JPH05112495A - Production of n-alkyl or alkenyl-n-methylamine - Google Patents

Abstract

PURPOSE:To provide a method for producing the corresponding N-alkyl or alkenyl-N-methylamine in high yield by using a higher alcohol and methylamine as starting raw materials. CONSTITUTION:A higher alcohol and methylamine are reacted in a reactional system in the presence of a catalyst of copper-transition metallic element (except Cr) of the fourth period which may contain a group VIII platinum group element while keeping the pressure of the reactional system at atmospheric pressure to 100 atm and the temperature of the reactional system at 100-250 deg.C, introducing hydrogen into the reactional system, removing the formed water of the reaction to the outside of the reactional system, keeping the amount of the methylamine in a waste gas after removing the produced water evacuated to the outside of the reactional system at 5-50vol.% (based on the waste gas) to afford the objective N-alkyl or alkenyl-N-methylamine.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing N-alkyl or alkenyl-N-methylamine. Aliphatic amines made from beef tallow, coconut oil, palm oil, etc. are important intermediates in household and industrial fields.
In particular, aliphatic secondary amines such as N-alkyl or alkenyl-N-methylamine are derived from quaternary ammonium salts and are used in a wide range of applications such as fiber softening agents, antistatic agents and rinse bases. ..

[0002]

As a method for producing an aliphatic secondary amine, a method of producing a fatty acid via a nitrile and a method of producing a higher alcohol by amination have been used. (Kaisho 62-149648).
Among these methods, the former method can produce only a secondary amine having a symmetrical alkyl chain (two kinds of alkyl chains are the same), while the latter method produces a long-chain alcohol and a long-chain first chain amine. A secondary amine having an asymmetric alkyl chain can be obtained by reacting with a primary amine (JP-A-2-202854). However, even when this method is used, efficient production of N-methyl long-chain alkylamine in which one alkyl chain is a methyl group produces a large amount of N, N.
-It has been considered difficult because di-long-chain alkyl-N-methylamine is produced as a by-product.

Therefore, an object of the present invention is to provide a method for producing a corresponding aliphatic secondary amine, that is, N-alkyl or alkenyl-N-methylamine, in a high yield, using a higher alcohol and methylamine as starting materials. To do.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that if a higher alcohol and methylamine are reacted under extremely specific conditions,
The inventors have found that the above problems can be solved and completed the present invention.

That is, the present invention is characterized in that a higher alcohol and methylamine are reacted under the conditions satisfying all of the following (a) to (e): N-alkyl or alkenyl-N-methyl. A method for producing an amine is provided. Condition (a) The reaction is carried out in the presence of a copper-fourth transition metal element (excluding Cr) catalyst which may contain a Group 8 platinum group element. (b) Reaction system of higher alcohol and methylamine (hereinafter,
The reaction is performed under the pressure of the reaction system) from atmospheric pressure to 100 atm. (c) Perform the reaction at a reaction system temperature of 100 ° C to 250 ° C. (d) Hydrogen is introduced into the reaction system to carry out the reaction while removing water produced by the reaction from the reaction system. (e) Gas excluding generated water exhausted outside the reaction system (hereinafter,
5-50% by volume of methylamine in exhaust gas)
The reaction is performed while (to the exhaust gas).

The catalyst used in the present invention is a catalyst composed of a copper-fourth transition metal element (however, excluding Cr) which may contain a Group 8 platinum group element. Here, the fourth period transition metal element is preferably nickel, cobalt,
It is at least one selected from zinc, and zinc is particularly preferable. The Group 8 platinum group element is preferably one or more selected from platinum, palladium and ruthenium, and particularly preferably palladium or ruthenium.

In the catalyst of the present invention, the weight ratio of metal atoms is such that copper / fourth transition metal element (excluding Cr) / eighth
The group platinum group element = 0.1 to 10/1/0 to 0.5 is preferable, and in the range excluding this range, the efficient production of N-alkyl or alkenyl-N-methylamine desired by the present invention is not achieved.

Various forms of catalyst suitable for the present invention can be selected. That is, according to the present invention, copper and the fourth period transition metal element (excluding Cr), or copper and the fourth period transition metal element (excluding Cr) and two or three components of the Group 8 platinum group element are used. When present in the reaction system as a catalyst composition, the effect of interaction between these components is exhibited for the first time, and these compositions have an essential catalytic function,
In reacting a higher alcohol with methylamine and hydrogen, catalytic activity is first expressed by an activation operation. Therefore, the difference in the morphology of the metal before the activation operation and the state in the system after the activation operation is not particularly limited in the present invention, and copper and the fourth period transition metal element (however, Cr ), Or copper, the fourth period transition metal element (excluding Cr), and the catalytic action of the Group 8 platinum group element.

Therefore, the form of the metal suitable for the method of the present invention is as follows: 1) a form in which these metals or their oxides or hydroxides and mixtures thereof are dispersed in a reaction medium. , Or 2) Copper, 4th period transition metal element (provided that
(Excluding Cr), a mixture of elements supported by Group 8 platinum group elements, or copper, a 4th period transition metal element (excluding Cr), and 2 or 3 components of Group 8 platinum group elements , Such that it is uniformly supported on the same carrier and dispersed in the reaction medium, or 3) an aliphatic carboxylate of these metals or a complex stabilized by a suitable ligand. In a reaction medium such that it becomes a metal colloid and becomes a homogeneous system, or 4) in the reaction medium such as 1) to 2) and in a reaction medium such as 3) In any case, such as a mixture with a uniform form in the inside, or a dispersed form before the activation operation and a uniform form after the activation operation, etc. The two or three component metals that become It may be expressed. In the method of the present invention, the more preferable form of the catalyst is to stabilize the catalytic metal, that is, to immobilize the active surface, and from the viewpoint of durability against the catalyst poisoning substance, to uniformly support these component metals on a suitable carrier. What I let you do is good.

When supporting 2 to 3 components of copper, the fourth period transition metal element (excluding Cr) and the Group 8 platinum group element of the present invention on a carrier, a suitable catalyst carrier is a general catalyst carrier. What is used, for example, alumina, silica alumina, magnesia, titania, diatomaceous earth, silica, activated carbon, natural and artificial zeolite, etc. can be used. The amount of the catalyst metal supported on the carrier can be arbitrarily determined, but is usually in the range of 5 to 70% by weight (based on the carrier).

Various methods can be selected for supporting these two or three component metals on the surface of the carrier. in this case,
As a form of the catalyst raw material metal, copper, a fourth period transition metal element (excluding Cr), an oxide of a platinum group 8 group element, a hydroxide or various metal salts can be used. For example,
Copper, fourth period transition metal element (excluding Cr), chloride of Group 8 platinum group element, sulfate, nitrate, acetate, aliphatic carboxylate, or metal complex thereof, for example, copper,
Fourth period transition metal elements (excluding Cr), acetylacetone complexes of Group 8 platinum group elements, dimethylglyoxime complexes, etc. Further, regarding Group 8 platinum group elements, carbonyl complexes, amine complexes, phosphine complexes, etc. Can be used. As a method of supporting on a carrier using these raw material species, for example, a carrier is added to a solution of copper, a fourth period transition metal element (excluding Cr), and an appropriate salt of a Group 8 platinum group element. A method of putting it in, sufficiently impregnating it, and then drying and baking it, or a carrier, copper, an aqueous solution of copper, a fourth period transition metal element (excluding Cr), and an appropriate salt of a Group 8 platinum group element are thoroughly mixed. After that, an alkaline aqueous solution such as sodium carbonate, sodium hydroxide, or ammonia water is added to precipitate the metal salt on the carrier, or copper, a fourth period transition metal element (excluding Cr) is added to the water slurry of the carrier, An aqueous solution of an appropriate salt of a Group 8 platinum group element and an aqueous alkali solution of sodium carbonate, sodium hydroxide, or ammonia water are added simultaneously so that the pH of the slurry becomes constant (eg, pH = 7 constant), and the metal salt is added onto the carrier. To settle Then, it is dried and calcined to prepare a copper-fourth period transition metal element (excluding Cr) catalyst or a copper-fourth period transition metal element (excluding Cr) -group VIII platinum group element catalyst. ..

In this way, only copper or only copper and the fourth period transition metal element (excluding Cr) are supported on the carrier by such a method, and the Group 8 platinum group element is supported before the reaction. It is also effective to add a compound or an aliphatic carboxylic acid salt or complex to form a complex with copper and a fourth period transition metal element (excluding Cr) and a platinum group 8 element. More preferably, the catalyst form is such that 2 or 3 components are uniformly supported on the same carrier. In the present invention, the copper, the fourth period transition metal element (excluding Cr), and the Group 8 platinum group element 2
The three components are essentially essential.

Examples of the catalyst activation operation in the present invention include reduction operations using a reducing agent such as hydrogen gas, formaldehyde water, and sodium borohydride. In the present invention, the amount of the catalyst used is 0.1-10% by weight.
(Against higher alcohols).

The higher alcohol as a raw material used in the present invention is a linear or branched, saturated or unsaturated aliphatic alcohol having 8 to 36 carbon atoms, such as octyl alcohol, lauryl alcohol, myristyl alcohol, stearyl alcohol, Behenyl alcohol, oleyl alcohol and the like, mixed alcohols thereof, etc., and branched chain alcohols such as Fineoxocol 180, 180N (manufactured by Nissan Kagaku Co., Ltd.), Diadol 18
G (manufactured by Mitsubishi Kasei Co., Ltd.), Dobanol 23-I (manufactured by Mitsubishi Yuka Co., Ltd.) and the like.

In the present invention, it is necessary to introduce hydrogen into the reaction system and carry out the reaction while removing water produced by the reaction outside the reaction system. The method of removing water to the outside of the reaction system may be intermittent or continuous. In the present invention, a catalyst previously reduced with hydrogen gas or the like may be used separately, but the catalyst before reduction is put into the reactor together with the higher alcohol which is a reaction raw material, and the temperature is raised to the reaction temperature while introducing hydrogen gas. The reduction may be performed by heating. Further, the amount of hydrogen to be introduced is 1 to 100 cm ³ / hr against the higher alcohol 1g as a raw material, more preferably 10 to 50 cm ³ /
hr.

Further, in the present invention, the amount of methylamine in the gas excluding the produced water exhausted outside the reaction system (hereinafter referred to as exhaust gas) is 5 to 50% by volume (relative to exhaust gas), preferably 10%. It is important to control to ~ 30% by volume, or else the desired objectives of the invention cannot be achieved. The amount of methylamine in the exhaust gas is determined by gas chromatography.

Further, in the present invention, it is necessary to carry out the reaction at a pressure of the reaction system of atmospheric pressure to 100 atm and a temperature of the reaction system of 100 ° C. to 250 ° C. If the pressure and temperature are outside the above range, the object of the present invention cannot be achieved.

An example of a preferred embodiment of the method of the present invention will be described. A higher alcohol as a raw material and a catalyst are charged in a reaction vessel equipped with a pipe for introducing hydrogen or nitrogen and a rectification column. The catalyst can be charged in any amount, but it is usually within the range of 0.1 to 10% by weight based on the charged alcohol.
When carrying out catalytic reduction in the reaction system, the inside of the reaction system is replaced with nitrogen gas, then the temperature is raised to the reduction temperature while introducing hydrogen, and this temperature is maintained for 0.5 to 3 hours. Reduction is usually 160
Perform at ~ 250 ° C. After the catalytic reduction, the reaction temperature and reaction pressure are set to a predetermined value. The reaction temperature is 100 to 250 ° C, and the reaction pressure is atmospheric pressure to 100 atm. After that, hydrogen is introduced at a constant flow rate. The amount of hydrogen introduced is 1 to 100 cm ³ / hr for 1 g of higher alcohol.

Next, methylamine is introduced to start the reaction. The amount of methylamine introduced is such that the amount of methylamine in the exhaust gas is 5 to 50% by volume. The amount of methylamine in the exhaust gas is determined by gas chromatography. The reaction is monitored by using gas chromatography, and the reaction end point is determined when the remaining amount of the raw material alcohol is within 1%. After completion of the reaction, removal of the catalyst by filtration and purification by distillation are carried out to obtain N-alkyl or alkenyl-N-methylamine.

[0020]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. The methods for preparing the catalysts used in the examples are summarized below.

<Preparation of catalyst> Copper-nickel catalyst (catalyst A), copper-zinc catalyst (catalyst B), copper-zinc-ruthenium catalyst (catalyst C), copper-cobalt-palladium catalyst (supported on a synthetic zeolite) Catalyst D), and copper-nickel-
A platinum catalyst (Catalyst E) was prepared as follows.

(1) Catalyst A A 1-liter flask was charged with synthetic zeolite, and then copper nitrate and nickel nitrate were mixed in a weight ratio of each metal atom of Cu: Ni =
It was dissolved in water at a ratio of 4: 1 and heated with stirring. A 10% Na ₂ CO ₃ aqueous solution was gradually added dropwise at 90 ° C. After aging for 1 hour, the precipitate was filtered, washed with water, dried at 100 ° C for 10 hours, and then calcined at 600 ° C for 3 hours. The amount of the obtained metal oxide supported on the carrier was 50% by weight.

(2) Catalyst B Titania was charged into a 1-liter flask, and then copper nitrate and zinc nitrate were dissolved in water so that the weight ratio of each metal atom was Cu: Zn = 5: 1, and the mixture was stirred. While raising the temperature. 10 at 90 ° C
% Na ₂ CO ₃ aqueous solution was gradually added dropwise. After aging for 1 hour,
The precipitate is filtered, washed with water, dried at 100 ° C for 10 hours, then 600 ° C.
It was baked for 3 hours. The amount of the obtained metal oxide supported on the carrier was 50% by weight.

(3) Catalyst C A synthetic zeolitic was charged into a 1-liter flask, and then copper nitrate, zinc nitrate, and ruthenium chloride were mixed so that the weight ratio of each metal atom was Cu: Zn: Ru = 4: 1: 0.01. Was dissolved in water and heated with stirring. A 10% Na ₂ CO ₃ aqueous solution was gradually added dropwise at 90 ° C. After aging for 1 hour, the precipitate was filtered, washed with water, dried at 100 ° C for 9 hours, and then calcined at 600 ° C for 1 hour. The amount of the obtained metal oxide supported on the carrier was 50% by weight.

(4) Catalyst D A 1 liter flask was charged with alumina, and then copper nitrate, cobalt nitrate and palladium chloride were mixed so that the weight ratio of each metal atom was Cu: Co: Pd = 2: 1: 0.1. It was dissolved in water and heated to 90 ° C. with stirring under reduced pressure to evaporate the water. Then, it baked at 400 degreeC for 3 hours. The amount of the obtained metal oxide supported on the carrier was 20% by weight.

(5) Catalyst E A liter flask was charged with diatomaceous earth, and then copper nitrate, nickel nitrate and platinum chloride were added in a weight ratio of each metal atom.
Dissolve in water so that Cu: Ni: Pt = 9: 1: 0.001,
The temperature was raised to 90 ° C. with stirring under reduced pressure to evaporate the water. Then, it was baked at 400 ° C. for 3 hours. The amount of the obtained metal oxide supported on the carrier was 20% by weight.

Example 1 and Comparative Example 1 In a 2-liter separable flask, 1200 g of stearyl alcohol (Ka-lcohl-80 manufactured by Kao Corporation) and 6 g of catalyst A were placed.
(0.5% by weight of raw material alcohol) was charged, the system was replaced with nitrogen while stirring, and the temperature rise was started. When the temperature reached 100 ° C, hydrogen gas was blown into the system at a flow rate of 40 liters / hr using a flow meter to raise the temperature to 190 ° C. At this temperature, methylamine gas is discharged and
The reaction was started by introducing the solution so that the volume of the solution would be%. The reaction was carried out under normal pressure until the residual amount of the raw material alcohol became 1% by weight or less. The residual amount of alcohol and the composition of the reaction-completed product were analyzed by gas chromatography. As a result, the desired secondary amine (N-methylstearylamine)
Was obtained in a yield of 85%.

Further, as Comparative Example 1, the same procedure as in Example 1 was carried out except that a Cu-Cr catalyst (manufactured by JGC Chemical Co., Ltd.) was used.
As a result, N-methylstearylamine was obtained in a yield of 51%.

Examples 2 to 5 and Comparative Example 2 Example 2 was conducted except that a branched alcohol (manufactured by Mitsubishi Kasei Co., Ltd., Diadol 18G) was used as a raw material, a reaction temperature was 210 ° C., and catalysts B to E were used as catalysts. The procedure was as in Example 1. Further, as Comparative Example 2, N-methylalkylamine was synthesized by using catalyst C and introducing methylamine at a constant flow rate of 40 l / hr (the amount of methylamine in the exhaust gas was 5 to 90% by weight). The results are shown in Table 1. The structure of Diadol 18G is as shown in the following formula (I).

[0030]

[Chemical 1]

[0031]

[Table 1]

(Note) * 1: The yield is less than 100% because it is a by-product of N, N-di long-chain alkyl-N-methylamine.

As a result, it can be seen that N-methylalkylamine can be produced in high yield by using this production method.

Examples 6 to 8 Fineoxochol 180N (manufactured by Nissan Chemical Co., Ltd.), Dobanol 23-I (manufactured by Mitsubishi Petrochemical Co., Ltd.), Calcol 20
(Manufactured by Kao Corporation) was used as a raw material, and the reaction was carried out in the same manner as in Example 1 except that the amount of methylamine in the exhaust gas was changed to the value shown in Table 2 by using catalyst C. The synthesis was carried out. The results are shown in Table 2. The structure of fine oxochol 180N is as shown in the following formula (II), the structure of dovanol 23-I is as shown in the following formula (III), and the structure of calcol 20 is shown in the following formula (IV). On the street.

[0035]

[Chemical 2]

(In the formula, R ¹ is an alkyl group having 1 to 5 carbon atoms,
R ² represents an alkyl group having 5 to 10 carbon atoms, and the total carbon number of R ¹ and R ² is 10 to 11. ) N-C ₁₂ H ₂₅ OH (IV)

[0037]

[Table 2]

(Note) * 1: The yield is less than 100% because it is a by-product of N, N-di long-chain alkyl-N-methylamine.

From the above results, it was found that N-methylalkylamine can be obtained in high yield by using the synthetic method of the present invention.

[0040]

According to the production method of the present invention, N-alkyl or alkenyl-N-methylamine can be provided very efficiently.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C07C 211/20 6917-4H // C07B 61/00 300

Claims (3)

[Claims] 1. An N-alkyl or alkenyl-N, characterized in that a higher alcohol and methylamine are reacted under conditions satisfying all of the following (a) to (e):
-A method for producing methylamine. Condition (a) The reaction is carried out in the presence of a copper-fourth transition metal element (excluding Cr) catalyst which may contain a Group 8 platinum group element. (b) Reaction system of higher alcohol and methylamine (hereinafter,
The reaction is performed under the pressure of the reaction system) from atmospheric pressure to 100 atm. (c) Perform the reaction at a reaction system temperature of 100 ° C to 250 ° C. (d) Hydrogen is introduced into the reaction system to carry out the reaction while removing water produced by the reaction from the reaction system. (e) Gas excluding generated water exhausted outside the reaction system (hereinafter,
5-50% by volume of methylamine in exhaust gas)
The reaction is performed while (to the exhaust gas). 2. The catalyst of condition (a), wherein the weight ratio of metal atoms is copper / the fourth transition metal element (excluding Cr) / the Group 8 platinum group element = 0.1 to 10/1/0. 2. The N-alkyl or alkenyl-N- according to claim 1, which is a catalyst of .about.0.5.
Method for producing methylamine. 3. The method for producing an N-alkyl or alkenyl-N-methylamine according to claim 1, wherein the fourth period transition metal element is zinc and the Group 8 platinum group element is ruthenium or palladium.