Preparation method of naphthalene diamine

Abstract

The invention relates to the technical field of aromatic amine preparation, and discloses a preparation method of naphthalene diamine, which comprises the following steps: in the presence of a catalyst and an auxiliary agent, enabling naphthalene diphenol to react with an ammoniation reagent to prepare the naphthalene diamine, the auxiliary agent comprises hydrophosphite and / or hydrophosphate. It needs to be explained that direct ammoniation of the naphthalene diphenol is not easy, so that hydrogen ions are introduced with the hydrogen phosphite and / or the hydrogen phosphate as an auxiliary, the hydrogen ion concentration is increased, after the hydrogen ions are combined with the naphthalene ring or hydroxyl of the naphthalene diphenol, the naphthalene ring electron density is reduced, the ammoniation step can be more easily carried out, and then the reaction time is shortened. If the concentration of hydrogen ions in the added auxiliary agent is too high, the hydrogen ions preferentially react with the ammoniation reagent to form ammonium ions, so that free ammonia molecules are reduced, the reaction time is prolonged, and the yield of the naphthylenediamine is reduced.

Description

Technical Field

[0001] This invention relates to the field of aromatic amine technology, and more specifically to a method for preparing naphthalenediamine. Background Technology

[0002] Naphthalenediamine is a crucial fine chemical product widely used in high-performance polyurethanes, liquid crystals, and optoelectronics. However, existing synthetic routes for naphthalenediamine all have limitations. Current techniques often utilize a Buchner reaction between naphthalenediol and concentrated ammonia to achieve phenol-amine conversion. The rate-determining step of this reaction is the attack of hydrogen ions on the naphthalene ring. However, adding a large amount of acid to the system affects the ammonia concentration and subsequent reactions. Currently, ammonium bisulfite and sodium bisulfite are commonly used as catalysts. While these methods can effectively synthesize naphthalenediamine, the long reaction time results in low yield. Therefore, adjusting the preparation method of naphthalenediamine to shorten the reaction time is one of the urgent technical problems to be solved in this field. Summary of the Invention

[0003] In view of this, the present invention provides a method for preparing naphthalenediamine to solve the problem of long reaction time in the existing methods for preparing naphthalenediamine.

[0004] In a first aspect, the present invention provides a method for preparing naphthalenediamine, comprising the following steps: Naphthodiamine is prepared by reacting naphthodiol with an amination reagent in the presence of a catalyst and an auxiliary agent. The adjuvants include hydrogen phosphite and / or hydrogen phosphate.

[0005] In one alternative embodiment, the hydrogen phosphite includes at least one of ammonium hydrogen phosphite and diammonium hydrogen phosphite.

[0006] In one optional embodiment, the hydrogen phosphate salt includes at least one of ammonium dihydrogen phosphate and diammonium hydrogen phosphate.

[0007] In one optional embodiment, the mass of the adjuvant is 0.5%-5% of the mass of the naphthol.

[0008] In one optional embodiment, the reaction temperature is 170℃-230℃ and the time is 3.5h-10h.

[0009] In one alternative embodiment, the catalyst comprises at least one of sodium sulfite, ammonium sulfite, sodium bisulfite, sodium metabisulfite, and ammonium bisulfite.

[0010] In one optional embodiment, the naphthol includes at least one selected from 2,6-naphthol, 1,6-naphthol, 1,7-naphthol, 2,7-naphthol, 1,8-naphthol, 1,4-naphthol, and 1,5-naphthol.

[0011] In one alternative embodiment, the amination reagent comprises ammonia.

[0012] In one optional embodiment, the molar ratio of the naphthol to the catalyst is 1:0.05-0.5.

[0013] In one optional embodiment, the molar ratio of the naphthol to the amination reagent is 1:6-14.5.

[0014] In one optional embodiment, after the reaction is completed, the reaction product is further further comprising the steps of washing with an alkaline solution, washing with deionized water, drying, and recrystallizing in sequence.

[0015] In one optional embodiment, the alkaline solution includes at least one of an aqueous solution of sodium hydroxide and an aqueous solution of potassium hydroxide.

[0016] In one optional embodiment, the alkaline reagent in the alkaline solution has a mass concentration of 1%-30%, optionally 5%-20%.

[0017] In one optional embodiment, the washing time of the alkaline solution is 1 min to 10 min.

[0018] Compared with the prior art, the technical solution of the present invention has the following advantages: 1. The method for preparing naphthalenediamine provided by this invention includes the following steps: Naphthodiol and an ammonifying agent react in the presence of a catalyst and an auxiliary agent to prepare naphthalenediamine; the auxiliary agent includes hydrogen phosphite and / or hydrogen phosphate. It should be noted that direct ammonification of naphthodiol is not easy. Therefore, this invention uses hydrogen phosphite and / or hydrogen phosphate as auxiliary agents to introduce hydrogen ions, increasing the hydrogen ion concentration. After the hydrogen ions combine with the naphthalene ring or hydroxyl group of naphthodiol, the electron density of the naphthalene ring is reduced, making the ammonification step easier to occur, thereby shortening the reaction time. If the added auxiliary agent has an excessively high hydrogen ion concentration, the hydrogen ions preferentially react with the ammonifying agent to form ammonium ions, resulting in fewer free ammonia molecules, prolonging the reaction time, and reducing the yield of naphthalenediamine. Attached Figure Description

[0019] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0020] Figure 1 This is the 1H NMR spectrum of 2,6-naphthyldiamine prepared in Example 2 of this invention. Detailed Implementation

[0021] The following embodiments are provided to better understand the present invention, but the following embodiments do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the scope of protection of the present invention.

[0022] Unless otherwise specified, the experimental steps or conditions in the examples were performed in accordance with conventional experimental procedures and conditions in the art. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0023] In a first aspect, the present invention provides a method for preparing naphthalenediamine, comprising the following steps: Naphthyldiamine is prepared by reacting naphthalenediol with an amination reagent in the presence of a catalyst and an auxiliary agent; the auxiliary agent includes a hydrogen phosphite and / or a hydrogen phosphate, wherein the hydrogen phosphite includes at least one selected from ammonium hydrogen phosphite and diammonium hydrogen phosphite; the hydrogen phosphate includes at least one selected from ammonium dihydrogen phosphate and diammonium hydrogen phosphate; the mass of the auxiliary agent is 0.5%-5% of the mass of the naphthalenediol, preferably 1.5%-5%; the reaction temperature is 170℃-230℃, preferably 170℃-190℃; the reaction time is 5h-10h; the catalyst includes at least one selected from sodium sulfite, ammonium sulfite, sodium bisulfite, sodium metabisulfite, and ammonium bisulfite; the naphthalenediol includes 2,6-naphthyldiol, 1,6-naphthyldiol, and 1... The reaction mixture comprises at least one of 7-naphthyldiol, 2,7-naphthyldiol, 1,8-naphthyldiol, 1,4-naphthyldiol, and 1,5-naphthyldiol; the ammonifying agent includes ammonia water; the molar ratio of the naphthyldiol to the catalyst is 1:0.05-0.5; the molar ratio of the naphthyldiol to the ammonifying agent is 1:6-14.5, preferably 1:8-12; after the reaction is completed, the reaction mixture further comprises the steps of washing the reaction product sequentially with an alkaline solution, washing with deionized water, drying, and recrystallizing; the alkaline solution comprises at least one of sodium hydroxide aqueous solution and potassium hydroxide aqueous solution; the mass concentration of the alkaline reagent in the alkaline solution is 1%-30%, preferably 5%-20%; the washing time of the alkaline solution is 1 min-10 min.

[0024] As an example, the mass of the adjuvant is 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5% of the mass of the naphthol, or within any range of the above values.

[0025] As an example, the reaction temperature is 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, or 230°C; the reaction time is 5h, 6h, 7h, 8h, 9h, or 10h, or within any range of the above values.

[0026] As an example, the molar ratio of the naphthol to the catalyst is 1:0.05, 1:0.1, 1:0.15, 1:0.2, 1:0.25, 1:0.3, 1:0.35, 1:0.4, 1:0.45, or 1:0.5, or within any of the above values.

[0027] As an example, the molar ratio of the naphthol to the amination reagent is 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14 or 1:14.5, or within any of the above values.

[0028] As an example, the mass concentration of the alkaline reagent in the alkaline solution is 1%, 3%, 5%, 8%, 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28%, or 30%, or falls within any of the above values.

[0029] The conditions for gas chromatography analysis in the following examples were as follows: Agilent DB-5 column, injection port temperature of 280°C, FID detector temperature of 300°C, column flow rate of 1.3 mL / min, hydrogen flow rate of 40 mL / min, air flow rate of 400 mL / min, and temperature program as follows: hold at 100°C for 2 min, increase to 280°C at 15°C / min, then increase to 300°C at 10°C / min and hold for 3 min.

[0030] Water content can be determined using chromatographic analysis with a thermal conductivity detector.

[0031] Unless otherwise specified, all raw materials used in the following examples or comparative examples are Aladdin reagent grade raw materials, wherein the mass fraction of ammonia water is 25%-30%.

[0032] In this invention, the high-pressure reactor was purchased from Shanghai Laibei Scientific Instruments Co., Ltd.

[0033] In this invention, naphthols with the hydroxyl group at the "equivalent site" (1,5-naphthol, 2,6-naphthol) exhibit a significantly higher reaction rate in the ammoniation reaction compared to isomers substituted at other positions (such as 1,7-naphthol, 2,7-naphthol, 1,6-naphthol, 1,8-naphthol, 1,4-naphthol). This may be because the para-substituted structure can more effectively stabilize the key intermediate (positive ion) in the substitution reaction process through its conjugated system, thereby lowering the activation energy of the reaction.

[0034] Example 1 This embodiment provides a method for preparing 2,6-naphthyldiamine, comprising the following steps: (1) Add 5g ammonium bisulfite, 2g ammonium biphosphite and 50g 2,6-naphthol to the reactor, purge with 1MPa nitrogen three times, check for leaks with 5MPa nitrogen for 30min, release pressure, add 244mL 25wt% ammonia water (3.5mol) through a funnel, stir at 600rpm, and then heat the reactor to 170℃ for 5h. After the reaction is completed, cool down to 20℃, depressurize and purge the residual ammonia in the reactor twice with nitrogen, open the reactor, release the ammonia in the space, transfer the reaction product to a Buchner funnel, filter to separate the solid and liquid phases, and use 200mL The filter cake was washed with 10wt% sodium hydroxide aqueous solution for 10 min, filtered, and then washed twice with deionized water. It was then dried at 60℃ and 100 mbar for 16 h to obtain 46.6 g of crude 2,6-naphthyldiamine, with a separation yield of 90.32%. Gas chromatography analysis showed that the purity of 2,6-naphthyldiamine in the product was 99.1%. (2) Weigh 44.0g of crude 2,6-naphthyldiamine and 160g of chlorobenzene solvent into a three-necked flask, mix and stir, heat to 80℃ and stir for 1h, then quickly cool to 0℃, filter, and vacuum dry to obtain 43g of 2,6-naphthyldiamine with a purity of 99.3% and a water content of less than 0.1%.

[0035] Example 2 This embodiment provides a method for preparing 2,6-naphthyldiamine, comprising the following steps: (1) Add 10.0g ammonium bisulfite, 2g ammonium dihydrogen phosphate and 50g 2,6-naphthol to the reactor. Purge with 1MPa nitrogen three times, check for leaks with 5MPa nitrogen for 30min, release the pressure, add 302mL ammonia water (4.38mol) through a funnel, stir at 600rpm, and then heat the reactor to 180℃ for 5h. After the reaction is complete, cool to 20℃, depressurize and purge the residual ammonia in the reactor twice with nitrogen. Open the reactor, release the ammonia in the space, transfer the reaction product to a Buchner funnel, filter to separate the solid and liquid phases, and use 200mL 10wt% The filter cake was washed with NaOH aqueous solution for 10 min, filtered, and then washed twice with deionized water. It was then dried at 80℃ and 80 mbar for 20 h to obtain 46.4 g of crude 2,6-naphthyldiamine. The yield of 2,6-naphthyldiamine was 93.9%, and the purity of the product was 99.0% as determined by gas chromatography. (2) Weigh 46.0g of crude 2,6-naphthyldiamine and 160g of chlorobenzene solvent into a three-necked flask, mix and stir, heat to 80℃ and react for 1h, then quickly cool to 0℃, filter, and vacuum dry to obtain 45.5g of 2,6-naphthyldiamine with a purity of 99.1% and a water content of less than 0.1%.

[0036] Figure 1 This is the 1H NMR spectrum of 2,6-naphthyldiamine prepared in this embodiment. Figure 1 As can be seen, 2,6-naphthyldiamine was successfully synthesized.

[0037] Example 3 This embodiment provides a method for preparing 2,6-naphthyldiamine, comprising the following steps: (1) Add 24.0g sodium bisulfite, 4g diammonium hydrogen phosphate and 80g 2,6-naphthol to the reactor. Purge with 1MPa nitrogen three times, check for leaks with 5MPa nitrogen for 30min, release the pressure, add 190mL water through a funnel and 51g (3.00mol) liquid ammonia through a liquid ammonia tank, stir at 600rpm, and then heat the reactor to 190℃ for 6h. After the reaction is complete, cool down to 20℃, depressurize and purge the residual ammonia in the reactor twice with nitrogen, open the reactor, release the ammonia in the space, transfer the reaction product to a Buchner funnel, filter to separate the solid and liquid phases, and use 200mL 10wt% The filter cake was washed with NaOH aqueous solution for 5 min, filtered, and then washed twice with deionized water. It was then dried at 70℃ and 50 mbar for 22 h to obtain 74.0 g of crude 2,6-naphthyldiamine. The yield of 2,6-naphthyldiamine was 93.65%, and the purity of the product was 99.5% as determined by gas chromatography. (2) Weigh 74.0g of crude 2,6-naphthyldiamine and 160g of chlorobenzene solvent into a three-necked flask, mix and stir, heat to 80℃ and react for 1.5h, then quickly cool to 0℃, filter, and vacuum dry to obtain 73.9g of 2,6-naphthyldiamine with a purity of 99.8% and a water content of less than 0.1%.

[0038] Example 4 This embodiment provides a method for preparing 2,6-naphthyldiamine, comprising the following steps: (1) Add 5.0g sodium metabisulfite, 2g ammonium hydrogen phosphite and 50g 2,6-naphthol to the reactor. Purge with 1MPa nitrogen three times, check for leaks with 5MPa nitrogen for 30min, release the pressure, add 237mL ammonia water (3.44mol) through a funnel, stir at 600rpm, and then heat the reactor to 180℃ for 5h. After the reaction is complete, cool to 20℃, depressurize and purge the residual ammonia in the reactor twice with nitrogen. Open the reactor, release the ammonia in the space, transfer the reaction product to a Buchner funnel, filter to separate the solid and liquid phases, and use 200mL 10wt% The filter cake was washed with NaOH aqueous solution for 10 min, filtered, and then washed twice with deionized water. It was then dried at 75℃ and 55 mbar for 24 h to obtain 48.0 g of crude 2,6-naphthyldiamine. The yield of 2,6-naphthyldiamine was 97.20%, and the purity of the product was 99.6% as determined by gas chromatography. (2) Weigh 48.0g of crude 2,6-naphthyldiamine and 160g of chlorobenzene solvent into a three-necked flask, mix and stir, heat to 80℃ and react for 1h, then quickly cool to 0℃, filter, and vacuum dry to obtain 47.4g of 2,6-naphthyldiamine with a purity of 99.9% and a water content of less than 0.1%.

[0039] Example 5 This embodiment provides a method for preparing 2,6-naphthyldiamine, comprising the following steps: (1) Add 7.5g ammonium sulfite, 2g diammonium hydrogen phosphate and 50g 2,6-naphthol to the reactor. Purge with 1MPa nitrogen three times, check for leaks with 5MPa nitrogen for 30min, release the pressure, add 190mL ammonia water (2.75mol) through a funnel, stir at 600rpm, and then heat the reactor to 180℃ for 4h. After the reaction is complete, cool to 20℃, depressurize and purge the residual ammonia in the reactor twice with nitrogen, open the reactor, release the ammonia in the space, transfer the reaction product to a Buchner funnel, filter to separate the solid and liquid phases, and use 200mL 10wt% The filter cake was washed with NaOH aqueous solution for 3 min, filtered, and then washed twice with deionized water. It was then dried at 80℃ and 60 mbar for 18 h to obtain 46.8 g of crude 2,6-naphthyldiamine. The yield of 2,6-naphthyldiamine was 94.8%, and the purity of the product was 99.0% as determined by gas chromatography. (2) Weigh 46.0g of crude 2,6-naphthyldiamine and 160g of chlorobenzene solvent into a three-necked flask, mix and stir, heat to 80℃ and react for 2h, then quickly cool to 0℃, filter, and vacuum dry to obtain 45.0g of 2,6-naphthyldiamine with a purity of 99.4% and a water content of less than 0.1%.

[0040] Example 6 This embodiment provides a method for preparing 2,6-naphthyldiamine, comprising the following steps: (1) Add 5g ammonium bisulfite, 0.25g ammonium biphosphite and 50g 2,6-naphthol to the reactor. Purge with 1MPa nitrogen three times, check for leaks with 5MPa nitrogen for 30min, release the pressure, add 244mL 25wt% ammonia water (3.5mol) through a funnel, stir at 600rpm, and then heat the reactor to 220℃ for 9h. After the reaction is completed, cool down to 20℃, depressurize and purge the residual ammonia in the reactor twice with nitrogen, open the reactor, release the ammonia in the space, transfer the reaction product to a Buchner funnel, filter to separate the solid and liquid phases, and use 200mL The filter cake was washed with 30wt% sodium hydroxide aqueous solution for 10 min, filtered, and then washed twice with deionized water. It was then dried at 60℃ and 100 mbar for 16 h to obtain 44.6 g of crude 2,6-naphthyldiamine, with a separation yield of 90.3%. Gas chromatography analysis showed that the purity of 2,6-naphthyldiamine in the product was 99.9%. (2) Weigh 44g of crude 2,6-naphthyldiamine and 160g of chlorobenzene solvent into a three-necked flask, mix and stir, heat to 80℃ and react for 1h, then quickly cool to 0℃, filter, and vacuum dry to obtain 43.5g of 2,6-naphthyldiamine with a purity of 99.9% and a water content of less than 0.1%.

[0041] Example 7 This embodiment provides a method for preparing 2,6-naphthyldiamine, comprising the following steps: (1) Add 5g ammonium bisulfite, 0.5g ammonium biphosphite and 50g 2,6-naphthol to the reactor. Purge with 1MPa nitrogen three times, check for leaks with 5MPa nitrogen for 30min, release the pressure, add 244mL 25wt% ammonia water (3.5mol) through a funnel, stir at 600rpm, and then heat the reactor to 230℃ and react for 10h. After the reaction is completed, cool down to 20℃, depressurize and purge the residual ammonia in the reactor twice with nitrogen, open the reactor, release the ammonia in the space, transfer the reaction product to a Buchner funnel, filter to separate the solid and liquid phases, and use 200mL The filter cake was washed with 1 wt% sodium hydroxide aqueous solution for 10 min, filtered, and then washed twice with deionized water. It was dried at 60℃ and 100 mbar for 16 h to obtain 45 g of crude 2,6-naphthyldiamine. The separation yield of 2,6-naphthyldiamine was 91.15%. The purity of 2,6-naphthyldiamine in the product was 99.5% as determined by gas chromatography.

[0042] (2) Weigh 44g of crude 2,6-naphthyldiamine and 160g of chlorobenzene solvent into a three-necked flask, mix and stir, heat to 80℃ and react for 1h, then quickly cool to 0℃, filter, and vacuum dry to obtain 43g of 2,6-naphthyldiamine with a purity of 99.8% and a water content of less than 0.1%.

[0043] Example 8 This embodiment provides a method for preparing 1,6-naphthyldiamine, comprising the following steps: (1) Add 16.0g sodium sulfite, 2g ammonium hydrogen phosphate, and 80g 1,6-naphthol to the reactor. Purge the reactor three times with 1MPa nitrogen, and check for leaks with 5MPa nitrogen for 30 minutes. Release the pressure, add 237mL ammonia water (3.44mol) through a funnel, stir at 600rpm, and then heat the reactor to 170℃ for 7h. After the reaction is complete, cool down to 20℃, depressurize, and purge the residual ammonia in the reactor twice with nitrogen. Open the reactor, release the ammonia in the space, transfer the reaction product to a Buchner funnel, filter to separate the solid and liquid phases, and use 200mL of 10wt% [ammonia solution] to [the solution]. The filter cake was washed with NaOH aqueous solution for 5 min, filtered, and then washed twice with deionized water. It was then dried at 65℃ and 55 mbar for 16 h to obtain 78.0 g of crude 1,6-naphthyldiamine. The separation yield of 1,6-naphthyldiamine was 98.71%, and the purity of the product was 98.5% as determined by gas chromatography. (2) Weigh 78.0g of crude 1,6-naphthyldiamine and 160g of chlorobenzene solvent into a three-necked flask, mix and stir, heat to 80℃ and react for 1.5h, then quickly cool to 0℃, filter, and vacuum dry to obtain 77.3g of 1,6-naphthyldiamine with a purity of 98.9% and a water content of less than 0.1%.

[0044] Example 9 This embodiment provides a method for preparing 1,7-naphthyldiamine, comprising the following steps: (1) Add 8.0g ammonium bisulfite, 2g ammonium dihydrogen phosphate and 80g 1,7-naphthol to the reactor. Purge with 1MPa nitrogen three times, check for leaks with 5MPa nitrogen for 30min, release the pressure, add 302mL ammonia water (4.38mol) through a funnel, stir at 600rpm, and then heat the reactor to 170℃ and react for 10h. After the reaction is complete, cool down to 20℃, depressurize and purge the residual ammonia in the reactor twice with nitrogen, open the reactor, release the ammonia in the space, transfer the reaction product to a Buchner funnel, filter to separate the solid and liquid phases, and use 200mL 10wt% The filter cake was washed with NaOH aqueous solution for 10 min, filtered, and then washed twice with deionized water. It was then dried at 75℃ and 55 mbar for 18 h to obtain 77.0 g of crude 1,7-naphthyldiamine. The yield of 1,7-naphthyldiamine was 97.45%, and the purity of the product was 98.9% as determined by gas chromatography. (2) Weigh 77.0g of crude 1,7-naphthyldiamine and 160g of dichloroethane solvent into a three-necked flask, mix and stir, heat to 80℃ and react for 0.5h, then quickly cool to 0℃, filter, and vacuum dry to obtain 76.0g of 1,7-naphthyldiamine with a purity of 98.9% and a water content of less than 0.1%.

[0045] Example 10 This embodiment provides a method for preparing 2,7-naphthyldiamine, comprising the following steps: (1) Add 10.0g sodium bisulfite, 2g diammonium hydrogen phosphate and 50g 2,7-naphthol to the reactor. Purge with 1MPa nitrogen three times, check for leaks with 5MPa nitrogen for 30min, release the pressure, add 207mL ammonia water (3.00mol) through a funnel, stir at 600rpm, and then heat the reactor to 180℃ for 7h. After the reaction is complete, cool to 20℃, depressurize and purge the residual ammonia in the reactor twice with nitrogen. Open the reactor, release the ammonia in the space, transfer the reaction product to a Buchner funnel, filter to separate the solid and liquid phases, and use 200mL 5wt% The filter cake was washed with KOH aqueous solution for 10 min, filtered, and then washed twice with deionized water. It was then dried at 70℃ and 50 mbar for 28 h to obtain 44.7 g of crude 2,7-naphthyldiamine. The yield of 2,7-naphthyldiamine was 90.5%, and the purity of the product was 98.9% as determined by gas chromatography. (2) Weigh 44.0g of crude 2,7-naphthyldiamine and 160g of dichloroethane solvent into a three-necked flask, mix and stir, heat to 80℃ and react for 3h, then quickly cool to 0℃, filter, and vacuum dry to obtain 43.5g of 2,7-naphthyldiamine with a purity of 99.2% and a water content of less than 0.1%.

[0046] Example 11 This embodiment provides a method for preparing 1,8-naphthyldiamine, comprising the following steps: (1) Add 10.0g sodium bisulfite, 1g ammonium hydrogen phosphite and 50g 1,8-naphthol to the reactor. Purge with 1MPa nitrogen three times, check for leaks with 5MPa nitrogen for 30min, release the pressure, add 259mL ammonia water (3.75mol) through a funnel, stir at 600rpm, and then heat the reactor to 190℃ for 7h. After the reaction is complete, cool to 20℃, depressurize and purge the residual ammonia in the reactor twice with nitrogen. Open the reactor, release the ammonia in the space, transfer the reaction product to a Buchner funnel, filter to separate the solid and liquid phases, and use 200mL 15wt% The filter cake was washed with NaOH aqueous solution for 5 min, filtered, and then washed twice with deionized water. It was then dried at 65℃ and 55 mbar for 16 h to obtain 46.0 g of crude 1,8-naphthyldiamine. The yield of 1,8-naphthyldiamine was 93.15%, and the purity of the product was 99.4% as determined by gas chromatography. (2) Weigh 46.0g of crude 1,8-naphthyldiamine and 160g of dichloroethane solvent into a three-necked flask, mix and stir, heat to 80℃ and react for 1.5h, then quickly cool to 0℃, filter, and vacuum dry to obtain 44.5g of 1,8-naphthyldiamine with a purity of 99.5% and a water content of less than 0.1%.

[0047] Example 12 This embodiment provides a method for preparing 1,4-naphthyldiamine, comprising the following steps: (1) Add 5.0g sodium sulfite, 1g diammonium hydrogen phosphate and 50g 1,4-naphthol to the reactor. Purge with 1MPa nitrogen three times, check for leaks with 5MPa nitrogen for 30min, release the pressure, add 190mL ammonia water (2.75mol) through a funnel, stir at 600rpm, and then heat the reactor to 180℃ for 4h. After the reaction is complete, cool to 20℃, depressurize and purge the residual ammonia in the reactor twice with nitrogen. Open the reactor, release the ammonia in the space, transfer the reaction product to a Buchner funnel, filter to separate the solid and liquid phases, and use 200mL 10wt% The filter cake was washed with KOH aqueous solution for 5 min, filtered, and then washed twice with deionized water. It was then dried at 65℃ and 55 mbar for 18 h to obtain 43.5 g of crude 1,4-naphthyldiamine. The yield of 1,4-naphthyldiamine was 88.08%, and the purity of the product was 98.9% as determined by gas chromatography. (2) Weigh 43.5g of crude 1,4-naphthyldiamine and 160g of dichloroethane solvent into a three-necked flask, mix and stir, heat to 80℃ and react for 1h, then quickly cool to 0℃, filter, and vacuum dry to obtain 42.5g of 1,4-naphthyldiamine with a purity of 98.9% and a water content of less than 0.1%.

[0048] Example 13 This embodiment provides a method for preparing 1,5-naphthyldiamine, comprising the following steps: (1) Add 7.5g sodium bisulfite, 1.5g diammonium hydrogen phosphate and 50g 1,5-naphthol to the reactor. Purge with 1MPa nitrogen three times, check for leaks with 5MPa nitrogen for 30min, release the pressure, add 166mL ammonia water (2.41mol) through a funnel, stir at 600rpm, and then heat the reactor to 170℃ for 3.5h. After the reaction is complete, cool down to 20℃, depressurize and purge the residual ammonia in the reactor twice with nitrogen, open the reactor, release the ammonia in the space, transfer the reaction product to a Buchner funnel, filter to separate the solid and liquid phases, and use 200mL 10wt% The filter cake was washed with KOH aqueous solution for 5 min, filtered, and then washed twice with deionized water. It was then dried at 60℃ and 50 mbar for 24 h to obtain 44.5 g of crude 1,5-naphthyldiamine, with a separation yield of 90.11%. Gas chromatography analysis showed that the purity of 1,5-naphthyldiamine in the product was 99%. (2) Weigh 40g of crude 1,5-naphthyldiamine and 160g of chlorobenzene solvent into a three-necked flask, mix and stir, heat to 80℃ and react for 2h, then quickly cool to 0℃, filter, and vacuum dry to obtain 39.2g of 1,5-naphthyldiamine with a purity of 99.5% and a water content of 0.1%.

[0049] Comparative Example 1 This comparative example provides a method for preparing 2,6-naphthyldiamine, comprising the following steps: 7g ammonium bisulfite and 50g 2,6-naphthol were added to the reactor. The reactor was purged three times with 1MPa nitrogen, and a leak test was performed for 30 minutes with 5MPa nitrogen. The pressure was released, and 244mL of 25wt% ammonia (3.5mol) was added through a funnel. The mixture was stirred at 600rpm, and the reactor was heated to 170℃ for 15 hours. After the reaction, the temperature was lowered to 20℃, the pressure was released, and the residual ammonia in the reactor was purged twice with nitrogen. The reactor was opened, and the ammonia in the space was released. The reaction product was transferred to a Buchner funnel, and the solid and liquid phases were separated by filtration using 200mL of nitrogen. The filter cake was washed with 10wt% sodium hydroxide aqueous solution for 10 min, filtered, and then washed twice with deionized water. It was dried at 60℃ and 100mbar for 16 h to obtain 30.5 g of crude 2,6-naphthyldiamine. The separation yield of 2,6-naphthyldiamine was 87.6%. The purity of 2,6-naphthyldiamine in the product was determined to be 85.5% by gas chromatography.

[0050] Comparative Example 2 This comparative example provides a method for preparing 2,6-naphthyldiamine, comprising the following steps: 12.0 g of ammonium bisulfite and 50 g of 2,6-naphthyldiamine were added to a reaction vessel. The mixture was purged three times with nitrogen at 1 MPa, and then leak-tested with nitrogen at 5 MPa for 30 min. The pressure was released, and 302 mL of ammonia water (4.38 mol) was added through a funnel. The mixture was stirred at 600 rpm, and the reaction vessel was heated to 180 °C for 26 h. After the reaction was completed, the temperature was lowered to 20 °C, the pressure was released, and the residual ammonia in the vessel was purged twice with nitrogen. The vessel was opened, and the ammonia in the space was released. The reaction product was transferred to a Buchner funnel, and the solid and liquid phases were separated by filtration. The filter cake was washed with 200 mL of 10 wt% NaOH aqueous solution for 10 min, filtered, and then washed twice with deionized water. The product was dried at 80 °C and 80 mbar for 20 h to obtain 43.8 g of crude 2,6-naphthyldiamine. The yield of 2,6-naphthyldiamine was 88.71%, and the purity of the product was 99.2% as determined by gas chromatography.

[0051] Comparative Example 3 This comparative example provides a method for preparing 2,6-naphthyldiamine, comprising the following steps: 28.0 g of sodium bisulfite and 80 g of 2,6-naphthol were added to the reactor. The mixture was purged three times with 1 MPa nitrogen, and a leak test was performed for 30 min with 5 MPa nitrogen. The pressure was released, and 190 mL of water and 51 g (3.00 mol) of liquid ammonia were added through a funnel and a liquid ammonia tank. The mixture was stirred at 600 rpm, and the reactor was heated to 190 °C for 16 h. After the reaction, the temperature was lowered to 20 °C, the pressure was released, and the residual ammonia in the reactor was purged twice with nitrogen. The reactor was opened, and the ammonia in the space was released. The reaction product was transferred to a Buchner funnel, and the solid and liquid phases were separated by filtration. 200 mL of 10 wt% [a specific reagent / method] was used. The filter cake was washed with NaOH aqueous solution for 5 min, filtered, and then washed twice with deionized water. It was dried at 70℃ and 50 mbar for 22 h to obtain 71.3 g of crude 2,6-naphthyldiamine. The separation yield of 2,6-naphthyldiamine was 90.25%, and the purity of the product was 98.6% as determined by gas chromatography.

[0052] Comparative Example 4 This comparative example provides a method for preparing 1,5-naphthyldiamine, comprising the following steps: Add 9g sodium bisulfite and 50g 1,5-naphthol to the reaction vessel, purge three times with 1MPa nitrogen, check for leaks with 5MPa nitrogen for 30 minutes, release the pressure, add 166mL ammonia water (2.41mol) through a funnel, stir at 600rpm, and then heat the reaction vessel to 170℃ and react for 11h. After the reaction is complete, cool to 20℃, depressurize, and purge the residual ammonia in the vessel twice with nitrogen. Open the vessel, release the ammonia in the space, transfer the reaction product to a Buchner funnel, separate the solid and liquid phases by filtration, and use 200mL of 10wt% [a specific reagent / method / method] to [the product / method ... The filter cake was washed with KOH aqueous solution for 5 min, filtered, and then washed twice with deionized water. It was dried at 60℃ and 50 mbar for 24 h to obtain 41.5 g of crude 1,5-naphthyldiamine. The separation yield of 1,5-naphthyldiamine was 84.06%. The purity of 1,5-naphthyldiamine in the product was 95.6% as determined by gas chromatography.

[0053] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will find that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the protection scope of this invention.

Claims

1. A method for preparing naphthalenediamine, characterized in that, Includes the following steps: Naphthodiamine is prepared by reacting naphthodiol with an amination reagent in the presence of a catalyst and an auxiliary agent. The adjuvants include hydrogen phosphite and / or hydrogen phosphate.

2. The method for preparing naphthalenediamine according to claim 1, characterized in that, The hydrogen phosphite includes at least one of ammonium hydrogen phosphite and diammonium hydrogen phosphite.

3. The method for preparing naphthalenediamine according to claim 1, characterized in that, The hydrogen phosphate includes at least one of ammonium dihydrogen phosphate and diammonium hydrogen phosphate.

4. The method for preparing naphthalenediamine according to claim 2 or 3, characterized in that, The mass of the auxiliary is 0.5%-5% of the mass of the naphthol.

5. The method for preparing naphthalenediamine according to claim 1, characterized in that, The reaction temperature is 170℃-230℃, and the time is 3.5h-10h.

6. The method for preparing naphthalenediamine according to claim 1, characterized in that, The catalyst includes at least one of sodium sulfite, ammonium sulfite, sodium bisulfite, sodium metabisulfite, and ammonium bisulfite. And / or, the naphthol includes at least one of 2,6-naphthol, 1,6-naphthol, 1,7-naphthol, 2,7-naphthol, 1,8-naphthol, 1,4-naphthol, and 1,5-naphthol; And / or, the amination reagent includes ammonia water.

7. The method for preparing naphthalenediamine according to claim 5, characterized in that, The molar ratio of the naphthol to the catalyst is 1:0.05-0.

5.

8. The method for preparing naphthalenediamine according to claim 5, characterized in that, The molar ratio of the naphthol to the amination reagent is 1:6-14.

5.

9. The method for preparing naphthalenediamine according to claim 1, characterized in that, After the reaction is complete, the steps also include washing the reaction product sequentially with an alkaline solution, washing with deionized water, drying, and recrystallizing.

10. The method for preparing naphthalenediamine according to claim 9, characterized in that, The alkaline solution includes at least one of sodium hydroxide aqueous solution and potassium hydroxide aqueous solution; And / or, in the alkaline solution, the mass concentration of the alkaline reagent is 1%-30%, optionally 5%-20%; And / or, the washing time of the alkaline solution is 1 min to 10 min.

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