CN85103212A - Liquid phase air oxidation preparation 3,3 ', 4,4 '-the benzophenone tetracarboxylic acid - Google Patents
Liquid phase air oxidation preparation 3,3 ', 4,4 '-the benzophenone tetracarboxylic acid Download PDFInfo
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- CN85103212A CN85103212A CN 85103212 CN85103212A CN85103212A CN 85103212 A CN85103212 A CN 85103212A CN 85103212 CN85103212 CN 85103212 CN 85103212 A CN85103212 A CN 85103212A CN 85103212 A CN85103212 A CN 85103212A
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- benzophenone
- acid
- tetracarboxylic acid
- benzophenone tetracarboxylic
- catalyzer
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Abstract
The present invention be by 3,3 ', 4,4 '-tetramethyl-benzophenone liquid phase air oxidation preparation 3,3 ', 4,4 '-method of benzophenone tetracarboxylic acid.Present method is a mixed solvent with acetic acid and monochloroacetic acid, is catalyzer with Cobaltous diacetate, Potassium Bromide and an amount of manganese acetate, under pressurization, heating condition, one step produced 3,3 ', 4,4 '-the benzophenone tetracarboxylic acid, product purity is not less than 95%, and yield is 76～84%.
Description
The present invention for liquid phase air oxidation preparation 3,3 ', 4,4 '-the relevant development of benzophenone tetracarboxylic acid.
3,3 ', 4,4 '-benzophenone tetracarboxylic acid and dianhydride thereof be used in the fire resistant special type material polyimide field in a large number.At present, 3,3 ', 4,4 '-the benzophenone tetracarboxylic acid is many to carry out industrial preparation by tetramethyl-hexichol alkane through two sections oxidations of nitric acid.This method will consume a large amount of nitric acid, and more nitrogenous impurity is arranged in the product, give refiningly to bring difficulty, and produce a large amount of waste water, spent acid needs to handle.Adopt liquid-phase air oxidation then can avoid these shortcomings.
About 3,3 ', 4,4 '-liquid phase air oxidation of tetramethyl-benzophenone, in the United States Patent (USP) 1167825,3287373, adopt catalyzer such as cobalt naphthenate, manganese naphthenate, in acetate solvate, carry out oxidation with oxygen or air, but can only obtain tri-methyl benzophenone monocarboxylic acid, dimethyl benzophenone dicarboxylic acid, the tricarboxylic mixture of monomethyl benzophenone.Adopting Cobaltous diacetate, brometo de amonio in the Soviet Union inventor certificate 300457 is that catalyzer, acetic acid are solvent, and has added a certain amount of Tricholroacetic Acid, at 20kg/cm
2Under pressure, 110～200 ℃ of conditions, use atmospheric oxidation, can make durol generate corresponding tetracarboxylic acid.Material that can be oxidized in this inventor's certificate also comprised 3,3 ', 4,4 '-the tetramethyl-benzophenone, but fail to describe in detail.
The objective of the invention is to improve by 3,3 ', 4,4 '-the tetramethyl-benzophenone through liquid phase air oxidation preparation 3,3 ', 4,4 '-process of benzophenone tetracarboxylic acid, improve reaction yield and product purity, fast reaction speed reduces the reaction times.
The key that realizes process of the present invention has been to adopt catalyzer and the efficient catalytic system of mixed solvent composition and the reaction conditions that adapts with it.The catalyzer that the present invention adopts is Cobaltous diacetate, Potassium Bromide and contains manganic compound.The consumption of Cobaltous diacetate is to add 0.012 to 0.068 mol in every liter of reaction mass; The consumption of Potassium Bromide is that every liter of reaction mass adds 0.011 to 0.025 mol, is preferably 0.018 to 0.022 mol; Contain manganic compound and be preferably manganese acetate, consumption is that every liter of reaction mass adds 0.004 to 0.032 mol.
The mixed solvent that the present invention adopts is made up of 98% to 75% acetic acid and 2% to 25% monochloroacetic acid.Mixed solvent consumption and 3,3 ', 4,4 '-weight ratio of tetramethyl-benzophenone charging capacity is 4: 1 to 3: 1, is preferably 6: 1 to 11: 1.
Among the present invention, temperature of reaction can change in the scope of broad, but the oxidation results in order to obtain, temperature should maintain 120 to 180 ℃, is preferably 155 to 175 ℃, and pressure is 5 to 28kg/cm
2, be preferably 22 to 25kg/cm
2, used oxygenant is an air, under above-mentioned reaction conditions, the time of finishing oxidation is 1.5 to 4.0 hours, isolated 3,3 from reaction solution ', 4,4 '-purity of benzophenone tetracarboxylic acid is not less than 95%, and yield is 76～84%.
Characteristics of the present invention and effect can further be understood from following example.
Example 1 in reactor, add altogether 9.5 the gram 3,3 ', 4,4 '-the tetramethyl-benzophenone, 0.42 the gram Cobaltous diacetate, 0.03 the gram manganese acetate, 0.25 the gram Potassium Bromide, 20 gram-monochloroacetic acids, 90 milliliters of Glacial acetic acid are at 25kg/cm
2, under 175 ℃ of conditions, blowing air oxidation 3 hours, reaction terminating, pressure release, cooling are after the question response liquid cooling but, filter precipitate, after washing drying, obtain 11.9 gram faint yellow solids, gas chromatographic analysis shows 3,3 ', 4,4 '-benzophenone tetracarboxylic acid purity is 98.8%, yield is 82.5%.
Monochloroacetic acid consumption in example 2 examples 1 is as being 5 grams, and by same catalyzer, the reaction of similarity condition spare obtained 11.3 gram solids, product purity 96.1%, yield 76.2% in 3 hours.
Reaction conditions in example 3 examples 1 changes 25kg/cm into
2, 165 ℃ were reacted 4 hours, can obtain 11.6 gram solids, product purity 98.0%, yield 81.0%.
Example 4 (Comparative Examples)
In the example 1, do not add manganese acetate, under same reaction conditions, oxidation 3 hours obtains 0.48 gram light red solid, and stratographic analysis shows does not have 3,3 ', 4,4 '-the benzophenone tetracarboxylic acid generates, and only is the mixture of each intermediate oxidation product.
Example 5 (Comparative Examples)
In the example 1, do not add monochloroacetic acid, under same reaction conditions, 4.4 gram solid products are had in oxidation 3 hours, and product purity is 82.5%, and yield is 26.0%.
Example 6 (Comparative Examples)
In the example 1, do not add manganese acetate and monochloroacetic acid, under same reaction conditions, oxidation 3 hours, reaction solution left standstill 72 hours, and no solid is separated out.
Claims (5)
1, a kind of preparation 3,3 ', 4,4 '-method of benzophenone tetracarboxylic acid is in the presence of solvent and catalyzer, with atmospheric oxidation 3,3 ', 4,4 '-the tetramethyl-benzophenone.The invention is characterized in and improve solvent and catalyst system, is mixed solvent with acetic acid and monochloroacetic acid, is catalyzer with cobalt, manganese, bromine compounds simultaneously, under selected proper temperature and pressure, obtains high purity, the product of high yield.
2, in claim 1, mixed solvent is made up of 2% to 25% monochloroacetic acid and 98% to 75% acetic acid.
3, in claim 1, mixed solvent and 3,3 ', 4,4 '-weight ratio of tetramethyl-benzophenone is 4: 1 to 13: 1.
4, in claim 1, catalyzer is that 0.014 to 0.025 molar Potassium Bromide and 0.004 to 0.020 molar manganese acetate are formed by interpolation 0.017 to 0.040 molar Cobaltous diacetate in every liter of reaction mass.
5, in claim 1, reaction pressure is 22 to 25kg/cm
2, temperature of reaction is 165～180 ℃, finishes oxidization time from 1.0 to 4.0 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85103212 CN85103212A (en) | 1985-04-01 | 1985-04-01 | Liquid phase air oxidation preparation 3,3 ', 4,4 '-the benzophenone tetracarboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85103212 CN85103212A (en) | 1985-04-01 | 1985-04-01 | Liquid phase air oxidation preparation 3,3 ', 4,4 '-the benzophenone tetracarboxylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN85103212A true CN85103212A (en) | 1987-01-17 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85103212 Pending CN85103212A (en) | 1985-04-01 | 1985-04-01 | Liquid phase air oxidation preparation 3,3 ', 4,4 '-the benzophenone tetracarboxylic acid |
Country Status (1)
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| CN (1) | CN85103212A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997285A (en) * | 2018-07-16 | 2018-12-14 | 山东冠森高分子材料科技股份有限公司 | The method of benzophenone tetracarboxylic dianhydride is synthesized in continuous flow micro passage reaction |
| CN112979446A (en) * | 2019-12-16 | 2021-06-18 | 赢创纤维有限公司 | Process for preparing 3,3',4,4' -benzophenonetetracarboxylic acids |
| CN114605363A (en) * | 2022-03-11 | 2022-06-10 | 大连新阳光材料科技有限公司 | Preparation method of 3,3',4,4' -benzophenone tetracarboxylic dianhydride |
-
1985
- 1985-04-01 CN CN 85103212 patent/CN85103212A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108997285A (en) * | 2018-07-16 | 2018-12-14 | 山东冠森高分子材料科技股份有限公司 | The method of benzophenone tetracarboxylic dianhydride is synthesized in continuous flow micro passage reaction |
| CN108997285B (en) * | 2018-07-16 | 2022-07-19 | 山东冠森高分子材料科技股份有限公司 | Method for synthesizing benzophenone tetracarboxylic dianhydride in continuous flow microchannel reactor |
| CN112979446A (en) * | 2019-12-16 | 2021-06-18 | 赢创纤维有限公司 | Process for preparing 3,3',4,4' -benzophenonetetracarboxylic acids |
| CN114605363A (en) * | 2022-03-11 | 2022-06-10 | 大连新阳光材料科技有限公司 | Preparation method of 3,3',4,4' -benzophenone tetracarboxylic dianhydride |
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