JPS6011021B2 - Production method of tertiary amine - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a tertiary amine having two corresponding long mirror alkyl groups in high yield by reacting an alcohol with a primary amine.

Alcohols or aldehydes or ketones are reacted with ammonia "primary amines or secondary amines in the presence of a hydrogenation-dehydrogenation catalyst and optionally hydrogen to form the corresponding primary amine, secondary amine or secondary amine. Reactions for converting into tertiary amines are known.

Among these, di-(last chain alkyl) methylamine type tertiary amine obtained by the reaction of a long chain primary alcohol with a primary amine having 1 or 4 carbon atoms, especially monomethylamine, can be converted into methyl chloride or It is an important intermediate because it is converted into a quaternary ammonium compound useful as a fabric softener base by reacting with dimethyl sulfate or the like. In Example 18 in U.S. Pat. No. 3,223,734, hardened beef tallow alcohol and monomethylamine were reacted at normal pressure in the presence of Funey nickel to produce di(hardened tallow alkyl) methylamine, which is the corresponding tertiary amine, at 79.1% % selectivity, but as a result of follow-up testing of this example, when Funehnickel was used as a catalyst, the raw material monomethylamine became significantly unbounded, and as a result, ammonia and dimethylamine were synthesized in large quantities as by-products. These amines and alcohol react to form dimethyl (hardened tallow alkyl), which is a tertiary amine other than the target product.
amines, tri-(hardened tallow alkyl)amines and secondary
It was found that di-(hardened beef tallow alkyl) amine, which is a class amine, was produced in large quantities.

Therefore, the selectivity of Example 18 in US Pat. No. 3,223,734 is higher than the actual value, which is not an industrially satisfactory method. In addition, West German Patent Office No. 2639648 discloses that a primary alcohol and monomethylamine are reacted at normal pressure using a mixture of Raney nickel or Raney cobalt and an inorganic base such as sodium carbonate as a catalyst to react with the corresponding tertiary alcohol. The reaction to obtain amines is described. Such patent publication specification and U.S. Patent No. 322
The essential difference with No. 3734 is that the latter conducts the reaction at a high temperature of about 20,000 °C, whereas the former conducts the reaction at a high temperature of about 100 to 16 °C.
It is to be carried out at a low temperature of 0°C. It is presumed that carrying out the process at this low temperature and using an inorganic base such as sodium carbonate together with Raney nickel or Raney cobalt are intended to prevent disproportionation of monomethylamine as much as possible. However, since the temperature is low, Example 1 of the patent publication specification
In this case, for 744 parts of dodecyl alcohol, 40 parts of Raney nickel as a catalyst and 1 part of sodium carbonate are used, which are extremely large amounts and cannot be said to be practical. As a preferred method, JP-A-52-19604 describes a reaction in which alcohol and monomethylamine are reacted at normal pressure in the presence of copper chromium oxide to obtain the corresponding tertiary amine. For example, in Example 10 of this publication, 500 g of methyldidecylyleamine and 15 g of copper chromium oxide catalyst
From the evening, decanol was continuously introduced into the mixture at 21,000 liters at a normal pressure of 60 t'lh and monomethylamine at a rate of 5 l/h for 5 hours, and then the introduction of monomethylamine was stopped.
Add the calculated amount of decanol and age for 2 hours.

Distillation of the reaction product resulted in a yield of 92.4% and a purity of 98%.
of methyldidecylamine was obtained.

In addition, in Example 11, the reaction between stearyl alcohol and monomethylamine was carried out in the same manner as in Example 10, resulting in 92.4
% yield and purity of 98.5%. However, in the method disclosed in this publication, it is necessary to add the product in advance at the start of the reaction, and it is also necessary to re-add the calculated amount of alcohol during the reaction.
Therefore, the reaction must be stopped midway and the amount of alcohol to be re-added must be calculated, which is very troublesome during operation. Such a complex operation is due above all to the activity and selectivity of the catalyst used. The present inventors have arrived at the present invention as a result of intensive research in order to improve the drawbacks of such conventional methods for producing tertiary amines.

That is, the present invention provides a primary alcohol or a secondary alcohol represented by the following general formula (1) [wherein R, , R2 is H
or represents a C, to C24 saturated or unsaturated alkyl group (
However, the sum of the carbon numbers of R and R2 is 3 or more)] or a polyether alcohol represented by the following general formula (D) or (m) [wherein R,, R2 is the formula (1 ) has the same meaning as

R3 represents H or a methyl group, R4 represents a C8-C,8 saturated or unsaturated alkyl group, and n represents an integer of 1-20. An alcohol selected from the group consisting of the following general formula (W), (wherein R5 represents a C, to C24 saturated or unsaturated alkyl group).

) When producing the corresponding tertiary amine by reacting with the primary aliphatic amine represented by
One or more types of carboxylates or intramolecular complexes of metals selected from copper acetylacetone key bodies as carboxylates of steel or intramolecular bodies of copper, and metal carboxylates or intramolecular complexes selected from Tsukuda, side group elements of the periodic table, manganese, and zinc. } Of one or more carboxylic acids or alkali metal salts or alkali metal salts of carboxylic acids, a mixture consisting of wind, 'B} and {q, or wind and {B) together ■ and { which are carboxylic acid salts
B}, or a mixture consisting of wind and [B}, one of which is a carboxylate and the other is an intramolecular compound, or hydrogen, hydrogen and the formula (W ) with amine or reduced with other reducing agents, and if necessary, the above mixture may include materials commonly used as supports or carriers for catalysts, such as silica gel, alumina, ultrafine anhydrous silica, Hydrogen, hydrogen and formula (W
) or reduced with another reducing agent as a catalyst, the reaction is carried out at 150 to 300 0, and in this case, the primary amine of general formula (W) or the primary amine of general formula (N)
A mixed gas of amine and hydrogen is introduced into liquid alcohol according to the rate of conversion of raw alcohol to amine, so as to avoid excess primary amine as described in detail below.

The reaction water generated at this time is separated and removed from the system, and the unreacted primary amine and unreacted alcohol that exit the system together with the reaction water are recycled and reused.If necessary at the end of the reaction, only hydrogen is recycled. After the reaction product is separated from the catalyst, distillation is performed if necessary, and if necessary, the initial distillate is reused as a raw material. By such a method, the last chain alkyl group is
These tertiary amines can be obtained extremely easily with excellent selectivity. According to the method of the present invention, if necessary, the primary amine may be introduced as a mixed gas with hydrogen into the alcohol and catalyst charged in advance, as in the method of JP-A-52-19604. The process is simple as there is no need to add the product in advance at the start of the reaction or to re-add the calculated amount of alcohol during the reaction.

The origin of this simple operation is the activity and selectivity of the catalyst used in the present invention. That is, in the presence of the catalyst used in the present invention, for example, when the flow rate of the primary amine is within the range of 0.05 to 0.5 mol/hour per mol of alcohol charged, the target product tertiary amine Intermediate of (V) (
The amount of W) is kept at a very low concentration. However,
In the case of the copper chromium oxide catalyst used in the method of Publication No. 2-19604, the amount of intermediate (W) accumulated is large (15%).
Therefore, during the reaction, an amount of alcohol equivalent to the amount of intermediate (W) is added, and this added alcohol is allowed to react with the remaining intermediate (of) to reconvert to the target product (V), increasing the conversion rate. This means that it needs to be made higher. As described above, the catalyst used in the present invention is extremely advantageous in terms of operation as long as the flow rate of the primary amine is controlled. Moreover, according to the method of the present invention, 92
The desired tertiary amine having two long-chain alkyl groups can be synthesized with a yield of ~96%. The reaction can also be carried out batchwise or continuously. That is, the present inventors previously filed a patent application (Patent Application No. 53-30149, Patent Application No. 54-19).
No. 58 (refer to each specification) As a result of further intensive research using a special catalyst, it was possible to efficiently react the alcohols represented by formulas (1) to (m) with the primary amines represented by formula (W). The present invention was achieved by discovering a method for producing the corresponding tertiary amine in a much higher yield than the method described in the above patent application specification.

Therefore, the present invention is disclosed in the existing patent application (Tokubuta 53-30149
This invention is an improvement of the previous invention of Iso (No. 1958 and Tokuiso Sho 54-1958). The essential difference between the present invention and the prior invention is that the feed rate of the primary amine is regulated. That is, the primary amine represented by the formula (W) is introduced in accordance with the conversion rate of the charged alcohol, and the raw material primary amine is prevented as much as possible from being in an excessive state. That is, excess primary amine causes disproportionation of the primary amine itself, creating ammonia and secondary amines. Along with this, tertiary amines and secondary amines other than the target products are produced as by-products. Furthermore, excess primary amine itself becomes a base catalyst, promotes aldol condensation, and increases the non-amine content of the target product. The feedstock primary amine is therefore fed at a rate not exceeding twice the amount that can be consumed in the reaction with the alcohol, preferably at a rate that does not exceed the amount that can be consumed in the reaction until the conversion of alcohol to amine reaches 70%. is introduced into the reaction system at a low feed rate. At this time, the feed rate can be adjusted stepwise and continuously so that the raw material primary amine does not become excessive as the reaction progresses. As mentioned above, the present invention is an improvement of the method for producing di-long-chain alkyl tertiary amines through the reaction of alcohol and primary amine, and the method of the present invention is faster than the amine supply rate carried out in the prior invention. By controlling low ~ di-long chain alkyl 3
The yield of the reaction itself is unexpectedly improved because the grade amine is obtained with very good selectivity, and side reactions such as aldol condensation are suppressed.

(See Comparative Example 1). In the method of the present invention, it is not preferable to supply the primary amine to the reaction system in excess of the amount required for the reaction, especially if the conversion rate from alcohol to tertiary amine after the start of the reaction is 70%. %, it is preferable to introduce into the reaction system in an amount not exceeding the amount necessary for the reaction.

After the conversion rate exceeds 70%, the reaction from alcohol to tertiary amine may have progressed considerably, so there is no problem even if the supply of primary amine exceeds the amount required for the reaction. do not have. Specifically, the feed rate of the primary amine that satisfies these conditions cannot be determined uniformly because it varies depending on the reaction level, but it is possible to achieve a reaction temperature of 150 to 300 pm using the catalyst of the present invention. Under the conditions, the rate of primary amine production is 0.05 per mole of raw alcohol per hour, 0.
．． If the amount is 5 mol, the reaction can proceed while satisfying the above-mentioned conditions. In the most preferred embodiment of the method of the present invention, the primary amine of general formula (W) is introduced into liquid alcohol at a rate commensurate with the conversion rate of the raw alcohol, ie, around the feed rate limit.

Particularly when converting to a tertiary amine by a sequential reaction as in the reaction carried out in the present invention (e.g. ROH + CH3N ratio →
RNH (CH3), RNH (CH3) + ROH → R (
For CH3)), the feed rate of the primary amine is a decisive factor that affects the yield of the target product, and therefore, the feed rate of the primary amine is a decisive factor that affects the yield of the target product. (ROH+(CH3)
Regarding 2NH→RN(CH3)2), it is considered that the flow rate control on the raw material amine side, which is employed in the present invention, cannot be a decisive factor. Although the flow rate control of the primary amine carried out in the present invention varies depending on reaction conditions such as reaction temperature and amount of catalyst added, the feed rate per mole of alcohol charged is generally in the range of 0.05 to 0.5 mole/hour. You can adjust it within. More specifically, for example, the reaction temperature is 220°C,
When the metal purity as a catalyst is 0.03 to 0.2% (based on the charged alcohol), the flow rate is 0.06 to 0.22 mol/hour/1 mol of the charged alcohol during the reaction, and at a constant feed rate. What is necessary is to introduce the raw material primary amine. In this case, the raw material primary ammonium reacts almost completely until the alcohol conversion rate reaches 70 to 90%, and is introduced almost under the control of the supply rate, and is rather insufficient under these conditions. Alternatively, in order to prevent the presence of unreacted primary amine as much as possible by referring to the amount of primary amine in the waste gas, the primary amine supply rate may be adjusted to 0.5 to 0.05 mol/hour/charged alcohol. - It may be reduced stepwise or continuously within the range of 1 mol depending on the alcohol conversion rate. The reason for adopting such a method of controlling the flow rate and introducing the primary amine is that the presence of the reactive amine is presumed to have a great effect on the yield in the case of a sequential reaction like the reaction carried out in the present invention. This is because it will be done. In other words, from the viewpoint of the raw alcohol, there is a competitive reaction between the m raw material primary amine and the {2' intermediate secondary amine, so in order to improve the yield of the desired tertiary amine, it is necessary to It is considered necessary to prevent the presence of primary amines as much as possible and to control the flow rate of primary amines. Therefore, if the reaction is not sequential, but the alcohol is converted to a tertiary amine in one step by reaction with a secondary amine such as dimethylamine, the flow rate restriction of the raw amine is not considered to be particularly important. In the present invention, the reaction proceeds satisfactorily even without introducing hydrogen during the reaction, but it is preferable to introduce hydrogen at a rate of 1 to 500 m/hour per mole of alcohol charged or 1 to 1000 m/hour per 1 kg of charged alcohol. It is better to introduce it at a flow rate.

Further, instead of hydrogen, a mixed gas of nitrogen and hydrogen in any proportion may be used. The mixing ratio of hydrogen and primary amine during the reaction is not particularly important and can be changed arbitrarily, but in the case of a batch reaction, the ratio of primary amine can be changed stepwise or continuously from the beginning to the end of the reaction. It is better to lower it. The wind component is steel acetylacetone complex or copper carboxylate. The carboxylic acid that forms the copper carboxylate may be one that has a carboxyl group in its molecule, even if it is aromatic, branched, or has a straight-chain alkyl group. carboxyl group,
It may have other substituents.

Preferred among these are carboxylic acids having 5 to 36 carbon atoms, which may be natural or synthetic, such as valeric acid, caproic acid, enanthic acid, caprylic acid, belargonic acid, capric acid, undecanoic acid, lauric acid,
Examples include tridecanoic acid, myristic acid, bentadecanoic acid, palmitic acid, margaric acid, stearic acid, arachic acid, behenic acid, oleic acid, and compounds in which two or more carboxyl groups are introduced. The 'B} component used in the present invention is an intramolecular body or carboxylate of a metal selected from blood group elements of the periodic table such as nickel, cobalt, iron, and palladium, manganese, and zinc; The inner flange body is an acetylacetone rust body or a dimethylglyoxime complex, and the carboxylic acid forming the carboxylate is exemplified by the above-mentioned carboxylic acids.

Preferred intramolecular rust bodies and carboxylic acid salts include, for example, nickel acetylacetone complex and nickel stearate. The 'C' component used in the present invention is a carboxylic acid or a carboxylate salt of an alkali metal or alkali metal, and the carboxylic acid has 5 to 5 carbon atoms.
36 carboxylic acids such as capric acid, lauric acid, and stearic acid, and carboxylic acids of alkali metals or alkali metals such as sodium, potassium, magnesium, calcium, and barium. salts, such as barium stearate,
Examples include barium laurate.

Catalysts used for the purpose of the present invention include the above ■ and 'B}
, (C-) A catalyst that combines certain specific components is effective.

That is, the combination of two of the three components above is a combination of the two components of and [B}, and moreover, the combination of the two components of sail and [B}
It is effective only when both are carboxylates, and when one of M and the leg is a carboxylate and the other is an intramolecular ring body; mixtures of other two components are less effective, or It has almost no effect.

Even worse, the third component ' is added to the two components of B-■
, [B}, in the case of a mixture of {q, it may be either a carboxylic acid salt or an intramolecular rust form,
Any combination is effective, and it is more effective than the combination of the two components of legs and (B}.
The catalyst used in the present invention is an apparently uniform catalyst, whereas conventional catalysts are solid catalysts.

Since the catalyst is in the form of a metal, the amount of the catalyst is preferably 100 to 500% of the charged alcohol in terms of metal purity.
The reaction can proceed sufficiently with about 70 melon skin, but
The smaller the amount of catalyst used, the lower the non-amine content in the product. The reaction may be allowed to proceed to the end, or may be stopped at a suitable alcohol conversion rate. Preferably, after the desired calculated amine value of the tertiary amine is reached, if necessary, the reaction is stopped after further treatment with hydrogen alone. After the reaction is terminated, the reaction product is treated with water or an aqueous alkali solution, whereby the catalyst coagulates or becomes a hydroxide and precipitates. The catalyst can also be adsorbed or aggregated using activated carbon or an inorganic or organic flocculant. In the case of activated carbon, the catalyst can be reused by eluting the catalyst adsorbed on the activated carbon with hot alcohol from which dissolved oxygen has been removed in advance. Alternatively, it is also possible to distill the reaction product and use the distillation residue again as a catalyst. After the catalyst is separated by the above method, a distillation operation is performed as necessary. The small amount of initial crab fraction obtained at this time mainly consists of unreacted alcohol and secondary amine as an intermediate for the desired product, and can be reused as a raw material. In particular, when an alcohol with a carbon number of 16 or more is used as a raw material, the boiling point of the target product is high, so it is a good idea to limit the distillation after catalyst separation to the extent of removing the first crab. The purity of the tertiary amine thus obtained is 97-99%,
The non-amine content is 1-3% and consists mainly of aldols and esters. The obtained tertiary amine is converted into the corresponding quaternary ammonium salt by reacting with methyl chloride, dimethyl sulfate, jetyl sulfate, etc. For example, by reacting an alcohol derived from beef tallow with methylamine under the conditions of the present invention, di-(hardened beef tallow alkyl) methylamine can be obtained with a yield of 95% and a purity of 10%. By quaternizing this tertiary ammonium with methyl chloride, a quaternary ammonium compound that can be used as a household softener base can be obtained. Instead of tallow alcohol, synthetic alcohols such as coconut alcohol, palm alcohol, or Ziegler alcohol, which are blended with alcohols having 16 and 18 carbon atoms in an appropriate ratio, can also be used. The alcohol used in the present invention is a primary or secondary alcohol represented by the above general formula (1), a general formula (b) or (
Examples include polyether alcohols represented by m), and more specifically, for example, those shown below can be used.

Primary alcohols include linear or branched saturated or unsaturated natural or synthetic alcohols with 1 or 24 carbon atoms, such as octanol, decanol, dodecanol, tetradecanol, hexadecanol, and octadecanol. , eicosanol, docosanol, tetracosanol, Ziegler alcohol, oxo alcohol, or a mixture thereof.

In addition, examples of secondary alcohols include 2-butanol,
Examples include secondary alcohols such as 2-bentanol, 2-octanol, 3-bentanol, 3-heptanol, and 3-nonanol.

Furthermore, the polyable alcohols of general formulas (D) and (m) include polyoxyethylene alkyl ethers having an alkyl group having 8 to 18 carbon atoms and an oxyalkylene group having an added mole number of 1 to 20; Examples include polyoxypropylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxypropylene alkyl phenyl ether, and the like. As the aliphatic amine to be reacted with these alcohols, primary amines such as methylamine, ethylamine, dodecylamine, and octadecylamine can be used.

In carrying out the present invention, it is possible to improve the catalytic activity by simultaneously using materials that are generally used as catalyst supports or catalysts, such as silica gel, colloidal silica, ultrafine anhydrous silica, alumina, diatomite, and activated carbon. I can do it.

The reaction method of the present invention is quite simple. That is, for example, the catalyst used in the present invention is dissolved in raw alcohol,
It is ready for use after being reduced with hydrogen, a mixture of hydrogen and amines, or other reducing agents at a temperature of 100-200°C. The reduction is very easy and can be completed in a short time during boiling at 100-200°C, and the resulting catalyst cannot be separated by ordinary filtration and is apparently a homogeneous colloidal catalyst. After the catalyst becomes a colloid, the first
grade amine is added to the reaction system. Although the reaction proceeds in the absence of hydrogen, it is preferably carried out in the presence of a small amount of hydrogen. Furthermore, since the catalyst used in the present invention has a reduced catalytic activity due to prolonged contact with water, water produced during the reaction is desirably distilled out of the system continuously. The reaction temperature is 150
The reaction temperature is preferably 180 to 240 qC, preferably 180 to 240 qC, and the reaction pressure can be reduced, but it is preferably carried out at atmospheric pressure or less (gauge pressure), more preferably at normal pressure. The reaction proceeds with the release of reaction water. The present invention will be explained below with reference to Examples.

As a comparative example, a case is shown in which copper chromium oxide and Raney nickel are used as catalysts. Example 1 1 with condenser and separator for separating reaction water
A 000' flask was charged with 300 ml of dodecanol and 3 ml, 0.6 ml, and 0.6 ml of copper stearate, nickel stearate, and barium stearate as catalysts, respectively.

The clarifier was rotated to replace the inside of the system with nitrogen and raise the temperature. 100
When the temperature reached 0.00, hydrogen gas was bubbled into the system at a flow rate of 60 m/hr through a flow meter.

The catalyst was reduced at 160 to 170 qo and became a colloidal catalyst with uniform appearance.

After 40 minutes, the temperature reached 20 pm, hydrogen was added at 30 pm/hour, and monomethylamine was bubbled into the system at 4.2 pm/hour as a mixed gas with hydrogen (monomethylamine concentration 1 ol%).

When the monomethylamine concentration at the reactor inlet and outlet was measured using gas chromatography, it was found that monomethylamine was not detected at the reactor outlet for 3 hours after the start of the reaction, indicating that the reaction was complete. At this time, the monomethylamine molar flow rate was 0.12 mol/hour/1 mol alcohol. 5
After a period of time, the reaction product was treated with hydrogen alone for 1 hour after stopping the introduction of monomethylamine.

The composition of the finished product at this time was as follows. Solaurylmetrilaurylmethytrilaurylthylamine Ruamine Amine 94-6% 0.0%
0.6% Aldol No reaction, Alco
Others 0.9% 0.5% 3.4% (
(Hereinafter, all percentages are by weight) Example 2 Into the same equipment as in Example 1, 300 tons of dodecanol, copper stearate, nickel stearate, and barium stearate were charged for 1 night, 0.2 tons, and 0.2 tons, respectively. .

The catalyst was reduced in the same manner as in Example 1, and 220 qo
The monomethylamine flow rate was gradually decreased as the reaction progressed, with the hydrogen flow rate remaining at 30/hour.

The monomethylamine flow rate program is shown below. The composition of the reaction product after 6 hours was as follows.

Jilawalilme Lawalilmethi Trilawalylthylamine Ruamine Amine 96.5% 0
．． 0% ・1.1% Cape Aldo Unreacted alcohol Other 0.9% 1.0%
After separating the catalyst from the 0.5% reaction product, a distillation operation was performed.

The result was a purity moth with a yield of 95.5%. 6% dilaurylmethylamine was obtained. As a result, the catalyst used in the present invention has a very high activity (the amount of catalyst used is Cu: 0.0%, Ni: 0.0% in terms of metal purity based on the charged alcohol).
0.007%, mother: 0.014%), and the selectivity was found to be high. Example 3 Using the same equipment as in Example 1, copper stearate, nickel stearate, and barium stearate were added at 1.0 liter and 0 liter, respectively, for 300 liters of alcohol derived from beef tallow.
．． Reduction operation was carried out with hydrogen at 60 m/h as in Example 1, with 2 m/h and 0.2 m/m charging.

Upon reaching 220° C., monomethylamine was introduced at a flow rate of 4.0 evening/hour.

The monomethylamine molar flow rate is 0.15 (mol/hour·1 mol alcohol). After 5 hours, the supply of monomethylamine was stopped and the mixture was treated with hydrogen for 1 hour.

Thereafter, when the colloidal catalyst was cooled to 80 qo and 1 tat of 20% sodium hydroxide solution was added, the apparently uniform colloidal catalyst was able to filter out the aggregates. By removing the first fraction of the obtained crude tertiary amine, the hue becomes Gardner 1 or less and the purity is Sat. 0% dialkylmethylamine was obtained with a yield of 94.8%. By quaternizing this tertiary amine with methyl chloride, a quaternary ammonium compound having a hue of Gardner 1 and a residual amine value of 1 or less was obtained. Example 4 Using the same equipment as in Example 1, dodecyl alcohol 300
I prepared dinner.

In Examples 1 to 3, the catalysts were all carboxylic acid salts, but in Example 4, the effects of various catalysts were examined. However, the amount of catalyst added is the same as in Example 2, in terms of metal components, copper is 0.0 mass Mt% and nickel is 0.006 mt% based on the alcohol used.
Fine t% and barium 0.013X% were set. Example 1
Perform reduction treatment with hydrogen at 60〆/hour in the same manner as above, and heat at 220°C.
When hydrogen reached 30 so/hour, methylamine was converted to 4.2
It was introduced at that time. Methylamine molar flow rate is 0.12 (
mole/hour・mole alcohol). The results are summarized in Table 1. Table 1 shows that in the case of dimethyldithiocarbamate containing sulfur, which is a catalyst poison, in the ligand (RUN4), and when the catalyst poison, 'B-, is a mixture of intramolecular complexes, {C
} does not coexist (RUN5), it can be seen that none of them can serve as the catalyst of the present invention. Table 1 Example 5 In the same apparatus as in Example 1, 300 days of ether alcohol prepared by adding 3 moles of ethylene oxide to cetyl alcohol, and 1 night and 0.2 days of steel stearate, nickel stearate, and barium stearate as catalysts were added. ,
0.29 was added, and reduction treatment was performed with hydrogen at 60 〆/hour in the same manner as in Example 1.

When the temperature reached 22 and 0, hydrogen was introduced at 30 m/hr and methylamine was introduced at a flow rate of 4.2 m/hr.

The methylamine molar flow rate is 0.23 (mol/hour·mole alcohol). After 6 hours, the corresponding tertiary amine was obtained with a yield of 91%.

Example 6 In the same equipment as in Example 1, dodecanol 300 hours and copper stearate, nickel stearate, and barium stearate as catalysts were charged for 3 hours, 0.6 hours, and 0.6 hours, respectively, and the rate was 60 Z/hour as in Example 1. Reduction treatment was performed with hydrogen.

When the temperature reached 22 mm, butylamine was added dropwise at a rate of 14 minutes/hour.

The butylamine molar flow rate is 0.12 (mol/hour·mol alcohol). After 8 hours, the corresponding tertiary amine was obtained with a yield of 93%.

Example 7 Into the same reactor as in Example 1, 300 g of alcohol, aldehyde, or ketone were charged, and copper stearate, nickel stearate, and barium stearate were used as catalysts, respectively, at concentrations of 0.1% and 0.0% as metals based on the charged raw materials. .02
%, 0.02%, reaction temperature 210°C, hydrogen gas 3
A mixed gas of 0〆/Hr and monomethylamine gas 42〆'Hr was flowed into the system to carry out a reaction.

The results are shown in Table 2. Table 2 * Portion distilled out of the system during reaction The results clearly show that even when aldehyde or ketone is used as the starting material, it shows the same activity as when alcohol is used as the starting material.

Example 8 Regarding metals other than Ni as the catalyst metal [B} described in the present invention, "carboxylate, acetylacetone rust,
We investigated the activity of a combination catalyst of dimethylglyoxime fins, wind, and [q] for this reaction.

Using the same reactor as in Example 1, 300 g of dodecyl alcohol was charged, (1) stearic acid steel or copper acetylacetone was used as a catalyst, and 0.0 g of metal steel was added to the alcohol.
1% charge, 'C} As catalyst, barium stearisoate as metal, 0.02% charge to alcohol, (
B-The activity was examined by changing the metal type and form of the catalyst (0.02% was used as the catalyst metal). The reaction was carried out at a reaction temperature of 210° C., and a mixed gas of hydrogen 30 min/hr and monomethylamine 4.2 min/hr was introduced into the system.

The results are shown in Table 3. Table 3 As a result, copper carponate and acetylacetone were used as bad catalysts, and cobalt, palladium, iron, manganese, and zinc among the elements of the periodic table group were used as catalysts, and their carboxylates, acetylacetone, and dimethylglyoxime were used as catalysts. It is clear that a combination catalyst of {B}, {B}, and a carboxylate of an alkali metal as a catalyst effectively acts on this reaction.

Example 9 The composition of the catalyst was investigated.

In a reactor similar to Example 1, dodecacyl alcohol 30
Copper stearate as a catalyst, [B] nickel stearate as a catalyst, 0.1% and 0.02% of the alcohol as a catalyst, [C] an alkali metal salt of carboxylic acid as a catalyst, Activity was investigated using alkaline earth metal salts and fatty acids.

The reaction was carried out at a reaction temperature of 210° C. and by a method in which a mixed gas of hydrogen gas at 30 m/hr and monomethylamine gas at 4.2 m/hr was introduced into the system.

The results are shown in Table 4. Table 4 *Amounts added to metals and tercols From this result, potassium stearate is used as a catalyst component as a carboxylate of fatty acids and alkali metals, and barium stearate is a carboxylate of alkali metals. It is clear that it is equally effective in improving activity.

Comparative Example 1 Using the same equipment as in Example 1, copper stearate, nickel stearate, and barium stearate were prepared for 300 hours, 0.6 hours, and 0.6 hours, respectively, to 300 hours of dodecanol, and 60 hours as in Example 1. Reduction operation was carried out with 1/h of hydrogen.

Upon reaching 220°C, the hydrogen flow rate was 30 m/h and the methylamine flow rate was introduced at 80 m/h.

The composition of the reaction product after 5 hours was as follows.

Lauryl methyl lauryl methylamine 52.1% 25.8
% 10.3% Unreacted alcohol Trilaurilamin Other 0.3% 8-5
% 3-0 Son At this time, the molar feed rate of methylamine per mole of alcohol charged is 2.2 moles/hour.

In other words, if the molar feed rate is 2 moles/hour or more and more methylamine than is required for the reaction is introduced into the reaction system, the yield of the tertiary amine having two last-chain alkyl groups will be low. This increases the production of secondary amines and other by-products. Comparative Example 2 Using the same equipment as in Example 1, a steel chromium oxide catalyst was charged to 300 kg of dodecanol for 3 nights, and the temperature was raised to 0° C. under a hydrogen stream of 60 kuna h.

When the temperature reached 220 qo, methylamine was introduced at a flow rate of 4.2/h for 5 hours while hydrogen was kept at 30/h.

The molar flow rate of methylamine is 0.12 (mol/hour·mole alcohol). Furthermore, when the reaction product was treated with hydrogen alone for 1 hour, the composition of the reaction product was as follows. Jirawalyl Methyl Aldols Thylamino
Ruamine 13-1% 30-3% 18
-5% unreacted alcohol trilawalylamine 22-
6% 15.5 omitted. Comparative Example 3 Using the same equipment as in Example 1, a Raney nickel catalyst was charged to 300 m2 of dodecanol for 3 nights, and the temperature was raised to 220°C under a hydrogen flow of 60 m/h.

When the temperature reached 220 qo, methylamine was introduced at a flow rate of 4.2 k'h for 5 hours while hydrogen was being fed at 30 som/h.

The molar flow rate of methylamine is 0.12 (mol/hour·mol alcohol). After further treatment with hydrogen alone for 1 hour, the composition of the reaction product was as follows. Dilawallyl methylamine Rawallyl methylamine 52.0%
2.5% Aldols Unreacted, Alcohol Solaurilamin 0.5% 1.3%
9.7 male trilaurilamin Other 30.6%
3.4 omitted

Claims (1)

[Claims] 1. A primary alcohol or a secondary alcohol represented by the following general formula (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 and R_2 are H or C_1 to C_2_4] Indicates a saturated or unsaturated alkyl group (however, R_1 and R_
The sum of the number of carbon atoms in 2 is 3 or more)] or polyether alcohol represented by the following general formula (II) or (III), ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1
, R_2 have the same meaning as in formula (I). R_3 represents H or a methyl group, R_4 represents C_8 to C_
1_8 saturated or unsaturated alkyl group, n is 1 to 2
Indicates an integer of 0. ] and the following general formula (IV) ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R_5 represents a saturated or unsaturated alkyl group of C_1 to C_2_4.) In producing the corresponding tertiary amine by reacting with the primary aliphatic amine (A
) a copper acetylacetone complex as a copper carboxylate or an intramolecular complex of copper; (B) a group VIII element of the periodic table;
one or more acetylacetone complexes or dimethylglyoxime complexes as a carboxylate or intramolecular complex of a metal selected from manganese and zinc; and (C) a carboxylic acid or an alkali metal salt or alkaline earth metal salt of a carboxylic acid. (A), (B) of one or more of the following:
and (C), or a mixture of (A) and (B), where both (A) and (B) are carboxylates, or a mixture where (A) and (B) are both carboxylates. A mixture of (A) and (B), the other of which is an intramolecular complex, is reduced with hydrogen, a mixture of hydrogen and the amine of formula (IV), or another reducing agent as a catalyst. used, 15
The reaction is carried out at a temperature of 0 to 300°C, and the amine represented by the general formula (IV) is introduced into the reaction system at a feed rate not exceeding twice the amount that can be consumed in the reaction. The third method is characterized in that the produced water is removed from the reaction system.
A method for producing grade amines. 2. The method according to claim 1, wherein the amine is fed at a rate that does not exceed the amount that can be consumed in the reaction until the conversion rate of alcohol to amine reaches 70%. 3. The amine feed rate is 0.00000000000000 per mole of alcohol per hour.
05 to 0.5 mol.