3-aminomethyl-3, 5, 5-trimethyl cyclohexylamine preparation method

• US 8,829,245 B2
• Filed: 09/06/2011
• Issued: 09/09/2014
• Est. Priority Date: 08/08/2011
• Status: Active Grant

• Current Assignee: Ningbo Wanhua Polyurethanes Company Limited, Wanhua Chemical Group Co., Ltd. (Wanhua Industrial Group Company Limited)
• Original Assignee: Wanhua Chemical (Ningbo) Co., Ltd., Wanhua Chemical Group Co., Ltd. (Wanhua Industrial Group Company Limited)
• Inventors: Chen, Changsheng, Li, Yuan, Zhao, Wenjuan, Cui, Hongyin, Hua, Weiqi
• Primary Examiner(s): Davis, Brian J
• Application Number:
  US14/113,907
• Publication Number:
  US 20140142341A1
• Time in Patent Office: 1,099 Days
• Field of Search: 564/448
• US Class Current: 564/448
• CPC Class Codes: C07C 209/48 by reduction of nitriles
• CPC Class Codes: C07C 209/52 by reduction of imines or imino-ethers C07C209/24 takes precedence
• CPC Class Codes: C07C 209/62 by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds C07C209/24 takes precedence
• CPC Class Codes: C07C 211/36 containing at least two amino groups bound to the carbon skeleton
• CPC Class Codes: C07C 253/30 by reactions not involving the formation of cyano groups
• CPC Class Codes: C07C 255/46 to carbon atoms of non-condensed rings
• CPC Class Codes: C07C 255/61 containing cyano groups and nitrogen atoms being part of imino groups bound to the same carbon skeleton
• CPC Class Codes: C07C 2601/14 The ring being saturated

Abstract

Provided is a 3-aminomethyl-3,5,5-trimethylcyclohexylamine preparation method. A feeding flow of 3-cyano-3,5,5-trimethylcyclohexylamine is reacted with NH3 and hydrogen in the presence of a hydrogenation catalyst; the method is characterized by: firstly adding a basic compound to the feeding flow of 3-cyano-3,5,5-trimethylcyclohexylamine, and then after a portion of 3-cyano-3,5,5-trimethylcyclohexylamine has reacted, adding an acidic compound to reaction materials for further hydrogenation reaction to prepare the product. The method ensures that the aminonitrile content in the product is low, thus effectively reducing the duration of the reaction and greatly reducing the consumption of the catalyst during the hydrogenation reaction process.

Claims

1. A method for preparing 3-aminomethyl-3,5,5-trimethylcyclohexylamine, the method comprising:

a) reacting 3-cyano-3,5,5-trimethyl-cyclohexanone with NH₃ to obtain a product containing 3-cyano-3,5,5-trimethyl-cyclohexylamine;

b) mixing the product of step a) with a basic compound in the presence of hydrogen, NH₃ and a first hydrogenation catalyst to obtain a product containing 3-aminomethyl-3,5,5-trimethylcyclohexylamine and 3-cyano-3,5,5-trimethyl-cyclohexylamine, wherein the space velocity on the first hydrogenation catalyst is 0.5-10 g of 3-cyano-3,5,5-trimethyl-cyclohexanone/(per ml catalyst per hour);

c) mixing the product of step b) with an acidic compound in the presence of hydrogen, NH₃ and a second hydrogenation catalyst, wherein the 3-cyano-3,5,5-trimethyl-cyclohexylamine in the product of step b) is converted into 3-aminomethyl-3,5,5-trimethyl-cyclohexylamine.

2. The method according to claim 1, wherein the content of 3-cyano-3,5,5-trimethyl-cyclohexylamine in the product of step b) is 5-20 wt %.

3. The method according to claim 2, wherein the acidic compound in step c) is an organic acid.

4. The method according to claim 3, wherein the mass ratio of the acidic compound in step c) to 3-cyano-3,5,5-trimethyl-cyclohexanone in step a) is 1:

100-1;

1000.

5. The method according to claim 4, wherein the acidic compound of step c) is in the form of a solution of the acidic compound, wherein the solvent is water, alcohol or ether;

and the concentration of the solution is 0.1-10 wt %.

6. The method according to 1, wherein the basic compound of step b) is alkali metal compounds.

7. The method according to claim 1, wherein the mass ratio of the basic compound in step b) to 3-cyano-3,5,5-trimethyl-cyclohexanone in step a) is 1:

100-1;

1000.

8. The method according to claim 1, wherein the basic compound of step b) is in the form of a solution of the basic compound, wherein the solvent is water, alcohol or ether;

and the concentration of the solution is 0.1-10 wt %.

9. The method according to claim 1, wherein step a) is carried out at a temperature of 20-100°

C. and a pressure of 0.5-30 MPa;

step b) is carried out at a temperature of 50-130°

C. and a pressure of 10-30 MPa; and

step c) is carried out at a temperature of 50-130°

C. and a pressure of 10-30 MPa.

10. The method according to claim 1, wherein the space velocity on the catalyst in step c) is 0.5-20 g of 3-cyano-3,5,5-trimethyl-cyclohexanone/(per ml catalyst per hour).

11. The method according to claim 1, wherein step a) is carried out in the presence of a catalyst which is an acidic metal oxide, an inorganic ion-exchange resin or an organic ion exchange resin;

and the space velocity on the catalyst is 0.5-20 g of 3-cyano-3,5,5-trimethylcyclohexanone/(per ml catalyst per hour).

12. The method according to claim 1, wherein the first hydrogenation catalyst in step b) and the second hydrogenation catalyst in step c) are the same or different, and the first hydrogenation catalyst and the second hydrogenation catalyst are independently hydrogenation catalysts having cobalt or nickel as the active component.

13. The method according to claim 1, wherein the molar ratio of NH₃ in step a) and step b) to 3-cyano-3,5,5-trimethyl-cyclohexanone is 5:

1-200;

1; and

the molar ratio of hydrogen in step b) and step c) to 3-cyano-3,5,5-trimethyl-cyclohexanone is 3;

1-1000;

1.

14. The method according to claim 1, wherein step a) is carried out in the presence of hydrogen, and the molar ratio of the hydrogen to 3-cyano-3,5,5-trimethyl-cyclohexanone is 3:

1-1000;

1.

15. The method according to claim 1, wherein step b) and step c) are carried out in a hydrogenation reactor.

21. The method according to claim 3, wherein the organic acid is selected from the group consisting of a C1-C40 organic monoacid, a C1-C40 organic diacid, and a C1-C40 organic polyacid.

22. The method according to claim 21, wherein the organic acid is selected from the group consisting of formic acid, acetic acid, methoxy acetic acid, propionic acid, caproic acid, lauric acid, benzoic acid, phthalic acid, phenylacetic acid, 2-ethylhexanoic acid, succinic acid, glutaric acid, adipic acid, and suberic acid.

23. The method according to claim 5, wherein the solvent of the solution of the acidic compound of step c) is methanol or ethanol.

24. The method according to claim 6, wherein the basic compound of step b) is selected from the group consisting of oxides, hydroxides or carbonates of alkali metals, oxides, hydroxides or carbonates of alkaline earth metals, and oxides, hydroxides or carbonates of a rare earth metals.

16. A method for preparing 3-aminomethyl-3,5,5-trimethyl-cyclohexylamine, the method comprising:

a) reacting 3-cyano-3,5,5-trimethyl-cyclohexanone with NH₃ to obtain a product containing 3-cyano-3,5,5-trimethyl-cyclohexylamine;

b) mixing the product of step a) with a basic compound in the presence of hydrogen, NH₃ and a first hydrogenation catalyst to obtain a product containing 3-aminomethyl-3,5,5-trimethylcyclohexylamine and 3-cyano-3,5,5-trimethyl-cyclohexylamine, wherein the space velocity on the first hydrogenation catalyst is 0.5-10 g of 3-cyano-3,5,5-trimethyl-cyclohexanone/(per ml catalyst per hour);

c) mixing the product of step b) with an acidic compound in the presence of hydrogen, NH₃ and a second hydrogenation catalyst, wherein the 3-cyano-3,5,5-trimethyl-cyclohexylamine in the product of step b) is converted into 3-aminomethyl-3,5,5-trimethyl-cyclohexylamine;

wherein the content of 3-cyano-3,5,5-trimethyl-cyclohexylamine in the product of step b) is 5-20 wt %;

wherein the acidic compound in step c) is an organic acid; and

wherein the space velocity on the catalyst in step c) is 0.5-20 g of 3-cyano-3,5,5-trimethylcyclohexanone/(per ml catalyst per hour).

17. The method according to claim 16, wherein the mass ratio of the acidic compound in step c) to 3-cyano-3,5,5-trimethyl-cyclohexanone in step a) is 1:

100-1;

1000;

wherein the acidic compound of step c) is in the form of a solution of the acidic compound, wherein the solvent is water, alcohol or ether; and

the concentration of the solution is 0.1-10 wt %.

25. The method according to claim 16, wherein the space velocity on the first hydrogenation catalyst in the step b) is 1-5 g of 3-cyano-3,5,5-trimethyl-cyclohexanone/(per ml catalyst per hour);

the content of 3-cyano-3,5,5-trimethyl-cyclohexylamine in the product of step b) is 10-15 wt %;

the acidic compound in step c) is selected from the group consisting of a C1-C40 organic monoacid, a C1-C40 organic diacid, and a C1-C40 organic polyacid;

the space velocity on the catalyst in step c) is 0.5-15 g of 3-cyano-3,5,5-trimethyl-cyclohexanone/(per ml catalyst per hour).

26. The method according to claim 25, wherein the acidic compound in step c) is selected from the group consisting of formic acid, acetic acid, methoxy acetic acid, propionic acid, caproic acid, lauric acid, benzoic acid, phthalic acid, phenylacetic acid, 2-ethylhexanoic acid, succinic acid, glutaric acid, adipic acid, and suberic acid.

18. A method for preparing 3-aminomethyl-3,5,5-trimethyl-cyclohexylamine, the method comprising:

a) reacting 3-cyano-3,5,5-trimethyl-cyclohexanone with NH₃ to obtain a product containing 3-cyano-3,5,5-trimethyl-cyclohexylamine;

b) mixing the product of step a) with a basic compound in the presence of hydrogen;

NH₃ and a first hydrogenation catalyst to obtain a product containing 3-aminomethyl-3,5,5-trimethylcyclohexylamine and 3-cyano-3,5,5-trimethyl-cyclohexylamine, wherein the space velocity on the first hydrogenation catalyst is 0.5-10 g of 3-cyano-3,5,5-trimethyl-cyclohexanone/(per ml catalyst per hour);

c) mixing the product of step b) with an acidic compound in the presence of hydrogen, NH₃ and a second hydrogenation catalyst, wherein the 3-cyano-3,5,5-trimethyl-cyclohexylamine in the product of step b) is converted into 3-aminomethyl-3,5,5-trimethyl-cyclohexylamine;

wherein the content of 3-cyano-3,5,5-trimethyl-cyclohexylamine in the product of step b) is 5-20 wt %;

wherein the acidic compound in step c) is an organic acid;

wherein the space velocity on the catalyst in step c) is 0.5-20 g of 3-cyano-3,5,5-trimethylcyclohexanone/(per ml catalyst per hour); and

wherein step b) and step c) are carried out in a hydrogenation reactor.

19. The method according to claim 18, wherein the mass ratio of the acidic compound in step c) to 3-cyano-3,5,5-trimethyl-cyclohexanone in step a) is 1:

100-1;

1000.

20. The method according to claim 19, wherein the acidic compound of step c) is in the form of a solution of the acidic compound, wherein the solvent is water, alcohol or ether;

and the concentration of the solution is 0.1-10 wt %.

27. The method according to claim 18, wherein the space velocity on the first hydrogenation catalyst in the step b) is 1-5 g of 3-cyano-3,5,5-trimethyl-cyclohexanone/(per ml catalyst per hour);

the content of 3-cyano-3,5,5-trimethyl-cyclohexylamine in the product of step b) is 10-15 wt %;

the acidic compound in step c) is selected from the group consisting of a C1-C40 organic monoacid, a C1-C40 organic diacid, and a C1-C40 organic polyacid;

the space velocity on the catalyst in step c) is 0.5-15 g of 3-cyano-3,5,5-trimethyl-cyclohexanone/(per ml catalyst per hour);

step b) and step c) are carried out in a tubular reactor.

28. The method according to claim 27, wherein the acidic compound in step c) is selected from the group consisting of formic acid, acetic acid, methoxy acetic acid, propionic acid, caproic acid, lauric acid, benzoic acid, phthalic acid, phenylacetic acid, 2-ethylhexanoic acid, succinic acid, glutaric acid, adipic acid, and suberic acid.