CN100567248C - Liquid-phase air oxidation preparation 3,3 ＇, the method for 4,4 ＇-benzophenone tetracarboxylic acid - Google Patents
Liquid-phase air oxidation preparation 3,3 ＇, the method for 4,4 ＇-benzophenone tetracarboxylic acid Download PDFInfo
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- CN100567248C CN100567248C CNB2007101447794A CN200710144779A CN100567248C CN 100567248 C CN100567248 C CN 100567248C CN B2007101447794 A CNB2007101447794 A CN B2007101447794A CN 200710144779 A CN200710144779 A CN 200710144779A CN 100567248 C CN100567248 C CN 100567248C
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- tetracarboxylic acid
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Abstract
Liquid-phase air oxidation preparation 3,3 ', 4,4 '-method of benzophenone tetracarboxylic acid, it relate to a kind of 3,3 ', 4,4 '-preparation method of benzophenone tetracarboxylic acid.Its solve prepare 3,3 in prior art ', 4,4 '-use hypertoxic purification solvent, reinforced difficulty, purity is low and yield is low problem in the benzophenone tetracarboxylic acid process.Its method steps is with 3,3 ', 4,4 '-after mixing in molar ratio, dissolve, tetramethyl-diphenylethane, Glacial acetic acid, Cobalt diacetate tetrahydrate, four water acetic acid manganese and tetrabromoethane join in the reactor, under pressurization, heating, agitation condition, react, release again, blowing, cooling and centrifugally obtain 3,3 ', 4,4 '-the benzophenone tetracarboxylic acid.Preparation process of the present invention is the weightening finish reaction, and product yield is up to 100～140%, and product purity reaches 97.5～99.8%.
Description
Technical field
The present invention relates to a kind of 3,3 ', 4,4 '-preparation method of benzophenone tetracarboxylic acid.
Background technology
Closely during the last ten years, because the needs of the science and technology and the national economic development, it is high temperature resistant, corrosion-resistant that requirement has, the synthetic materials of various characteristicses such as good insulation preformance, wherein polyimide is exactly most important a kind of in this material, and 3,3 ', 4,4 '-the benzophenone tetracarboxylic acid is used in the polyimide field in large quantities, can produce extraordinary synthetic materials.By 3,3 ', 4,4 '-polyimide that the benzophenone tetracarboxylic acid is produced, have good processibility, it can make film, veneer sheet, coating, caking agent, insulating material and strongthener etc.; Its goods have excellent thermostability, outstanding insulation and mechanical property.
Preparation 3,3 at present ', 4,4 '-the benzophenone tetracarboxylic acid adopt nitric acid oxidation 3,3 ', 4,4 '-the tetramethyl-diphenylethane obtains, but will be with 70% concentrated nitric acid in oxidising process, and under higher pressure and temperature, carry out; Contain tint permanence impurity in the products therefrom, product purity is low, and its weight yield only is 50～70%, and by product nitrogen oxide recovery difficulty, causes atmosphere, water pollution.In addition, have adopt 3,3 ', 4,4 '-the tetramethyl-benzophenone is a raw material, liquid-phase air oxidation preparation 3,3 ', 4,4 '-the benzophenone tetracarboxylic acid, but 3,3 ', 4,4 '-the tetramethyl-benzophenone needs to use the benzene of hypertoxicity to carry out recrystallization as the purification solvent in the synthetic process, and operator's health is brought negative impact, and this method also will add the solid monochloroacetic acid simultaneously, this gives and reinforcedly to bring difficulty, and product purity is 95～98%, and yield only is 76～84%.
Summary of the invention
The present invention seeks to prepare 3,3 in the prior art in order to solve ', 4,4 '-use hypertoxic purification solvent, reinforced difficulty, purity is low and yield is low problem in the benzophenone tetracarboxylic acid process, and provide a kind of preparation 3,3 ', 4,4 '-method of benzophenone tetracarboxylic acid.
Liquid-phase air oxidation preparation 3,3 ', 4,4 '-method of benzophenone tetracarboxylic acid implements according to the following steps: one, in proportion with 1 mole 3,3 ', 4,4 '-tetramethyl-diphenylethane, 15～35 moles of Glacial acetic acid, 0.01～0.05 mole of Cobalt diacetate tetrahydrate, 0.001～0.1 mole of four water acetic acid manganese and 0.005～0.08 mole of tetrabromoethane mix, heating for dissolving gets mixing solutions; Two, step 1 gained mixing solutions is added in the reactor, with 0.5～1.0m
3The air flow quantity of/h is pressurized to 1.5～2.0MPa, and stirs 60～90min under 150～180 ℃ of conditions, be pressurized to 2.0～3.0MPa then, continue stir 60～90min, release again, blowing, cooling and centrifugally obtain 3,3 ', 4,4 '-the benzophenone tetracarboxylic acid.
The present invention adopt liquid-phase air oxidation preparation 3,3 ', 4,4 '-the benzophenone tetracarboxylic acid, reaction solvent can be recycled, but also has improved the purity of reaction yield and product, has accelerated speed of response, has reduced the reaction times.In the raw material 3,3 ', 4,4 '-the tetramethyl-diphenylethane is a liquid, by rectifying just can obtain purity reach 99.0～99.8% 3,3 ', 4,4 '-the tetramethyl-diphenylethane, this helps improving the purity that liquid phase oxidation reaction obtains the finished product; Raw material uses omnidistance nontoxic, and liquid feedstock purification is simple and reinforced convenient.Preparation process of the present invention is the weightening finish reaction, and product yield is up to 100～140%, and product purity reaches 97.5～99.8%.
Embodiment
Embodiment one: present embodiment liquid-phase air oxidation preparation 3,3 ', 4,4 '-the benzophenone tetracarboxylic acid implements according to the following steps: one, in proportion with 1 mole 3,3 ', 4,4 '-tetramethyl-diphenylethane, 15～35 moles of Glacial acetic acid, 0.01～0.05 mole of Cobalt diacetate tetrahydrate, 0.001～0.1 mole of four water acetic acid manganese and 0.005～0.08 mole of tetrabromoethane mix, heating for dissolving gets mixing solutions; Two, step 1 gained mixing solutions is added in the reactor, with 0.5～1.0m
3The air flow quantity of/h is pressurized to 1.5～2.0MPa, and stirs 60～90min under 150～180 ℃ of conditions, be pressurized to 2.0～3.0MPa then, continue stir 60～90min, release again, blowing, cooling and centrifugally obtain 3,3 ', 4,4 '-the benzophenone tetracarboxylic acid.
Embodiment two: not being both in the step 1 of present embodiment and embodiment one in proportion with 1 mole 3,3 ', 4,4 '-tetramethyl-diphenylethane, 25 moles of Glacial acetic acid, 0.03 mole of Cobalt diacetate tetrahydrate, 0.05 mole of four water acetic acid manganese and 0.04 mole of tetrabromoethane mix.Other step and parameter are identical with embodiment one.
Embodiment three: present embodiment and embodiment one be not both in the step 13,3 ', 4,4 '-purity of tetramethyl-diphenylethane is 99.0～99.8%.Other step and parameter are identical with embodiment one.
Embodiment four: present embodiment and embodiment one be not both in the step 13,3 ', 4,4 '-purity of tetramethyl-diphenylethane is 99.5%.Other step and parameter are identical with embodiment one.
Embodiment five: present embodiment and embodiment one be not both that reactor is a titanium material reactor in the step 2.Other step and parameter are identical with embodiment one.
Embodiment six: not being both in the step 2 of present embodiment and embodiment one with 0.8m
3The air flow quantity of/h is pressurized to 1.8MPa.Other step and parameter are identical with embodiment one.
Embodiment seven: not being both in the step 2 of present embodiment and embodiment one stirred 70min under 170 ℃ of conditions.Other step and parameter are identical with embodiment one.
Embodiment eight: not being both of present embodiment and embodiment one is pressurized to 2.5MPa in the step 2, continues to stir 70min.Other step and parameter are identical with embodiment one.
Claims (7)
1, liquid-phase air oxidation preparation 3,3 ', 4,4 '-method of benzophenone tetracarboxylic acid, it is characterized in that liquid-phase air oxidation preparation 3,3 ', 4,4 '-benzophenone tetracarboxylic acid method steps is as follows: one, in proportion with 1 mole 3,3 ', 4,4 '-tetramethyl-diphenylethane, 15～35 moles of Glacial acetic acid, 0.01～0.05 mole of Cobalt diacetate tetrahydrate, 0.001～0.1 mole of four water acetic acid manganese and 0.005～0.08 mole of tetrabromoethane mix, heating for dissolving gets mixing solutions; Two, step 1 gained mixing solutions is added in the reactor, with 0.5～1.0m
3The air flow quantity of/h is pressurized to 1.5～2.0MPa, and stirs 60～90min under 150～180 ℃ of conditions, be pressurized to 2.0～3.0MPa then, continue stir 60～90min, release again, blowing, cooling and centrifugally obtain 3,3 ', 4,4 '-the benzophenone tetracarboxylic acid.
2, liquid-phase air oxidation preparation 3 according to claim 1,3 ', 4,4 '-method of benzophenone tetracarboxylic acid, it is characterized in that in the step 1 in proportion with 1 mole 3,3 ', 4,4 '-tetramethyl-diphenylethane, 25 moles of Glacial acetic acid, 0.03 mole of Cobalt diacetate tetrahydrate, 0.05 mole of four water acetic acid manganese and 0.04 mole of tetrabromoethane mix.
3, liquid-phase air oxidation according to claim 1 preparation 3,3 ', 4,4 '-method of benzophenone tetracarboxylic acid, it is characterized in that in the step 13,3 ', 4,4 '-purity of tetramethyl-diphenylethane is 99.0～99.8%.
4, liquid-phase air oxidation according to claim 1 preparation 3,3 ', 4,4 '-method of benzophenone tetracarboxylic acid, it is characterized in that in the step 13,3 ', 4,4 '-purity of tetramethyl-diphenylethane is 99.5%.
5, liquid-phase air oxidation according to claim 1 preparation 3,3 ', 4,4 '-method of benzophenone tetracarboxylic acid, it is characterized in that reactor is a titanium material reactor in the step 2.
6, liquid-phase air oxidation according to claim 1 preparation 3,3 ', 4,4 '-method of benzophenone tetracarboxylic acid, it is characterized in that in the step 2 with 0.8m
3The air flow quantity of/h is pressurized to 1.8MPa.
7, liquid-phase air oxidation according to claim 1 preparation 3,3 ', 4,4 '-method of benzophenone tetracarboxylic acid, it is characterized in that under 170 ℃ of conditions, stirring 70min in the step 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101447794A CN100567248C (en) | 2007-12-07 | 2007-12-07 | Liquid-phase air oxidation preparation 3,3 ＇, the method for 4,4 ＇-benzophenone tetracarboxylic acid |
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| CNB2007101447794A CN100567248C (en) | 2007-12-07 | 2007-12-07 | Liquid-phase air oxidation preparation 3,3 ＇, the method for 4,4 ＇-benzophenone tetracarboxylic acid |
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| CN101177395A CN101177395A (en) | 2008-05-14 |
| CN100567248C true CN100567248C (en) | 2009-12-09 |
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| CNB2007101447794A Expired - Fee Related CN100567248C (en) | 2007-12-07 | 2007-12-07 | Liquid-phase air oxidation preparation 3,3 ＇, the method for 4,4 ＇-benzophenone tetracarboxylic acid |
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| 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 |
| EP3838883B1 (en) * | 2019-12-16 | 2023-07-12 | Evonik Fibres GmbH | Method for oxidizing a 1,1-bis-(3,4-dimethylphenyl)-alkane to 3,3',4,4'-benzophenone tetracarboxylic acid |
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Granted publication date: 20091209 Termination date: 20101207 |