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Preparation method of 3, 3', 4, 4'-biphenyltetracarboxylic dianhydride

A technology of biphenyltetracarboxylic dianhydride and phthalic anhydride, which is applied in the field of preparation of 3,3',4,4'-biphenyltetracarboxylic dianhydride, can solve the problem that 4-chlorophthalic anhydride is expensive and unfavorable for large-scale industrial production , serious pollution and other problems, to achieve the effect of low production cost, low pollution and simplified production process

Inactive Publication Date: 2019-12-13
上海固创化工新材料有限公司
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  • Application Information

AI Technical Summary

Problems solved by technology

[0003] Chinese patent 2006101176001 discloses a preparation method of biphenyltetracarboxylic dianhydride by Shanghai Guchuang Chemical Co., Ltd., using 4-chlorophthalic anhydride as raw material to synthesize 3,3',4,4'-biphenyltetracarboxylic dianhydride, but 4 -Chlorophthalic anhydride is very expensive, and the industry has been looking for synthetic routes to other raw materials
The patent of BYD Co., Ltd. (CN101659647) discloses the synthesis of biphenyltetracarboxylic dianhydride with o-xylene as raw material, but it must go through the oxidation reaction stage, and the oxidation reaction of potassium permanganate is not easy to control in industrial production, causing serious pollution , not conducive to large-scale industrial production

Method used

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  • Preparation method of 3, 3', 4, 4'-biphenyltetracarboxylic dianhydride
  • Preparation method of 3, 3', 4, 4'-biphenyltetracarboxylic dianhydride

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Add 550g of water to a four-necked flask equipped with a thermometer, a stirrer, a dropping device and a reflux device, add 250g of phthalic anhydride under stirring, and then dropwise add 1325g of sodium hypochlorite (10% concentration, 1% free alkali (calculated as NaOH)) and 110g of liquid alkali (32% concentration). Control the dropping speed, keep the temperature at 28°C-30°C, prevent punching, and drop adding time at about 17 hours. After the dropwise addition, use about 40g of hydrochloric acid (30% concentration) to adjust the pH value to about 5.5, keep it warm at about 30°C for 0.5-1.0 hours, filter to obtain the crude product of 4-chlorophthalic acid monosodium salt, and filter cake for use.

[0027] Add 400g of water to a three-necked flask equipped with a thermometer, agitator and reflux device, add the above-mentioned filter cake material under stirring, raise the temperature to 90°C, keep it warm for 1-2 hours, then lower it to about 30°C, filter to obtai...

Embodiment 2

[0033] Add 550g of water to a four-necked flask equipped with a thermometer, a stirrer, a dropping device and a reflux device, add 250g of phthalic anhydride under stirring, and then dropwise add 1272g of sodium hypochlorite (10% concentration, 1% free alkali (calculated as NaOH)) and 85g liquid caustic soda (32% concentration) mixed solution. Control the dropping speed, keep the temperature at 28°C-30°C, prevent punching, and drop adding time for about 18 hours. After the dropwise addition, use about 40g of hydrochloric acid (30% concentration) to adjust the pH value to about 5.5, keep it warm at about 30°C for 0.5-1.0 hours, filter to obtain the crude product of 4-chlorophthalic acid monosodium salt, and filter cake for use.

[0034] Purification of the following 4-chlorophthalic acid monosodium salt, coupling into 3,3',4,4'-sodium biphenyltetracarboxylate, acidification to 3,3',4,4'-biphenyltetracarboxylic acid and It is washed with water, refined, and anhydrided at high t...

Embodiment 3

[0036] Obtain refined 4-chlorophthalic acid monosodium salt by phthalic anhydride and sodium hypochlorite with embodiment 1.

[0037] Add 300g of water and 380g of liquid caustic soda (32% concentration) into a four-necked flask equipped with a thermometer, a stirrer, a dropping device and a reflux device, and add 185g of refined 4-chlorophthalic acid monosodium salt under stirring 1. Add 1.5g palladium carbon catalyst (dry basis), heat up to reflux, drop the mixed solution of 80g hydroxylamine sulfate and 300g water, control the rate of addition, keep the liquid level stable, keep the reflux state, and the dropping time is about 6 hours. After the dropwise addition, keep warm for 1.5 hours. Cool down to 85°C and filter while hot to obtain a filtrate of sodium 3,3',4,4'-biphenyltetracarboxylate, which is set aside for use.

[0038] Add 500g of water and 175g of sulfuric acid (98% concentration) into a four-neck flask equipped with a thermometer, agitator, reflux device and dr...

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Abstract

The invention discloses a preparation method of 3, 3', 4, 4'-biphenyltetracarboxylic dianhydride. The method includes the reactions of: (1) chlorination reaction: taking phthalic anhydride as the rawmaterial, adding a mixed solution of sodium hypochlorite aqueous solution and sodium hydroxide aqueous solution dropwise, carrying out chlorination reaction, and adjusting the pH value to generate 4-chlorophthalic acid monosodium salt; (2) coupling and hydrolysis: carrying out coupling reaction and hydrolysis reaction on the 4-chlorophthalic acid monosodium salt in the presence of a catalyst and acocatalyst under an alkaline condition to generate 3, 3', 4, 4'-biphenyltetracarboxylic acid sodium salt, wherein the catalyst is a palladium-carbon catalyst or a nickel-palladium-carbon catalyst, and the cocatalyst is hydroxylamine sulfate or hydroxylamine hydrochloride; and (3) acidification into 3, 3', 4, 4'-biphenyltetracarboxylic acid, and then drying and dehydration, thus obtaining 3, 3', 4, 4'-biphenyltetracarboxylic dianhydride. The method provided by the invention adopts phthalic anhydride as the raw material for reaction with sodium hypochlorite to synthesize 3, 3', 4, 4'-biphenyltetracarboxylic dianhydride, is low in production cost, avoids the use of potassium permanganate oxidation, simplifies the production process, and has small pollution, and high yield.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a preparation method of 3,3',4,4'-biphenyltetracarboxylic dianhydride. Background technique [0002] 3,3',4,4'-Biphenyltetracarboxylic dianhydride is one of the important monomers for the synthesis of polyimide, a special engineering plastic. Polyimide synthesized from it and diamines such as 1,4'-p-phenylenediamine and 4,4'-diaminodiphenyl ether has excellent heat resistance, mechanical properties and electrical insulation properties, and is widely used in Aviation, aerospace, electronics, laser, new energy and other fields. Among them, the 5% thermal weight loss temperature (in nitrogen atmosphere) of polyimide polymerized by 3,3',4,4'-biphenyltetracarboxylic dianhydride and 1,4'-p-phenylenediamine exceeds 600°C , which is very high among known polyimides. Therefore, the synthesis method of 3,3',4,4'-biphenyltetracarboxylic dianhydride has aroused the attention and continuou...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D307/89
CPCC07D307/89
Inventor 刘少华
Owner 上海固创化工新材料有限公司
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