Preparation method of dicyanoethyl tertiary amine

A technology of dicyanoethyl tertiary amine mother and dicyanoethyl, applied in the field of preparation of dicyanoethyl tertiary amine, can solve the problems of large steric hindrance effect, low yield, heat release, etc., and achieve fast reaction rate , the effect of high yield

Active Publication Date: 2022-06-07
WANHUA CHEM GRP CO LTD
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Problems solved by technology

[0003] For amine molecules, the activity of primary amine is relatively higher, so nitrile ethylation can be easily achieved by single substitution to obtain mononitrile ethyl secondary amine; however, compared with primary amine, secondary amine is too large due to steric hindrance effect Because of this reason, it is difficult to synthesize dicyanoethyl tertiary amine by secondary addition; in order to meet the needs of the market, breaking through the key technology to synthesize tertiary amine with wider application is not only a key task in the field of epoxy resin curing agent, but also a difficulty Work
[0004] CN 103524717 A discloses a modified alicyclic amine curing agent. The invention uses acrylonitrile to modify methylcyclohexanediamine, but the amount of acrylonitrile is only 1 to 50% of the total amount of raw materials, failing to achieve a The dicyanoethyl addition of cyclohexanediamine; US3231601 discloses a cyanoethylation process of aromatic amines, the invention uses strong acid as a catalyst, and uses acrylonitrile to carry out cyanoethylation addition to aromatic amines, but the preparation The process is complex, very corrosive to equipment, and the technical content is limited; CN108383756 A discloses a preparation method of cyanoethylated amine compounds, which uses acrylonitrile to modify polyamines under the action of a basic catalyst. Also cause the same problem; CN 113372241 A discloses a method for synthesizing bis-nitrile ethyl tertiary amine in one step from aliphatic primary amine
Under the catalysis of glycolic acid, this invention uses acrylonitrile to add aliphatic primary amines, but the method of removing glycolic acid is not introduced in the article, and using both acid and amine as substrates will cause serious exothermic problems , the product yield will also be affected
[0005] So far, in the field of amine curing agents, the technology of dicyanoethyl addition of amines mostly adopts the method of acid or base catalysis, which not only has low yield, complicated post-treatment, but also has adverse effects on the environment. Seriously affected the application of amine curing agent

Method used

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  • Preparation method of dicyanoethyl tertiary amine

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0050] Preparation catalyst: 24.2 g Fe (NO 3 ) 3 and 2.42 g Cu(NO 3 ) 2Together dissolved in PW water to prepare 161.33g of metal salt solution, and then 242g H-ZSM-5 molecular sieve was added to the three-neck flask containing the metal salt solution, stirred at 100 °C heated reflux state for 3h, through vacuum filtration, and then washed 3 times with ethanol and water, 10h drying at 100 °C, and then roasted at 500 °C for 3h to obtain Catalyst A.

[0051] Addition process: using semi-intermittent process, with 15.2g monocyanatoethyl cyclohexylamine and 3g methanol compound solution and 0.15g homemade catalyst A for laying, with nitrogen purged 3 times after heating to the reaction temperature of 100 ° C, and then 407.69g concentration of 5wt% of the aqueous solution of 3-cyanopropionic acid at a rate of 2g / min gradually added into the monocyanatoethyl cyclohexylamine alcohol solution stirred, after all the feeding is over, continue to react for 2h, cooling, Cryogenic collection...

Embodiment 2

[0053] Preparation catalyst: 24.2 g Fe (NO 3 ) 3 and 4.48g Bi(NO 3 ) 3 Together dissolved in PW water to prepare 69.14g of metal salt solution, and then 363g H-β molecular sieve was added to the three-neck flask containing metal salt solution, stirred at 150 °C heated reflux state for 5h, filtered by vacuum, and then washed 3 times with ethanol and water, dried at 120 °C for 10h, and then roasted at 600 °C for 5h to obtain catalyst B.

[0054]Addition process: using semi-intermittent process, 15.2g monocyanatoethyl cyclohexylamine and 5g ethanol compound solution and 0.76g homemade catalyst B for laying the bottom, with nitrogen purged 3 times after heating to the reaction temperature of 120 ° C, and then the 161.78g concentration of 15wt% of the aqueous solution of 3-cyanopropionic acid at a rate of 3g / min gradually added dropwise into the alcohol solution of monocyanatoethyl cyclohexylamine for stirring, after all the feeding is completed, continue to react for 3h, cooling, Cr...

Embodiment 3

[0056] Preparation catalyst: 16.2 g FeCl 3 and 1.62g CuCl 2 Dissolved in PW water to prepare 64.8g of metal salt solution, and then 194.4g H-ZSM-5 molecular sieve was added to the three-neck flask containing metal salt solution, stirred at 120 °C heated reflux state for 4h, filtered by vacuum, and then washed 3 times with ethanol and water, dried at 110 °C for 10h, and then roasted at 550 °C for 4h to obtain catalyst C.

[0057] Addition process: using a semi-batch process, with 14.6g monocyanatoaniline and 3.65g of methanol to form a solution and 0.58g of homemade catalyst C for laying the bottom, with nitrogen purged 3 times after heating to the reaction temperature of 110 ° C, and then the 266.94g concentration of 8wt% of the aqueous solution of 3-cyanopropionic acid at a rate of 2.5g / min gradually added into the alcohol solution of monocyanatoethylaniline for stirring, after all the feeding is completed, continue to react for 4h, cooling, Cryogenic collection of dicyanoethyl...

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Abstract

The invention provides a preparation method of dicyanoethyl tertiary amine. The preparation method comprises the following steps: carrying out catalytic reaction on mono-nitrile ethyl secondary amine and 3-cyanopropionic acid to obtain dicyanoethyl tertiary amine mother liquor; and carrying out post-treatment on the dicyanoethyl tertiary amine mother liquor to obtain a dicyanoethyl tertiary amine product. Wherein a Fe-containing catalyst is adopted in the catalytic reaction. The 3-cyanopropionic acid provided by the invention is a biomass raw material 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-cyanopropionic acid catalyzed by the Fe-containing catalyst can reach 98%, the reaction rate is high, and the yield is high.

Description

Technical field [0001] The present invention belongs to the field of organic synthesis, providing a method for preparing dicyanogen ethyl tertiary amines. Background [0002] With the continuous expansion of the application field of epoxy resin, the quality of amine curing agents has put forward corresponding higher requirements; At present, the method of further modification of amine molecules has shown diversified characteristics, among which the synthesis of cyanoethyl amines is a very suitable technical means, and is gradually being recognized and promoted by the epoxy curing agent market. [0003] For amine molecules, the activity of primary amines is relatively higher, so nitrile ethylation can be easily achieved by single substitution to obtain mononitrile ethyl secondary amine; However, compared with primary amines, secondary amines are difficult to synthesize dicyanoethyl tertiary amine due to the reason that the space steric hindrance effect is too large; In order to be...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C255/24C07C253/30
CPCC07C255/24C07C253/30C07C2601/14Y02P20/584
Inventor 于波张聪颖刘振国李显赫周萌张昊尚永华
Owner WANHUA CHEM GRP CO LTD
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