CN114591200B - Preparation method of dicyanoethyl tertiary amine - Google Patents
Preparation method of dicyanoethyl tertiary amine Download PDFInfo
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- CN114591200B CN114591200B CN202210233643.5A CN202210233643A CN114591200B CN 114591200 B CN114591200 B CN 114591200B CN 202210233643 A CN202210233643 A CN 202210233643A CN 114591200 B CN114591200 B CN 114591200B
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- C07—ORGANIC CHEMISTRY
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- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/24—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton
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Abstract
The invention provides a preparation method of dicyanoethyl tertiary amine. The preparation method comprises the following steps: the mono-nitrile ethyl secondary amine and 3-cyano propionic acid are subjected to catalytic reaction to obtain dicyanoethyl tertiary amine mother liquor; the dicyanoethyl tertiary amine mother liquor is subjected to aftertreatment to obtain dicyanoethyl tertiary amine products; wherein, the catalytic reaction adopts a catalyst containing Fe. The 3-cyano propionic acid is a biomass raw material which can be continuously obtained by oxidative decarboxylation of glutamic acid, is an acidic catalyst, and does not need a post-treatment deacidification link; the yield of 3-cyano propionic acid catalyzed by the Fe-containing catalyst can reach 98 percent, and the reaction rate and the yield are high.
Description
Technical Field
The invention belongs to the field of organic synthesis, and provides a preparation method of dicyanoethyl tertiary amine.
Background
Along with the continuous expansion of the application field of the epoxy resin, correspondingly higher requirements are put forward on the quality of the amine curing agent; at present, the method for further modifying amine molecules has the characteristic of diversification, wherein the synthesis of cyanoethylamine is a very applicable technical means, and the epoxy curing agent market is also gradually accepted and popularized.
Primary amines are relatively more reactive for amine molecules, so that nitrile ethylation can be readily achieved by single substitution to give mononitrile secondary ethyl amines; however, secondary amines are difficult to undergo secondary addition synthesis of dicyanoethyl tertiary amine due to the large steric hindrance effect compared to primary amines; in order to meet the market demands, the tertiary amine with wider synthetic application in the key technology is not only an important work in the field of epoxy resin curing agents, but also a difficult work.
CN 103524717A discloses a modified alicyclic amine curing agent, which adopts acrylonitrile to modify methylcyclohexanediamine, but the dosage of acrylonitrile is only 1-50% of the total raw material, and the dicyanoethyl addition of methylcyclohexanediamine cannot be realized; US3231601 discloses a cyanoethylation process of aromatic amine, which uses strong acid as catalyst and acrylonitrile to carry out cyanoethylation addition on aromatic amine, but the preparation process is complex, the corrosion to equipment is very strong, and the technical content is limited; CN 108383756A discloses a preparation method of cyanoethylated amine compound, the invention uses acrylonitrile to modify polyamine under the action of alkaline catalyst, and the same problem is caused; CN 113372241A discloses a method for synthesizing dinitrile ethyl tertiary amine by aliphatic primary amine one-step method. The invention utilizes acrylonitrile to carry out addition on aliphatic primary amine under the catalysis of glycollic acid, but a glycollic acid removal method is not described, and the adoption of acid and amine as substrates simultaneously causes serious exothermic problems, so that the product yield is also affected.
The acid or base catalysis mode adopted in the field of amine curing agents for realizing the dicyanoethyl addition of amines is low in yield, complex in post-treatment and harmful to the environment, which seriously affects the application of the amine curing agents.
Disclosure of Invention
The invention aims to provide a preparation method of dicyanoethyl tertiary amine, aiming at the problems existing in the prior amine curing agent synthesis field.
A process for the preparation of dicyanoethyl tertiary amine, the process comprising the steps of:
s1: the mono-nitrile ethyl secondary amine and 3-cyano propionic acid are subjected to catalytic reaction to obtain dicyanoethyl tertiary amine mother liquor;
s2: the dicyanoethyl tertiary amine mother liquor is subjected to aftertreatment to obtain dicyanoethyl tertiary amine products;
wherein, the catalytic reaction of S1 adopts a catalyst containing Fe.
In one embodiment, a semi-batch process is adopted, an alcohol solution of mononitrile secondary amine and a self-made catalyst are used for bottom paving, nitrogen is used for purging, then the temperature is raised to the reaction temperature, an aqueous solution of 3-cyanopropionic acid is gradually and dropwise added into the alcohol solution of mononitrile secondary amine for stirring, after all the feeding is finished, the reaction is continued for a period of time, cooling is carried out, and the product composition is collected and analyzed at a low temperature. After the reaction is finished, the dicyanoethyl tertiary amine mother liquor is distilled to remove light to further obtain dicyanoethyl tertiary amine samples.
Taking mono cyanoethyl cyclohexylamine and mono cyanoethyl aniline as examples, respectively carrying out addition reaction with 3-cyanopropionic acid, wherein the reaction equations are respectively shown as follows:
from the molecular level, the mono-cyanoethyl secondary amine is difficult to be further converted into dicyanoethyl tertiary amine due to the steric hindrance effect, and the di-cyanoethyl tertiary amine can be realized only in a specific acid catalytic system; the invention takes 3-cyano propionic acid as a raw material, can be taken as a reaction raw material to carry out decarboxylation under the action of Fe salt catalyst to generate an intermediate so as to replace secondary amine molecules, and simultaneously can be taken as an acid catalyst to promote the substitution reaction of the intermediate due to the self-carried carboxylic acid group, thereby solving the problem of poor activity of the cyano raw material in the traditional process, and realizing the multidimensional action effect of the raw material; in addition, other acid catalysts are not additionally introduced in the process, a post-treatment deacidification link is not needed, and the whole process is simple and easy to operate and is easier to realize.
In the present invention, the secondary mono-cyanoethyl amine in S1 is one or more of mono-cyanoethylcyclopentylamine, 2-methyl-mono-cyanoethylcyclopentylamine, mono-cyanoethylcyclohexylamine, mono-cyanoethylaniline, 2-methyl-mono-cyanoethylcyclohexylamine, 2-methyl-mono-cyanoethylaniline, 2, 3-dimethyl-mono-cyanoethylcyclohexylamine, 2, 3-dimethyl-mono-cyanoethylaniline, preferably mono-cyanoethylcyclohexylamine and/or mono-cyanoethylaniline.
In the invention, the molar ratio of the 3-cyanopropionic acid to the secondary mono-cyanoethyl amine of S1 is 1.8-2.5:1, preferably 2.1-2.5:1; preferably, the 3-cyanopropionic acid is added as an aqueous solution, the concentration of the 3-cyanopropionic acid aqueous solution being 1 to 50wt%, preferably 5 to 15wt%; preferably, the secondary mono-cyanoethyl amine is an alcoholic solution of secondary mono-cyanoethyl amine, preferably the alcohol is one or more of methanol, ethanol, isopropanol, more preferably methanol and/or ethanol; preferably, the mass ratio of the secondary mono-cyanoethyl amine to the alcohol in the secondary mono-cyanoethyl amine alcohol solution is 1-10:1, preferably 3-5:1.
In the present invention, the catalyst of S1 comprises one or more of the co-metals Cu, ag, zn, co, bi, sn, la, preferably Cu and/or Bi; preferably, the Fe and the co-metal are in the form of metal salts, preferably one or more of hydrochloride, nitrate, sulfate, oxalate, acetate, phosphate, more preferably hydrochloride and/or nitrate; preferably, the mass ratio of the Fe salt to the auxiliary metal salt is (20-2): 1, preferably (10-5): 1.
In the invention, the carrier of S1 is one or more of H-type molecular sieves, preferably H-ZSM-5, H-beta, H-SBA-15, H-MCM-41 and H-US, more preferably H-ZSM-5 and/or H-beta; preferably, the mass ratio of the carrier to the Fe salt is (5-20): 1, preferably (10-15): 1.
In one embodiment, the main metal Fe salt and other auxiliary metal salts are mixed together to prepare a solution, a certain amount of H-type molecular sieve is added into a three-neck flask filled with the metal salt solution, and the mixture is stirred for a certain period of time under a heating reflux state, and is prepared through a series of links such as filtering, washing, drying, roasting and the like.
In the invention, the mass ratio of the secondary mono-cyanoethyl amine to the catalyst in the secondary mono-cyanoethyl amine alcohol solution of S1 is 5-50:1, preferably 20-30:1.
In the invention, 3-cyano propionic acid in the S1 is added dropwise; preferably, the 3-cyanopropionic acid is added at a rate of 1 to 10g/min, preferably 2 to 3g/min.
In the present invention, after the completion of the dropwise addition in S1, the reaction is continued for 1 to 6 hours, preferably 2 to 5 hours.
In the present invention, the reaction temperature in S1 is 50 to 150℃and preferably 100 to 120 ℃.
In the invention, the post-treatment of S2 comprises distillation of dicyanoethyl tertiary amine mother liquor to remove light components; preferably, the distillation temperature is 50-150 ℃, preferably 70-100 ℃, absolute pressure is 1-50 KPa, preferably 20-30 KPa, and distillation duration is 0.5-3 h, preferably 1-2 h.
It is another object of the present invention to provide a dicyanoethyl tertiary amine product.
The dicyanoethyl tertiary amine is prepared by adopting the preparation method.
It is a further object of the present invention to provide a process for the preparation of dicyanoethyl tertiary amine.
The use of the preparation method of the dicyanoethyl tertiary amine is the preparation method of the dicyanoethyl tertiary amine or the preparation method of the dicyanoethyl tertiary amine, wherein the use is to prepare dicyanoethyl cyclopentylamine, 2-methyl-dicyanoethyl cyclopentylamine, dicyanoethyl cyclohexylamine, dicyanoethyl aniline, 2-methyl-dicyanoethyl cyclohexylamine, 2-methyl-dicyanoethyl aniline, 2, 3-dimethyl-dicyanoethyl cyclohexylamine and 2, 3-dimethyl-dicyanoethyl aniline, and the preferred use is to prepare dicyanoethyl cyclohexylamine and dicyanoethyl aniline.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
(1) The biomass 3-cyanopropionic acid can be obtained by oxidative decarboxylation of glutamic acid, and the glutamic acid is mainly prepared by biological fermentation of corn, rice, wheat, lignocellulose and other raw materials, so that the 3-cyanopropionic acid is a sustainable biomass raw material and can be used as an acidic catalyst without post-treatment deacidification link.
(2) The yield of dicyanoethyl tertiary amine obtained by catalyzing 3-cyanopropionic acid with Fe-containing catalyst can reach 98%, and the process has the technical advantages of high reaction rate and high yield.
Detailed Description
The invention will be further illustrated with reference to examples, but the invention is not limited to the examples listed.
The sources of the reaction raw materials are as follows:
mono cyanoethyl cyclohexylamine: purity is more than or equal to 99wt percent, and Wanhua chemistry;
mono cyanoethylaniline: purity is more than or equal to 99wt percent, and Wanhua chemistry;
3-cyanopropionic acid: purity is more than or equal to 99.5%, and the Ala is high;
catalyst carrier: a south-opening catalyst;
acrylonitrile: purity is more than or equal to 99.5%, beijing enokie;
Fe(NO 3 ) 3 : purity is more than or equal to 99.9%, and the Ala is high;
Cu(NO 3 ) 2 : purity is more than or equal to 99.9%, and the Ala is high;
Bi(NO 3 ) 3 : purity is more than or equal to 99.9%, and the Ala is high;
FeCl 3 : purity is more than or equal to 99.9%, and the Ala is high;
CuCl 2 : purity is more than or equal to 99.9%, and the Ala is high;
glycolic acid: purity is more than or equal to 99.9%, and the Ala is high;
sodium hydroxide: the purity is more than or equal to 99.9 percent, and the Ala is also provided.
The testing method comprises the following steps:
gas chromatography: agilent 7890 and DB-5 (30 mm. Times.0.25 mmID. Times.0.25 μm) were used, the injector temperature was 280℃and the detector temperature was 300 ℃. The temperature program is as follows: the initial column temperature is 50 ℃, and the temperature is kept for 2min; raising the temperature to 80 ℃ at 5 ℃/min, and keeping for 0min; raising the temperature to 300 ℃ at 15 ℃/min, and keeping for 15min. The component content was determined by normalization.
After the addition reaction, the invention can confirm that 3-cyanopropionic acid and the mono-cyanoethyl secondary amine are completely reacted when the content of the dicyanoethyl alicyclic primary amine in the obtained product is basically maintained unchanged by gas chromatography analysis, and the main dicyanoethyl tertiary amine in the product.
Example 1
Preparing a catalyst: 24.2g of Fe (NO) 3 ) 3 2.42g Cu (NO) 3 ) 2 Dissolving in PW water to obtain 161.33g metal salt solution, adding 242-g H-ZSM-5 molecular sieve into three-neck flask containing metal salt solution, stirring under reflux at 100deg.CStirring for 3 hours, vacuum filtering, washing with ethanol and water for 3 times respectively, drying at 100 ℃ for 10 hours, and roasting at 500 ℃ for 3 hours to prepare the catalyst A.
The addition process comprises the following steps: adopting a semi-batch process, preparing a solution by 15.2g of mono-cyanoethyl cyclohexylamine and 3g of methanol, paving a bottom by 0.15g of self-made catalyst A, purging with nitrogen for 3 times, heating to a reaction temperature of 100 ℃, then gradually dropwise adding 407.69g of 5wt% 3-cyanopropionic acid aqueous solution into the mono-cyanoethyl cyclohexylamine alcohol solution at a speed of 2g/min for stirring, continuing to react for 2h after all feeding is finished, cooling, and collecting the dicyanoethyl cyclohexylamine mother solution at a low temperature; after the reaction is finished, heating the dicyanoethyl cyclohexylamine mother liquor to 70 ℃, and distilling and purifying for 1h under the absolute pressure of 20Kpa, wherein the dicyanoethyl cyclohexylamine mother liquor is further subjected to distillation and light removal to obtain a dicyanoethyl cyclohexylamine sample; the content of the cyanoethyl cyclohexylamine in the reaction solution was 3.2wt% and the content of the dicyanoethyl cyclohexylamine was 95.5wt%, as obtained by chromatographic analysis.
Example 2
Preparing a catalyst: 24.2g of Fe (NO) 3 ) 3 4.48g Bi (NO) 3 ) 3 Dissolving the above materials in PW water to prepare 69.14g of metal salt solution, adding 363g H-beta molecular sieve into a three-necked flask filled with the metal salt solution, stirring at 150 ℃ under heating and refluxing conditions for 5h, vacuum filtering, washing with ethanol and water for 3 times respectively, drying at 120 ℃ for 10h, and roasting at 600 ℃ for 5h to prepare the catalyst B.
The addition process comprises the following steps: adopting a semi-batch process, preparing a solution by 15.2g of mono-cyanoethyl cyclohexylamine and 5g of ethanol and 0.76g of self-made catalyst B, heating to the reaction temperature of 120 ℃ after purging with nitrogen for 3 times, then gradually dropwise adding 161.78g of aqueous solution of 3-cyanopropionic acid with the concentration of 15wt% into the alcoholic solution of mono-cyanoethyl cyclohexylamine at the speed of 3g/min for stirring, continuing to react for 3h after all feeding is finished, cooling, and collecting dicyanoethyl cyclohexylamine mother liquor at low temperature; after the reaction is finished, heating the dicyanoethyl cyclohexylamine mother liquor to 100 ℃, and distilling and purifying for 2 hours under the absolute pressure of 30Kpa, wherein the dicyanoethyl cyclohexylamine mother liquor is further subjected to distillation and light removal to obtain a dicyanoethyl cyclohexylamine sample; the content of the cyanoethyl cyclohexylamine in the reaction solution was 1.6wt% and the content of the dicyanoethyl cyclohexylamine was 97.8wt%, as determined by chromatographic analysis.
Example 3
Preparing a catalyst: 16.2g FeCl 3 1.62g CuCl 2 Dissolving in PW water to prepare 64.8g of metal salt solution, adding 194.4g H-ZSM-5 molecular sieve into a three-neck flask filled with the metal salt solution, stirring for 4 hours at 120 ℃ under heating reflux, filtering under vacuum, washing with ethanol and water for 3 times respectively, drying at 110 ℃ for 10 hours, and roasting at 550 ℃ for 4 hours to prepare the catalyst C.
The addition process comprises the following steps: adopting a semi-batch process, preparing a solution by 14.6g of mono-cyanoethylaniline and 3.65g of methanol and 0.58g of self-made catalyst C for bottom laying, heating to a reaction temperature of 110 ℃ after purging with nitrogen for 3 times, then gradually dropwise adding 266.94g of aqueous solution of 3-cyanopropionic acid with the concentration of 8wt% into an alcohol solution of mono-cyanoethylaniline at the speed of 2.5g/min for stirring, continuing to react for 4 hours after all feeding is finished, cooling, and collecting a mother solution of the di-cyanoethylaniline at a low temperature; after the reaction is finished, heating the dicyanoethylaniline mother liquor to 80 ℃, and distilling and purifying for 1.5 hours under the absolute pressure of 25Kpa, wherein the dicyanoethylaniline mother liquor is further subjected to distillation and light removal to obtain a dicyanoethylaniline sample; the content of the mono cyanoethylaniline in the reaction solution is 3.8wt percent and the content of the dicyanoethyl cyclohexylamine is 95.8wt percent.
Example 4
Preparing a catalyst: 16.2g FeCl 3 3.24g CuCl 2 Dissolving in PW water to prepare 54g of metal salt solution, adding 226.8g H-beta molecular sieve into a three-neck flask filled with the metal salt solution, stirring for 5h at 150 ℃ under heating reflux, vacuum filtering, drying at 120 ℃ for 10h after using ethanol and water respectively for 3 times, and roasting at 600 ℃ for 3h to prepare the catalyst D.
The addition process comprises the following steps: adopting a semi-batch process, preparing a solution by 14.6g of mono-cyanoethylaniline and 2.92g of ethanol and 0.73g of self-made catalyst D, heating to the reaction temperature of 120 ℃ after purging with nitrogen for 3 times, then gradually dropwise adding 194.14g of aqueous solution of 3-cyanopropionic acid with the concentration of 12wt% into the alcoholic solution of mono-cyanoethylaniline at the speed of 3g/min for stirring, continuing to react for 5h after all feeding is finished, cooling, and collecting the mother liquor of the di-cyanoethylaniline at low temperature; after the reaction is finished, heating the dicyanoethylaniline mother liquor to 90 ℃, and distilling and purifying for 2 hours under the absolute pressure of 30Kpa, wherein the dicyanoethylaniline mother liquor is further subjected to distillation and light removal to obtain a dicyanoethylaniline sample; the content of the mono cyanoethylaniline in the reaction solution was 4.2wt% and the content of the dicyanoethyl cyclohexylamine was 95.2wt% as obtained by chromatographic analysis.
Comparative example 1
The same primary mono cyanoethyl secondary amine as in example 1 was used, except that the cyanoethylation feed used was acrylonitrile and the catalyst was replaced with glycolic acid. Adopting a semi-batch process, preparing a solution by 15.2g of mono-cyanoethyl cyclohexylamine and 5g of ethanol and 3g of glycollic acid for bottoming, heating to a reaction temperature of 100 ℃ after purging with nitrogen for 3 times, adding 11.8g of acrylonitrile into an alcohol solution of the mono-cyanoethyl cyclohexylamine at a speed of 0.3g/min for stirring, continuing to react for 6 hours after all feeding is finished, cooling, and collecting a dicyanoethyl cyclohexylamine mother solution at a low temperature; after the reaction is finished, heating the dicyanoethyl cyclohexylamine mother liquor to 90 ℃, distilling and purifying for 2 hours under the absolute pressure of 30Kpa, and adsorbing the reaction liquid after the distillation and purification by anion resin to further obtain dicyanoethyl cyclohexylamine samples; the content of the cyanoethyl cyclohexylamine in the reaction solution was 4.6wt% and the content of the dicyanoethyl cyclohexylamine was 94.8wt%, as determined by chromatographic analysis.
Comparative example 2
The same primary mono cyanoethyl secondary amine as in example 4 was used, except that the cyanoethylation feed used was acrylonitrile and the catalyst was replaced with sodium hydroxide. Adopting a semi-batch process, preparing a solution by 14.6g of mono-cyanoethylaniline and 4g of methanol and 3g of sodium hydroxide for bottom paving, heating to the reaction temperature of 120 ℃ after purging with nitrogen for 3 times, adding 12.2g of acrylonitrile into an alcohol solution of the mono-cyanoethylaniline at 0.3g/min for stirring, continuing to react for 10 hours after all feeding is finished, cooling, and collecting a mother solution of the di-cyanoethylaniline at low temperature; after the reaction is finished, heating the dicyanoethylaniline mother liquor to 90 ℃, distilling and purifying for 2 hours under the absolute pressure of 30Kpa, and cleaning the reaction liquid after the distillation and purification by using an aqueous solution of glycollic acid to further obtain a dicyanoethylaniline sample; the content of the mono cyanoethylaniline in the reaction solution was 5.6wt% and the content of the dicyanoethyl cyclohexylamine was 92.4wt% as obtained by chromatographic analysis.
The application of the present invention is not limited to the above embodiments, but any modifications or variations within the spirit of the present invention will be included in the scope of the present invention as intended by those skilled in the art.
Claims (18)
1. A process for the preparation of dicyanoethyl tertiary amine, said process comprising the steps of:
s1: the dicyanoethyl tertiary amine mother liquor is obtained by the catalytic reaction of the cyanoethyl secondary amine and the 3-cyanopropionic acid;
s2: the dicyanoethyl tertiary amine mother liquor is subjected to aftertreatment to obtain dicyanoethyl tertiary amine products;
wherein, the catalytic reaction in S1 adopts a catalyst containing Fe, the catalyst contains one or more of auxiliary metals Cu, ag, zn, co, bi, fe and the auxiliary metals are in the form of metal salts, and the carrier is an H-type molecular sieve.
2. The process according to claim 1, wherein S1 said secondary mono-cyanoethyl amine is one or more of mono-cyanoethyl cyclopentylamine, 2-methyl-mono-cyanoethyl cyclopentylamine, mono-cyanoethyl cyclohexylamine, mono-cyanoethyl aniline, 2-methyl-mono-cyanoethyl cyclohexylamine, 2-methyl-mono-cyanoethyl aniline, 2, 3-dimethyl-mono-cyanoethyl cyclohexylamine, 2, 3-dimethyl-mono-cyanoethyl aniline;
and/or the molar ratio of the 3-cyanopropionic acid to the secondary mono-cyanoethyl amine in the S1 is 1.8-2.5:1.
3. The preparation method according to claim 2, wherein the secondary mono-cyanoethyl amine is mono-cyanoethyl cyclohexylamine and/or mono-cyanoethyl aniline as S1;
and/or the molar ratio of the 3-cyanopropionic acid to the secondary mono-cyanoethyl amine in the S1 is 2.1-2.5:1;
the 3-cyanopropionic acid is added in the form of an aqueous solution, and the concentration of the 3-cyanopropionic acid aqueous solution is 1-50wt%;
the secondary mono-cyanoethyl amine is an alcohol solution of secondary mono-cyanoethyl amine;
the mass ratio of the secondary mono-cyanoethyl amine to the alcohol in the secondary mono-cyanoethyl amine alcohol solution is 1-10:1.
4. The method according to claim 3, wherein the concentration of the aqueous solution of 3-cyanoacrylic acid of S1 is 5 to 15wt%;
the alcohol of the alcohol solution is one or more of methanol, ethanol and isopropanol;
the mass ratio of the secondary mono-cyanoethyl amine to the alcohol in the secondary mono-cyanoethyl amine alcohol solution is 3-5:1.
5. The method according to claim 4, wherein the alcohol of the alcohol solution of S1 is methanol and/or ethanol.
6. The preparation method according to claim 1 or 2, characterized in that the catalyst of S1 comprises a co-metal Cu and/or Bi;
the Fe and the auxiliary metal are one or more of hydrochloride, nitrate, sulfate, oxalate, acetate and phosphate;
and/or the carrier of S1 is one or more of H-ZSM-5, H-beta, H-SBA-15, H-MCM-41 and H-US.
7. The method according to claim 6, wherein S1 is the Fe and the auxiliary metal is hydrochloride and/or nitrate;
the mass ratio of the Fe salt to the auxiliary metal salt is (20-2): 1;
and/or the carrier of S1 is H-ZSM-5 and/or H-beta;
the mass ratio of the carrier to the Fe salt is (5-20): 1.
8. The preparation method according to claim 7, wherein the mass ratio of the Fe salt to the auxiliary metal salt is (10-5) 1;
the mass ratio of the carrier to the Fe salt is (10-15): 1.
9. The method according to claim 3, wherein the mass ratio of the secondary monocyanoethyl amine to the catalyst in the secondary monocyanoethyl amine alcohol solution of S1 is 5-50:1.
10. The preparation method according to claim 9, wherein the mass ratio of the secondary mono-cyanoethyl amine to the catalyst in the secondary mono-cyanoethyl amine alcohol solution of S1 is 20-30:1.
11. The method according to claim 1, wherein the 3-cyanopropionic acid in S1 is added dropwise;
and/or after the dripping in the step S1 is finished, continuing to react for 1-6 h;
and/or the reaction temperature in S1 is 50-150 ℃.
12. The method according to claim 11, wherein the 3-cyanopropionic acid in S1 is added at a rate of 1 to 10g/min;
and/or after the dripping in the step S1 is finished, continuing to react for 2-5 hours;
and/or the reaction temperature in S1 is 100-120 ℃.
13. The process according to claim 12, wherein the 3-cyanopropionic acid in S1 is added at a rate of 2 to 3g/min.
14. The process of claim 1 wherein the post-treatment of S2 comprises distillation of dicyanoethyl tertiary amine mother liquor to remove light components.
15. The method according to claim 14, wherein the distillation is carried out at a temperature of 50 to 150 ℃, an absolute pressure of 1 to 50KPa, and a distillation time period of 0.5 to 3 hours.
16. The method according to claim 15, wherein the distillation is carried out at a temperature of 70 to 100 ℃, an absolute pressure of 20 to 30KPa, and a distillation time period of 1 to 2 hours.
17. Use of a process for the preparation of dicyanoethyl tertiary amine according to any one of claims 1 to 5 for the preparation of dicyanoethyl cyclopentylamine, 2-methyl-dicyanoethyl cyclopentylamine, dicyanoethyl cyclohexylamine, dicyanoethyl aniline, 2-methyl-dicyanoethyl cyclohexylamine, 2-methyl-dicyanoethyl aniline, 2, 3-dimethyl-dicyanoethyl cyclohexylamine, 2, 3-dimethyl-dicyanoethyl aniline.
18. Use according to claim 17, characterized in that it is the preparation of dicyanoethyl cyclohexylamine, dicyanoethyl aniline.
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| 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 |
| CN1076189A (en) * | 1992-09-19 | 1993-09-15 | 董源 | The preparation method of cyanoethyl alkyl aryl tertiary amine |
| 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 |
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