Process for synthesis of aryl bis-ether dianhydrides monomer

A synthesis method and aryl diether technology are applied in the synthesis field of dianhydride monomers, which can solve the problems of large amount of solvent, waste of solvent, low solid content, etc., and achieve the improvement of reaction yield, the reduction of three-waste pollution, and the recovery of waste. high rate effect

Inactive Publication Date: 2005-07-06
NANJING UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Due to the large amount of solvent used in the reaction process and the low solid content, if the reaction solution is directly poured into acid or other solutions to precipitate the product, it will cause a great waste of solvent

Method used

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  • Process for synthesis of aryl bis-ether dianhydrides monomer
  • Process for synthesis of aryl bis-ether dianhydrides monomer
  • Process for synthesis of aryl bis-ether dianhydrides monomer

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0052] Add 11.0g of hydroquinone to a 500ml three-necked flask, blow nitrogen, add 50ml of dimethyl sulfoxide, 16g of 50% sodium hydroxide aqueous solution, and then add 20ml of benzene, reflux to remove water for 5 hours, and distill the benzene out. After cooling to 80°C, add 41.2g of 4-nitro-N-methylphthalimide, 1.8g of catalyst, and 300ml of dimethyl sulfoxide, and react at 80°C for 12 hours. After the reaction, the solvent was distilled off under reduced pressure. Add 400ml of hydrochloric acid, filter, and recrystallize the solid with ethylene glycol to obtain triphenylbis(ether) diphthalimide.

[0053] Weigh 42.8 g of the condensation product obtained above, add 267 g of 12% NaOH aqueous solution, heat to reflux for 24 hours under nitrogen flow, filter after cooling, add hydrochloric acid to the solution to make the pH ≤ 1, and filter to obtain triphenyl ether tetraacid.

[0054] Weigh 43.8 g of the triphenylenedither tetraacid obtained above, add 20.4 g of acetic anh...

Embodiment 2

[0056] Add 25.0g bisphenol S to a 1000ml three-necked flask, blow nitrogen, add 120ml dimethyl sulfoxide, 16g 50% sodium hydroxide aqueous solution, then add 40ml benzene, reflux to remove water for 5 hours, and steam the benzene out after the water separation is completed . After cooling to 70°C, add 41.2g of 4-nitro-N-methylphthalimide, 1.2g of catalyst, and 320ml of dimethyl sulfoxide, raise the temperature to 90°C, and react for 18 hours. After the reaction, the solvent was distilled off under reduced pressure. Add 400ml of hydrochloric acid, filter, and recrystallize the solid from methanol.

[0057] Weigh 56.8g of the condensation product obtained above, add 210g of 15% NaOH aqueous solution, heat to reflux for 24 hours under nitrogen, filter after cooling, add hydrochloric acid to the solution to make the pH ≤ 1, and filter to obtain bisphenol S-type diether tetraacid.

[0058] Weigh 57.8 g of the diether tetraacid obtained above, add 25 g of acetic anhydride and 70 g...

Embodiment 3

[0060] Add 18.6g of biphenol into a 1000ml three-necked flask, blow nitrogen into it, add 90ml of dimethyl sulfoxide, 16g of 50% sodium hydroxide aqueous solution, and then add 30ml of benzene, reflux to remove water for 5 hours, and evaporate the benzene after the water separation is completed. out. After cooling to 70°C, add 41.2g of 4-nitro-N-methylphthalimide, 1.0g of catalyst, and 400ml of dimethyl sulfoxide, raise the temperature to 90°C, and react for 24 hours. After the reaction, the solvent was distilled off under reduced pressure. Add 400ml of hydrochloric acid, filter, and recrystallize the solid with methanol to obtain biphenyl-type diether diphthalimide.

[0061] Weigh 50.4 g of the condensation product obtained above, add 420 g of 12% NaOH aqueous solution, heat and reflux for 24 hours under nitrogen flow, filter after cooling, add hydrochloric acid to the solution to make the pH ≤ 1, and filter to obtain biphenyl bis-ether tetra-acid.

[0062] Weigh 51.4 g of ...

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Abstract

The invention relates to a method for synthesizing dianhydride monomer, especially a method for synthesizing aryl diether dianhydride by condensation, hydrolysis, acidification, and dehydration. In the invention, catalyst is added in the process of condensation for improving the yield of product; the solid content is 10-20%, reaction temperature is 7-100C., and reaction time is 15-48 hours; and the solvent consumption is reduced for reducing the impurity in condensed product. And diether tetracid in the diether dianhydride treated by dehydration is removed by dehydration in toluene or acetic acid and acetic anhydride and high temperature dehydration in vacuum oven sequentially, and the targeted product processed by said method has melting range less than 1C. and high purity.

Description

technical field [0001] The invention relates to a method for synthesizing dianhydride monomers, in particular to a method for synthesizing aryl bis-ether dianhydride monomers. Background technique [0002] Diether dianhydride is an important monomer for the synthesis of ether anhydride polyimide (PI). By introducing ether bonds into the dianhydride monomer molecules, the original insoluble PI can be dissolved in common solvents such as NMP and DMF, and it has a lower glass transition temperature, which improves its processing performance. [0003] There are usually three synthetic routes for bis-ether dianhydride: [0004] [0005] where R:C 6～30 Aryl; [0006] R 1 :C 1～8 Alkyl or C 6～13 Aryl; X: halogen or nitro; M: K + or Na + . [0007] The phenol used in method 1 is easily oxidized by oxygen, and the feeding and reaction process must be absolutely anhydrous and oxygen-free, and the sealing performance of the device is extremely high. Nitrogen must first be de...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D307/60
Inventor 黄培王岚程茹王晓东刘俊英
Owner NANJING UNIV OF TECH
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