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CN-121991112-A - 1, 4-Bis (4-phenoxybenzoyl) benzene-AlCl3Process for preparing complex

CN121991112ACN 121991112 ACN121991112 ACN 121991112ACN-121991112-A

Abstract

The invention discloses a preparation method of a 1, 4-bis (4-phenoxybenzoyl) benzene-AlCl 3 complex, which belongs to the technical field of polymer monomer preparation, and is characterized in that aromatic diacid chloride and aromatic ether are used as raw materials, a 1, 4-bis (4-phenoxybenzoyl) benzene-AlCl 3 complex crude product is continuously synthesized under the catalysis of a Lewis acid catalyst, and the 1, 4-bis (4-phenoxybenzoyl) benzene-AlCl 3 complex product with high purity is obtained through crystallization and purification, and can be used as a polyether ketone active monomer, and the active monomer can be played without aluminum in the polymerization reaction process.

Inventors

  • ZHAI YUNGE
  • ZHAO KAI
  • LI CONGCONG
  • ZHANG MEI
  • ZHANG XIAOMENG
  • SHI FEIYU
  • SUN YIMIN

Assignees

  • 山东凯盛新材料股份有限公司

Dates

Publication Date
20260508
Application Date
20251202

Claims (9)

  1. 1. A preparation method of a1, 4-bis (4-phenoxybenzoyl) benzene-AlCl 3 complex is characterized in that aromatic diacid chloride and aromatic ether are used as raw materials, a crude 1, 4-bis (4-phenoxybenzoyl) benzene-AlCl 3 complex is continuously synthesized under the catalysis of a Lewis acid catalyst, and the crude 1, 4-bis (4-phenoxybenzoyl) benzene-AlCl 3 complex is obtained through crystallization and purification.
  2. 2. The process for preparing a 1, 4-bis (4-phenoxybenzoyl) benzene-AlCl 3 complex according to claim 1, comprising the steps of: 1) The method comprises the steps of pre-activating raw materials, namely adding 60-80% of the total mass of aromatic ether and Lewis acid catalyst into 20-50% of the total mass of solvent, heating to 20-40 ℃ for dissolution, and filtering to obtain a solution A for standby; 2) Preheating a continuous reactor module, a primary crystallizer and a secondary crystallization kettle to 0-100 ℃, inputting the solution A prepared in the step 1) into the continuous reactor module, continuously inputting the solution B prepared in the step 1) into the continuous reactor module after the solution A is filled in a first microchannel reactor, continuously crystallizing the obtained reaction liquid in the primary crystallizer after the solution B stays for 0.5-10 s, cooling and crystallizing the reaction liquid in the secondary crystallization kettle, and filtering the reaction liquid to obtain a crystal; The continuous reactor module is formed by connecting 1-5 micro-channel reactors in series; 3) And 3) purifying, namely washing the crystal prepared in the step 2) with a solvent, and recrystallizing to obtain the 1, 4-bis (4-phenoxybenzoyl) benzene-AlCl 3 complex.
  3. 3. The process for preparing a1, 4-bis (4-phenoxybenzoyl) benzene-AlCl 3 complex of claim 2, wherein the aromatic ether in step 1) is one or two of diphenyl ether, 4' -dichlorodiphenyl ether and 1, 4-bis (4-phenoxybenzoyl) benzene, and the aromatic diacid chloride in step 1) is one or two of isophthaloyl chloride and terephthaloyl chloride.
  4. 4. The process for preparing a 1, 4-bis (4-phenoxybenzoyl) benzene-AlCl 3 complex according to claim 2, wherein the solvent in step 1) and step 3) is o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, o-difluorobenzene, m-difluorobenzene or p-difluorobenzene.
  5. 5. The method for preparing a1, 4-bis (4-phenoxybenzoyl) benzene-AlCl 3 complex according to claim 2, wherein the molar ratio of the aromatic ether to the aromatic diacid chloride in step 1) is 2-3:1, the molar ratio of the total amount of the solvent to the aromatic diacid chloride is 15-20:1, the Lewis acid catalyst in step 1) is aluminum trichloride, and the molar ratio of the total amount of the Lewis acid catalyst to the aromatic diacid chloride is 2-3:1.
  6. 6. The process for preparing a1, 4-bis (4-phenoxybenzoyl) benzene-AlCl 3 complex according to claim 2, wherein the reaction solution obtained in step 2) is introduced into a primary crystallizer for continuous crystallization for 60-600 s.
  7. 7. The process for preparing a1, 4-bis (4-phenoxybenzoyl) benzene-AlCl 3 complex according to claim 2, wherein the primary crystallizer in step 2) is a crystallizer with a guide cylinder and a baffle plate.
  8. 8. The method of claim 2, wherein the microchannel reactor in step 2) is made of silicon carbide or stainless steel, and the internal turbulence structure is heart-shaped.
  9. 9. The method for preparing a1, 4-bis (4-phenoxybenzoyl) benzene-AlCl 3 complex according to claim 2, wherein the primary crystallizer in step 2) is a DTB crystallizer, and the continuous reactor module, the primary crystallizer and the secondary crystallization kettle in step 2) are preheated to 60-90 ℃.

Description

Preparation method of 1, 4-bis (4-phenoxybenzoyl) benzene-AlCl 3 complex Technical Field The invention belongs to the technical field of polymer monomer preparation, and particularly relates to a preparation method of a 1, 4-bis (4-phenoxybenzoyl) benzene-AlCl 3 complex. Background Polyetherketoneketone (PEKK) is a high strength, high temperature, chemical corrosion resistant engineering plastic whose properties are highly dependent on the purity and activity of the monomer. In the synthesis of PEKK, a1, 4-bis (4-phenoxybenzoyl) benzene-aluminum trichloride complex (EKKE-2 AlCl 3) is a key intermediate, and the synthesis generally involves Friedel-Crafts acylation reaction, and Lewis acid (such as aluminum trichloride) is required to catalyze the reaction, however, in the traditional kettle-type method, the use amount of AlCl 3 is large, the residue is large, the reaction selectivity is poor, side reactions often occur, the product purity is reduced, and the post-treatment process is complex and the wastewater amount is large. Patent CN119371297B discloses a synthesis process of 1, 4-bis (4-phenoxybenzoyl) benzene, which mainly uses excessive diphenyl ether and terephthaloyl chloride as reaction raw materials, uses o-dichlorobenzene as reaction solvent, prepares 1, 4-bis (4-phenoxybenzoyl) benzene-aluminum trichloride complex under the catalysis of aluminum trichloride, and then decomplexes the complexed aluminum trichloride to obtain 1, 4-bis (4-phenoxybenzoyl) benzene through the action of proton solvent. Patent US10793669B2 discloses a process for the manufacture of Polyetherketoneketone (PEKK) comprising (i) providing a1, 4-bis (4-phenoxybenzoyl) benzene-lewis acid complex, (ii) purifying the 1, 4-bis (4-phenoxybenzoyl) benzene-lewis acid complex, (iii) optionally adding an additional lewis acid to a reaction solvent, reacting the 1, 4-bis (4-phenoxybenzoyl) benzene-lewis acid complex with at least one difunctional aromatic acid chloride to obtain a product mixture comprising PEKK-lewis acid complex, and (iv) dissociating the PEKK-lewis acid complex to obtain a PEKK polymer. Although the PEKK is generated by taking the 1, 4-bis (4-phenoxybenzoyl) benzene-Lewis acid compound as a starting point, the PEKK is a kettle type batch process, the method is extremely easy to be influenced by environmental humidity under batch operation, the complexed Lewis acid is dissociated, and the method is inferior to continuous production of the 1, 4-bis (4-phenoxybenzoyl) benzene-aluminum trichloride complex in terms of product purity, intrinsic safety, productivity, stability and the like. Therefore, a high-efficiency method which can control the dosage of AlCl 3, stabilize complexation, improve the purity of the product and is suitable for continuous flow synthesis is developed, and the method has important industrial application value. Disclosure of Invention In order to solve the problems, the invention aims to provide a preparation method of a1, 4-bis (4-phenoxybenzoyl) benzene-AlCl 3 complex. The invention aims to achieve the aim, and the aim is achieved by the following technical scheme: a preparation method of 1, 4-bis (4-phenoxybenzoyl) benzene-AlCl 3 complex takes aromatic diacid chloride and aromatic ether as raw materials, continuously synthesizes 1, 4-bis (4-phenoxybenzoyl) benzene-AlCl 3 complex crude product under the catalysis of Lewis acid catalyst, and obtains 1, 4-bis (4-phenoxybenzoyl) benzene-AlCl 3 complex by crystallization and purification. The method specifically comprises the following steps: 1) The method comprises the steps of pre-activating raw materials, namely adding 60-80% of the total mass of aromatic ether and Lewis acid catalyst into 20-50% of the total mass of solvent, heating to 20-40 ℃ for dissolution, and filtering to obtain a solution A for standby; 2) Preheating a continuous reactor module, a primary crystallizer and a secondary crystallization kettle to 0-100 ℃, inputting the solution A prepared in the step 1) into the continuous reactor module, continuously inputting the solution B prepared in the step 1) into the continuous reactor module after the solution A is filled in a first microchannel reactor, continuously crystallizing the obtained reaction liquid in the primary crystallizer after the solution B stays for 0.5-10 s, cooling and crystallizing the reaction liquid in the secondary crystallization kettle, and filtering the reaction liquid to obtain a crystal; The continuous reactor module is formed by connecting 1-5 micro-channel reactors in series; 3) And 3) purifying, namely washing the crystal prepared in the step 2) with a solvent, and recrystallizing to obtain the 1, 4-bis (4-phenoxybenzoyl) benzene-AlCl 3 complex. The aromatic ether in the step 1) is one or two of diphenyl ether, 4' -dichloro diphenyl ether and 1, 4-bis (4-phenoxybenzoyl) benzene. The aromatic diacid chloride in the step 1) is one or two of isophthaloyl dichloride and terephthaloyl dichloride. The solv