The invention relates to N, N, Napos; , Napos, Napos; preparation method of-tetra (p-aminophenyl) p-phenylenediamine

Abstract

The invention discloses a preparation method of N, N, N ', N'-tetra (p-aminophenyl) p-phenylenediamine. The preparation method specifically comprises the following steps: S1, carrying out substitution reaction to obtain N, N, N ', N'-tetra (p-nitrophenyl) p-phenylenediamine; s2, carrying out a reduction reaction to obtain N, N, N ', N'-tetra (p-nitrophenyl) p-phenylenediamine; the N, N, N ', N'-tetra (p-nitrophenyl) p-phenylenediamine is obtained from cheap and easily-purchased industrial raw materials p-nitrofluorobenzene and p-diphenylamine under the alkali condition, the selectivity is good, and the product is single and easy to purify; the N, N, N ', N'-tetra (p-aminophenyl) p-phenylenediamine is prepared from industrial raw materials tetrabutylammonium iodide and formic acid, the operation is simple, the safety is high, the environment is not polluted, and industrialization is convenient to realize.

Description

Technical Field

[0001] The present invention relates to the technical field of organic compound production, and particularly to a preparation method of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine. Background Art

[0002] Alkyl derivatives of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine can be used as starting materials for near-infrared absorbing dye compounds for imaging materials, infrared-sensitive thermal recording materials, optical recording elements, and optical thin film materials. N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine is a key intermediate for synthesizing such materials, and the key step in synthesizing this intermediate is the reduction of nitro groups.

[0003] Deficiencies of the prior art:

[0004] Currently, methods for reducing nitro groups include catalytic reduction with hydrogen in the presence of a catalyst, reduction with a hydrazine compound or an olefin compound such as cyclohexene or formic acid in the presence of a catalyst, reduction with a carbonyl iron compound, reduction with a hydroaluminum compound such as lithium aluminum hydride, reduction with a borohydride compound such as sodium borohydride, or reduction with a combination of this compound and a metal compound (such as nickel chloride, copper acetate), reduction with zinc or tin in the presence of hydrochloric acid, reduction with activated iron powder, reduction with a sulfide, reduction with sodium dithionite. However, these methods have safety and environmental problems, are not suitable for large-scale amplification, or have high costs. Summary of the Invention

[0005] The purpose of the present invention is to provide a preparation method of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine to solve the problems raised in the above background art.

[0006] To achieve the above purpose, the present invention provides the following technical solution: A preparation method of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine, which specifically includes the following steps:

[0007] S1. Obtain N,N,N',N'-tetrakis(p-nitrophenyl)-p-phenylenediamine through a substitution reaction;

[0008] S2. Obtain N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine through a reduction reaction.

[0009] Preferably, the step S1 specifically includes the following steps:

[0010] a1. Using p-nitrofluorobenzene and p-phenylenediamine as raw materials, adding a base and heating for a substitution reaction;

[0011] a2. Cooling down and adding water to precipitate a solid, filtering and washing with water to obtain N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine.

[0012] Preferably, the step S2 specifically includes the following steps:

[0013] b1. Add the N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine obtained in step a2 into formic acid, add tetrabutylammonium iodide, and heat for a reduction reaction;

[0014] b2. Remove the solvent, add saturated sodium bicarbonate solution for pulping, filter, wash with water and dry to obtain N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine.

[0015] Preferably, the solvent in step a1 is DMF, NMP, or DMSO.

[0016] Preferably, the weight ratio of p-phenylenediamine to the volume of the solvent in step a1 is 1:25 - 30 g / mL.

[0017] Preferably, the molar ratio of p-phenylenediamine, p-nitrofluorobenzene, and base in step a1 is 1:3 - 6:3 - 6.

[0018] Preferably, the molar ratio of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine to tetrabutylammonium iodide in step b1 is 1:0.1 - 0.3.

[0019] Preferably, the base added in step a1 is K2CO3 or Na2CO3.

[0020] Preferably, the substitution reaction temperature in step a1 is set to 130 - 200 °C, and the optimal temperature is 150 - 170 °C.

[0021] Preferably, the reduction reaction temperature in step b1 is set to 110 - 150 °C, and the optimal temperature is 120 - 130 °C.

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0023] The present invention provides a preparation method of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine. The present invention uses inexpensive and easily purchasable industrial raw materials, p-nitrofluorobenzene and p-phenylenediamine, as raw materials to obtain N,N,N',N'-tetrakis(p-nitrophenyl)-p-phenylenediamine under alkaline conditions, with good selectivity, a single product, and easy purification; uses industrial raw materials, tetrabutylammonium iodide and formic acid, to prepare N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine, with simple operation, high safety, no environmental pollution, and easy industrialization. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is a process schematic diagram provided by the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0025] The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0026] In the description of the present invention, it should be understood that the orientation or positional relationships indicated by the terms "center", "longitudinal", "transverse", "length", "width", "thickness", "upper", "lower", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", etc. are based on the orientation or positional relationships shown in the drawings. These are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus should not be construed as a limitation of the present invention.

[0027] In the description of this patent, it should be noted that unless otherwise clearly specified and limited, the terms "installation", "connection", "setting" should be understood in a broad sense. For example, it can be fixedly connected and set, or detachably connected and set, or integrally connected and set. For those of ordinary skill in the art, the specific meanings of the above terms in this patent can be understood according to specific circumstances.

[0028] In addition, the terms "first" and "second" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, the features defined with "first" and "second" may explicitly or implicitly include one or more of such features. In the description of the present invention, "several" means two or more unless otherwise specifically defined.

[0029] Embodiment 1

[0030] Please refer to Figure 1 As shown, the technical solution provided by the present invention: A preparation method of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine. This preparation method specifically includes the following steps:

[0031] S1. Obtain N,N,N',N'-tetrakis(p-nitrophenyl)-p-phenylenediamine through a substitution reaction;

[0032] a1. In a 1000L stainless steel reactor, using 56.7 kg of p-nitrofluorobenzene and 10.8 kg of p-phenylenediamine as raw materials, adding 58.05 kg of K2CO3 and heating for a substitution reaction. The solvent is 300L of DMF. The weight-to-volume ratio of p-phenylenediamine to the solvent is 1:25 - 30 g / mL. The molar ratio of p-phenylenediamine, p-nitrofluorobenzene, and the base is 1:3 - 6:3 - 6. The substitution reaction temperature is set at 150 °C, and the reaction time is 18 hours;

[0033] a2. Cool down and add 300L of water to precipitate a red solid. Filter and wash with 50L of water to obtain 55 kg of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine, with a yield of 92.9%;

[0034] S2. Obtain N,N,N',N'-tetrakis(p-nitrophenyl)-p-phenylenediamine through a reduction reaction;

[0035] b1. In a 500L stainless steel reactor, add 10 kg of the N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine obtained in step a2 to 200L of formic acid, add 623.4 g of tetrabutylammonium iodide, and heat for a reduction reaction. The molar ratio of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine to tetrabutylammonium iodide is 1:0.1 - 0.3. The reduction reaction temperature is set at 120 °C, and the reaction time is 5 hours;

[0036] b2. Remove the solvent, add 50L of saturated sodium bicarbonate solution and slurry for 1 hour, filter, wash with 50L of water, and dry to obtain 7.5 kg of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine, with a yield of 94%.

[0037] Example 2

[0038] This preparation method specifically includes the following steps:

[0039] S1. Obtain N,N,N',N'-tetrakis(p-nitrophenyl)-p-phenylenediamine through a substitution reaction;

[0040] a1. In a 1000L stainless steel reactor, using 56.7 kg of p-nitrofluorobenzene and 10.8 kg of p-phenylenediamine as raw materials, adding 44.5 kg of Na2CO3 and heating for a substitution reaction. The solvent is 300L of NMP. The weight-to-volume ratio of p-phenylenediamine to the solvent is 1:25 - 30 g / mL. The molar ratio of p-phenylenediamine, p-nitrofluorobenzene, and the base is 1:3 - 6:3 - 6. The substitution reaction temperature is set at 170 °C, and the reaction time is 20 hours;

[0041] a2. Cool down and add 300L of water to precipitate a red solid. Filter and wash with 50L of water to obtain 52.5 kg of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine, with a yield of 88.7%;

[0042] S2. Obtain N,N,N',N'-tetrakis(p-nitrophenyl)-p-phenylenediamine through a reduction reaction;

[0043] b1. In a 500L stainless steel reactor, add 10 kg of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine obtained in step a2 to 200L of formic acid, add 623.4 g of tetrabutylammonium iodide, and heat for a reduction reaction. The molar ratio of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine to tetrabutylammonium iodide is 1:0.1 - 0.3. Set the reduction reaction temperature to 120°C and the reaction time to 5 hours;

[0044] b2. Remove the solvent, add 50L of saturated sodium bicarbonate solution and slurry for 1 hour, filter, wash with 50L of water and dry to obtain 7.5 kg of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine, with a yield of 94%.

[0045] Example 3

[0046] The specific preparation method includes the following steps:

[0047] S1. Obtain N,N,N',N'-tetrakis(p-nitrophenyl)-p-phenylenediamine through a substitution reaction;

[0048] a1. In a 1000L stainless steel reactor, use 56.7 kg of p-nitrofluorobenzene and 10.8 kg of p-phenylenediamine as raw materials, add 58.05 kg of K2CO3 and heat for a substitution reaction. The solvent is 300L of DMSO. The weight ratio of p-phenylenediamine to the volume of the solvent is 1:25 - 30 g / mL. The molar ratio of p-phenylenediamine, p-nitrofluorobenzene and the base is 1:3 - 6:3 - 6. Set the substitution reaction temperature to 150°C and the reaction time to 20 hours;

[0049] a2. Cool down and add 300L of water to precipitate a red solid. Filter and wash with 50L of water to obtain 53.7 kg of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine, with a yield of 90.8%;

[0050] S2. Obtain N,N,N',N'-tetrakis(p-nitrophenyl)-p-phenylenediamine through a reduction reaction;

[0051] b1. In a 500L stainless steel reactor, add 10 kg of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine obtained in step a2 to 200L of formic acid, add 623.4 g of tetrabutylammonium iodide, and heat for a reduction reaction. The molar ratio of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine to tetrabutylammonium iodide is 1:0.1 - 0.3. Set the reduction reaction temperature to 120°C and the reaction time to 5 hours;

[0052] b2. Remove the solvent, add 50 L of saturated sodium bicarbonate solution and slurry for 1 hour, filter, wash with 50 L of water and dry to obtain 7.5 kg of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine, with a yield of 94%.

[0053] Example 4

[0054] The specific preparation method includes the following steps:

[0055] S1. Obtain N,N,N',N'-tetrakis(p-nitrophenyl)-p-phenylenediamine through a substitution reaction;

[0056] a1. In a 1000 L stainless steel reactor, using 56.7 kg of p-nitrofluorobenzene and 10.8 kg of p-phenylenediamine as raw materials, add 58.05 kg of K2CO3 and heat for a substitution reaction. The solvent is 300 L of DMSO. The weight ratio of p-phenylenediamine to the volume of the solvent is 1:25 - 30 g / mL. The molar ratio of p-phenylenediamine, p-nitrofluorobenzene and the base is 1:3 - 6:3 - 6. The substitution reaction temperature is set at 150 °C and the reaction time is 20 hours;

[0057] a2. Cool down and add 300 L of water to precipitate a red solid. Filter and wash with 50 L of water to obtain 53.7 kg of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine, with a yield of 90.8%;

[0058] S2. Obtain N,N,N',N'-tetrakis(p-nitrophenyl)-p-phenylenediamine through a reduction reaction;

[0059] b1. In a 500 L stainless steel reactor, add 10 kg of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine obtained in step a2 to 100 L of formic acid, add 100 L of NMP, add 623.4 g of tetrabutylammonium iodide, and heat for a reduction reaction. The molar ratio of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine to tetrabutylammonium iodide is 1:0.1 - 0.3. The reduction reaction temperature is set at 120 °C and the reaction time is 12 hours;

[0060] b2. Remove the solvent, add 50 L of saturated sodium bicarbonate solution and slurry for 1 hour, filter, wash with 50 L of water and dry to obtain 6.9 kg of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine, with a yield of 86.5%.

[0061] The basic principles, main features and advantages of the present invention have been shown and described above. Those skilled in the art should understand that the present invention is not limited by the above embodiments. The above embodiments and the descriptions in the specification are only preferred examples of the present invention and are not used to limit the present invention. Without departing from the spirit and scope of the present invention, the present invention will have various changes and improvements, and these changes and improvements all fall within the scope of the present invention claimed. The scope of the present invention claimed is defined by the appended claims and their equivalents.

Claims

1. A preparation method of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine, characterized in that: The preparation method specifically includes the following steps: S1. Obtain N,N,N',N'-tetra(p-nitrophenyl)-p-phenylenediamine through a substitution reaction; S2. Obtain N,N,N',N'-tetra(p-nitrophenyl)-p-phenylenediamine through a reduction reaction.

2. The preparation method of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine according to claim 1, characterized in that: The step S1 specifically includes the following steps: a1. Use p-nitrofluorobenzene and p-phenylenediamine as raw materials, add a base and heat for a substitution reaction; a2. Cool down and add water to precipitate a solid, filter and wash with water to obtain N,N,N',N'-tetra(p-aminophenyl)-p-phenylenediamine.

3. The preparation method of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine according to claim 2, characterized in that: The step S2 specifically includes the following steps: b1. Add the N,N,N',N'-tetra(p-aminophenyl)-p-phenylenediamine obtained in step a2 into formic acid, add tetrabutylammonium iodide, and heat for a reduction reaction; b2. Remove the solvent, add saturated sodium bicarbonate solution for pulping, filter, wash with water and dry to obtain N,N,N',N'-tetra(p-aminophenyl)-p-phenylenediamine.

4. The preparation method of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine according to claim 2, characterized in that: The solvent in the step a1 is DMF, NMP or DMSO.

5. The preparation method of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine according to claim 2, characterized in that: In the step a1, the weight ratio of p-phenylenediamine to the volume of the solvent is 1:25 - 30 g / mL.

6. The preparation method of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine according to claim 2, characterized in that: In the step a1, the molar ratio of p-phenylenediamine, p-nitrofluorobenzene and the base is 1:3 - 6:3 - 6.

7. The preparation method of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine according to claim 3, characterized in that: In the step b1, the molar ratio of N,N,N',N'-tetra(p-aminophenyl)-p-phenylenediamine to tetrabutylammonium iodide is 1:0.1 - 0.

3.

8. The preparation method of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine according to claim 2, wherein: The base added in the step a1 is K2CO3 or Na2CO3.

9. The preparation method of N,N,N',N'-tetra(p-aminophenyl)-p-phenylenediamine according to claim 2, characterized in that: In the step a1, the substitution reaction temperature is set at 130 - 200 °C, preferably 150 - 170 °C.

10. The preparation method of N,N,N',N'-tetrakis(p-aminophenyl)-p-phenylenediamine according to claim 3, characterized in that: In the step b1, the reduction reaction temperature is set at 110 - 150 °C, preferably 120 - 130 °C.

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