CN117384065B - Preparation method of 2-methyleneglutaronitrile - Google Patents
Preparation method of 2-methyleneglutaronitrile Download PDFInfo
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- CN117384065B CN117384065B CN202311704235.4A CN202311704235A CN117384065B CN 117384065 B CN117384065 B CN 117384065B CN 202311704235 A CN202311704235 A CN 202311704235A CN 117384065 B CN117384065 B CN 117384065B
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- NGCJVMZXRCLPRQ-UHFFFAOYSA-N 2-methylidenepentanedinitrile Chemical compound N#CC(=C)CCC#N NGCJVMZXRCLPRQ-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000000047 product Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 21
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 9
- 239000011343 solid material Substances 0.000 claims abstract description 9
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012065 filter cake Substances 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000004064 recycling Methods 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000012450 pharmaceutical intermediate Substances 0.000 abstract description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 10
- 238000004821 distillation Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000006471 dimerization reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 239000002920 hazardous waste Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- DHVLDKHFGIVEIP-UHFFFAOYSA-N 2-bromo-2-(bromomethyl)pentanedinitrile Chemical compound BrCC(Br)(C#N)CCC#N DHVLDKHFGIVEIP-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000036561 sun exposure Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0279—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the cationic portion being acyclic or nitrogen being a substituent on a ring
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention belongs to the technical field of pharmaceutical intermediate production, and discloses a preparation method of 2-methyleneglutaronitrile, which comprises the steps of heating a solid material to be slowly melted under stirring by using triethylamine hydrochloride and anhydrous aluminum trichloride in a weight ratio of 3.3-4.7:1, and cooling to room temperature after the reaction is finished to prepare a liquid ion catalyst; then, acrylonitrile and a liquid ion catalyst with the weight ratio of 1:1-2 are reacted at 15-40 ℃ for 2-6 h, then, the materials are cooled to minus 12-15 ℃, and the temperature is kept for 1-3 h until 2-methylene glutaronitrile is separated out; filtering the materials, wherein the filtrate is a liquid ionic catalyst, and recycling; washing the filter cake with water of 40-60 deg.c and standing to separate the water layer to obtain 2-methylene glutaronitrile product. The method has the advantages of simplicity in operation, good safety and lower production cost, and has good application prospect.
Description
Technical Field
The invention belongs to the technical field of pharmaceutical intermediate production, and particularly relates to a preparation method of 2-methyleneglutaronitrile.
Background
2-methylene glutaronitrile is a main intermediate for preparing the bactericide bromothalonil. The synthesis is now obtained by double condensation of molecular acrylonitrile under the action of a catalyst, and the common synthesis method in factories is to obtain 2-methylene glutaronitrile by polymerization reaction of triethylamine as a solvent and a catalyst for 40 hours in the presence of zinc chloride or cuprous chloride at a temperature of 40 ℃. The production method is universal in China for many years and is mature, but the method also has great defects:
1) The reaction has serious safety hazards: about 10 to 20% of the acrylonitrile polymer is formed in the 40 hour double condensation reaction of acrylonitrile; in order to ensure that the subsequent reaction is well carried out, the crude 2-methyleneglutaronitrile needs to be subjected to vacuum distillation treatment; 2-methylene glutaronitrile with lower boiling point is distilled under the high vacuum condition, when the temperature in the kettle exceeds 120 ℃, discharging is started, along with the distillation of the 2-methylene glutaronitrile, the residual acrylonitrile and the non-distilled dimers in the distillation kettle can be polymerized to generate polymers, the temperature in the kettle can be rapidly increased, and when the temperature at the top of the kettle is increased to 180 ℃, the polymers can be decomposed to generate fire or explosion accidents. In order to avoid such unexpected accidents, polymerization inhibitors such as hydroquinone are added in advance in a distillation still in factories, but due to the operation contingency (mainly that sulfuric acid for washing is not removed, sulfuric acid water is evaporated at high temperature and becomes a strong oxidizer), the safety accidents occur more or less in factories producing 2-methyleneglutaronitrile by the method.
2) The distillation yield is too low, and the production cost of the product is improved: after rectification, dimer 2-methylene glutaronitrile with the content of more than 97% can be obtained; however, in order to avoid production accidents, more kettle residues with higher boiling points are left in the later stage of rectification, so that the actual rectification yield can only reach about 60%, and the production cost of the product is greatly increased.
3) The treatment of the kettle residue is troublesome: most of the kettle residues are polymers of acrylonitrile, and the substances are treated as hazardous waste, but cannot be treated as general hazardous waste, because the kettle residues can be polymerized under the condition of high temperature (sun exposure) or no ventilation (the kettle residues have residual temperature during distillation) and natural or explosion can occur; such accidents have also occurred at the manufacturer.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: the preparation method of the 2-methylene glutaronitrile has the advantages of overcoming the defects in the prior art, along with simple operation method, good safety and lower production cost, and has good application prospect.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for preparing 2-methylene glutaronitrile, which comprises the following steps:
a. preparing a liquid ion catalyst: air in the closed container is replaced by inert gas, triethylamine hydrochloride and anhydrous aluminum trichloride with the weight ratio of 3.3-4.7:1 are sequentially added under the stirring at the speed of 250-350 rpm, the temperature is raised to 75-85 ℃ until the solid materials are slowly melted, and the reaction lasts for 1-4 hours; after the reaction is finished, cooling to room temperature to obtain a liquid ionic catalyst, and hermetically preserving;
b. the preparation reaction: sequentially adding acrylonitrile and the liquid ion catalyst obtained in the step a in a weight ratio of 1:1-2 into a closed container under the stirring at the speed of 250-300 rpm, reacting at 15-40 ℃ for 2-6 h, then cooling the materials to minus 12-15 ℃, and preserving heat for 1-3 h until 2-methyleneglutaronitrile is separated out; filtering the materials, wherein the filtrate is a liquid ionic catalyst, and recycling; washing the filter cake with water of 40-60 deg.c and standing to separate the water layer to obtain 2-methylene glutaronitrile product.
Preferably, in the step a, the stirring speed is 300rpm, the weight ratio of triethylamine hydrochloride to anhydrous aluminum trichloride is 4:1, the reaction temperature is 80 ℃, and the reaction time is 4 hours.
Preferably, the inert gas in the step a is nitrogen.
Preferably, in the step b, the stirring speed is 300rpm, the weight ratio of the acrylonitrile to the liquid ionic catalyst is 1:1.5, and the reaction is carried out for 4 hours at 30 ℃; cooling the materials to 15 ℃ below zero, and preserving heat for 2 h; the filter cake was washed with water at 50℃in the weight used for acrylonitrile.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the liquid ionic catalyst used in the invention replaces zinc chloride catalyst and triethylamine catalyst which are used independently in the prior art, and performs acrylonitrile polymerization reaction with acrylonitrile to obtain qualified products; various liquid ion catalysts are used in chemical synthesis, and the existing liquid ion catalyst only plays a role in promoting the catalysis of the reaction, but the liquid ion catalyst is used as a catalyst for promoting the reaction and a solvent for the reaction; the product 2-methylene glutaronitrile after the reaction is liquid at normal temperature, and the 2-methylene glutaronitrile is crystallized and separated out by cooling to-15 ℃, so that the product can be easily filtered out, and the liquid ion catalyst can be smoothly recovered, thereby avoiding the potential safety hazard of distilling the product at high temperature; the liquid ionic catalyst composed of triethylamine hydrochloride and aluminum trichloride has very high activity on the dimerization of acrylonitrile, plays an acceleration role on the dimerization of acrylonitrile, and has very good rejection on the polymerization of acrylonitrile.
2. The invention overcomes the defect that the existing production technology cannot perform low-temperature separation (after the existing production technology is cooled, a large amount of triethylamine with the freezing point of-113 ℃ is mixed in the reaction liquid, and crystallization separation of products cannot be realized, so that only a distillation technology can be adopted), and the defects of potential safety hazard and low yield caused by the existing high-temperature distillation technology are overcome.
In a word, the method is simple, the safety is good, the yield is high, and the content of the obtained 2-methyleneglutaronitrile is high; has good application prospect.
Drawings
FIG. 1 is a gas chromatogram of the product of example 1 of the present invention;
FIG. 2 is a gas chromatogram of the product of example 2 of the present invention;
FIG. 3 is a gas chromatogram of the product of embodiment 3 of the invention;
FIG. 4 is a gas chromatogram of the comparative product.
Detailed Description
The invention is further illustrated by the following examples.
Example 1
a. Preparing a liquid ion catalyst: replacing air in a sealed 500 ml three-necked bottle by nitrogen, sequentially adding 165 g of triethylamine hydrochloride and 35 g of anhydrous aluminum trichloride under the stirring of 350rpm, heating to 85 ℃, slowly melting solid materials under the stirring of 350rpm, converting the solid materials from a viscous state into a liquid with better fluidity, and reacting for 1h until the reaction liquid is light brown; after the reaction is finished, cooling to room temperature to obtain a liquid ionic catalyst, and hermetically preserving;
b. the preparation reaction: adding 100 g of acrylonitrile and 200 g of the liquid ionic catalyst obtained in the step a into a closed three-necked bottle with the speed of 350rpm stirring in sequence, and reacting at 40 ℃ for 2 h, wherein the color of the material is changed from light brown to light yellow; then cooling the material to minus 12 ℃, and preserving heat for 3 h until 2-methylene glutaronitrile is separated out; filtering the materials in a suction filter, wherein the filtrate is a liquid ionic catalyst, and recycling; washing the filter cake with 100 g of water at 60 ℃, then loading the material into a separating funnel for static layering, and separating a washing water layer at the bottom layer to obtain 91.53 g of product, wherein the yield is 91.53%; the content of the 2-methylene glutaronitrile finished product is 99.25%; the gas chromatogram is shown in figure 1.
Example 2
a. Preparing a liquid ion catalyst: air in a sealed 500 ml three-necked bottle is replaced by nitrogen, 115 g of triethylamine hydrochloride and 35 g of anhydrous aluminum trichloride are sequentially added under the stirring of 250rpm, the temperature is raised to 75 ℃, the solid materials are slowly melted under the stirring of 250rpm, the solid materials are changed into liquid with better fluidity from a viscous state, and the liquid is reacted for 4 hours until the reaction liquid is light brown; after the reaction is finished, cooling to room temperature to obtain a liquid ionic catalyst, and hermetically preserving;
b. the preparation reaction: adding 100 g of acrylonitrile and 100 g of the liquid ionic catalyst obtained in the step a into a closed three-necked bottle with stirring at the speed of 250rpm in sequence, and reacting at 15 ℃ for 6h, wherein the color of the material is changed from light brown to light yellow; then cooling the material to 15 ℃ below zero, and preserving heat for 1h until 2-methylene glutaronitrile is separated out; filtering the materials in a suction filter, wherein the filtrate is a liquid ionic catalyst, and recycling; washing the filter cake with 100 g of water at 40 ℃, then loading the material into a separating funnel for static layering, and separating a washing water layer at the bottom layer to obtain 92.85 g of a product, wherein the yield is 92.85%, and the content of a 2-methyleneglutaronitrile finished product is 99.23%; the gas chromatogram is shown in FIG. 2.
Example 3
a. Preparing a liquid ion catalyst: replacing air in a sealed 500 ml three-necked bottle by nitrogen, sequentially adding 120 g of triethylamine hydrochloride and 30 g of anhydrous aluminum trichloride under stirring at 300rpm, heating to 80 ℃, slowly melting solid materials under stirring at 300rpm, converting the solid materials from a viscous state into a liquid with better fluidity, and reacting for 4 hours until the reaction liquid is light brown; after the reaction is finished, cooling to room temperature to obtain a liquid ionic catalyst, and hermetically preserving;
b. the preparation reaction: adding 100 g of acrylonitrile and 150 g of liquid ionic catalyst obtained in the step a into a closed three-necked bottle with the speed of 300rpm stirring in sequence, and reacting at 30 ℃ for 4h, wherein the color of the material is changed from light brown to light yellow; then cooling the material to 15 ℃ below zero, and preserving heat for 2 h until 2-methylene glutaronitrile is separated out; filtering the materials in a suction filter, wherein the filtrate is a liquid ionic catalyst, and recycling; washing the filter cake with 100 g of water at 50 ℃, then loading the material into a separating funnel for static layering, and separating a washing water layer at the bottom layer to obtain 94.18 g of a product, wherein the yield is 94.18%, and the content of a 2-methyleneglutaronitrile finished product is 99.51%; the gas chromatogram is shown in FIG. 3.
Comparative example: (prior art production Process)
100 g of acrylonitrile, 30 g of triethylamine, 20 g of zinc chloride and 300rpm of stirring are sequentially added into a 250 ml three-necked flask to react for 36 hours at 40 ℃; after the reaction is finished, dropwise adding the reaction solution into a 500 ml three-necked bottle containing 200 ml of 30% sulfuric acid with the concentration by weight under stirring at the speed of 300rpm, stirring for half an hour, layering, separating an acid water layer on the lower layer, washing the oil layer (2-methyleneglutaronitrile) once by using 200 ml of clear water, and discharging the water layer; the oil layer enters a distillation tower for vacuum distillation; discharging when the temperature of the kettle reaches 120 ℃, stopping distillation when the temperature of the top of the kettle rises to 170 ℃, and placing the kettle residue into a cool water tank when the kettle is hot; 84.56 g of the product was distilled off, wherein the yield was 84.56%, and the content of 2-methyleneglutaronitrile finished product was 91.00%; the gas chromatogram is shown in FIG. 4.
Analysis of results: from the experimental data, the highest yield of the 2-methylene acrylonitrile prepared in the embodiment 3 can reach more than 94%, and the effect is obvious compared with the prior art; and the liquid ion catalyst can be recycled, so that the production cost is greatly reduced, and the method has good application prospect.
It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Claims (4)
1. A method for preparing 2-methyleneglutaronitrile, which is characterized by comprising the following steps:
a. preparing a liquid ion catalyst: air in the closed container is replaced by inert gas, triethylamine hydrochloride and anhydrous aluminum trichloride with the weight ratio of 3.3-4.7:1 are sequentially added under the stirring at the speed of 250-350 rpm, the temperature is raised to 75-85 ℃ until the solid materials are slowly melted, and the reaction lasts for 1-4 hours; after the reaction is finished, cooling to room temperature to obtain a liquid ionic catalyst, and hermetically preserving;
b. the preparation reaction: sequentially adding acrylonitrile and the liquid ion catalyst obtained in the step a in a weight ratio of 1:1-2 into a closed container under the stirring at the speed of 250-300 rpm, reacting at 15-40 ℃ for 2-6 h, then cooling the materials to minus 12-15 ℃, and preserving heat for 1-3 h until 2-methyleneglutaronitrile is separated out; filtering the materials, wherein the filtrate is a liquid ionic catalyst, and recycling; washing the filter cake with water of 40-60 deg.c and standing to separate the water layer to obtain 2-methylene glutaronitrile product.
2. The process for producing 2-methyleneglutaronitrile according to claim 1, wherein: in the step a, the stirring speed is 300rpm, the weight ratio of triethylamine hydrochloride to anhydrous aluminum trichloride is 4:1, the reaction temperature is 80 ℃, and the reaction time is 4 hours.
3. The process for producing 2-methyleneglutaronitrile according to claim 1, wherein: the inert gas in the step a is nitrogen.
4. The process for producing 2-methyleneglutaronitrile according to claim 1, wherein: in the step b, the stirring speed is 300rpm, the weight ratio of the acrylonitrile to the liquid ionic catalyst is 1:1.5, and the reaction is carried out for 4 hours at 30 ℃; cooling the materials to 15 ℃ below zero, and preserving heat for 2 h; the filter cake was washed with water at 50℃in the weight used for acrylonitrile.
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| CN105837470A (en) * | 2015-01-12 | 2016-08-10 | 华东理工大学 | Method for preparing 2-methyleneglutaronitrile (MGN) through dimerization of acrylonitrile |
| CN115368273A (en) * | 2022-09-29 | 2022-11-22 | 山东理工大学 | Preparation method of 2-methylene glutaronitrile |
| CN116768757A (en) * | 2023-08-23 | 2023-09-19 | 潍坊裕凯化工有限公司 | Synthesis method of 2-methyleneglutaronitrile |
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2023
- 2023-12-13 CN CN202311704235.4A patent/CN117384065B/en active Active
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| US3946066A (en) * | 1973-10-01 | 1976-03-23 | Imperial Chemical Industries Limited | Dimerisation process and catalyst |
| WO2000041809A1 (en) * | 1999-01-15 | 2000-07-20 | Bp Chemicals Limited | Ionic liquid catalyst for alkylation |
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