CN114890913B - Method for preparing dicyanoethyl cyclohexylamine - Google Patents
Method for preparing dicyanoethyl cyclohexylamine Download PDFInfo
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- CN114890913B CN114890913B CN202210637538.8A CN202210637538A CN114890913B CN 114890913 B CN114890913 B CN 114890913B CN 202210637538 A CN202210637538 A CN 202210637538A CN 114890913 B CN114890913 B CN 114890913B
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- 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
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- 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
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- 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
- B01J31/0285—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 also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
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- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
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- C07C2601/14—The ring being saturated
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Abstract
The invention provides a method for preparing dicyanoethyl cyclohexylamine, which comprises the steps of preparing mono-cyanoethyl cyclohexylamine by taking cyclohexylamine and acrylonitrile as raw materials, and continuously reacting with acrylonitrile under the action of an acidic ionic liquid catalyst to obtain the dicyanoethyl cyclohexylamine. The method provided by the invention has the advantages that the adopted acidic ionic liquid has high catalytic activity and can be recycled, the reaction condition is mild, the process is simple, the yield of dicyanoethyl cyclohexylamine is more than or equal to 98%, the byproduct amide is not contained, the acid content in the product is less than or equal to 50ppm, and the method can be applied to the field of hydrogenation of nitrile into amine and has a good application prospect.
Description
Technical Field
The invention relates to a method for dicyanoethylation by monoprimary amine, in particular to a method for preparing dicyanoethyl cyclohexylamine.
Background
The reaction of organic amines (primary and secondary) with acrylonitrile to form the corresponding cyanoethylated products is reported to have a wide variety of industrial uses. For example, the dyes can be prepared as components of coupling agents, and hydrogenation to the corresponding amines can also be carried out in the epoxy curing agent field and in the isocyanate field.
Generally, the reaction of amine and acrylonitrile is easy, and can be carried out at room temperature or low temperature, and the reaction process can obtain the mono-cyanoethylamine with high yield without adding a catalyst or adopting water as a catalyst to accelerate the reaction. Secondary amines are particularly difficult to produce on monoprimary amines with two molecules of acrylonitrile due to the large steric hindrance and the electronic effect of the substituents, as compared to primary amines. At present, the patent literature of dicyanoethyl cyclohexylamine is rarely reported at home and abroad.
CN113372241a discloses a method for synthesizing dicyanoethyl tertiary amine by aliphatic primary amine one-step method. The invention comprises the following steps: the method comprises the steps of adding aliphatic primary amine into acrylonitrile by using aqueous solution of glycollic acid as a catalyst, synthesizing dicyanoethyl tertiary amine compound by a one-step method under a heating reflux condition, removing low-boiling components by reduced pressure distillation after the reaction is finished, and decomposing glycollic acid at an operating temperature to obtain the dicyanoethyl tertiary amine compound with the yield higher than 95%. The method mainly has the following two advantages: 1) The single cyanoethylation reaction and the double cyanoethylation reaction are carried out simultaneously, so that the reaction efficiency can be improved; 2) The reaction mother liquor does not need to be added with alkali for neutralization treatment, so that a large amount of salt-containing wastewater is avoided, and the post-treatment flow is simplified. However, since the two reactions of the process are carried out simultaneously, the aliphatic primary amine and the glycollic acid are easy to react to generate corresponding amide. Taking cyclohexylamine as an example, the amide by-product is formed as follows:
in addition, glycolic acid is removed by pyrolysis, and because the binding force between acid and amine is strong, trace glycolic acid is inevitably present in the product, and the cyanoethylation product containing trace acid has little problem in the general application field, but the catalyst is easy to be deactivated in the field of nitrile hydrogenation, and the selectivity of amine is not high, which is also known.
CN1172906C discloses a process for cyanoethylation of cycloaliphatic primary diamines. The invention takes water as a catalyst, and acrylonitrile reacts with diamine to mainly obtain products of mono-cyanoethylated amine and dicyanoethylated amine, and a small amount of tri-cyanoethylated amine and tetra-cyanoethylated amine can be produced. The invention is a general method for preparing cyanoethylation products of amine, but corresponding dicyano can not be obtained on monoprimary amine in high yield.
EP1229021A1 also discloses a process for cyanoethylation of cycloaliphatic primary diamines. The invention uses water and acetic acid as catalyst (pKa is between-3.0 and 7.5), and the acrylonitrile reacts with alicyclic primary diamine to produce corresponding cyanoethylation mixture. Although the invention can obtain the tricyanoethylamine and the tetracyanoethylamine to a certain extent, a plurality of by-products of the amides are generated at the same time, and according to the example, the highest selectivity of the tricyanoethylamine and the tetracyanoethylamine is only 79 percent.
Thus, the prior art still has the following disadvantages:
1) The monoprimary amine dicyanoethylation product has low selectivity, and a small amount of amide substances are produced as byproducts, so that if the monoprimary amine dicyanoethylation product is used as a raw material for hydrogenation, the catalyst can be deactivated.
2) The catalyst can not be reused, so that the waste of resources and the improvement of production cost are caused, and meanwhile, the product contains a small amount of acid, so that the further hydrogenation is affected to a certain extent.
Overall, the cyanoethylation products of the above prior art do not have a good solution for the hydrogenation of the starting materials, and it is not possible to obtain dicyanoethylcyclohexylamine in high yields and with high purity.
Disclosure of Invention
Based on the defects existing in the prior art, the invention provides a method for synthesizing high-purity dicyanoethyl cyclohexylamine by reacting cyclohexylamine with acrylonitrile in high yield. The method has extremely high yield (more than or equal to 98 percent) of dicyanoethyl cyclohexylamine, does not contain byproduct amide, has the acid content of less than or equal to 50ppm, and can be directly used for the next hydrogenation without complex treatment process; in addition, the catalyst of the invention can be recycled, greatly simplifies the post-treatment process, avoids the generation of three wastes and reduces the production cost.
In order to achieve the above object, the present invention adopts the following technical scheme:
a process for preparing dicyanoethyl cyclohexylamine, comprising the steps of:
s1, preparing mono-cyanoethyl cyclohexylamine by taking cyclohexylamine and acrylonitrile as raw materials;
s2, under the action of an acidic ionic liquid catalyst, the mono-cyanoethyl cyclohexylamine obtained in the step S1 continuously reacts with acrylonitrile to obtain dicyanoethyl cyclohexylamine.
Step S1 of the present invention may be performed with reference to the prior art, for example, with water as a catalyst, or without adding a catalyst, and it will be understood by those skilled in the art that adding a catalyst may increase the reaction rate and shorten the reaction time.
In a specific embodiment, a process for preparing dicyanoethyl cyclohexylamine comprises the steps of:
s1, dropwise adding acrylonitrile into cyclohexylamine at a certain reaction temperature by taking water as a catalyst, and preserving heat for a period of time to obtain a mother liquor of the mono-cyanoethyl cyclohexylamine reaction;
s2, adding an acidic ionic liquid catalyst into the mono-cyanoethyl cyclohexylamine reaction mother liquor, dropwise adding acrylonitrile into the solution at a certain reaction temperature, and carrying out reflux reaction for a period of time to obtain the di-cyanoethyl cyclohexylamine reaction mother liquor;
s3, carrying out phase separation on the dicyanoethyl cyclohexylamine reaction mother liquor at a certain temperature, wherein the water phase mainly comprises a catalyst and water, the oil phase is a dicyanoethyl cyclohexylamine crude product, and the oil phase is continuously subjected to reduced pressure rotary evaporation to remove excessive acrylonitrile and water, so that the high-purity dicyanoethyl cyclohexylamine product can be obtained.
The main reaction equations involved in the method of the invention are as follows:
in a specific embodiment, the molar ratio of water to cyclohexylamine in step S1 is from 0.2 to 2:1, including, for example, but not limited to, 0.25: 1. 0.3: 1. 0.4: 1. and 5: 1. 0.6: 1. 0.7: 1. 0.8: 1. 0.9: 1.1: 1. 1.1: 1. 1.2: 1. 1.3: 1. 1.4: 1. 1.5: 1. 1.6: 1. 1.7: 1. 1.8: 1. 1.9:1, preferably 0.5-1:1; the molar ratio of acrylonitrile to cyclohexylamine is 1.05 to 1.3:1, including, for example, but not limited to, 1.1: 1. 1.15: 1. 1.2: 1. 1.25: 1. 1.3:1, preferably 1.1-1.2:1; the reaction temperature is 40-70 ℃, including for example but not limited to 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, preferably 50-60 ℃; the incubation time is 0.5 to 3 hours, including for example but not limited to 1 hour, 1.5 hours, 2 hours, 2.5 hours, preferably 1 to 2 hours.
It is noted that the molar ratio of acrylonitrile to cyclohexylamine in S1 is usually greater than 1, ensuring complete reaction of cyclohexylamine in the reaction mother liquor of step S1, so that no amide by-products are formed in the next cyanoethylation reaction.
In a specific embodiment, the mass ratio of the acidic ionic liquid of step S2 to the cyclohexylamine of step S1 is from 0.05 to 0.2:1, including, for example, but not limited to, 0.1: 1. 0.15: 1. 0.17: 1. 0.185:1, preferably 0.1-0.15:1; the molar ratio of acrylonitrile added in step S2 to cyclohexylamine of step S1 is 1.05-1.3:1, including, for example, but not limited to, 1.1: 1. 1.15: 1. 1.2: 1. 1.25:1, preferably 1.1-1.2:1; the reaction temperature is 60-100deg.C, including for example but not limited to 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, preferably 70-80 ℃; the incubation time is 2-8h, including for example but not limited to 3h, 4h, 5h, 6h, 7h, preferably 4-6h.
In a specific embodiment, the acidic ionic liquid catalyst has the general structural formula of formula (1):
wherein X is Cl, br, I, CH 3 SO 3 、BF 4 、HSO 4 、H 2 PO 4 Any of them is preferably CH 3 SO 3 。
The acidic ionic liquid catalyst is prepared by the following steps:
1) Dropwise adding N, N-dimethyl cyclohexylamine into 1, 3-propane sultone at a certain temperature, stirring, filtering, washing and drying after the reaction is finished to obtain cations in the structure shown in the formula (1), and marking as [ DMCHA-PS ];
2) And (3) dropwise adding HX into the [ DMCHA-PS ] aqueous solution at a certain temperature by taking water as a solvent, and performing reduced pressure rotary evaporation to remove water after stirring and refluxing are finished to obtain the acidic ionic liquid catalyst with the structure shown in the formula (1).
Wherein the temperature in step 1) is 50-80 ℃, including for example but not limited to 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, preferably 60-70 ℃; the molar ratio of the N, N-dimethylcyclohexylamine to the 1, 3-propane sultone is 1:1; the reaction time is 12-48h, including for example but not limited to 14h, 16h, 18h, 20h, 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h, 40h, 42h, 44h, 46h, preferably 24-36h.
Wherein the temperature in step 2) is 70-90 ℃, including for example but not limited to 75 ℃, 80 ℃, 85 ℃, preferably 75-85 ℃; the molar ratio of HX to [ DMCHA-PS ] is 1:1; the reaction time is 6 to 24 hours, including for example but not limited to 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 24 hours, preferably 12 to 18 hours.
In a specific embodiment, the phase separation temperature of step S3 is 10-30deg.C, including, for example, but not limited to, 15deg.C, 20deg.C, 25deg.C, 30deg.C, preferably 15-25deg.C; the temperature of the reduced pressure rotary steaming is 60-80 ℃, including, for example, but not limited to, 65 ℃, 70 ℃, 75 ℃, and the pressure is 1-2KPa.
According to the invention, the acidic ionic liquid and the dicyanoethyl cyclohexylamine product are subjected to phase separation at low temperature, so that the acidic ionic liquid in the lower water phase can be continuously recycled for the next batch of reaction; the upper coarse product can be used for extracting redundant acrylonitrile and water through reduced pressure rotary evaporation, so that recycling of materials can be realized, waste liquid is reduced, and production cost is reduced.
Compared with the prior art, the invention has the following positive effects:
(1) The invention adopts [ DMCHA-PS ] cation, because the structure is similar to that of the mono-cyanoethyl cyclohexylamine, the cation can quickly activate hydrogen on N atoms of the mono-cyanoethyl cyclohexylamine, and carbon-carbon double bonds on acrylonitrile polarize in an anionic acidic environment, so that Michael addition reaction occurs, the reaction can quickly occur at a lower temperature, the reaction time is reduced, and the production efficiency is improved. Compared with the prior art, the reaction temperature can be reduced by 10-20 ℃, and the reaction time can be greatly shortened by about 50-60%.
(2) The acidic ionic liquid catalyst has the characteristic of phase separation with dicyanoethyl cyclohexylamine at low temperature, can realize the recycling of the catalyst by utilizing phase separation operation, not only reduces the production cost, but also has extremely low acid content (less than or equal to 50 ppm) in the prepared product, can be directly used for the next step of hydrogenation of nitrile into corresponding amine, and can not cause the deactivation of the hydrogenation catalyst due to the problem of excessively high acid content.
(3) The preparation method of dicyanoethyl cyclohexylamine adopts stepwise reaction, can ensure that the product does not contain amide byproducts, and can further improve the activity and stability of the downstream hydrogenation catalyst.
(4) The acidic ionic liquid catalyst and the process steps of the invention have mild reaction conditions, simple process, high dicyanoethyl cyclohexylamine yield (more than or equal to 98 percent), no byproduct amide, and the acid content in the product of less than or equal to 50ppm, can be applied to the field of hydrogenation of nitrile into amine, and has good application prospect.
Detailed Description
The following examples will further illustrate the method provided by the present invention for a better understanding of the technical solution of the present invention, but the present invention is not limited to the examples listed but should also include any other known modifications within the scope of the claims of the present invention.
The conditions for performing the gas chromatographic analysis in the following examples were: agilent DB-5 chromatographic column, sample inlet temperature 280 ℃, FID detector temperature 300 ℃, column flow rate 1.3ml/min, hydrogen flow rate 40ml/min, air flow rate 400ml/min, and programmed temperature rising mode: the temperature was maintained at 50deg.C for 2min, at 5deg.C/min to 80deg.C, and then at 15deg.C/min to 300deg.C for 15min.
The conditions for the acid content analysis in the following examples are as follows.
Instrument: a swiss universal potentiometric titrator;
standard solution: 0.02mol/L potassium hydroxide-methanol standard solution;
solvent: 100ml of methanol;
an electrode: a non-aqueous phase acid-base electrode;
the operation steps are as follows: 10g of sample is weighed, 100ml of methanol is added, and after stirring and dissolution, titration is carried out on a potentiometric titrator by taking a non-aqueous acid-base electrode as an indication electrode and 0.02mol/L potassium hydroxide-methanol standard solution.
The starting materials used in the following examples or comparative examples were all grade a Ding Shiji starting materials.
Example 1
Preparation of the No. 1 catalyst:
61g (0.5 mol) of 1, 3-propane sultone is added into a three-neck flask, 63.5g (0.5 mol) of N, N-dimethyl cyclohexylamine is slowly dripped into the system after the temperature is raised to 60 ℃, the dripping time is controlled to be 2 hours, then the reaction is carried out for 24 hours by heat preservation and stirring, suction filtration is carried out after the reaction is finished, diethyl ether is washed for 3 times, and the reaction is carried out in a vacuum oven at 80 ℃ for 12 hours, thus obtaining the intermediate [ DMCHA-PS ].
50g of water is added into a three-neck flask, the temperature is raised to 90 ℃, 49.3g (0.5 mol) of 37wt% concentrated hydrochloric acid is slowly added into the system in a dropwise manner, the dropwise addition time is controlled to be 2 hours, then the mixture is stirred for 24 hours under heat preservation, and water is removed by rotary evaporation under reduced pressure, so that an acidic ionic liquid [ DMCHA-PS ] Cl is obtained and is marked as a No. 1 catalyst.
Synthesis of dicyanoethyl cyclohexylamine:
99g (1 mol) of cyclohexylamine and 9g (0.5 mol) of water are added into a three-neck flask, 58.3g (1.1 mol) of acrylonitrile is slowly dripped into the system after the temperature is raised to 50 ℃, the dripping time is controlled to be 2h, and the heat is preserved for 1h after the dripping is finished, so that the mono-cyanoethyl cyclohexylamine reaction mother solution is obtained.
9.9g1# catalyst is added into a three-neck flask, the temperature is raised to 70 ℃, 63.6g (1.2 mol) of acrylonitrile is slowly added into the system in a dropwise manner, the dropwise addition time is controlled to be 2 hours, and the temperature is kept for 6 hours after the dropwise addition is finished, so as to obtain dicyanoethyl cyclohexylamine reaction mother liquor. Then cooling the reaction mother liquor to 20 ℃ for phase separation, wherein the lower layer of the mother liquor is a catalyst, and the catalyst is reserved for the next recycling; the upper layer of the mother liquor is subjected to rotary evaporation under reduced pressure at the absolute pressure of 1KPa and the temperature of 60 ℃ to remove acrylonitrile and water, the purity of the acrylonitrile in the tower top material is 100% through chromatographic analysis, the acrylonitrile can be reused next time, the content of dicyanoethyl cyclohexylamine in the tower bottom material is 98.5% through chromatographic analysis, the content of mono cyanoethyl cyclohexylamine is 1.3%, no amide byproduct is contained, and the acid content is 30ppm through titration analysis.
Example 2
Preparation of the No. 2 catalyst:
61g (0.5 mol) of 1, 3-propane sultone is added into a three-neck flask, 63.5g (0.5 mol) of N, N-dimethyl cyclohexylamine is slowly dripped into the system after the temperature is raised to 80 ℃, the dripping time is controlled to be 2 hours, then the reaction is carried out for 12 hours by heat preservation and stirring, suction filtration is carried out after the reaction is finished, diethyl ether is washed for 3 times, and the reaction is dried for 12 hours in a vacuum oven at 80 ℃ to obtain an intermediate [ DMCHA-PS ].
50g of water is added into a three-neck flask, the temperature is raised to 70 ℃, 45g (0.5 mol) of 40wt% hydrobromic acid is slowly added into the system in a dropwise manner, the dropwise addition time is controlled to be 2 hours, then the mixture is stirred for 18 hours under heat preservation, and water is distilled off in a rotary manner under reduced pressure to obtain acidic ionic liquid [ DMCHA-PS ] Br, which is marked as a No. 2 catalyst.
Synthesis of dicyanoethyl cyclohexylamine:
99g (1 mol) of cyclohexylamine and 18g (1 mol) of water are added into a three-neck flask, 63.6g (1.2 mol) of acrylonitrile is slowly dripped into the system after the temperature is raised to 40 ℃, the dripping time is controlled to be 2h, and the temperature is kept for 3h after the dripping is finished, so that the mono-cyanoethyl cyclohexylamine reaction mother solution is obtained.
19.8g of a 2# catalyst was added to the three-necked flask, the temperature was raised to 80℃and 58.3g (1.1 mol) of acrylonitrile was slowly added dropwise to the system, the dropwise addition time was controlled to 2 hours, and the temperature was kept for 4 hours after the dropwise addition was completed, to obtain a dicyanoethyl cyclohexylamine reaction mother solution. Then cooling the reaction mother liquor to 10 ℃ for phase separation, wherein the lower layer of the mother liquor is a catalyst, and the catalyst is reserved for the next recycling; the upper layer of the mother liquor is subjected to rotary evaporation under reduced pressure at an absolute pressure of 2KPa and a temperature of 80 ℃ to remove acrylonitrile and water, the purity of the acrylonitrile in the tower top material is 100% through chromatographic analysis, the acrylonitrile can be reused next time, the content of dicyanoethyl cyclohexylamine in the tower bottom material is 98.7% through chromatographic analysis, the content of mono cyanoethyl cyclohexylamine is 1.1%, no amide byproduct is contained, and the acid content is 25ppm through titration analysis.
Example 3
Preparation of 3# catalyst:
61g (0.5 mol) of 1, 3-propane sultone is added into a three-neck flask, 63.5g (0.5 mol) of N, N-dimethyl cyclohexylamine is slowly dripped into the system after the temperature is raised to 70 ℃, the dripping time is controlled to be 2 hours, then the reaction is carried out for 36 hours by heat preservation and stirring, suction filtration is carried out after the reaction is finished, diethyl ether is washed for 3 times, and the reaction is carried out in a vacuum oven at 80 ℃ for 12 hours, thus obtaining the intermediate [ DMCHA-PS ].
Adding 50g of water into a three-neck flask, heating to 80 ℃, slowly dropwise adding 48.5g (0.5 mol) of methane sulfonic acid into the system, controlling the dropwise adding time to be 2 hours, then carrying out heat preservation and stirring for 24 hours, and carrying out reduced pressure rotary evaporation to remove water to obtain acidic ionic liquid [ DMCHA-PS ]]CH 3 SO 3 The catalyst was designated 3# catalyst.
Synthesis of dicyanoethyl cyclohexylamine:
99g (1 mol) of cyclohexylamine and 36g (2 mol) of water are added into a three-neck flask, 55.65g (1.05 mol) of acrylonitrile is slowly dripped into the system after the temperature is raised to 70 ℃, the dripping time is controlled to be 2h, and the heat is preserved for 2h after the dripping is finished, so that the mono-cyanoethyl cyclohexylamine reaction mother solution is obtained.
14.85g of 3# catalyst is added into a three-neck flask, the temperature is raised to 100 ℃, 68.9g (1.3 mol) of acrylonitrile is slowly dripped into the system, the dripping time is controlled to be 2 hours, and the temperature is kept for 2 hours after the dripping is finished, so as to obtain dicyanoethyl cyclohexylamine reaction mother liquor. Then cooling the reaction mother liquor to 25 ℃ for phase separation, wherein the lower layer of the mother liquor is a catalyst, and the catalyst is reserved for the next recycling; the upper layer of the mother liquor is subjected to rotary evaporation under reduced pressure at the absolute pressure of 1KPa and the temperature of 60 ℃ to remove acrylonitrile and water, the purity of the acrylonitrile in the tower top material is 100% through chromatographic analysis, the acrylonitrile can be reused next time, the content of dicyanoethyl cyclohexylamine in the tower bottom material is 99.1% through chromatographic analysis, the content of mono cyanoethyl cyclohexylamine is 0.8%, no amide byproduct is contained, and the acid content is 35ppm through titration analysis.
Example 4
Preparation of the No. 4 catalyst:
61g (0.5 mol) of 1, 3-propane sultone is added into a three-neck flask, 63.5g (0.5 mol) of N, N-dimethyl cyclohexylamine is slowly dripped into the system after the temperature is raised to 50 ℃, the dripping time is controlled to be 2 hours, then the reaction is carried out for 48 hours by heat preservation and stirring, suction filtration is carried out after the reaction is finished, diethyl ether is washed for 3 times, and the reaction is carried out in a vacuum oven at 80 ℃ for 12 hours, thus obtaining the intermediate [ DMCHA-PS ].
50g of water is added into a three-neck flask, the temperature is raised to 75 ℃, 44.4g (0.5 mol) of boric acid is slowly added dropwise into the system, the dropwise adding time is controlled to be 2 hours, then the mixture is stirred for 6 hours under heat preservation, and water is distilled off under reduced pressure in a rotary way, so that an acidic ionic liquid [ DMCHA-PS ] BF4 is obtained and is marked as a No. 4 catalyst.
Synthesis of dicyanoethyl cyclohexylamine:
99g (1 mol) of cyclohexylamine and 3.6g (0.2 mol) of water are added into a three-neck flask, 58.3g (1.1 mol) of acrylonitrile is slowly dripped into the system after the temperature is raised to 60 ℃, the dripping time is controlled to be 2h, and the temperature is kept for 3h after the dripping is finished, so that the mono-cyanoethyl cyclohexylamine reaction mother solution is obtained.
4.95g of a No. 4 catalyst is added into a three-neck flask, the temperature is raised to 90 ℃, 63.6g (1.2 mol) of acrylonitrile is slowly dripped into the system, the dripping time is controlled to be 2 hours, and the temperature is kept for 8 hours after the dripping is finished, so as to obtain dicyanoethyl cyclohexylamine reaction mother liquor. Then cooling the reaction mother liquor to 30 ℃ for phase separation, wherein the lower layer of the mother liquor is a catalyst, and the catalyst is reserved for the next recycling; the upper layer of the mother liquor is subjected to rotary evaporation under reduced pressure at the absolute pressure of 1KPa and the temperature of 60 ℃ to remove acrylonitrile and water, the purity of the acrylonitrile in the tower top material is 100% through chromatographic analysis, the acrylonitrile can be reused next time, the content of dicyanoethyl cyclohexylamine in the tower bottom material is 98.3% through chromatographic analysis, the content of mono cyanoethyl cyclohexylamine is 1.6%, no amide byproduct is contained, and the acid content is 40ppm through titration analysis.
Example 5
Preparation of the No. 5 catalyst:
61g (0.5 mol) of 1, 3-propane sultone is added into a three-neck flask, 63.5g (0.5 mol) of N, N-dimethyl cyclohexylamine is slowly dripped into the system after the temperature is raised to 65 ℃, the dripping time is controlled to be 2 hours, then the reaction is carried out for 30 hours by heat preservation and stirring, suction filtration is carried out after the reaction is finished, diethyl ether is washed for 3 times, and the reaction is carried out in a vacuum oven at 80 ℃ for 12 hours, thus obtaining the intermediate [ DMCHA-PS ].
50g of water is added into a three-neck flask, the temperature is raised to 85 ℃, 50g (0.5 mol) of 98 percent concentrated sulfuric acid is slowly added into the system in a dropwise manner for 2 hours, then the mixture is stirred for 15 hours under heat preservation, and the pressure is reducedSpin-evaporating water to obtain acidic ionic liquid [ DMCHA-PS ]]HSO 4 The catalyst was designated as # 5.
Synthesis of dicyanoethyl cyclohexylamine:
99g (1 mol) of cyclohexylamine and 13.5g (0.75 mol) of water are added into a three-neck flask, 68.9g (1.3 mol) of acrylonitrile is slowly dripped into the system after the temperature is raised to 65 ℃, the dripping time is controlled to be 2h, and the temperature is kept for 0.5h after the dripping is finished, so that the mono-cyanoethyl cyclohexylamine reaction mother solution is obtained.
Adding 12.38g of 5# catalyst into a three-neck flask, heating to 60 ℃, slowly dripping 55.65g (1.05 mol) of acrylonitrile into the system, controlling the dripping time to be 2h, and preserving heat for 8h after the dripping is finished to obtain dicyanoethyl cyclohexylamine reaction mother liquor. Then cooling the reaction mother liquor to 15 ℃ for phase separation, wherein the lower layer of the mother liquor is a catalyst, and the catalyst is reserved for the next recycling; the upper layer of the mother liquor is subjected to rotary evaporation under reduced pressure at the absolute pressure of 1KPa and the temperature of 70 ℃ to remove acrylonitrile and water, the purity of the acrylonitrile in the tower top material is 100% through chromatographic analysis, the acrylonitrile can be reused next time, the content of dicyanoethyl cyclohexylamine in the tower bottom material is 98.1% through chromatographic analysis, the content of mono cyanoethyl cyclohexylamine is 1.7%, no amide byproduct is contained, and the acid content is 30ppm through titration analysis.
Example 6
Preparation of the No. 6 catalyst:
61g (0.5 mol) of 1, 3-propane sultone is added into a three-neck flask, 63.5g (0.5 mol) of N, N-dimethyl cyclohexylamine is slowly dripped into the system after the temperature is raised to 75 ℃, the dripping time is controlled to be 2 hours, then the reaction is carried out for 40 hours by heat preservation and stirring, suction filtration is carried out after the reaction is finished, diethyl ether is washed for 3 times, and the reaction is carried out in a vacuum oven at 80 ℃ for 12 hours, thus obtaining the intermediate [ DMCHA-PS ].
Adding 50g of water into a three-neck flask, heating to 70 ℃, slowly dropwise adding 57.65g (0.5 mol) of 85% phosphoric acid into the system, controlling the dropwise adding time to be 2 hours, then carrying out heat preservation and stirring for 15 hours, and carrying out reduced pressure rotary evaporation to remove water to obtain an acidic ionic liquid [ DMCHA-PS ]]H 2 PO 4 The catalyst was designated as 6# catalyst.
Synthesis of dicyanoethyl cyclohexylamine:
99g (1 mol) of cyclohexylamine and 9g (0.5 mol) of water are added into a three-neck flask, 58.3g (1.1 mol) of acrylonitrile is slowly dripped into the system after the temperature is raised to 60 ℃, the dripping time is controlled to be 2h, and the heat is preserved for 2h after the dripping is finished, so that the mono-cyanoethyl cyclohexylamine reaction mother solution is obtained.
9.9g of 6# catalyst is added into a three-neck flask, 58.3g (1.1 mol) of acrylonitrile is slowly dripped into the system after the temperature is raised to 85 ℃, the dripping time is controlled to be 2h, and the temperature is kept for 4h after the dripping is finished, so as to obtain dicyanoethyl cyclohexylamine reaction mother liquor. Then cooling the reaction mother liquor to 20 ℃ for phase separation, wherein the lower layer of the mother liquor is a catalyst, and the catalyst is reserved for the next recycling; the upper layer of the mother liquor is subjected to rotary evaporation under reduced pressure at an absolute pressure of 2KPa and a temperature of 80 ℃ to remove acrylonitrile and water, the purity of the acrylonitrile in the tower top material is 100% through chromatographic analysis, the acrylonitrile can be reused next time, the content of dicyanoethyl cyclohexylamine in the tower bottom material is 98.4% through chromatographic analysis, the content of mono cyanoethyl cyclohexylamine is 1.5%, no amide byproduct is contained, and the acid content is 15ppm through titration analysis.
Comparative example 1 (one-step Synthesis Process)
Synthesis of dicyanoethyl cyclohexylamine:
99g (1 mol) of cyclohexylamine and 9g (0.5 mol) of water are added into a three-neck flask, 9.9g of the No. 1 catalyst of the example 1 are added, the temperature is raised to 70 ℃, 121.9g (2.3 mol) of acrylonitrile is slowly added dropwise into the system, the dropwise adding time is controlled to be 4 hours, and the temperature is kept for 7 hours after the dropwise adding is finished, so that dicyanoethyl cyclohexylamine reaction mother liquor is obtained. Then cooling the reaction mother liquor to 20 ℃ for phase separation, wherein the lower layer of the mother liquor is a catalyst, and the catalyst is reserved for the next recycling; the upper layer of the mother liquor is subjected to rotary evaporation under reduced pressure at the absolute pressure of 1KPa and the temperature of 60 ℃ to remove acrylonitrile and water, the purity of the acrylonitrile in the tower top material is 100% through chromatographic analysis, the acrylonitrile can be reused next time, the content of dicyanoethyl cyclohexylamine in the tower bottom material is 95.9% through chromatographic analysis, the content of mono cyanoethyl cyclohexylamine is 2.1%, the content of amide byproducts is 1.8%, and the acid content is 30ppm through titration analysis.
Comparative example 2 (two-step Synthesis Process, but with the catalyst being glycolic acid according to the prior art)
Synthesis of dicyanoethyl cyclohexylamine:
99g (1 mol) of cyclohexylamine and 18g (1 mol) of water are added into a three-neck flask, 63.6g (1.2 mol) of acrylonitrile is slowly dripped into the system after the temperature is raised to 40 ℃, the dripping time is controlled to be 2h, and the temperature is kept for 3h after the dripping is finished, so that the mono-cyanoethyl cyclohexylamine reaction mother solution is obtained.
19.8g of 70% aqueous ethanol acid solution is added into a three-neck flask, the temperature is raised to 80 ℃, 58.3g (1.1 mol) of acrylonitrile is slowly dripped into the system, the dripping time is controlled to be 2h, and the temperature is kept for 4h after the dripping is finished, so as to obtain dicyanoethyl cyclohexylamine reaction mother liquor. Then cooling the reaction mother liquor to 10 ℃ for phase separation, wherein the lower layer of the mother liquor is a catalyst, and the catalyst is reserved for the next recycling; the upper layer of the mother liquor is subjected to rotary evaporation under reduced pressure at an absolute pressure of 2KPa and a temperature of 80 ℃ to remove acrylonitrile and water, the purity of the acrylonitrile in the tower top material is 100% through chromatographic analysis, the acrylonitrile can be reused next time, the content of dicyanoethyl cyclohexylamine in the tower bottom material is 56.5% through chromatographic analysis, the content of mono cyanoethyl cyclohexylamine is 43.1%, the content of amide byproducts is 0.2%, and the acid content is 8000ppm through titration analysis.
While the present invention has been described in detail through the foregoing description of the preferred embodiment, it should be understood that the foregoing description is not to be considered as limiting the invention. Those skilled in the art will appreciate that certain modifications and adaptations of the invention are possible and can be made under the teaching of the present specification. Such modifications and adaptations are intended to be within the scope of the present invention as defined in the appended claims.
Claims (15)
1. A process for preparing dicyanoethyl cyclohexylamine, comprising the steps of:
s1, preparing mono-cyanoethyl cyclohexylamine by taking cyclohexylamine and acrylonitrile as raw materials;
s2, under the action of an acidic ionic liquid catalyst, the mono-cyanoethyl cyclohexylamine obtained in the step S1 continuously reacts with acrylonitrile to obtain dicyanoethyl cyclohexylamine;
the acidic ionic liquid catalyst has a structural general formula shown in a formula (1):
wherein X is Cl, br, I, CH 3 SO 3 、BF 4 、HSO 4 、H 2 PO 4 Any one of the following.
2. The method according to claim 1, comprising the steps of:
s1, dropwise adding acrylonitrile into cyclohexylamine at a certain reaction temperature by taking water as a catalyst, and preserving heat for a period of time to obtain a mother liquor of the mono-cyanoethyl cyclohexylamine reaction;
s2, adding an acidic ionic liquid catalyst into the mono-cyanoethyl cyclohexylamine reaction mother liquor, dropwise adding acrylonitrile into the solution at a certain reaction temperature, and carrying out reflux reaction for a period of time to obtain the di-cyanoethyl cyclohexylamine reaction mother liquor;
s3, carrying out phase separation on the dicyanoethyl cyclohexylamine reaction mother liquor at a certain temperature, wherein the oil phase is a dicyanoethyl cyclohexylamine crude product, and continuously carrying out reduced pressure rotary evaporation on the oil phase to remove excessive acrylonitrile and water, thereby obtaining a high-purity dicyanoethyl cyclohexylamine product.
3. Process according to claim 1 or 2, characterized in that the molar ratio of water to cyclohexylamine in step S1 is 0.2-2:1; the molar ratio of acrylonitrile to cyclohexylamine is 1.05-1.3:1; the reaction temperature is 40-70 ℃; the heat preservation time is 0.5-3h.
4. A process according to claim 3, characterized in that the molar ratio of water to cyclohexylamine in step S1 is 0.5-1:1; the molar ratio of acrylonitrile to cyclohexylamine is 1.1-1.2:1; the reaction temperature is 50-60 ℃; the heat preservation time is 1-2h.
5. Process according to claim 1 or 2, characterized in that the mass ratio of acidic ionic liquid in step S2 to cyclohexylamine of step S1 is 0.05-0.2:1; the molar ratio of the acrylonitrile added in the step S2 to the cyclohexylamine in the step S1 is 1.05-1.3:1; the reaction temperature is 60-100 ℃; the heat preservation time is 2-8h.
6. The process according to claim 5, wherein the mass ratio of acidic ionic liquid to cyclohexylamine of step S1 in step S2 is from 0.1 to 0.15:1; the molar ratio of the acrylonitrile added in the step S2 to the cyclohexylamine in the step S1 is 1.1-1.2:1; the reaction temperature is 70-80 ℃; the heat preservation time is 4-6h.
7. The method according to claim 1, wherein X in the structural general formula of the acidic ionic liquid catalyst is CH 3 SO 3 。
8. The method according to claim 1 or 7, wherein the acidic ionic liquid catalyst is prepared by:
1) Dropwise adding N, N-dimethyl cyclohexylamine into 1, 3-propane sultone at a certain temperature, stirring, filtering, washing and drying after the reaction is finished to obtain cations in the structure shown in the formula (1), and marking as [ DMCHA-PS ];
2) And (3) dropwise adding HX into the [ DMCHA-PS ] aqueous solution at a certain temperature by taking water as a solvent, and performing reduced pressure rotary evaporation to remove water after stirring and refluxing are finished to obtain the acidic ionic liquid catalyst with the structure shown in the formula (1).
9. The method according to claim 8, wherein the temperature in step 1) is 50-80 ℃; the molar ratio of the N, N-dimethylcyclohexylamine to the 1, 3-propane sultone is 1:1; the reaction time is 12-48h.
10. The method according to claim 9, wherein the temperature in step 1) is 60-70 ℃; the reaction time is 24-36h.
11. The method according to claim 8, wherein the temperature in step 2) is 70-90 ℃; the molar ratio of HX to [ DMCHA-PS ] is 1:1; the reaction time is 6-24h.
12. The method according to claim 11, wherein the temperature in step 2) is 75-85 ℃; the reaction time is 12-18h.
13. The method according to claim 2, wherein the phase separation temperature in step S3 is 10-30 ℃; the temperature of the reduced pressure rotary steaming is 60-80 ℃ and the pressure is 1-2KPa.
14. The method according to claim 13, wherein the phase separation temperature in step S3 is 15-25 ℃.
15. Process according to claim 1 or 2, characterized in that the yield of dicyanoethyl cyclohexylamine is not less than 98% and the acid content of the dicyanoethyl cyclohexylamine product is not more than 50ppm.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3660460A (en) * | 1968-08-19 | 1972-05-02 | Toyo Boseki | Process for preparing n n-bis-cyanoethylated derivatives of aliphatic primary amine branched at the alpha-position |
| CN1070635A (en) * | 1992-09-19 | 1993-04-07 | 董源 | The joint process of aromatic nitrile base |
| US6245932B1 (en) * | 2000-08-09 | 2001-06-12 | Air Products And Chemicals, Inc. | Cyanoethylation of cycloaliphatic vicinal primary diamines |
| CN1342645A (en) * | 2001-08-21 | 2002-04-03 | 赵莹 | Process for preparing N,N-dicyanoethyl arylamine |
| US6433212B1 (en) * | 2001-01-31 | 2002-08-13 | Air Products And Chemicals, Inc. | Synthesis of new polynitriles from cycloaliphatic vicinal primary diamines |
| CN102241606A (en) * | 2011-05-10 | 2011-11-16 | 浙江闰土股份有限公司 | Clean production method of N-cyanoethylaniline |
| CN104003905A (en) * | 2014-06-05 | 2014-08-27 | 浙江洪翔化学工业有限公司 | Method for producing N-cyanoethylaniline and N,N-dicyanoethylaniline by adopting one-step cleaning process |
| CN105111101A (en) * | 2015-09-08 | 2015-12-02 | 河南省科学院高新技术研究中心 | Method for preparing N-cyanoethyl-N-ethoxylaniline by using ionic liquid |
| CN106800522A (en) * | 2015-11-26 | 2017-06-06 | 南亚塑胶工业股份有限公司 | Preparation method of N, N' -bis (2-cyanoethyl) -1, 2-ethylenediamine |
| CN113372241A (en) * | 2020-03-09 | 2021-09-10 | 万华化学集团股份有限公司 | Method for synthesizing dinitrile ethyl tertiary amine by aliphatic primary amine one-step method |
-
2022
- 2022-06-07 CN CN202210637538.8A patent/CN114890913B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3660460A (en) * | 1968-08-19 | 1972-05-02 | Toyo Boseki | Process for preparing n n-bis-cyanoethylated derivatives of aliphatic primary amine branched at the alpha-position |
| CN1070635A (en) * | 1992-09-19 | 1993-04-07 | 董源 | The joint process of aromatic nitrile base |
| US6245932B1 (en) * | 2000-08-09 | 2001-06-12 | Air Products And Chemicals, Inc. | Cyanoethylation of cycloaliphatic vicinal primary diamines |
| CN1337393A (en) * | 2000-08-09 | 2002-02-27 | 气体产品与化学公司 | Cyanoethylation of alicyclic hypodiamine |
| US6433212B1 (en) * | 2001-01-31 | 2002-08-13 | Air Products And Chemicals, Inc. | Synthesis of new polynitriles from cycloaliphatic vicinal primary diamines |
| CN1342645A (en) * | 2001-08-21 | 2002-04-03 | 赵莹 | Process for preparing N,N-dicyanoethyl arylamine |
| CN102241606A (en) * | 2011-05-10 | 2011-11-16 | 浙江闰土股份有限公司 | Clean production method of N-cyanoethylaniline |
| CN104003905A (en) * | 2014-06-05 | 2014-08-27 | 浙江洪翔化学工业有限公司 | Method for producing N-cyanoethylaniline and N,N-dicyanoethylaniline by adopting one-step cleaning process |
| CN105111101A (en) * | 2015-09-08 | 2015-12-02 | 河南省科学院高新技术研究中心 | Method for preparing N-cyanoethyl-N-ethoxylaniline by using ionic liquid |
| CN106800522A (en) * | 2015-11-26 | 2017-06-06 | 南亚塑胶工业股份有限公司 | Preparation method of N, N' -bis (2-cyanoethyl) -1, 2-ethylenediamine |
| CN113372241A (en) * | 2020-03-09 | 2021-09-10 | 万华化学集团股份有限公司 | Method for synthesizing dinitrile ethyl tertiary amine by aliphatic primary amine one-step method |
Non-Patent Citations (2)
| Title |
|---|
| N-(2-氰乙基)丁胺的合成研究;陈朝阳 等;化学工程师;第92卷(第5期);第12-14页 * |
| 酸性离子液体催化合成N-氰乙基-N-羟乙基苯胺;郭辉 等;《应用化学》;第37卷(第5期);第512-517页 * |
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