JPH06219995A - Production of 3-aminomethyl-3,5,5-trimethylcyclohexylamine - Google Patents

Abstract

PURPOSE:To obtain the subject compound used for as an epoxy resin hardening agent, etc., by subjecting 3-cyano-3,5,5-trimethylcyclohexanone to react with ammonia and hydrogen in the presence of a reduced cobalt catalyst and a glycol. CONSTITUTION:In a shaking type stainless steel autoclave the inside of which has been replaced with nitrogen gas, 3-cyano-3,5,5-trimethylcyclohexanone, a glycol such as propylene glycol, etc., and a powdery reduced cobalt zirconium kieselguhr catalyst are filled and the inside of the autoclave is replaced with hydrogen gas. Then, ammonia and hydrogen are filled until a pressure of the system reaches 130kg/cm<2> and the whole is allowed to react at 120 deg.C reaction temperature for 50 minutes to obtain the objective 3-aminomethyl-3,5,5- trimethylcyclohexylamine useful as a raw material, etc., of producing isophorone diisocyanate used for an epoxy resin hardening agent and non-yellowing polyurethane, controlling a by production of aminoalcohols and simplifying the reaction process.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a process for producing 3-aminomethyl-3,5,5-trimethylcyclohexylamine from 3-cyano-3,5,5-trimethylcyclohexanone. 3-Aminomethyl-3,5,5-trimethylcyclohexylamine is a compound useful as a raw material for isophorone diisocyanate from which epoxy resin curing agents, non-yellowing polyurethane or polyurea are produced.

[0002]

2. Description of the Related Art A method for producing 3-aminomethyl-3,5,5-trimethylcyclohexylamine from 3-cyano-3,5,5-trimethylcyclohexanone is known and is disclosed in Japanese Examined Patent Publication No. 39-109.
No. 23 shows a method of reacting 3-cyano-3,5,5-trimethylcyclohexanone with hydrogen in the presence of ammonia. In this method, the amount of ammonia used is 10 to 30 per mol of 3-cyano-3,5,5-trimethylcyclohexanone.
The molar range is Fe, Co and N as hydrogenation catalysts.
A catalyst containing i has been used. It is also disclosed to use alcohols such as methanol and ethanol, ethers and hydrocarbons such as cyclohexane as a solvent. Further, in Example 1 of this publication, a Co catalyst was used in a methanol solvent, and the reaction product was 3-aminomethyl-
3,5,5-Trimethylcyclohexylamine 81.4%, 3-aminomethyl-3,5,5-trimethylcyclohexanol (hereinafter referred to as aminoalcohol) 9.4%, imine compounds that are low boiling point compounds 2.4% ing.

Further, JP-A-62-123154 discloses a method of using a Raney cobalt catalyst in order to moderate the reaction pressure and improve the reaction yield. According to the result of the gas chromatographic analysis of the reaction products in this example (area percentages except for methanol), 3-aminomethyl-3,5,5-trimethylcyclohexylamine 83.3
~ 89.6%, amino alcohols 3.9 ~ 5.6%. Therefore, in the one-step hydrogenation method, a considerable amount of amino alcohol is produced as a by-product. This by-product of the aminoalcohol not only leads to a decrease in the yield of 3-aminomethyl-3,5,5-trimethylcyclohexylamine, but also because the boiling points of both are relatively close to each other, the load of the separation operation by distillation increases.

On the other hand, Japanese Patent Application Laid-Open No. 28030/1982 discloses a method for suppressing by-products such as amino alcohol which causes a loss of distillation by preliminarily adding 3-cyano-3,5,5-trimethylcyclohexanone to an imine-forming catalyst. It is proposed to carry out the pre-reaction with ammonia in the presence of ## STR3 ## and then to hydrogenate by the known method as described above. This method is excellent in that by-products such as aminoalcohols can be significantly reduced, but compared with the above one-step method, the number of reaction steps is increased by one,
Also, since the catalyst and reaction conditions are different in each reaction step,
There are problems in the process such as complicated driving operation.

[0005]

As described above, in the conventional one-step method, the by-product of the aminoalcohol is unavoidable, which lowers the yield and imposes a heavy load on the separation operation by distillation. The process is complicated in the two-step method in which hydrogen is added after a pre-reaction with ammonia in the presence of an imine-forming catalyst.
An object of the present invention is to provide a method for industrially advantageously producing 3-aminomethyl-3,5,5-trimethylcyclohexylamine by suppressing the by-production of aminoalcohol in a one-step method.

[0006]

The present inventor produces 3-aminomethyl-3,5,5-trimethylcyclohexylamine from 3-cyano-3,5,5-trimethylcyclohexanone having the above problems. As a result of earnest research on the method,
By reacting 3-cyano-3,5,5-trimethylcyclohexanone with ammonia and hydrogen in the presence of glycols using a reduced cobalt catalyst, the by-production of amino alcohol is suppressed and at the same time, 3-amino Methyl-3,5,5
-The present invention has been completed by finding that the yield of trimethylcyclohexylamine is improved.

That is, the present invention is characterized in that 3-cyano-3,5,5-trimethylcyclohexanone is reacted with ammonia and hydrogen in the presence of a reduced cobalt catalyst and glycols. It is a method for producing 1,5-trimethylcyclohexylamine.

The method for carrying out the present invention will be specifically described below. The amount of ammonia used in the present invention is in the range of 1 to 30, preferably 5 to 20, in terms of molar ratio to 3-cyano-3,5,5-trimethylcyclohexanone. If the amount of ammonia used is less than this range, 3-aminomethyl-3,5,5
-The yield of trimethylcyclohexylamine decreases, and when it is more than this range, the effect of suppressing the side reaction to the amino alcohol compound is small.

The glycols used in the present invention include ethylene glycol, propylene glycol, 1,3-
Propanediol, 1,4-butanediol, 1,3-butanediol, diethylene glycol, triethylene glycol and the like can be mentioned. The amount of glycols used is 3-cyano
Weight ratio to -3,5,5-trimethylcyclohexanone
It is in the range of 2 to 20, preferably 3 to 15. If the amount of glycols used is less than this range, the effect of suppressing side reactions to the amyl alcohol compound is less, and if it is more than this range, space-time of 3-aminomethyl-3,5,5-trimethylcyclohexylamine This is not preferable because the yield is small. As other solvents, for example, alcohols such as methanol and ethanol, ethers such as 1,4-dioxane,
Hydrocarbons such as benzene and toluene may be used together. However, in this case as well, the amounts of ammonia and glycols used need to correspond to the above ranges.

The catalyst used in the present invention is a reduced cobalt catalyst, and a form including a carrier is preferable for practical use. As the carrier, diatomaceous earth, carbon, alumina, activated alumina, silica, calcium carbonate, titanium oxide, bentonite, barium sulfate or the like is used. The cobalt content in the catalyst is
It is 10 to 90% by weight, preferably 30 to 70%. Further, a cobalt catalyst containing zirconium, molybdenum or the like can be used as the second component. These commercially available catalysts or prepared catalysts are subjected to a conventional reduction treatment in advance,
Used in the reaction. The amount of the catalyst used varies depending on the reaction mode, but in the case of batch reaction, for example, the weight ratio of cobalt contained in the catalyst to 3-cyano-3,5,5-trimethylcyclohexanone is 0.05 to 5, and preferably 0.1 ~
It is in the range of 1.

[0011] hydrogen partial pressure used in the reaction is at 10 kg / cm ² or more, the industrial preferably in the range of 50~150kg / cm ^2.
As the hydrogen gas source, a mixed gas containing inert nitrogen, helium, argon or the like can be used, but in this case, it is necessary to correspond to the above hydrogen partial pressure. Reaction temperature is 50-180
C., preferably in the range of 80 to 150.degree. At reaction temperatures lower than this range, the reaction rate is low, and at reaction temperatures higher than this range, side reactions increase.

The reaction time varies depending on the conditions such as the starting materials 3-cyano-3,5,5-trimethylcyclohexanone, ammonia, glycols and the amount of catalyst used, hydrogen partial pressure, reaction temperature, etc. , Usually in the range of 0.2-5 hours.

The reaction product solution obtained by the method of the present invention has a high purity by well-known separation and purification means, for example, distillation under reduced pressure.
3-Aminomethyl-3,5,5-trimethylcyclohexylamine can be separated and recovered. The reaction of the present invention is
Both the batch method and the continuous method can be preferably carried out.

[0014]

EXAMPLES The method of the present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto. The reduced cobalt catalyst used in each of the examples and comparative examples was subjected to a reduction treatment in advance by the method described below and then used in the reaction of the present invention. <Catalyst reduction treatment> Quartz glass tube (8 mm ФX 800
) And installed in an electric furnace for heating. After replacing the inside of the system with nitrogen under normal pressure, the temperature of the catalyst layer was raised to 450 ° C. while flowing nitrogen gas. Nitrogen gas was gradually changed to hydrogen gas while maintaining this temperature, and finally the gas flow rate was 200 ml.
Heat-treated with / mim for 2.5 hours. After the reduction treatment was completed, it was cooled to room temperature while flowing hydrogen gas. The prepared reduced cobalt catalyst was transferred from a quartz glass tube into an autoclave previously replaced with nitrogen in a nitrogen gas atmosphere and used.

Example 1 After the inside of a shaking autoclave made of stainless steel having an internal volume of 100 ml was previously replaced with nitrogen gas, 3 g of raw material 3-cyano-3,5,5-trimethylcyclohexanone and 3 g of propylene glycol were used.
7.5 g and 2 g of powdered cobalt-zirconium-diatomaceous earth catalyst subjected to reduction treatment (Co = 56%, Zr = 2.5%) were charged and sealed. After replacing the inside of the autoclave with hydrogen gas, the system pressure of ammonia 3.5 g and hydrogen gas was 130 kg / cm ²
Filled until. At this time, the feeding molar ratio of ammonia to 3-cyano-3,5,5-trimethylcyclohexanone was 11.3, and the feeding weight ratio of propylene glycol was
It is 5.83. The autoclave was installed in an electric furnace attached to a shaker, and the reaction temperature was raised to 120 ° C for reaction.
Hydrogen absorption was completed in about 50 minutes. After cooling the autoclave and releasing the pressure, the reaction product liquid was taken out and the composition was analyzed by gas chromatography. As a result, the raw material 3-cyano-
All 3,5,5-trimethylcyclohexanone had reacted. The ratio of each product was 3-aminomethyl-3,5,5-trimethylcyclohexylamine 91.8%, and the low boiling point imine derivative 8.15%, and 3-aminomethyl-3,5,5-trimethylcyclohexanol ( Amino alcohol form) was not detected.

Example 2 A reaction was carried out in the same manner as in Example 1 except that ethylene glycol was used instead of propylene glycol. Hydrogen absorption was completed in about 50 minutes. As a result, all the raw materials reacted and the ratio of each product was 3-aminomethyl-3,5,5-
Trimethylcyclohexylamine 91.1%, imine
It was 8.90%, and amino alcohol was not formed.

Example 3 In the same manner as in Example 1, starting material 3-cyano-3,5,5-trimethylcyclohexanone 3 g, propylene glycol 13.8
g, and 2 g of powdered cobalt-zirconium-diatomaceous earth catalyst subjected to reduction treatment were charged, and then 7.2 g of ammonia and hydrogen gas were charged until the pressure in the autoclave reached 130 kg / cm ² . At this time, the feed molar ratio of ammonia to 3-cyano-3,5,5-trimethylcyclohexanone was 23.3, and the feed weight ratio of propylene glycol was 4.6. Then, the reaction was carried out at a temperature of 120 ° C. Hydrogen absorption was completed in about 50 minutes. As a result, all the raw materials reacted, and the ratio of each product was 3-aminomethyl-3,5,5-trimethylcyclohexylamine 91.5%, amino alcohol 0.23%,
The low boiling point component of imine was 8.27%.

Example 4 In Example 1, the reduced cobalt zirconium
Cobalt / diatomite catalyst (Co =
The reaction was performed in the same manner except that (67%) was used.
Hydrogen absorption was completed in about 50 minutes. As a result, all the raw materials reacted and the ratio of each product was 3-aminomethyl-3,5,5-trimethylcyclohexylamine 92.2% and imines 7.8%, and amino alcohol was not produced.

Example 5 In Example 4, 1,4- was used instead of propylene glycol.
The reaction was carried out in the same manner except that butanediol was used. Hydrogen absorption was completed in about 50 minutes. As a result, all the raw materials reacted and the ratio of each product was 3-aminomethyl-3,5,5.
-Trimethylcyclohexylamine 89.6%, imines
The content was 10.3% and the content of aminoalcohol was 0.10% or less.

Comparative Examples 1 to 3 In Example 1, methanol was used in place of glycols,
The reaction was carried out using 1,4-dioxane and pseudocumene. The molar ratio of ammonia charged to 3-cyano-3,5,5-trimethylcyclohexanone was 11.3, and the weight ratio of each solvent charged was 5.83. In each experiment, hydrogen absorption was completed in 50 to 60 minutes, and all the raw materials had reacted. The ratio of the product in each experiment is shown in Table 1. From this, comparison with Example 1 reveals that a lot of amyl alcohol is produced when methanol, 1,4-dioxane, pseudocumene or the like is used instead of glycols.

Comparative Example 4 In Example 1, the amount of propylene glycol used was 17.
The reaction was carried out in the same manner except that the amount of ammonia used was changed from 5 g to 10 g and the amount of ammonia used was changed from 3.5 g to 11 g. At this time, the feed molar ratio of ammonia to 3-cyano-3,5,5-trimethylcyclohexanone was 35.6, and the feed weight ratio of propylene glycol was 3.33. Hydrogen absorption was completed in about 50 minutes. As a result, all the raw materials reacted, and the ratio of each product was 3-aminomethyl-3,5,5-trimethylcyclohexylamine 84.2%, amino alcohol
It was 8.80% and imine bodies 7.00%.

Comparative Example 5 The amount of propylene glycol used in Example 4 was 17.5 g.
Was changed to 5 g in the same manner as above. At this time, the charged molar ratio of ammonia to 3-cyano-3,5,5-trimethylcyclohexanone was 11.3, and the charged weight ratio of propylene glycol was 1.43. Hydrogen absorption was completed in about 50 minutes. As a result, all the raw materials reacted and the ratio of each product was 3-aminomethyl-3,5,5-trimethylcyclohexylamine 85.9%, aminoalcohol form 7.68%, and imine form 6.40%.

From Example 1 and Comparative Example 4, and Example 4 and Comparative Example 5, the molar ratio of the charged ammonia to 3-cyano-3,5,5-trimethylcyclohexanone and the charged weight ratio of glycols were out of the claimed range. Then, it can be seen that there is no inhibitory effect of the aminoalcohol form.

Comparative Example 6 The reaction was carried out in the same manner as in Example 1 except that the reduced nickel-diatomaceous earth catalyst (Ni = 56%) was used in place of the reduced cobalt-zirconium-diatomaceous earth catalyst. Hydrogen absorption was completed in about 50 minutes. As a result, all the raw materials reacted and the ratio of each product was 3-aminomethyl-3,5,5.
-Trimethylcyclohexylamine 52.8%, aminoalcohol 16.5%, and imine 30.6%. Example 1
By comparison with, it is found that the nickel-based catalyst does not suppress the by-product of amino alcohol.

[0025]

According to the method of the present invention, 3-cyano-3,5,5-
In the method of directly reacting trimethylcyclohexanone with ammonia and hydrogen, by-product of amino alcohol is suppressed and 3-aminomethyl-3,5,5-trimethylcyclohexylamine can be obtained in high yield. In the method of the present invention, by-products can be suppressed by the one-step reaction, so that the process can be simplified as compared with the conventional two-step reaction method. In addition, since the by-product of amino alcohol is suppressed,
It becomes easy to separate and recover 3-amino-3,5,5-trimethylcyclohexylamine from the reaction product solution by distillation. Therefore, the method of the present invention is an industrially excellent method.

Front page continuation (72) Inventor Yoshifumi Sato Niigata City, Niigata City, Tayuhama, Niiwari 182, Mitsubishi Gas Chemical Co., Ltd.

Claims (2)

[Claims] 1. 3-Aminomethyl-3,5,5-characterized by reacting 3-cyano-3,5,5-trimethylcyclohexanone with ammonia and hydrogen in the presence of a reduced cobalt catalyst and glycols. Method for producing trimethylcyclohexylamine. 2. The amount of ammonia used relative to 3-cyano-3,5,5-trimethylcyclohexanone in a molar ratio of 1 to 30, and the amount of glycols used in a weight ratio of 2 to 20. Production method.