A method for preparing high quality 2,2-bis(3-amino-4-hydroxyphenyl)propane

Abstract

The application provides a preparation method of high-quality 2,2-bis(3-amino-4-hydroxyphenyl)propane, which comprises the following steps: uniformly stirring o-aminophenol, 2,2-dichloropropane and a catalyst, increasing the temperature, and performing heat preservation reaction; after the reaction is completed, the temperature is reduced, white solids are precipitated, filtration is performed, a filtrate and solids are obtained, and the solids are washed, filtered and vacuum-dried to obtain 2,2-bis(3-amino-4-hydroxyphenyl)propane. The preparation method adopts a new process system, raw materials and a catalyst are low in price, environment-friendly, safe in operation, and high in product quality, and 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 high-quality 2,2-bis(3-amino-4-hydroxyphenyl)propane. BACKGROUND

[0002] Polyimide (PI) is a polymer of imide monomer containing two acyl groups bonded to nitrogen. Due to its unique structure, it has excellent comprehensive performance and is at 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 mechanical properties and thermal stability due to the presence of rigid imide rings and benzene rings. 2,2-bis(3-amino-4-hydroxyphenyl)propane is an important polyimide monomer, and the polyimide synthesized therefrom has broad application prospects.

[0004] At present, the common synthesis method is mainly as follows: taking bisphenol A as a starting material, an intermediate nitro compound is obtained after nitration, and 2,2-bis(3-amino-4-hydroxyphenyl)propane is synthesized by reduction. In the nitration process, the total yield is low, nitric acid and sulfuric acid are used, and the three wastes are too much, causing environmental pollution, and the reaction is dangerous and the production cost is high. SUMMARY

[0005] Therefore, the present application aims to provide a preparation method of high-quality 2,2-bis(3-amino-4-hydroxyphenyl)propane to solve the problems of low synthesis yield, high production cost, dangerous reaction, too much three wastes and environmental pollution.

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

[0007] A preparation method of high-quality 2,2-bis(3-amino-4-hydroxyphenyl)propane, comprising the following steps:

[0008] The o-aminophenol, 2,2-dichloropropane and catalyst are uniformly stirred, the temperature is raised, and the reaction is kept warm; after the reaction is completed, the temperature is lowered, white solids are precipitated, filtered, and the filtrate and solids are obtained, and the solids are washed, filtered, and vacuum dried to obtain 2,2-bis(3-amino-4-hydroxyphenyl)propane.

[0009] Further, the molar ratio of the catalyst, 2,2-dichloropropane and o-aminophenol is 0.05-0.2:8-15:1.

[0010] Further, the catalyst is one or more of ferric chloride, zinc chloride, zinc bromide, zinc iodide and sodium benzenesulfonate, and is preferably zinc bromide.

[0011] Further, the solid is washed with ultrapure water and methanol respectively.

[0012] Further, the mass ratio of the o-aminophenol, ultrapure water and methanol is 1:7-12:6-10.

[0013] Further, the filtrate is recovered 2,2-dichloropropane by reduced pressure distillation.

[0014] Further, the purity of the recovered 2,2-dichloropropane is 98.3%-99.6%, which can be reused.

[0015] Further, the reaction temperature is 50-70℃, and the reaction time is 3-8h.

[0016] Further, the vacuum drying temperature is 90-130℃, and the vacuum drying time is 7-15h.

[0017] Further, the colority YI of the high-quality 2,2-bis(3-amino-4-hydroxyphenyl)propane product is less than 0.4, and the total metal ions are less than 150ppb.

[0018] Further, the polymerization viscosity of the high-quality 2,2-bis(3-amino-4-hydroxyphenyl)propane product with hexafluorodiphthalic anhydride (6FDA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) and 4,4'-diphenyl ether dianhydride (ODPA) is at least 1.35 million, preferably 1.45-1.8 million.

[0019] Compared with the prior art, the preparation method of the high-quality 2,2-bis(3-amino-4-hydroxyphenyl)propane has the following advantages:

[0020] The preparation method uses a new process system, and innovatively uses o-aminophenol and 2,2-dichloropropane as raw materials to react to prepare high-quality 2,2-bis(3-amino-4-hydroxyphenyl)propane, which provides a brand-new idea for the industrial production of high-quality 2,2-bis(3-amino-4-hydroxyphenyl)propane. Moreover, the preparation method is simple, safe to operate, has high product yield and high purity, has small environmental pollution, and is suitable for large-scale production. BRIEF DESCRIPTION OF DRAWINGS

[0021] The drawings constituting a part of this application are used to provide a further understanding of the application, and the schematic embodiments of the application and the description thereof are used to explain the application, and do not constitute an improper limitation on the application. In the drawings:

[0022] Figure 1 The synthesis route map of the 2,2-bis(3-amino-4-hydroxyphenyl)propane of the application;

[0023] Figure 2 HPLC chart of 2,2-bis(3-amino-4-hydroxyphenyl)propane prepared for Example 1 of the present application. DETAILED DESCRIPTION

[0024] It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other without conflict. Unless defined, the technical terms used in the following embodiments have the same meaning as generally understood by those skilled in the art to which the present application belongs. The test reagents used in the following embodiments are all conventional biochemical reagents unless otherwise specified; and the experimental methods are all conventional methods unless otherwise specified.

[0025] The present application will be described in detail below with reference to the accompanying drawings and in conjunction with the embodiments.

[0026] Example 1

[0027] 20 g of o-aminophenol, 4.12 g of zinc bromide and 207.06 g of 2,2-dichloropropane were stirred uniformly, and reacted at 60°C for 4.5 h; reduced to room temperature, a large amount of white solid was precipitated, after filtration, the filtrate and solid were obtained; the solid was washed with 200 g of deionized water for 2 h and then washed with 160 g of methanol for 1 h, and the solid was dried at 110°C under vacuum for 12 h to obtain 22.46 g of 2,2-bis(3-amino-4-hydroxyphenyl)propane, with a molar yield of 94.87%, a purity of 99.99%, YI = 0.12, a total metal ion of 60 ppb, and a polymerization viscosity with 6FDA of 1.67 million; the filtrate obtained after the reaction was recovered by distillation at 70°C under normal pressure to obtain 160.3 g of 2,2-dichloropropane with a purity of 99.1%.

[0028] Example 2

[0029] 20 g of o-aminophenol, 3.74 g of zinc chloride and 210.26 g of 2,2-dichloropropane were stirred uniformly, and reacted at 70°C for 7 h; reduced to room temperature, a large amount of white solid was precipitated, after filtration, the filtrate and solid were obtained; the solid was washed with 180 g of deionized water for 2 h and then washed with 150 g of methanol for 1 h, and the solid was dried at 110°C under vacuum for 10 h to obtain 22.15 g of 2,2-bis(3-amino-4-hydroxyphenyl)propane, with a molar yield of 93.56%, a purity of 99.97%, YI = 0.23, a total metal ion of 70 ppb, and a polymerization viscosity with ODPA of 1.52 million; the filtrate obtained after the reaction was recovered by distillation at 70°C under normal pressure to obtain 158.4 g of 2,2-dichloropropane with a purity of 98.9%.

[0030] Example 3

[0031] Example 2

[0032] Example 3

[0033] Example 4

[0034] Comparative Example 1

[0035] (I) 2,2-Bis(3-nitro-4-hydroxyphenyl)propane

[0036] Example 2

[0037] (II) 2,2-Bis(3-amino-4-hydroxyphenyl)propane

[0038] Into 300 g of methanol, 25.48 g of bis(3-nitro-4-hydroxyphenyl) sulfone and 1.02 g of palladium-carbon were added, and the temperature was raised to 50°C, hydrogen was introduced, the pressure was maintained at 0.6 MPa, and the reaction was maintained for 8 h. After the reaction was completed, the reaction liquid was hot-filtered, 300 g of deionized water was added to the filtrate, white solids were precipitated, the white solids were washed with 200 g of deionized water for 2 h, and then washed with 200 g of methanol for 1 h. After filtration, the solids were dried at 110°C under vacuum for 12 h to obtain 17.20 g of 2,2-bis(3-amino-4-hydroxyphenyl) propane, the molar yield was 83.17%, the purity was 99.31%, YI = 32.4, the total metal ions were 3.4 ppm, and the polymerization viscosity with 6FDA was 340,000.

[0039] 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(3-amino-4-hydroxyphenyl)propane, characterized in that: The method comprises the following steps: The o-aminophenol, 2,2-dichloropropane and a catalyst are stirred uniformly, the temperature is raised, and the reaction is kept; after the reaction is completed, the temperature is lowered, white solid is precipitated, filtration is performed, a filtrate and a solid are obtained, the solid is washed with ultrapure water and methanol, filtration is performed, and vacuum drying is performed to obtain 2,2-bis(3-amino-4-hydroxyphenyl)propane; The molar ratio of the catalyst, 2,2-dichloropropane and o-aminophenol is 0.05-0.2:8-15:1; The catalyst is one or more of zinc chloride, zinc bromide and zinc iodide. The reaction temperature is 50-70 DEG C, and the reaction time is 3-8 h.

2. A process for the preparation of 2,2-bis(3-amino-4-hydroxyphenyl)propane according to claim 1, characterized in that: The catalyst is zinc bromide.

3. The process for the preparation of 2,2-bis(3-amino-4-hydroxyphenyl)propane according to claim 1, characterized in that: The mass ratio of the o-aminophenol, ultrapure water and methanol is 1:7-12:6-10.

4. The process for the preparation of 2,2-bis(3-amino-4-hydroxyphenyl)propane according to claim 1, characterized in that: The filtrate is subjected to vacuum distillation to recover 2,2-dichloropropane.

5. A process for the preparation of 2,2-bis(3-amino-4-hydroxyphenyl)propane according to claim 4, characterized in that: The purity of the recovered 2,2-dichloropropane is 98.3%-99.6%.

6. The process for the preparation of 2,2-bis(3-amino-4-hydroxyphenyl)propane according to claim 1, characterized in that: The vacuum drying temperature is 90-130 DEG C, and the vacuum drying time is 7-15 h.

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