic anhydride to dimethyl 2-cyanosuccinate is 1.0:3.0. Under nitrogen protection, 500 mL of DMF and 60% sodium hydride (122.4 g, 3.0 eq) are added to a 2 L four-necked flask. Dimethyl 2-cyanosuccinate (523.6 g, 3.0 eq) is added dropwise with stirring. The temperature is controlled at 0-10°C and the addition is completed in about 1 hour. Maleic anhydride (100 g, 1.0 eq) is then added and the temperature is maintained at 10°C with stirring for 5 hours. After the reaction is completed as determined by GC, 500 mL of 10% hydrobromic acid is added, the mixture is heated to 90°C and reacted for 2 hours, the temperature is lowered, the mixture is filtered, the mixture is washed with water, and vacuum dried at 200°C for 24 hours to obtain 187.7 g of 1,2,3,4-butanetetracarboxylic dianhydride, a compound of formula II, with a yield of 92.9%.

[0026] 1,2,3,4-Butanetetracarboxylic dianhydride was prepared according to the method described in Example 3. Sodium tert-butoxide was added to tetrahydrofuran, and then dimethyl 2-cyanosuccinate was added under temperature control. Finally, maleic anhydride was added for condensation, and then hydrolyzed and heated to anhydride to obtain 1,2,3,4-butanetetracarboxylic dianhydride. The nuclear magnetic hydrogen spectrum of 1,2,3,4-butanetetracarboxylic dianhydride synthesized in this example with deuterated acetonitrile as solvent is as follows Figure 1 As shown, the hydrogen spectrum shows that the product structure is correct.

[0027] Comparative Example 1 The difference from Example 3 is that sodium tert-butoxide was not added, and sodium methoxide (110.2 g sodium methoxide, 1.5 eq) was added to obtain the compound 1,2,3,4-butanetetracarboxylic dianhydride represented by Formula II with a yield of 83.8%.

[0028] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention should be included in the scope of protection of the present invention.

Claims

1. A method for preparing 1,2,3,4-butanetetracarboxylic dianhydride, characterized in that: The method comprises the following steps: adding a base to an organic solvent under protective gas, adding dimethyl 2-cyanosuccinate and maleic anhydride, carrying out a heat-insulating reaction, adding an acid to carry out a reaction after the reaction is completed, and obtaining 1,2,3,4-butanetetracarboxylic dianhydride after post-treatment; The structural formula of 1,2,3,4-butanetetracarboxylic dianhydride is 。 2. The method for preparing 1,2,3,4-butanetetracarboxylic dianhydride according to claim 1, wherein: The molar ratio of maleic anhydride, dimethyl 2-cyanosuccinate and base is 1.0:(1.1~3.0):(1.1~3.0).

3. The method for preparing 1,2,3,4-butanetetracarboxylic dianhydride according to claim 1, wherein: The temperature of the insulation reaction is 5-15°C.

4. The method for preparing 1,2,3,4-butanetetracarboxylic dianhydride according to claim 1, wherein: The reaction time is 4-6 h.

5. The method for preparing 1,2,3,4-butanetetracarboxylic dianhydride according to claim 1, wherein: The base includes one or more of sodium methoxide, potassium tert-butoxide, sodium tert-butoxide, sodium ethoxide, potassium ethoxide, sodium hydride, and potassium hydride.

6. The method for preparing 1,2,3,4-butanetetracarboxylic dianhydride according to claim 1, wherein: The acid includes one or more of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, perchloric acid, hydroiodic acid, and hydrobromic acid. Preferably, the acid concentration is 8-12%.

7. The method for preparing 1,2,3,4-butanetetracarboxylic dianhydride according to claim 1, wherein: The temperature for the reaction when the acid is added is 85-95°C, and the reaction time is 1.5-2.5h.

8. The method for preparing 1,2,3,4-butanetetracarboxylic dianhydride according to claim 1, wherein: Organic solvents include methanol, ethanol, tetrahydrofuran, ethylene glycol dimethyl ether, dioxane, N,N -dimethylformamide, N,N - one or more of dimethylacetamide.

9. The method for preparing 1,2,3,4-butanetetracarboxylic dianhydride according to claim 1, wherein: The protective atmosphere was nitrogen.

10. The method for preparing 1,2,3,4-butanetetracarboxylic dianhydride according to claim 1, wherein: The post-treatment includes cooling, filtering, washing with water, and vacuum drying to obtain the compound 1,2,3,4-butanetetracarboxylic dianhydride represented by formula I.

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