CN112209835B - Method for preparing p-phenylenediamine - Google Patents

Method for preparing p-phenylenediamine Download PDF

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CN112209835B
CN112209835B CN202010983176.9A CN202010983176A CN112209835B CN 112209835 B CN112209835 B CN 112209835B CN 202010983176 A CN202010983176 A CN 202010983176A CN 112209835 B CN112209835 B CN 112209835B
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reaction
phenylenediamine
preparing
nitrobenzene
catalyst
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CN112209835A (en
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王农跃
张启俊
沙艳松
陈莉
李斌
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Jiangsu Fangyuan Aramid Research Institute Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/02—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of hydrogen atoms by amino groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The application discloses a method for obtaining 4-nitrosoaniline and 4-nitroaniline by adopting nitrobenzene and ammonia to react under the action of a catalyst, and then obtaining high-purity p-phenylenediamine by hydrogenation. The nitrobenzene reacts with ammonia under the action of the catalyst to generate 4-nitrosoaniline and 4-nitroaniline, the reaction has high selectivity, no ortho-position or meta-position products are generated, and the yield is high. The 4-nitrosoaniline and 4-nitroaniline are subjected to catalytic hydrogenation to obtain the p-phenylenediamine with high selectivity and high purity, so that the method is suitable for industrial production.

Description

Method for preparing p-phenylenediamine
Technical Field
The application relates to the field of chemical synthesis, in particular to a method for preparing p-phenylenediamine, and more particularly relates to a method for preparing 4-nitrosoaniline and 4-nitroaniline by adopting nitrobenzene and ammonia to react under the action of a catalyst and then carrying out hydrogenation.
Background
P-phenylenediamine is a widely used chemical intermediate, and can be used for preparing azo dyes, fur dyes, antioxidants and photographic developers, and particularly can be used as a raw material of aramid fibers and rubber additives.
At present, two main technological methods for producing p-phenylenediamine are available. The first method is that chlorobenzene reacts with nitric acid to obtain paranitrochlorobenzene, then the paranitrochlorobenzene reacts with ammonia to generate paranitroaniline, and finally the paranitroaniline is reduced to obtain p-phenylenediamine. The conversion rate of the paranitroaniline in the production process is low, the purity of the obtained paranitroaniline is low, and a large amount of wastewater is generated in the production process. The second method is that aniline diazotization is carried out, then the aniline diazotization reacts with excessive aniline to generate 1, 3-diphenyl triazene, then the molecule rearrangement is carried out to obtain 4-amino azobenzene, and finally the 4-amino azobenzene is hydrogenated to obtain p-phenylenediamine. The method has the problems of low reaction efficiency, low product purity, serious three wastes and the like.
In addition, US6245943 discloses a process for the preparation of p-phenylenediamine comprising reacting urea with nitrobenzene in the presence of a base to give 4-nitrosoaniline and 4-nitroaniline and then subjecting the mixture to catalytic hydrogenation. Since urea reacts with nitrobenzene, a large amount of urea is consumed in order to avoid the formation of 4,4' -dinitrodiphenylamine.
Disclosure of Invention
The present application has been completed in order to overcome the above-described drawbacks. The application provides a method for obtaining 4-nitrosoaniline and 4-nitroaniline by adopting nitrobenzene and ammonia to react under the action of a catalyst, and then obtaining high-purity p-phenylenediamine by hydrogenation.
In the prior art, the problems of low reaction conversion rate, poor selectivity and environmental pollution exist, and the inventor surprisingly discovers that nitrobenzene and ammonia react under the action of a catalyst to generate 4-nitrosoaniline and 4-nitroaniline, the selectivity of the reaction is high, products in ortho-position or meta-position are not generated, and the yield is high. The 4-nitrosoaniline and 4-nitroaniline are subjected to catalytic hydrogenation to obtain the p-phenylenediamine with high selectivity and high purity, so that the method is suitable for industrial production.
Accordingly, the present application relates to a process for the preparation of p-phenylenediamine comprising: in the presence of a condensation catalyst, nitrobenzene reacts with ammonia in an organic solvent to obtain 4-nitrosoaniline and 4-nitroaniline, and then hydrogenation is carried out in an alcohol solvent by adopting a hydrogenation catalyst to obtain p-phenylenediamine.
The condensation catalyst used in the present application is a mixture of a base and an amide or a base, preferably a mixture of a base and an amide.
The amides include, but are not limited to, substituted benzamides, substituted aliphatic amides, diamides.
The substituted benzamide refers to benzamide containing one or more substituents on a benzene ring, wherein the substituents are independently selected from hydrogen, halogen, nitro, amino, alkoxy, sulfonate, sulfonic acid, hydroxyl, aldehyde, carboxyl and alkyl, aryl and aralkyl containing at least one amino group.
Examples of substituted benzamides useful in the present application include, but are not limited to, one of benzamide, 4-methylbenzamide, 4-methoxybenzamide, 4-chlorobenzamide, 2-methylbenzamide, 4-nitrobenzamide, 4-aminobenzamide, or combinations thereof.
The substituted aliphatic amide is represented by formula (I). The structural formula of formula (I) is as follows:
wherein n is 0 or 1, R is selected from the group consisting of alkyl, aralkyl, alkenyl, aralkenyl, cycloalkyl and cycloalkenyl, and X is selected from the group consisting of hydrogen, halogen, nitro, amine, alkoxy, sulfonate, hydroxyl, aldehyde, carboxyl, and alkyl, aryl, aralkyl containing at least one amine group.
Examples of substituted aliphatic amides useful in the present application include, but are not limited to, one of isobutyramide, urea, acetamide, propionamide, or a combination thereof.
The diamide is represented by formula (II). The structural formula of the formula (II) is as follows:
wherein R1 and R2 are independently selected from aryl, aliphatic and direct bond, A is selected from-SO 2-, -O-, -S-, and,And a direct bond.
The diamides used in the present application include, but are not limited to, one of adipoamide, oxamide, terephthalamide, 4' -biphenyldicarboxamide, or a combination thereof.
The alkali is organic alkali or inorganic alkali or a mixture thereof. Inorganic bases include, but are not limited to, for example, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide. For the inorganic base, one compound may be used alone or a mixture thereof may be used. Organic bases include, but are not limited to, for example, alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium propoxide, potassium ethoxide, potassium tert-butoxide; tetra-substituted amine hydroxides. For tetra-substituted ammonium hydroxides, wherein each substituent is selected from alkyl, aryl, aralkyl, preferably containing 1 to 18 carbon atoms, more preferably tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, methyltributylammonium hydroxide, methyltripropylammonium hydroxide, methyltriethylammonium hydroxide, trimethylbenzylammonium hydroxide, N-trimethylphenylammonium hydroxide, particularly preferably tetramethylammonium hydroxide. For selectivity and conversion of the product, the base is preferably tetramethylammonium hydroxide.
The molar ratio of the nitrobenzene to the condensation catalyst is 1:1-1:0.2. Further, when the condensation catalyst is alkali and amide, the molar ratio of nitrobenzene to the condensation catalyst is 1:1-1:0.2, preferably 1:0.9-1:0.5, wherein the molar ratio of alkali to amide is 1:1-1.5:1; when the condensation catalyst is alkali, the molar ratio of nitrobenzene to the condensation catalyst is 1:1-1:0.5, preferably 1:0.9-1:0.7.
Optionally, a phase transfer catalyst such as a quaternary ammonium salt, a quaternary ammonium base, a quaternary phosphonium salt, polyethylene glycol, a polyethylene glycol dialkyl ether, pyridine, a cyclic crown ether, etc., preferably a quaternary ammonium salt, is added to the reaction system. They may be used alone or in combination. The quaternary ammonium salt is preferably benzyltriethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, benzyltrimethylammonium chloride, benzyltributylammonium chloride, tetramethylammonium chloride, tetrabutylammonium bromide, dodecyltrimethylammonium bromide, tetradecyltrimethylammonium bromide, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, benzyltrimethylammonium bromide, benzyltriethylammonium bromide, benzyltributylammonium bromide, tetramethylammonium bromide, more preferably tetrabutylammonium bromide, tetramethylammonium bromide, tetraethylammonium bromide, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium chloride, particularly preferably tetramethylammonium bromide.
In the preparation method of the present application, the organic solvent includes, but is not limited to, dimethyl sulfoxide, dimethylformamide, ethylene glycol, methanol, N-methylpyrrolidone, preferably dimethyl sulfoxide. The solvent may be used alone or in combination, and is not limited to the above. The weight ratio of the organic solvent to the nitrobenzene is in the range of 45:1 to 6:1, preferably 18:1 to 12:1.
The molar ratio of nitrobenzene to ammonia is preferably 1:1.5-1:4, more preferably 1:1.8-1:2.5.
The reaction temperature of nitrobenzene and ammonia in the present application is preferably 25 to 100℃and more preferably 80 to 90 ℃. If the reaction temperature is too low, the reaction rate is slow; the reaction temperature is too high, which increases by-products, resulting in reduced yields of 4-nitrosoaniline and 4-nitroaniline.
The pressure of the reaction of nitrobenzene and ammonia is 0.15-3 MPa, preferably 0.15-1 MPa.
The water produced during the reaction of nitrobenzene with ammonia has a significant effect on yield. In order to remove moisture generated at the start of the reaction or during the reaction from the reaction solution, vacuum distillation may be performed or a desiccant may be used to increase the yield of the reaction. Materials used as the drying agent include anhydrous sodium carbonate, anhydrous sodium sulfate, anhydrous magnesium sulfate, calcium oxide, calcium chloride, potassium hydroxide, sodium hydroxide, molecular sieves, anhydrous aluminum oxide, but are not limited thereto. They may be used alone or in combination.
The reaction of nitrobenzene with ammonia needs to be carried out in an oxygen-containing atmosphere, for example oxygen, air. This is to avoid the production of by-products of azoxybenzene, azobenzene and the like.
The alcohol solvent used in the hydrogenation reaction is one or a combination of methanol, ethanol, propanol and isopropanol, and the amount of the alcohol solvent used is 2 to 6 times the sum of the mass of 4-nitrosoaniline and 4-nitroaniline, preferably methanol.
The hydrogenation catalyst is preferably a noble metal catalyst such as palladium on carbon, platinum on carbon, ruthenium on carbon, or other conventional hydrogenation catalysts such as nickel-based catalysts, supported on a carrier. The nickel-based catalyst is skeletal nickel, amorphous nickel, nickel/silicon dioxide and the like. A more preferred hydrogenation catalyst is palladium on carbon. Wherein the addition amount of the catalyst is 0.1-10% of the sum of the mass of the 4-nitrosoaniline and the mass of the 4-nitroaniline, and preferably 1-5%.
The reaction temperature of the hydrogenation reaction is 50-150 ℃, preferably 80-100 ℃; the reaction pressure is 0.2-3.0 MPa.
The term "halogen" is selected from fluorine, chlorine, bromine, iodine.
The term "alkoxy" refers to an alkoxy group containing 1 to 6 carbon atoms. The alkoxy groups may be substituted or unsubstituted, and when substituted, the substituents may be substituted at any useful point of attachment, independently optionally substituted with one or more substituents selected from halogen, alkyl, haloalkyl, alkoxy, hydroxy, nitro.
The term "sulfonate group" includes alkyl sulfonate, aryl sulfonate, aralkyl sulfonate.
The term "alkyl" refers to an alkyl group containing 1 to 6 carbon atoms. The alkyl group may be substituted or unsubstituted, and when substituted, the substituent may be substituted at any available point of attachment, independently optionally substituted with one or more substituents selected from halogen, alkyl, haloalkyl, alkoxy, hydroxy, nitro.
The term "aryl" is a 6 to 14 membered all carbon monocyclic ring or fused polycyclic ring having a conjugated pi electron system, preferably an all carbon monocyclic ring, such as phenyl. Aryl groups may be substituted or unsubstituted, and when substituted, substituents may be substituted at any useful point of attachment, independently optionally substituted with one or more substituents selected from halogen, alkyl, alkoxy, amino, nitro, cyano.
The term "aralkyl" refers to an alkyl substituted aryl group.
The term "alkenyl" refers to alkenyl groups containing 1 to 6 carbon atoms. Alkenyl groups may be substituted or unsubstituted, and when substituted, substituents may be substituted at any useful point of attachment, independently optionally substituted with one or more substituents selected from halogen, alkyl, haloalkyl, alkoxy, hydroxy, nitro.
The term "aralkenyl" refers to an aryl group containing an alkenyl group of 1 to 6 carbon atoms. Alkenyl groups may be substituted or unsubstituted, and when substituted, substituents may be substituted at any useful point of attachment, independently optionally substituted with one or more substituents selected from halogen, alkyl, haloalkyl, alkoxy, hydroxy, nitro.
The term "cycloalkyl" refers to a monocyclic alkyl group containing 3 to 6 carbon atoms.
The term "cycloalkenyl" refers to a monocyclic alkenyl group containing 3 to 6 carbon atoms.
Compared with the prior art, the method for preparing the p-phenylenediamine has the following beneficial effects: the prepared 4-nitrosoaniline and 4-nitroaniline do not contain by-products of ortho-position or meta-position, and have high selectivity, so that the prepared p-phenylenediamine has high purity, and the products do not need to be separated and purified.
Detailed Description
The gas chromatographs used in the examples were: agilent 7820A GC. Manual sample injection is adopted in the measurement, and a person skilled in the art can understand that errors caused by manual operation are also within an acceptable range. The products in the following examples were determined by gas chromatography and quantitatively analyzed.
Example 1
The air pressure kettle is purged by compressed air, 7.44 g of nitrobenzene, 120 g of dimethyl sulfoxide and 2.2 g of tetramethyl ammonium hydroxide pentahydrate are added into the kettle, 10.6 g of desiccant calcium oxide and 1.2 g of benzyl trimethyl ammonium chloride are added into the kettle, the pressure kettle is closed, 1.63 g of liquid ammonia is filled into the kettle, the pressure in the kettle reaches 1.6 megapascals, the kettle is stirred for 10 minutes under the pressure, and the volume concentration of ammonia in the gas phase in the kettle is measured to be 12%. The reaction mixture was heated to 80℃with stirring and reacted at this temperature for 7 hours. After the reaction, the autoclave was depressurized, cooled, the reaction mixture was weighed and sampled for gas chromatography, and the yield of 4-nitroaniline was calculated to be 56.4% and 42.3% based on nitrobenzene.
Adding the mixed solution obtained by the condensation reaction into a hydrogenation pressure kettle, adding 300 milliliters of methanol, 3 grams of palladium/carbon with the content of 5 percent, sealing the pressure kettle, starting stirring, replacing air in the kettle with nitrogen, detecting that the content of residual oxygen is qualified, introducing hydrogen under stirring, and carrying out hydrogenation reaction at the temperature of 120 ℃ and the pressure of 2.3 megapascals. Detecting that the residual amounts of nitroso and nitro in the reaction liquid are qualified after 4 hours of hydrogenation reaction, and ending the reaction. The hydrogenation autoclave was depressurized, cooled, the reaction mixture was weighed and sampled for gas chromatography analysis, and the yield of p-phenylenediamine calculated as nitrobenzene was calculated to be 95.4%.
Example 2
The empty pressure kettle is purged by compressed oxygen, 7.44 g of nitrobenzene, 240 g of N, N-dimethylformamide, 1.94 g of sodium methoxide and 50 g of anhydrous magnesium sulfate as a drying agent are added into the kettle, then the pressure kettle is closed, 4 g of liquid ammonia is filled, the pressure in the kettle reaches 2 MPa, stirring is carried out for 10 minutes under the pressure, and the volume concentration of ammonia in the gas phase in the kettle is measured to be 85%. The reaction mixture was heated to 96℃with stirring and reacted at this temperature for 7 hours. After the reaction, the autoclave was depressurized, cooled, the reaction mixture was weighed and sampled for gas chromatography, and the yield of 4-nitroaniline calculated as nitrobenzene was 54.7% and the yield of 4-nitroaniline was 43.7%.
Adding the mixed solution obtained by the condensation reaction into a hydrogenation pressure kettle, adding 300 ml of methanol and 3 g of skeleton nickel, sealing the pressure kettle, starting stirring, replacing air in the kettle with nitrogen, detecting that the residual oxygen content is qualified, introducing hydrogen under stirring, and carrying out hydrogenation reaction at a temperature of 150 ℃ and a pressure of 0.8 megapascal. Detecting that the residual amounts of nitroso and nitro in the reaction liquid are qualified after 4 hours of hydrogenation reaction, and ending the reaction. The hydrogenation autoclave was depressurized, cooled, the reaction mixture was weighed and sampled for gas chromatography analysis, and the yield of p-phenylenediamine calculated as nitrobenzene was calculated to be 97.3%.
Example 3
The empty pressure kettle is purged by compressed oxygen, 7.44 g of nitrobenzene, 51 g of N-methyl pyrrolidone and 3.36 g of potassium hydroxide are added into the kettle, 63.6 g of anhydrous sodium carbonate and 3.5 g of tetramethyl ammonium bromide are added into the kettle, the pressure kettle is closed, 2.45 g of liquid ammonia is filled into the kettle, the pressure in the kettle reaches 1.7 megapascals, the kettle is stirred for 10 minutes under the pressure, and the volume concentration of ammonia in the gas phase in the kettle is measured to be 67%. The reaction mixture was heated to 100℃with stirring and reacted at that temperature for 7 hours. After the reaction, the autoclave was depressurized, cooled, the reaction mixture was weighed and sampled for gas chromatography, and the yield of 4-nitroaniline calculated as nitrobenzene was 54.7% and the yield of 4-nitroaniline was 43.7%.
Adding the mixed solution obtained by the condensation reaction into a hydrogenation pressure kettle, adding 300 milliliters of methanol, 3 grams of palladium/carbon with the content of 5 percent, sealing the pressure kettle, starting stirring, replacing air in the kettle with nitrogen, detecting that the content of residual oxygen is qualified, introducing hydrogen under stirring, and carrying out hydrogenation reaction at the temperature of 80 ℃ and the pressure of 0.3 megapascal. Detecting that the residual amounts of nitroso and nitro in the reaction liquid are qualified after 4 hours of hydrogenation reaction, and ending the reaction. The hydrogenation autoclave was depressurized, cooled, the reaction mixture was weighed and sampled for gas chromatography analysis, and the yield of p-phenylenediamine calculated as nitrobenzene was calculated to be 96.2%.
Example 4
The air pressure kettle is purged by compressed air, 7.44 g of nitrobenzene, 90 g of dimethyl sulfoxide, 1.8 g of urea, 5.43 g of tetramethyl ammonium hydroxide pentahydrate, 50 g of anhydrous sodium sulfate as a drying agent and 4 g of tetraethylammonium bromide are added into the kettle, the pressure kettle is closed, 3.2 g of liquid ammonia is filled, the pressure in the kettle reaches 2.5 megapascals, stirring is carried out for 10 minutes under the pressure, and the volume concentration of ammonia in the gas phase in the kettle is measured to be 35%. The reaction mixture was heated to 100℃with stirring and reacted at that temperature for 7 hours. After the reaction, the autoclave was depressurized, cooled, the reaction mixture was weighed and sampled for gas chromatography, and the yield of 4-nitroaniline calculated as nitrobenzene was 54.8% and the yield of 4-nitroaniline was 43.5%.
Adding the mixed solution obtained by the condensation reaction into a hydrogenation pressure kettle, adding 300 ml of methanol, 3 g of skeleton nickel, sealing the pressure kettle, starting stirring, replacing air in the kettle with nitrogen, detecting that the residual oxygen content is qualified, introducing hydrogen under stirring, and carrying out hydrogenation reaction at a temperature of 55 ℃ and a pressure of 1.2 megapascals. Detecting that the residual amounts of nitroso and nitro in the reaction liquid are qualified after 4 hours of hydrogenation reaction, and ending the reaction. The hydrogenation autoclave was depressurized, cooled, the reaction mixture was weighed and sampled for gas chromatography analysis, and the yield of p-phenylenediamine calculated as nitrobenzene was calculated to be 97.2%.
Examples 5 to 10
The reaction was carried out under the same conditions as in example 4 except that the type and amount of the amide were changed
Examples 10 to 13
The reaction was carried out under the same conditions as in example 4 except that the temperature and pressure of the condensation reaction were changed
Examples 14 to 16
The reaction was carried out under the same conditions as in example 4 except that the solvent for the condensation reaction was changed
Examples 17 to 19
The reaction was carried out under the same conditions as in example 4 except that the type and amount of the catalyst for hydrogenation reaction were changed. (the amount of the catalyst used in this example means the percentage of the sum of the mass of 4-nitrosoaniline and 4-nitroaniline) added
Examples Catalyst for hydrogenation Catalyst amount for hydrogenation Yield of p-phenylenediamine (%)
17 Palladium on carbon 1％ 98.6％
18 Palladium on carbon 5％ 99.1％
19 Amorphous nickel 3％ 98.3％
The foregoing describes specific embodiments of the present application. It is to be understood that the application is not limited to the above-described embodiments, which are described in the foregoing description only for the purpose of illustrating the principles of the application. Various insubstantial changes and modifications of the application can be made by those skilled in the art without departing from the spirit of the application, and such changes and modifications are intended to be within the scope of the application as claimed.

Claims (10)

1. A process for preparing p-phenylenediamine comprising: reacting nitrobenzene with ammonia in an organic solvent in the presence of a condensation catalyst to obtain 4-nitrosoaniline and 4-nitroaniline, and then carrying out hydrogenation in an alcohol solvent by using a hydrogenation catalyst to obtain p-phenylenediamine; the condensation catalyst is alkali and amide, the amide is urea, the temperature of the reaction of nitrobenzene and ammonia is 40-100 ℃, the pressure of the reaction is 0.15-3 MPa, the molar ratio of the nitrobenzene to the condensation catalyst is 1:1-1:0.2, and the molar ratio of the alkali to the amide is 1:1-1.5:1; in order to remove moisture generated at the start of the reaction or during the reaction from the reaction solution, vacuum distillation is performed or a drying agent is used, and materials used as the drying agent include anhydrous sodium carbonate, anhydrous sodium sulfate, anhydrous magnesium sulfate, calcium oxide, calcium chloride, potassium hydroxide, sodium hydroxide, molecular sieves, and anhydrous aluminum oxide.
2. The process for preparing p-phenylenediamine according to claim 1, wherein the base is selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alkoxides and tetra-substituted ammonium hydroxides.
3. The process for preparing p-phenylenediamine according to claim 2, wherein the tetra-substituted ammonium hydroxide is a tetraalkylammonium hydroxide.
4. The process for preparing p-phenylenediamine according to claim 1, wherein the organic solvent is dimethyl sulfoxide, N-dimethylformamide, ethylene glycol, methanol, N-methylpyrrolidone.
5. The process for producing p-phenylenediamine according to claim 1, wherein the hydrogenation catalyst is a noble metal catalyst supported on a carrier.
6. The process for preparing p-phenylenediamine according to claim 1, wherein the molar ratio of nitrobenzene to condensation catalyst is from 1:1 to 1:0.2.
7. The process for preparing p-phenylenediamine according to claim 1, wherein the molar ratio of nitrobenzene to ammonia is from 1:1.5 to 1:4.
8. The process for preparing p-phenylenediamine according to claim 1, wherein the alcoholic solvent is one of methanol, ethanol, propanol, isopropanol or a combination thereof.
9. The method for preparing p-phenylenediamine according to claim 1 or 4, wherein the catalyst is added in an amount of 0.1 to 10% by mass of 4-nitrosoaniline and 4-nitroaniline.
10. The process for producing p-phenylenediamine according to claim 1, wherein the hydrogenation reaction is carried out at a reaction temperature of 50 to 150℃and a reaction pressure of 0.2 to 3.0MPa.
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CN1267279A (en) * 1997-08-21 2000-09-20 帝国化学工业公司 Process for production of aromatic amines
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