A process for the preparation of 2,2-bis[4-(4-aminophenoxy)phenyl]propane

Abstract

The application provides a preparation method of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, which comprises the following steps: S1: 2,2-bis[4-(4-nitrophenoxy)phenyl]propane, a catalyst and a hydrogen source reagent are added into a solvent to react at a certain temperature; S2: after the reaction is completed, the catalyst is removed, activated carbon and resin are added, decolorization and deionization are carried out, and then a filtrate is obtained by filtration; the temperature is reduced, and white solids are precipitated; and the solids are dried to obtain 2,2-bis[4-(4-aminophenoxy)phenyl]propane. The application has the beneficial effects that: the preparation method uses a new process system, is simple to prepare, safe to operate, and the catalyst can be reused, the quality of the synthesized product is high, and the method is suitable for large-scale production.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of organic synthesis, and particularly relates to a preparation method of 2,2-bis[4-(4-aminophenoxy)phenyl]propane. BACKGROUND

[0002] Polyimide (PI) is a kind of high polymer material containing imide ring in the main chain. Due to its unique structure, it has excellent comprehensive performance and is located in the forefront of high polymer materials. PI has been widely used in flexible display, aerospace, electrical insulation, microelectronics, battery, photoresist and other fields.

[0003] Aromatic polyimide has more excellent thermal stability, mechanical properties and thermal stability due to containing rigid imide ring and benzene ring. 2,2-bis[4-(4-aminophenoxy)phenyl]propane is an important polyimide monomer, and the polyimide synthesized by using the same has broad application prospect.

[0004] At present, the common synthesis method mainly includes two steps, i.e. 2,2-bis[4-(4-nitrophenoxy)phenyl]propane is synthesized by using bisphenol A and p-chloronitrobenzene through coupling reaction; and 2,2-bis[4-(4-aminophenoxy)phenyl]propane is synthesized by reducing the nitro compound. The coupling reaction process in the first step has become mature and stable, and the reduction reaction in the second step mainly includes the reduction methods of palladium-carbon-hydrogen, palladium-carbon-hydrate, iron powder-hydrochloric acid and the like. The above methods all have certain disadvantages, for example, the palladium-carbon is used as catalyst, which is relatively expensive and has high cost; and the common hydrogen sources are hydrogen and hydrate, the reduction process of hydrogen needs high pressure condition and is flammable, and the hydrate is toxic, so that there is certain risk when it is used in large amount; the reduction of iron powder-hydrochloric acid system produces a large amount of waste, and the quality of the synthesized product is poor. SUMMARY

[0005] Therefore, the present application aims to provide a preparation method of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, and aims to provide a preparation method of 2,2-bis[4-(4-aminophenoxy)phenyl]propane with simple process, low production cost, green environmental protection, high product quality and yield and being suitable for large-scale production.

[0006] To achieve the above-mentioned purpose, the technical scheme of the present application is as follows:

[0007] A preparation method of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, comprising the following steps:

[0008] S1: 2,2-bis[4-(4-nitrophenoxy)phenyl]propane, a catalyst and a hydrogen source reagent are added into a solvent to react at a certain temperature;

[0009] S2: After the reaction is completed, the catalyst is removed, activated carbon and resin are added, and after decolorization and deionization, the filtrate is obtained by filtration, the temperature is lowered, and white solids are precipitated. The solids are dried to obtain 2,2-bis[4-(4-aminophenoxy)phenyl]propane.

[0010] Further, the hydrogen source reagent in step S1 is one or more of hydrazine hydrate, ammonium formate, and triethylsilane, and preferably the hydrogen source reagent is triethylsilane.

[0011] Further, the solvent in step S1 is one or more of methanol, ethanol, tetrahydrofuran, and dioxane, and preferably the solvent in step S1 is ethanol.

[0012] Further, the mass ratio of the catalyst to 2,2-bis[4-(4-nitrophenoxy)phenyl]propane in step S1 is 0.3-0.8:1;

[0013] The molar ratio of the solvent, the hydrogen source reagent, and 2,2-bis[4-(4-nitrophenoxy)phenyl]propane in step S1 is 50-80:4-7:1;

[0014] Preferably, the temperature in step S1 is 25-45°C;

[0015] Preferably, the reaction time in step S1 is 5-8h.

[0016] Further, the mass ratio of activated carbon, resin, and 2,2-bis[4-(4-nitrophenoxy)phenyl]propane in step S2 is 0.05-0.2:0.8-1.5:1;

[0017] The temperature in step S2 is lowered to -10-0°C.

[0018] The preparation method of the catalyst comprises the following steps:

[0019] 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane, and nickel chloride are added to dimethylacetamide to form polyamic acid; the polyamic acid is briefly stirred with 4,4',4"-triaminotriphenylmethane, a dehydrating agent, and a catalyst, then is placed in a beaker, aged at a certain temperature for a certain time, immersed in acetone, treated with a supercritical carbon dioxide extraction process, and then hydrogen is introduced and treated at a certain temperature. After vacuum drying, the catalyst is obtained.

[0020] Further, the molar ratio of acetone, the dehydrating agent, the catalyst, and 3,3',4,4'-biphenyl tetracarboxylic dianhydride is 70-90:3-5:0.5-1.2:1.

[0021] Further, the supercritical processing condition of the mesoporous carbon dioxide in the aerogel is that the pressure is 6-8 MPa, the temperature is 45-65 DEG C, and the time is 3-5 h.

[0022] Preferably, the pressure is 3-5 MPa, and the temperature is 30-50 DEG C.

[0023] Further, the dehydrating agent includes acetic anhydride, and the catalyst includes triethylamine.

[0024] Further, the polyamide acid is added with 4,4',4"-triaminotriphenylmethane, and then is stirred with the dehydrating agent and the catalyst for a short time, is placed in a beaker, is aged for 40-80 h at a certain temperature, and is transferred into acetone for impregnation treatment for 10-18 h.

[0025] Compared with the prior art, the preparation method of the 2,2-bis[4-(4-aminophenoxy)phenyl]propane has the following advantages:

[0026] The preparation method uses a new process system, is simple to prepare, safe to operate, small in environmental pollution, high in product yield and purity, and suitable for large-scale production. BRIEF DESCRIPTION OF DRAWINGS

[0027] The accompanying drawings, which form a part of the present application, are used to provide further understanding of the present application, and serve as an aid in explaining the present application. The schematic embodiments of the present application and their descriptions serve to explain the present application, and do not constitute an improper limitation on the present application.

[0028] In the drawings:

[0029] Figure 1 The synthesis route diagram of the 2,2-bis[4-(4-aminophenoxy)phenyl]propane prepared in the embodiment 1 of the present application is shown in the figure.

[0030] Figure 2 The HPLC diagram of the 2,2-bis[4-(4-aminophenoxy)phenyl]propane prepared in the embodiment 1 of the present application is shown in the figure. DETAILED DESCRIPTION

[0031] It should be noted that, in the case of no conflict, the embodiments in the present application and the features in the embodiments can be combined with each other.

[0032] The present application will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

[0033] Embodiment 1

[0034] (I) Preparation of GDX-2 (catalyst)

[0035] 10 g of 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 9.31 g of 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane, 3.51 g of nickel chloride were added to 88.59 g of dimethylacetamide and stirred at room temperature for 8 h to form a polyamic acid. 1.47 g of 4,4',4"-triaminotriphenylmethane, 13.84 g of acetic anhydride, 3.43 g of triethylamine were added to the above solution in turn and stirred for 20 min, then transferred to a 250 mL beaker, aged at 50°C for 60 h, then added to 158 g of acetone and soaked for 15 h. The solvent was removed by filtration to obtain an aerogel intermediate, which was placed in an autoclave, carbon dioxide was introduced, the pressure was kept at 7 MPa, the temperature was 50°C, and the treatment was 3.5 h. The carbon dioxide was exhausted, hydrogen was introduced, the pressure was 4 MPa, the temperature was 40°C, and the treatment was 12 h. After the solid was vacuum dried at 100°C for 12 h, it was ground to obtain 15.76 g of catalyst GDX-2.

[0036] (II) Synthesis of 2,2-bis[4-(4-aminophenoxy)phenyl]propane

[0037] 50 g of 2,2-bis[4-(4-nitrophenoxy)phenyl]propane, 73.31 g of triethylsilane, 25 g of GDX-2 were added to 295 g of ethanol, stirred uniformly, and then heated to 35°C for 6 h. After the reaction was completed, the catalyst was removed by filtration. 5 g of activated carbon and 60 g of resin were added to the filtrate, stirred for 1 h, filtered, and the filtrate changed from dark yellow to colorless and transparent. The temperature was lowered to -5°C, and a large amount of white solid was precipitated from the system. The solid was filtered, and the solid was vacuum dried at 90°C for 10 h to obtain 42.99 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, with a molar yield of 98.54%, a purity of 99.99%, and YI = 0.28.

[0038] Example 2

[0039] 50 g of 2,2-bis[4-(4-nitrophenoxy)phenyl]propane, 79.42 g of triethylsilane, 30 g of GDX-2 were added to 420 g of tetrahydrofuran, stirred uniformly, and then heated to 30°C for 6 h. After the reaction was completed, the catalyst was removed by filtration. 3 g of activated carbon and 50 g of resin were added to the filtrate, stirred for 1 h, filtered, and the filtrate changed from dark yellow to colorless and transparent. The temperature was lowered to 0°C, and a large amount of white solid was precipitated from the system. The solid was filtered, and the solid was vacuum dried at 90°C for 10 h to obtain 42.67 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, with a molar yield of 97.81%, a purity of 99.92%, and YI = 0.37.

[0040] Example 3

[0041] (I) Regeneration and use of GDX-2

[0042] The filtered catalyst GDX-2 in Example 1 was added into 200 g of ethanol, soaked for 24 h at 40 ℃, filtered, and vacuum dried at 80 ℃ for 12 h to obtain the regenerated catalyst GDX-2-(recovered).

[0043] 50 g of 2,2-bis[4-(4-nitrophenoxy)phenyl]propane, 73.31 g of triethylsilane, and GDX-2-(recovered) were added into 295 g of ethanol, stirred to be uniform, and heated to 35 ℃, and reacted for 6 h. After the reaction was completed, the catalyst was removed by filtration. 5 g of activated carbon and 60 g of resin were added into the filtrate, stirred for 1 h, filtered, the filtrate changed from dark yellow to colorless and transparent, cooled to -5 ℃, a large amount of white solid was precipitated in the system, the solid was filtered, and the solid was vacuum dried at 90 ℃ for 10 h to obtain 42.48 g of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, with a molar yield of 97.36%, a purity of 99.94%, and YI = 0.32.

[0044] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A process for the preparation of 2,2-bis[4-(4-aminophenoxy)phenyl]propane, characterized in that: The method comprises the following steps: S1: 2,2-bis[4-(4-nitrophenoxy)phenyl]propane, a catalyst, a hydrogen source reagent are added to a solvent to react at a certain temperature; S2: after the reaction is completed, the catalyst is removed, activated carbon and resin are added, and after decolorization and deionization, the filtrate is obtained by filtration, white solids are precipitated by reducing the temperature, and the solids are dried to obtain 2,2-bis[4-(4-aminophenoxy)phenyl]propane; The preparation method of the catalyst comprises the following steps: 3,3',4,4'-biphenyl tetracarboxylic dianhydride, 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane, and nickel chloride are added to dimethylacetamide to form polyamic acid; the polyamic acid is briefly stirred with 4,4',4"-triaminotriphenylmethane, a dehydrating agent, and a catalyst, then is placed in a beaker, is aged at a certain temperature for a certain time, is immersed in acetone for treatment, is treated by supercritical carbon dioxide after the mesoporous state of aerogel, is treated by hydrogen at a certain temperature, and is vacuum dried to obtain the catalyst; The hydrogen source reagent in the step S1 is triethylsilane; The mass ratio of the catalyst to 2,2-bis[4-(4-nitrophenoxy)phenyl]propane in the step S1 is 0.3-0.8:1; The molar ratio of the solvent, the hydrogen source reagent, and 2,2-bis[4-(4-nitrophenoxy)phenyl]propane in the step S1 is 50-80:4-7:1; The mass ratio of the activated carbon, the resin, and 2,2-bis[4-(4-nitrophenoxy)phenyl]propane in the step S2 is 0.05-0.2:0.8-1.5:1; The temperature in the step S2 is reduced to -10-0°C.

2. A process for the preparation of 2,2-bis[4-(4-aminophenoxy)phenyl]propane according to claim 1, characterized in that: The solvent in the step S1 is one or more of methanol, ethanol, tetrahydrofuran, and dioxane.

3. A process for the preparation of 2,2-bis[4-(4-aminophenoxy)phenyl]propane according to claim 2, characterized in that: The solvent in the step S1 is ethanol.

4. A process for the preparation of 2,2-bis[4-(4-aminophenoxy)phenyl]propane according to claim 3, characterized in that: The temperature in the step S1 is 25-45°C.

5. A process for the preparation of 2,2-bis[4-(4-aminophenoxy)phenyl]propane according to claim 3, characterized in that: The reaction time in the step S1 is 5-8h.

6. A process for the preparation of 2,2-bis[4-(4-aminophenoxy)phenyl]propane according to claim 1, characterized by: The molar ratio of acetone, the dehydrating agent, the catalyst, and 3,3',4,4'-biphenyl tetracarboxylic dianhydride is 70-90:3-5:0.5-1.2:

1.

7. A process for the preparation of 2,2-bis[4-(4-aminophenoxy)phenyl]propane according to claim 1, characterized by: The supercritical carbon dioxide treatment conditions of the mesoporous state of aerogel are as follows: the pressure is 6-8 MPa, the temperature is 45-65°C, and the time is 3-5h.

8. A process for the preparation of 2,2-bis[4-(4-aminophenoxy)phenyl]propane according to claim 7, characterized in that: The pressure is 3-5 MPa, and the temperature is 30-50°C.

9. A process for the preparation of 2,2-bis[4-(4-aminophenoxy)phenyl]propane according to claim 1, characterized by: The dehydrating agent comprises acetic anhydride, and the catalyst comprises triethylamine.

10. A process for the preparation of 2,2-bis[4-(4-aminophenoxy)phenyl]propane according to claim 1, characterized by: The polyamic acid is added with 4,4',4"-triaminotriphenylmethane, a dehydrating agent, and a catalyst, is briefly stirred, is placed in a beaker, is aged at a certain temperature for 40-80h, and is immersed in acetone for treatment for 10-18h.

Images