CN107011211A - A kind of preparation method of para-Phthalonitrile - Google Patents
A kind of preparation method of para-Phthalonitrile Download PDFInfo
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- CN107011211A CN107011211A CN201610057612.3A CN201610057612A CN107011211A CN 107011211 A CN107011211 A CN 107011211A CN 201610057612 A CN201610057612 A CN 201610057612A CN 107011211 A CN107011211 A CN 107011211A
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- phthalonitrile
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/22—Preparation of carboxylic acid nitriles by reaction of ammonia with carboxylic acids with replacement of carboxyl groups by cyano groups
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Abstract
The present invention relates to a kind of preparation method of para-Phthalonitrile, terephthalic acid (TPA) is added in cyanation device, and adds ethylmethylimidazolium biphosphate ionic liquid, its consumption is the 15~50% of terephthalic acid (TPA) volume；Logical ammonia, is then reacted；After completion of the reaction, para-Phthalonitrile crude product carries out rectification and purification, produces.During the inventive method prepares para-Phthalonitrile as solvent and catalyst using ethylmethylimidazolium biphosphate ionic liquid for terephthalic acid (TPA) nitrilation, compared with the prior art, raw material is easy to get, simple to operate, catalyst preparation is simple, reaction temperature reduction.
Description
Technical field
The invention belongs to organic synthesis field, and in particular to a kind of preparation method of para-Phthalonitrile.
Background technology
Aromatic dicarboxylic nitrile is the fine-chemical intermediate with extensive use, using the chemical activity of its cyano group, can be synthesized
A series of agricultural chemicals, medicine, dyestuff, spices etc., are widely used in the every field of national economy.
The traditional preparation method of aromatic dicarboxylic nitrile includes sandmeyer reactions, halogenated hydrocarbons and the direct cyaniding of cyanide and fragrance
Aldehyde is dehydrated or gas phase catalysis ammonification etc. through aldoxime, these method General reactions routes are longer, complex process, difficulty are isolated and purified,
Seriously polluted, particularly raw material is more difficult to get or need to use reagent costly, thus production cost is higher, is not suitable for industry
Metaplasia is produced.
At this stage, the main method that the production of aromatic dicarboxylic nitrile is used is aromatic hydrocarbon ammoxidation technology, ammonia oxidation and tradition side
Method is compared, although with the advantage such as raw material is cheap and easy to get, reaction scheme is short, product is disposable, but still there is reaction temperature
Spend higher (more than 410 DEG C), the problems such as very high is required to catalyst preparation.
The content of the invention
It is an object of the invention to solve the problem of aromatic dicarboxylic nitrile is produced in the prior art, there is provided a kind of para-Phthalonitrile
Preparation method, the raw materials technology is cheap and easy to get, reaction scheme is short, product is disposable, and catalyst preparation is simple, reaction
Temperature is low.
Technical scheme
Ionic liquid has many excellent properties, and many ionic liquids have the dual-use function of solvent and catalyst, with height
Heat endurance, acidic ion liquid, particularly bronsted acid ionic liquid is due to green non-pollution, to inorganic
The dissolubility being respectively provided with organic compound, acidic site difference is uniform, it is easy to the features such as being separated with product.This hair
A person of good sense uses ethylmethylimidazolium biphosphate ionic liquid simultaneously as catalysts and solvents, for terephthalic acid (TPA) nitrilation
During preparing para-Phthalonitrile.It is specific as follows：
A kind of preparation method of para-Phthalonitrile, comprises the following steps：
(1) terephthalic acid (TPA) is added in cyanation device, and adds ethylmethylimidazolium biphosphate ionic liquid,
Its consumption is 15~50%, preferably the 20~40% of terephthalic acid (TPA) volume；
(2) lead to ammonia, then reacted；
(3) after completion of the reaction, para-Phthalonitrile crude product is subjected to rectification and purification, produced.
In step (1), the preparation method of ethylmethylimidazolium biphosphate ionic liquid：In ice bath and it is stirred continuously
Under the conditions of, by diethyl sulfide acid esters be slowly dropped into etc. amount of substance 1- methylimidazoles in, after completion of dropping continue stirring treat
Reaction carries out completely, obtaining ethylmethylimidazolium base sulfate ion liquid；Obtained ionic liquid is slowly added dropwise to and contained
In NaOH ethanol solution, after after complete reaction, colorless cleared solution is filtrated to get；Then toward in colorless cleared solution plus
Enter phosphoric acid, colourless transparent solution is obtained after filtering, evaporation, vacuum drying obtains ethylmethylimidazolium biphosphate ionic liquid.
In step (2), reaction temperature is 320~340 DEG C, and the reaction time is 50~90min.
In step (3), during rectification and purification, rectifying column kettle temperature is 250~300 DEG C, and tower top temperature is 230~280 DEG C, very
Reciprocal of duty cycle is 0.005~0.001MPa.
Beneficial effect：The technological operation is simple, raw material is cheap and easy to get, reaction scheme is short, product is disposable, and catalyst
Prepare simply, reaction temperature is low.
Embodiment
Below by embodiment, the invention will be further described, but it is necessary to note that following examples are served only for the content of the invention
Further illustrate, do not constitute limiting the scope of the invention.
Embodiment 1
Prepare ethylmethylimidazolium biphosphate ionic liquid：0.1mol 1- methylimidazoles are added in there-necked flask, by
0.1mol diethyl phosphates are added dropwise to, continue to stir 2h after adding, reaction obtains water white transparency ionic liquid 1- methyl -3-
Ethyl imidazol(e) ethyl phosphate；The NaOH of twice 1- methyl -3- ethyl imidazol(e) ethyl phosphate molal quantitys is taken to be dissolved in ethanol
In, it is added dropwise in 1- methyl -3- ethyl imidazol(e) ethyl phosphate ethanol solutions, produces white precipitate, be filtrated to get nothing
Color transparency liquid, adds equimolar phosphoric acid solution in the liquid, has a small amount of solid to produce, liquid is filtrated to get again；
Aforesaid liquid evaporation is removed into water and alcohol, then obtains product ethylmethylimidazolium biphosphate ionic liquid after being dried in vacuo,
Yield 97%；
50g terephthalic acid (TPA)s are added in cyanation device, and add ethylmethylimidazolium biphosphate ionic liquid
10mL, leads to ammonia, is warming up to 320 DEG C, insulation reaction 50min, after completion of the reaction, para-Phthalonitrile crude product carry out rectifying and carried
Pure, rectifying column kettle temperature is 260 DEG C, and tower top temperature is 240 DEG C (vacuum is 0.002MPa), and yield is 64%.
Embodiment 2
Prepare ethylmethylimidazolium biphosphate ionic liquid：0.5mol 1- methylimidazoles are added in there-necked flask, by
0.5mol diethyl phosphates are added dropwise to, continue to stir 1.5h after adding, reaction obtains water white transparency ionic liquid 1- methyl -3-
Ethyl imidazol(e) ethyl phosphate；The NaOH of twice 1- methyl -3- ethyl imidazol(e) ethyl phosphate molal quantitys is taken to be dissolved in ethanol
In, it is added dropwise in 1- methyl -3- ethyl imidazol(e) ethyl phosphate ethanol solutions, produces white precipitate, be filtrated to get nothing
Color transparency liquid, adds equimolar phosphoric acid solution in the liquid, has a small amount of solid to produce, liquid is filtrated to get again；
Aforesaid liquid evaporation is removed into water and alcohol, then obtains product ethylmethylimidazolium biphosphate ionic liquid after being dried in vacuo,
Yield 98%；
100g terephthalic acid (TPA)s are added in cyanation device, and add ethylmethylimidazolium biphosphate ionic liquid
20mL, is warming up to 340 DEG C, insulation reaction 100min, after completion of the reaction, para-Phthalonitrile crude product carry out rectification and purification,
Rectifying column kettle temperature is 260 DEG C, and tower top temperature is 240 DEG C (vacuum is 0.002MPa), and yield is 60%.
Claims (5)
1. a kind of preparation method of para-Phthalonitrile, it is characterised in that comprise the following steps：
(1) terephthalic acid (TPA) is added in cyanation device, and adds ethylmethylimidazolium biphosphate ionic liquid, its
Consumption is the 15~50% of terephthalic acid (TPA) volume；
(2) lead to ammonia, then reacted；
(3) after completion of the reaction, para-Phthalonitrile crude product is subjected to rectification and purification, produced.
2. the preparation method of para-Phthalonitrile as claimed in claim 1, it is characterised in that in step (1), ethyl-methyl miaow
The preparation method of azoles biphosphate ionic liquid is：In ice bath and under conditions of being stirred continuously, diethyl sulfide acid esters is slowly dripped
Enter to etc. amount of substance 1- methylimidazoles in, continue to stir question response after completion of dropping and carry out complete, obtain ethylmethylimidazolium base
Sulfate ion liquid；Obtained ionic liquid is slowly added dropwise in the ethanol solution containing NaOH, after reacting completely, mistake
Filter obtains colorless cleared solution；Then toward adding phosphoric acid in colorless cleared solution, after filtering colourless transparent solution, evaporation, very
Sky is dried to obtain ethylmethylimidazolium dihydric phosphate.
3. the preparation method of para-Phthalonitrile as claimed in claim 1, it is characterised in that in step (1), ethyl-methyl
The consumption of imidazoles biphosphate ionic liquid is the 20~40% of terephthalic acid (TPA) volume.
4. the preparation method of para-Phthalonitrile as claimed in claim 1, it is characterised in that in step (2), reaction temperature
For 320~340 DEG C, the reaction time is 50~90min.
5. the preparation method of para-Phthalonitrile as claimed in claim 1 or 2 or 3 or 4, it is characterised in that step (3)
In, during rectification and purification, rectifying column kettle temperature be 250~300 DEG C, tower top temperature be 230~280 DEG C, vacuum be 0.005~
0.001MPa。
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610057612.3A CN107011211B (en) | 2016-01-27 | 2016-01-27 | A kind of preparation method of para-Phthalonitrile |
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| CN201610057612.3A CN107011211B (en) | 2016-01-27 | 2016-01-27 | A kind of preparation method of para-Phthalonitrile |
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| CN107011211A true CN107011211A (en) | 2017-08-04 |
| CN107011211B CN107011211B (en) | 2018-10-02 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113666872A (en) * | 2021-09-28 | 2021-11-19 | 烟台大学 | Preparation method of halogen-free hydroxyl imidazolium |
| CN115135634A (en) * | 2020-10-30 | 2022-09-30 | 锦湖石油化学株式会社 | System for producing phthalonitrile compound and method for producing phthalonitrile compound using same |
| TWI818294B (en) * | 2021-07-23 | 2023-10-11 | 韓商錦湖石油化學股份有限公司 | A method for preparing phthalonitrile-based compound |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006058710A1 (en) * | 2004-12-01 | 2006-06-08 | Degussa Gmbh | Method for producing amino- or hydroxybenzonitriles |
| CN105016942A (en) * | 2014-04-16 | 2015-11-04 | 中国石化扬子石油化工有限公司 | Preparation methods of nitrile and corresponding amine |
-
2016
- 2016-01-27 CN CN201610057612.3A patent/CN107011211B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006058710A1 (en) * | 2004-12-01 | 2006-06-08 | Degussa Gmbh | Method for producing amino- or hydroxybenzonitriles |
| CN105016942A (en) * | 2014-04-16 | 2015-11-04 | 中国石化扬子石油化工有限公司 | Preparation methods of nitrile and corresponding amine |
Non-Patent Citations (1)
| Title |
|---|
| 兴可等: ""锌、铝氧化物催化合成十二烷二腈"", 《化工生产与技术》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115135634A (en) * | 2020-10-30 | 2022-09-30 | 锦湖石油化学株式会社 | System for producing phthalonitrile compound and method for producing phthalonitrile compound using same |
| TWI818294B (en) * | 2021-07-23 | 2023-10-11 | 韓商錦湖石油化學股份有限公司 | A method for preparing phthalonitrile-based compound |
| CN113666872A (en) * | 2021-09-28 | 2021-11-19 | 烟台大学 | Preparation method of halogen-free hydroxyl imidazolium |
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| CN107011211B (en) | 2018-10-02 |
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