A method for preparing high-quality 1,3-bis(3-aminophenoxy)benzene

Abstract

The invention provides a method for preparing high-quality 1,3-bis(3-aminophenoxy)benzene, comprising the following steps: adding resorcinol, m-chloroaniline, alkaline resin and solvent to a reaction flask, reacting at a certain temperature, filtering to remove the resin, obtaining filtrate A, decolorizing the filtrate A, filtering to obtain filtrate B, cooling the filtrate B to precipitate a white solid, washing, and drying to obtain 1,3-bis(3-aminophenoxy)benzene. The method for preparing high-quality 1,3-bis(3-aminophenoxy)benzene of the invention is simple to prepare, safe to operate, has little environmental pollution, has a high yield of a synthetic product, and is high in purity, and is suitable for large-scale production.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis, and in particular relates to a method for preparing high-quality 1,3-bis(3-aminophenoxy)benzene. Background Art

[0002] Polyimide (PI) is a type of polymer with an amide structure in the main chain. Due to its unique molecular structure, it has excellent comprehensive properties and is at the forefront of polymer materials. PI has been widely used in flexible displays, aerospace, electrical insulation, microelectronics, batteries, photoresists and other fields.

[0003] Aromatic polyimide has more excellent thermal stability, mechanical properties and chemical stability because it contains rigid imide ring and benzene ring. 1,3-Bis(3-aminophenoxy)benzene is an important polyimide monomer, and the polyimide synthesized from it has broad application prospects.

[0004] At present, the common synthesis method mainly uses resorcinol and m-chloronitrobenzene as starting materials, and then synthesizes them through coupling and reduction methods. The coupling reaction process generally involves the reaction of a high boiling point solvent and potassium carbonate under high temperature and high pressure. This process not only has high energy consumption, but also poor repeatability. The second step reduction process system includes hydrazine hydrate + ferric chloride, hydrazine hydrate + palladium carbon and hydrogen + palladium carbon, etc. These processes are difficult to industrialize due to their disadvantages such as large hydrogen source hazards, expensive catalysts, serious environmental pollution, complex post-treatment, and large amounts of three wastes. Summary of the invention

[0005] In view of this, the present invention aims to propose a preparation method for high-quality 1,3-bis(3-aminophenoxy)benzene which has simple process, low production cost, is green and environmentally friendly, has high product quality and yield, and is suitable for large-scale production.

[0006] To achieve the above object, the technical solution of the present invention is achieved as follows:

[0007] A method for synthesizing high-quality 1,3-bis(3-aminophenoxy)benzene comprises the following steps:

[0008] Add resorcinol, m-chloroaniline, alkaline resin and solvent to the reaction flask, react at a certain temperature, and the reaction ends. Filter to remove the resin, add activated carbon and modified SBA-15 to the filtrate in turn, stir for a period of time, decolorize it and remove metal ions, filter to obtain the filtrate, cool it to precipitate a white solid, wash it, and dry it to obtain 1,3-bis(3-aminophenoxy)benzene.

[0009] Furthermore, the reaction temperature is 10-30°C.

[0010] Furthermore, the alkaline resin used is one or more of PA-306S, IRA-400, and A-520E, preferably PA-306S resin.

[0011] Furthermore, the solvent used is one or more of ethylene glycol dimethyl ether, cyclopentane, acetonitrile, dioxane, and succinonitrile, preferably ethylene glycol dimethyl ether.

[0012] Furthermore, the molar ratio of m-chloroaniline, solvent and resorcinol is 2.1-3:15-30:1.

[0013] Furthermore, the mass ratio of the basic resin to resorcinol is 0.8-1.5:1

[0014] Furthermore, the modified SBA-15 is prepared by refluxing SBA-15 molecular sieve with 3-aminopropyltriethoxysilane in ethanol.

[0015] Furthermore, the mass ratio of activated carbon, modified SBA-15, and resorcinol is 0.5-0.8:0.7-1.1:1

[0016] Furthermore, in the step, the recovered alkaline resin is soaked in deionized water at room temperature and can be reused.

[0017] Furthermore, in the step, the metal ion concentration of the prepared high-quality 1,3-bis(3-aminophenoxy)benzene is less than 300 ppb and the color YI is less than 1.

[0018] Furthermore, in the step, the prepared 1,3-bis(3-aminophenoxy)benzene is polymerized with commercial dianhydrides, hexafluorodianhydride (6FDA), 3,3′,4,4′-benzophenone tetracarboxylic dianhydride (BTDA), and 4,4′-diphenyl ether dianhydride (ODPA) to obtain a polymer with a molecular weight of 500,000-900,000.

[0019] Compared with the prior art, the method for preparing high-quality 1,3-bis(3-aminophenoxy)benzene described in the present invention has the following beneficial effects:

[0020] The preparation method of the present invention uses a new process system, has simple preparation, safe operation, little environmental pollution, high yield and purity of the synthesized product, and is suitable for large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] The accompanying drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the accompanying drawings:

[0022] The preparation method of the present invention uses a new process system, has simple preparation, safe operation, little environmental pollution, high yield and high purity of the synthesized product, and is suitable for large-scale production.

[0023] Figure 1 The synthetic route of 1,3-bis(3-aminophenoxy)benzene in the present invention is as follows;

[0024] Figure 2 This is the HPLC chart of 1,3-bis(3-aminophenoxy)benzene prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0025] It should be noted that, in the absence of conflict, the embodiments of the present invention and the features in the embodiments may be combined with each other.

[0026] The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with embodiments.

[0027] Example 1

[0028] 50g of resorcinol, 133.23g of m-chloroaniline, 60g of PA-306S alkaline resin and 820g of ethylene glycol dimethyl ether were added to a 2L three-necked flask, reacted at 20℃ for 24h, monitored the reaction by TLC plate, and filtered to remove the alkaline resin. 30g of activated carbon was added to the filtrate and stirred at room temperature for 1h, and the filtrate was filtered and continued to add 40g of modified SBA-15 and stirred at room temperature for 0.5h. The filtrate was cooled to -20℃, and a large amount of white solid precipitated. After the solid was washed with methanol for 0.5h, it was vacuum dried for 12h to obtain 131.05g of 1,3-bis(3-aminophenoxy)benzene, with a molar yield of 98.72%, a purity of 99.91%, a metal ion content of 197ppb, and YI=0.67. The polymer obtained by polymerization with 6FDA has a molecular weight of 898,000.

[0029] Example 2

[0030] 50g of resorcinol, 133.23g of m-chloroaniline, 70g of IRA-400 basic resin and 1000g of acetonitrile were added to a 2L three-necked flask, reacted at 25℃ for 36h, monitored by TLC plate to complete the reaction, and filtered to remove the basic resin. 30g of activated carbon was added to the filtrate, stirred at room temperature for 1h, filtered to obtain the filtrate, and 40g of modified SBA-15 was added to the room temperature for 0.5h, filtered to obtain the filtrate, cooled to -30℃, and a large amount of white solid precipitated. The solid was washed with methanol for 0.5h and vacuum dried for 12h to obtain 129.64g of 1,3-bis(3-aminophenoxy)benzene, with a molar yield of 97.66%, a purity of 99.82%, a metal ion content of 210ppb, and YI=0.74. The polymer obtained by polymerization with ODPA has a molecular weight of 735,000.

[0031] Example 3

[0032] 50g of resorcinol, 139.03g of m-chloroaniline, 70g of A-520E basic resin and 820g of ethylene glycol dimethyl ether were added to a 2L three-necked flask, reacted at 30°C for 24h, the reaction was monitored by TLC plate, and the basic resin was removed by filtration. 40g of activated carbon was added to the filtrate and stirred at room temperature for 1h, and the filtrate was filtered to obtain a filtrate. 50g of modified SBA-15 was added to the room temperature and stirred for 0.5h, and the filtrate was cooled to -20°C, and a large amount of white solid precipitated. The solid was washed with methanol for 0.5h and vacuum dried for 12h to obtain 127.29g of 1,3-bis(3-aminophenoxy)benzene, with a molar yield of 95.89%, a purity of 99.76%, a metal ion content of 200ppb, and YI=0.86. The polymer obtained by polymerization with BTDA has a molecular weight of 589,000.

[0033] Example 4

[0034] The recovered resin in Example 1 was added into 500 g of deionized water and immersed for 24 h, and then vacuum dried at 110° C. for 24 h to obtain the recovered resin, which was recorded as PA-306S-Recovered.

[0035] 50g of resorcinol, 133.23g of m-chloroaniline, alkaline resin (PA-306S-recovered) and 820g of ethylene glycol dimethyl ether were added to a 2L three-necked flask, reacted at 20℃ for 24h, monitored the reaction by TLC plate, and filtered to remove the alkaline resin. 30g of activated carbon was added to the filtrate and stirred at room temperature for 1h, filtered to obtain the filtrate, and 40g of modified SBA-15 was added to stir at room temperature for 0.5h, filtered to obtain the filtrate, cooled to -20℃, and a large amount of white solid precipitated. The solid was washed with methanol for 0.5h and vacuum dried for 12h to obtain 129.48g of 1,3-bis(3-aminophenoxy)benzene, with a molar yield of 97.54%, a purity of 99.87%, a metal ion content of 187ppb, and YI=0.71. The polymer obtained by polymerization with 6FDA has a molecular weight of 715,400.

[0036] Comparative Example 1

[0037] 50 g of resorcinol, 133.23 g of m-chloroaniline, 160 g of potassium carbonate and 820 g of ethylene glycol dimethyl ether were added into a 2 L three-necked flask and reacted at 20°C for 24 h. No reaction was observed by TLC plate. The reaction temperature was raised to 120°C and reacted for 24 h. No reaction was observed by TLC plate.

[0038] Comparative Example 2

[0039] 50 g of resorcinol, 133.23 g of m-chloroaniline, 45 g of strong sodium oxide and 1000 g of acetonitrile were added to a 2 L three-necked flask and reacted at 25 °C for 36 h. No reaction was observed under TLC plate monitoring. The reaction temperature was raised to 80 °C and reacted for 36 h. No reaction was observed under TLC plate monitoring.

[0040] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for preparing 1,3-bis(3-aminophenoxy)benzene, characterized in that: The steps include: Resorcinol, m-chloroaniline, alkaline resin and solvent are added to a reaction flask, reacted at a certain temperature, filtered to remove the resin, and obtained filtrate A, decolorized the filtrate A, filtered to obtain filtrate B, cooled the filtrate B to precipitate a white solid, washed, and dried to obtain 1,3-bis(3-aminophenoxy)benzene; the alkaline resin model used is one or more of PA-306S, IRA-400, and A-520E.

2. The method for preparing 1,3-bis(3-aminophenoxy)benzene according to claim 1, characterized in that: The reaction temperature is 10-30°C.

3. The method for preparing 1,3-bis(3-aminophenoxy)benzene according to claim 1, characterized in that: The decolorization treatment includes the following steps: adding activated carbon and molecular sieves to the filtrate A in sequence, stirring for a period of time, decolorizing it and removing metal ions.

4. The method for preparing 1,3-bis(3-aminophenoxy)benzene according to claim 1, characterized in that: The alkaline resin used is PA-306S resin.

5. The method for preparing 1,3-bis(3-aminophenoxy)benzene according to claim 1, characterized in that: The solvent used is one or more of ethylene glycol dimethyl ether, cyclopentane, acetonitrile, dioxane and succinonitrile.

6. The method for preparing 1,3-bis(3-aminophenoxy)benzene according to claim 1, characterized in that: The solvent is ethylene glycol dimethyl ether.

7. The method for preparing 1,3-bis(3-aminophenoxy)benzene according to claim 1, characterized in that: The molar ratio of m-chloroaniline, solvent and resorcinol is 2.1-3:15-30:

1.

8. The method for preparing 1,3-bis(3-aminophenoxy)benzene according to claim 1, characterized in that: The mass ratio of the alkaline resin to resorcinol is 0.8-1.5:

1.

9. The method for preparing 1,3-bis(3-aminophenoxy)benzene according to claim 3, characterized in that: The mass ratio of activated carbon, molecular sieve and resorcinol is 0.5-0.8:0.7-1.1:

1.

10. The method for preparing 1,3-bis(3-aminophenoxy)benzene according to claim 1, characterized in that: The metal ion concentration of the prepared 1,3-bis(3-aminophenoxy)benzene is less than 300 ppb, and the chromaticity YI is less than 1.

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