JP3127480B2 - Method for producing aliphatic tertiary amine and surfactant - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing an aliphatic tertiary amine and a surfactant derived from the aliphatic tertiary amine produced by the method.

[0002]

2. Description of the Related Art Long-chain aliphatic tertiary amines, specifically,
Di long chain alkyl (alkenyl) mono short chain alkyl amines or tri long chain alkyl (alkenyl) amines are nonionic, amphoteric and cationic surfactants such as amine oxides, amine salts, quaternary ammonium salts and aminobetaines. These surfactants are important compounds as raw materials for these products, and these surfactants are used in a wide range of fields such as dyeing assistants, hair rinse agents, textile softeners, antistatic agents, bactericides, and emulsifiers.

When these surfactants are used as components of cosmetics, cosmetics and industrial products, particularly when used as components of cosmetics and cosmetics, they are required to be more colorless and odorless. Further, it is required that the heating stability does not change with time. If the hue is poor, a large amount of colorant is required, and it is difficult to obtain a desired color tone. In addition, despite the tendency to reduce the amount of perfume recently, if the odor or off-flavor is strong, there is a drawback that the perfume cannot be perfumed unless a large amount of perfume is used.

[0004] As a typical method for producing a long-chain aliphatic tertiary amine, a method in which a fatty acid and ammonia are used as starting materials and via a nitrile (eg, Oil Chemistry , 28 , (6) 379 (197)
9), US 2,355,356, US 2,784,232, GB 759,291,
Hereinafter, it is referred to as “nitrile method”. However, in this case, the product has disadvantages such as remaining of a nitrile odor and easy coloring.

On the other hand, as a method capable of solving the above problems, there is a method of directly producing a target product from an aliphatic alcohol and ammonia or an aliphatic primary amine (hereinafter, referred to as a "direct method"). This method has a simple manufacturing process,
Various studies have been made on the merits of having an advantage such as low odor of the product, and a copper-based catalyst has been used as a kind of reaction catalyst.

[0006] In the aliphatic tertiary amine produced by the conventional method, a metal component derived from the applied copper-based catalyst is often dissolved. This metal component is an aliphatic third
Surfactants that are amines and their derivatives, such as the corresponding quaternary ammonium salts, reduce the stability of the heated hue and the hue over time, and also promote oxidation deterioration,
It is desirable that it be removed as much as possible.
m or less).

[0007] However, for a long-chain aliphatic tertiary amine having a high boiling point, to which a means such as distillation, which is a general-purpose purification means, cannot be applied, there is no suitable alternative purification method, and the purification becomes insufficient. Surfactants derived therefrom are colored or have an odor, and improvement of these has been strongly desired.

[0008] Attempts have been made to prevent the elution of catalytic metals. For example, Japanese Patent Application Laid-Open No. 61-60636 discloses a mixed catalyst system comprising a copper compound and a tin compound containing no carrier. In Japanese Patent Application Laid-Open No. 64-13060, a mixed catalyst system comprising copper (copper oxide) and zinc (zinc oxide) alkaline earth metal base is proposed as a catalyst.

As described above, it is considered significant to search for a new catalyst system that is effective for the reaction and in which metal elution is suppressed, but on the other hand, when the industrial aspect is taken into consideration, special catalysts are considered. It is preferable to use a commonly used copper-based catalyst, for example, a copper-chromite-based catalyst, without being limited to a particular catalyst system, in order to establish a general-purpose technique. However, metal elution is remarkable in the catalyst system.

[0010]

The inventors of the present invention have conducted intensive studies in order to solve such a trade-off problem. As a result, not only special catalysts but also general copper-based catalysts have been developed. By controlling the reaction conditions such as the partial pressure of ammonia or an aliphatic primary amine, (1) the elution of the metal derived from the copper-based catalyst can be extremely suppressed, and the oxidation stability can be significantly improved; 2) Various surfactants derived from such aliphatic tertiary amines were found to have improved odor, hue, and stability over time, and the present invention was completed based on such findings.

That is, the present invention is intended to prevent the elution of copper derived from a copper-based catalyst under general-purpose and industrially advantageous conditions, and to provide a high-purity, high-quality aliphatic high-quality aliphatic oxidant. It is an object of the present invention to provide a novel and useful method by which a tertiary amine can be produced, and a high-quality surfactant derived from an aliphatic tertiary amine prepared by such a method.

[0012]

According to the present invention, there is provided an aliphatic third compound according to the present invention.
The method for producing an amine is a method of producing an aliphatic alcohol having 8 to 36 carbon atoms and ammonia or an aliphatic primary amine having 1 to 3 carbon atoms (hereinafter, collectively referred to as “raw material amine”) under a stream of hydrogen to produce water. In producing the aliphatic tertiary amine represented by the general formula (I) by performing a heat reaction while removing, copper-chromite, copper-zinc oxide, copper-molybdenum oxide, copper-tungsten oxide, One or more copper catalysts selected from copper-nickel oxide, copper-chromium-zinc oxide, copper oxide and barium modified, manganese modified, cobalt modified and Raney copper of these oxides And controlling the hydrogen partial pressure to 6 to 100 atm and the raw material amine partial pressure to 0.1 atm or less.

Wherein R ¹ and R ² are the same or different and each represent an alkyl group or an alkenyl group having 8 to 36 carbon atoms. R ³
Represents an alkyl group having 1 to 3 carbon atoms or an alkyl group or alkenyl group having 8 to 36 carbon atoms. ]

The starting alcohol used in the present invention is a linear or branched saturated or unsaturated aliphatic alcohol having 8 to 36 carbon atoms. Specifically, octyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, oleyl alcohol, stearyl alcohol, behenyl alcohol, erucyl alcohol, 2-hexyl decanol, 2-isoheptyl isoundecanol, 2-octyl dodecanol, 2-octyl alcohol
Various alcohols such as decyltetradecanol, 2-cetylstearyl alcohol, mixed alcohols thereof, Ziegler alcohol obtained by Ziegler method, and oxo alcohol obtained by oxo synthesis are exemplified. The polyether alcohol, for example, the alkyl group (or alkenyl group) has 8 to 36 carbon atoms, and the oxyalkylene group (2 to 4 carbon atoms) has 1 to 20 additional moles.
Polyoxyalkylene alkyl (or alkenyl) ethers and the like can also be used.

The aliphatic primary amine to be reacted with these starting alcohols is a monoalkylamine having an alkyl group having 1 to 3 carbon atoms, and monomethylamine is particularly preferred.

The amount of the starting amine to be applied is selected from aliphatic primary
In the case of an amine, the amount is preferably at least 0.4 times the mole of the starting alcohol, and if the amount is at least 0.5 times the mole, the reaction can be completed. At most 0.7 times the mole is not required. In the case of ammonia, the amount is about 0.3 to 0.4 times the mole of the raw material alcohol.

The copper catalyst used in the present invention includes copper-chromite, copper-zinc oxide, copper-molybdenum oxide, copper-tungsten oxide, copper-nickel oxide, copper-chromium-zinc oxide, Copper oxide and one or more catalyst systems selected from barium-modified, manganese-modified, cobalt-modified and Raney copper of these oxides are exemplified.

In general, the catalyst is often used by being supported on a carrier such as alumina, silica-alumina, or zeolite for the purpose of expanding the surface area and preventing sintering. However, with respect to the method of the present invention, the dissolution of copper metal into the tertiary amine is promoted by these carrier substances, and the tendency of oxidative stability to decrease is recognized. Systems are preferred.

The amount of the copper-based catalyst to be added is usually 0.5 to 10% by weight, preferably 1 to 10% by weight, based on the starting alcohol.
It may be appropriately selected within a range of about 5% by weight according to a desired reaction rate.

The hydrogen introduced during the reaction is necessary for activating the copper-based catalyst and promoting removal of generated water. The hydrogen gas used here may partially contain nitrogen, carbon dioxide or other inert gas.

Conventionally, the reaction pressure is suitably about atmospheric pressure, and the reaction in a pressurized system makes it difficult to distill off the produced water.
It has been disadvantageous because of an increase in by-products. However, regardless of the degree of conversion of the raw material alcohol, the partial pressure of the raw material amine is controlled to 0.1 atm or less, more preferably 0.05 atm or less, and the hydrogen partial pressure is set to 6 to 100 atm throughout the reaction steps. By controlling the pressure to preferably about 8 to 50 atm, it is possible to reduce undesirable by-products (for example, condensates of aldehydes or by-products generated by the alkyl group exchange reaction or hydrolysis of amines), The content of copper dissolved in the product can be significantly suppressed.

When the partial pressure of hydrogen is less than 6 atm, even if the partial pressure of the starting amine is kept at 0.1 atm or less, the amount of by-products increases and the purity of the aliphatic tertiary amine decreases.
The amount of copper dissolved in the tertiary amine increases rapidly.
When a hydrogen partial pressure exceeding 100 atm is applied,
Moreover, it requires special pressure-resistant equipment, which is economically disadvantageous.

The control of each partial pressure of the hydrogen gas and the raw material amine can be easily performed by appropriately selecting the respective supply speeds using an appropriate control valve. The method for supplying the raw material amine may be intermittent or continuous.

The amount of hydrogen gas introduced is an important factor in determining the success or failure of an industrial process, such as the amount of hydrogen consumed, thermal energy, and, if the gas is circulated, the gas circulation capacity. That is, in order to suppress side reactions, increase the purity of the aliphatic tertiary amine, and further reduce the dissolution of copper in the tertiary amine, it is desirable to introduce a large amount of hydrogen gas. In addition, the equipment is enormous, which is disadvantageous in terms of energy. From this point of view, the amount of hydrogen gas introduced in the method of the present invention is usually 5 to 150 l in terms of normal temperature under the employed pressure per mole of raw material alcohol.
/ Hour, preferably about 10 to 100 l / hour. At a rate of less than 5 l / hour, the generated water is less likely to escape from the reaction system, the amount of copper dissolved in the tertiary amine increases, and the purity of the target tertiary amine tends to decrease. Even if introduced over 150 l / h, there is no particular significant difference, which is economically disadvantageous.

The reaction temperature is about 160-260 ° C, preferably about 190-240 ° C. The reaction temperature only affects the reaction rate, and has little effect on the purity and yield of the tertiary amine and the dissolution of copper in the tertiary amine.

Hereinafter, the manufacturing method according to the present invention will be specifically exemplified. An aliphatic primary alcohol and copper were placed in an autoclave equipped with a magnetic stirrer equipped with a hydrogen gas inlet and a raw material amine inlet at the lower part of the reactor, and a hydrogen gas, product water and excess raw material amine at the upper part of the reactor. After charging the system catalyst and replacing the inside of the system with an inert gas such as nitrogen gas, hydrogen gas is introduced into the reaction mixture, and stirred while controlling the inside of the reaction system under a predetermined pressure using a control valve. While heating.
When the temperature reaches the predetermined temperature, the supply of the raw material amine is started. During the reaction, the supply of the starting amine is controlled so that the partial pressure of the starting amine is always 0.1 atmosphere or less.

The vapor of hydrogen gas, produced water, unreacted raw material amine and the like discharged from the outlet of the reactor is cooled and separated into a gaseous substance containing hydrogen as a main component and a liquid substance. The raw material amine partial pressure can be determined by measuring the raw material amine concentration in the gaseous substance by gas chromatography, neutralization titration, ultraviolet absorption measurement, or the like.

The liquid is separated to remove the aqueous phase, and the oil is returned to the reaction system. The gaseous substance can be reacted while being discharged out of the system. However, it is preferable to return the gaseous substance to the reaction system by a circulator and use it repeatedly, since the consumption of the raw material amine and hydrogen gas can be reduced. In this case, the circulating gas is
It can be used until the reaction is completed without any special purification treatment, purging part of the circulating gas,
There is almost no need to supplement with new hydrogen.

The catalyst is usually reduced during the temperature rise and becomes active. However, when a high temperature is required for the reduction, it is convenient to perform a reduction treatment in advance before use.

After the reaction is completed, the reactants are removed from the autoclave and the catalyst is filtered off. Next, low-boiling substances are removed by distillation under reduced pressure.

The method of the present invention can be applied not only to a batch type but also to a continuous reaction. For example, a gas-liquid co-current method of supplying raw material alcohol, raw material amine, hydrogen gas and a catalyst from the lower part to a vertically elongated multi-stage reactor, or supplying raw material alcohol and a catalyst from the upper part and hydrogen gas and a raw material amine from the lower part A gas-liquid countercurrent method or the like can be adopted.

The thus obtained high-purity aliphatic tertiary amine which is almost colorless and transparent and in which the dissolution of copper metal is suppressed, can be used for various types of surfactants such as nonionic surfactants, amphoteric surfactants and cationic surfactants. It is effective as a raw material for activators.

Here, the nonionic surfactant is dialkylmethylamine oxide, and the amphoteric surfactant is dialkylmethylaminoacetate betaine, dialkyl-N- (2-hydroxy-3-sulfopropyl).
Examples of ammonium and cationic surfactants include dialkyldimethylammonium halide, dialkylmethylbenzylammonium halide, and dialkylmethylammonium ethosulfate.

These surfactants can be prepared by a usual method. This preparation is usually in the form of an aqueous solution or solid, but if necessary, a solvent such as ethanol or isopropyl alcohol can be used.

The surfactant thus obtained comprises a softener,
Rinsing agent, conditioning agent, cleaning agent, fiber refining agent, dyeing aid, antistatic agent, bactericide, emulsifying / dispersing agent, etc.
Used in a wide range of fields.

The surfactant may be, if necessary, other known nonionic surfactants (eg, polyoxyalkylene alkyl ethers, higher fatty acid alkanolamides, etc.), and anionic surfactants (eg, soaps, alkyl sulfates). Ester salts, α-sulfofatty acid ester salts, monoalkyl phosphates, etc.) and amphoteric surfactants (eg, alkyl amide betaines) can be used in combination.

If necessary, dyes, fragrances, builders,
Preservatives, chelating agents, buffers, corrosion inhibitors and the like can be appropriately selected and blended depending on the use.

[0037]

The present invention will be described in detail below with reference to examples. The properties of the aliphatic tertiary amine prepared in each example were measured and evaluated by the following methods. Copper content (ppm) : Determined by atomic absorption spectrometry. Hue : Hue (APHA) is measured by a colorimetric method. Heating hue : 50 g of the test substance was placed in a 100 ml beaker,
It is left at 100 ° C. for 3 hours in the air, and the hue at that time is measured and evaluated by a colorimetric method (APHA). Odor : Determined by panelists. Hue stability over time : The test article was left at 50 ° C. for 3 months,
The hue change (initial hue and temporal hue) at that time is visually observed.

Example 1 A 500 ml autoclave equipped with a magnetic stirrer equipped with a hydrogen gas inlet and a monomethylamine inlet at the bottom of the reactor and hydrogen, product water and excess raw material amine at the top of the reactor was provided. After charging 186 g (1 mol) of dodecyl alcohol and 3.7 g of a copper-chromite catalyst containing no carrier, replacing the inside of the system with nitrogen gas, introducing hydrogen gas into the reaction product at a rate of 20 l / hour, The temperature was raised while stirring under the condition of a partial pressure of 10 atm. The temperature in the system is 130
When the temperature reached ° C, the supply of monomethylamine was started.
The supply of monomethylamine during the reaction was performed while controlling the partial pressure of monomethylamine in the extracted gas to be 0.0005 to 0.05 atm. The gaseous matter discharged from the outlet of the reactor was cooled and separated into gas and liquid, and the gaseous matter was circulated to the reaction system. The oil layer in the liquid was also returned to the reaction system.
The reaction was carried out for about 2.5 hours after the temperature of the reactor reached 220 ° C. to prepare monomethyldidodecylamine. The alcohol conversion of the reaction product was 99.2%, and the amount of monomethylamine used during this period was 0.53 mol. The hydrogen gas supplemented only the amount consumed for the reduction of the catalyst. The catalyst was separated from the reaction product by filtration and distilled under reduced pressure to remove a small amount of low-boiling amine and the like. As a result of analyzing the composition of the obtained reaction product by gas chromatography, the purity of monomethyldilaurylamine was 98.
5% and its yield (relative to the starting alcohol, hereinafter the same)
Was 96.2%. The hue of the reaction product is 10,
The copper content was 0.05 ppm. The heating hue was 10.

Example 2 Using 200 g (0.74 mol) of stearyl alcohol and 4.0 g of a carrier-free copper-chromite catalyst, the hydrogen partial pressure was controlled at 8 atm, and hydrogen gas was supplied at a rate of 15 l / hour. A monomethyldistearylamine was prepared in the same manner as in Example 1 except for the introduction. As a result, purity 98.7%
Was obtained in a yield of 95.9%. The hue of the reaction product was 10, and the copper content was 0.08 ppm. The heating hue was 10.

Example 3 Monomethyldistearylamine was prepared in the same manner as in Example 2 except that the hydrogen partial pressure was controlled at 50 atm and hydrogen gas was introduced at a rate of 30 l / hour. As a result, purity 98.
4% of the desired product was obtained in a yield of 96.4%. The color of the reaction product was 10, and the copper content was 0.1 ppm. The heating hue was 10.

Example 4 Monomethyldistearylamine was prepared in the same manner as in Example 2 except that the hydrogen partial pressure was controlled at 100 atm and hydrogen gas was introduced at a rate of 50 l / hour. The purity was 97.1.
% Of the desired product was obtained in a yield of 95.4%. The hue of the reaction product was 10, and the copper content was 0.4 ppm. or,
The heating hue was 20.

Example 5 200 g (1.54 mol) of octyl alcohol and 4.0 g of a carrier-free copper-chromite-barium modified catalyst
A monomethyldioctylamine was prepared in the same manner as in Example 1 except for using. As a result, the desired product having a purity of 98.1% was obtained in a yield of 95.2%. The hue of the reaction product was 10, and the copper content was 0.04 ppm. The heating hue was 10.

Example 6 200 g (0.93 mol) of myristyl alcohol and a carrier-free copper-chromite-manganese modified catalyst 4.0
Monomethyldimyristylamine was prepared in the same manner as in Example 1 except that g was used. As a result, the target product having a purity of 98.2% was obtained in a yield of 96.0%. The hue of the reaction product was 10, and the copper content was 0.07 ppm. The heating hue was 10.

Example 7 Monomethyldistearylamine was prepared in the same manner as in Example 1 except that 200 g (0.74 mol) of stearyl alcohol and 4.0 g of a copper-zinc oxide catalyst containing no carrier were used. As a result, 95.3% of the target product was 95.3% pure.
% Yield. The hue of the reaction product was 10, and the copper content was 0.05 ppm. The heating hue was 10.

Example 8 Example 1 except that 200 g (0.61 mol) of behenyl alcohol and 4.0 g of a copper oxide catalyst containing no carrier were used.
Monomethyl dibehenylamine was prepared in the same manner as described above.
As a result, the desired product having a purity of 98.3% was obtained in a yield of 95.7%. The reaction product has a hue of 10 and a copper content of 0.1.
It was 0 ppm. The heating hue was 10.

Example 9 200 g of hydrogenated tallow alcohol and 4.0 g of Raney copper catalyst
A monomethyldihydrogenated tallow alkylamine was prepared in the same manner as in Example 1 except for using. As a result, the purity was 97.8.
% Of the desired product in a yield of 95.1%. The hue of the reaction product was 10, and the copper content was 0.50 ppm. The heating hue was 10.

Example 10 Example 1 was repeated except that 200 g (1.54 mol) of octyl alcohol and 4.0 g of a copper chromite catalyst containing no carrier were used and ammonia was used instead of monomethylamine.
The reaction was carried out for 5 hours in the same manner as described above to prepare trioctylamine. The amount of ammonia used during this period was 27 g.
As a result, the conversion of octyl alcohol was 99.2%,
The yield of the desired product was 93.5% and its purity was 96.2%. The reaction product had a hue of 10 and a copper content of 0.1.
It was 05 ppm. The heating hue was 20.

Example 11 Monomethyl distearylamine was prepared in the same manner as in Example 2 except that 4.0 g of a 50% supported copper-zinc oxide / zeolite catalyst was used as a catalyst. As a result, purity 9
7.5% of the desired product is obtained in a yield of 95.0%. The content of copper in this reaction product was 5 ppm. The heating hue was 30.

EXAMPLE 12 Monomethyldi (2-methyl-2- (2-methyl)-(2-methyl) (2-methyl) (2-methyl) Octyldodecyl) amine was prepared. As a result, the purity was 97.5.
% Of the desired product in a yield of 80.2%. The hue of the reaction product was 10, and the copper content was 0.05 ppm. The heating hue was 10.

Comparative Example 1 Monomethyldidodecylamine was prepared in the same manner as in Example 1 except that the partial pressure of monomethylamine was 0.2 to 0.5 atm and the reaction time was 1.8 hours. As a result, purity 8
5.5% of the desired product was obtained in a yield of 80.4%. The copper content of the reaction product was 150 ppm. The heating hue was 140.

Comparative Example 2 Monomethyl distearylamine was prepared in the same manner as in Example 2 except that the hydrogen partial pressure was changed to 3 atm. As a result, the desired product having a purity of 91.2% was obtained in a yield of 85.3%. The copper content of the reaction product was 95 ppm. The heating hue was 120.

Comparative Example 3 Monomethyl dibehenylamine was prepared in the same manner as in Comparative Example 1 except that behenyl alcohol was used. The reaction product had a hue of 10, a copper content of 150 ppm, and a heated hue of 1
It was 40.

Example 1 74.1 g (0.2) of the monomethyldilaurylamine obtained in Example 1 (total amine value 152.9, tertiary amine value 151.4) in a 500 ml autoclave equipped with a magnetic stirrer.
Mol), 10 g (0.2 mol) of methyl chloride, 13 g of sodium carbonate (0.6 times mol with respect to the starting amine) and an isopropanol / water mixture (mixing weight ratio = 80/2).
0) 75 g was charged and reacted at 100 ° C. for 3 hours. To remove by-product sodium chloride, 50 g (30% by weight of the reaction crude) of isopropanol was added, followed by filtration. Finally, a tetraalkylammonium-type cationic surfactant of isopropanol / water system (solid content: 80%) Was prepared. The resulting surfactant had a hue of 20, good stability over time (initial hue, no more than 30 hue over time), and good odor (solvent odor).

Example 2 A 1 l four-necked flask equipped with a stirrer, a thermometer and a condenser was charged with 474 g of an aqueous solution containing 74.1 g (0.2 mol) of monomethyldilaurylamine obtained in Example 1, In this, benzyl chloride 26 at 70 ° C for 30 minutes.
g (0.2 mol) were added dropwise. After dropping, 70 ° C
After holding for 3 hours at 98 ° C., the reaction was continued for 2 hours to prepare an aqueous solution of a trialkylbenzylammonium-type cationic surfactant (solid content: 20%). The resulting surfactant had a hue of 15, good stability over time (initial hue 15 and hue over time 20), and good odor (no off-odor).

Example 3 Monomethyl distearylamine obtained in Example 2 (total amine value 105.5, tertiary amine value 104.4) 107.
Except that 5 g (0.2 mol) was applied, the same as in Example 1
An isopropanol / water-based tetraalkylammonium-type cationic surfactant (solid content: 80% by weight) was prepared. The resulting surfactant had a hue of 10 or less, good stability over time (initial hue 10 or less, hue 15 with time), and good odor (solvent odor was recognized).

Example 4 104 g of the monomethyldistearylamine obtained in Example 2 in a four-necked flask equipped with a stirrer, a thermometer and a condenser.
(0.2 mol) and 23.3 g of sodium monochloroacetate (0.2 mol).
2 mol) and 840 g of water, and reacted at 85 ° C. for 8 hours to prepare an aqueous solution of an alkyl betaine-type amphoteric surfactant (solid content: 15% by weight). The hue of the obtained surfactant was 10 or less, the stability with time was good (10 or less initial hue, 10 with time), and the odor was good (no off-odor).

Example 5 166 g of the monomethyldimyristylamine obtained in Example 6 (total amine value: 136, tertiary amine value: 135.4) (0.4 g)
Mol) as a raw material, and an aqueous solution of an alkyl betaine-type amphoteric surfactant (solid content 15% by weight) was prepared in the same manner as in Example 4 . The hue of the obtained surfactant was 10 or less, the stability with time was good (10 or less initial hue, 10 with time), and the odor was good (no off-odor).

Example 6 In the same reactor as in Example 4 , the monomethyl dibehenylamine obtained in Example 8 (total amine value 91.5, tertiary amine value 90.
0) 1137 g of an aqueous solution containing 124.7 g (0.2 mol)
And 21.4 g of 35% aqueous hydrogen peroxide was gradually added dropwise at 90 ° C. for 3 hours. After dropping is completed, 90
The reaction was continued at 4 ° C. for 4 hours. Thereafter, the mixture was neutralized with an alkali to prepare an aqueous solution of an alkylamine oxide type nonionic surfactant (solid content: 10% by weight). The resulting surfactant has a hue of 10 or less and has good stability over time (initial hue 1).
0 or less, time-dependent hue 10), good odor (no off-flavor).

Example 7 Monomethyldi (2-octyldodecylamine) obtained in Example 12 (total amine value 101.1) was prepared in the same reactor as in Example 4 .
2,20 g (0.15 mol) of an aqueous solution containing 85 g (0.15 mol) of tertiary amine value 99.0 were charged, and 19 g (0.15 mol) of benzyl chloride was added dropwise at 70 ° C. for 30 minutes. After completion of the dropwise addition, the mixture was further kept at 70 ° C. for 4 hours,
The temperature was raised to ° C., and the reaction was continued for 2 hours to prepare a trialkylbenzylammonium salt type cationic surfactant aqueous solution (solid content: 10% by weight). The resulting surfactant has a hue of 15 and a good stability over time (initial hue 15, hue 2 over time)
0), good odor (no off-flavor).

Example 8 In the same reactor as in Example 4 , the trioctylamine obtained according to Example 10 (total amine value 158.0, tertiary amine value 1
54.9) Aqueous solution 630 containing 72.4 g (0.2 mol)
Then, 26 g (0.2 mol) of benzyl chloride was added dropwise at 70 ° C. for 30 minutes. After completion of the dropwise addition, the mixture was further maintained at 70 ° C. for 4 hours, and the reaction was continued at 98 ° C. for 2 hours to prepare a trialkylbenzylammonium-type cationic surfactant aqueous solution (solid content: 15%). The resulting surfactant has a hue of 15, and has good stability over time (initial hue 1).
5, hue 25) and good odor (no off-flavor).

Example 9 In the same reactor as in Example 4 , the trioctylamine obtained in Example 10 (total amine value 158.0, tertiary amine value 154.
9) An aqueous solution of an alkyl betaine-type amphoteric surfactant (solid content 15% by weight) was prepared in the same manner as in Example 4 except that 72.4 g (0.2 mol) of the raw material was used. The resulting surfactant had a hue of 10, a good stability over time (initial hue of 10, and a good hue of 15) and good odor (no off-odor).

Example 10 Monomethyldistearylamine (hue 1) prepared by a nitrile method using stearic acid and ammonia as raw materials
50, heavy metal 0.5 ppm, total amine value 110, tertiary amine value 109), except that an isopropanol / water-based tetraalkylammonium-type cationic surfactant (solid content 80% by weight) was used in the same manner as in Example 3. Prepared. The hue of the obtained surfactant was 150, and the stability over time was 15 in the initial hue.
At 0 and a hue of 250, a nitrile smell was recognized in addition to the solvent smell.

Example 11 An aqueous solution of an alkyl betaine-type amphoteric surfactant (solid content: 15% by weight) was prepared in the same manner as in Example 3 except that the monomethyl distearylamine used in Example 10 was applied. The hue of the obtained surfactant was 50, and the stability over time was 50 as the initial hue.
At a hue of 90 over time, a nitrile smell was observed.

Example 12 An aqueous solution of an alkylamine oxide type nonionic surfactant (solid content: 15% by weight) was prepared in the same manner as in Example 6 , except that the monomethyl dibehenylamine obtained in Comparative Example 3 was applied. The resulting surfactant had a hue of 20, and the stability with time was 20 in the initial hue and 70 in the hue, and a slight amine odor was observed.

[0065]

According to the method of the present invention, an aliphatic tertiary amine having high purity and extremely low dissolved metal can be produced under industrially advantageous conditions. Such aliphatic third
By applying amine as a raw material, hue, odor,
Surfactants can be prepared that have dramatically improved stability over time in any of the properties.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI B01J 23/85 B01J 25/00 23/889 C07C 211/08 25/00 A61K 7/00 B C07C 211/08 C // A61K 7 / 00 7/02 A C07B 61/00 300 7/02 C11D 3/30 C07B 61/00 300 B01J 23/74 321X C11D 3/30 23/84 311X (56) References JP-A-2-234 (JP, A) JP-A-64-13060 (JP, A) JP-A-59-222448 (JP, A) JP-A-59-106441 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) ) C07C 209/16 C07C 211/03-211/08 C07B 61/00 300

Claims (1)

(57) [Claims] An aliphatic alcohol having 8 to 36 carbon atoms and ammonia or an aliphatic primary amine having 1 to 3 carbon atoms are heated and reacted under a hydrogen stream while removing generated water to obtain a compound represented by the general formula (1): In producing the aliphatic tertiary amine represented by, copper-chromite, copper-zinc oxide, copper-
Selected from molybdenum oxide, copper-tungsten oxide, copper-nickel oxide, copper-chromium-zinc oxide, copper oxide and barium-modified, manganese-modified, cobalt-modified and Raney copper of these oxides Using one or more copper-based catalysts, the hydrogen partial pressure is set to 6 to 100 atm, and the partial pressure of ammonia or the aliphatic primary amine is set to 0.1.
A method for producing an aliphatic tertiary amine, characterized in that the pressure is controlled to be at most atmospheric pressure. [Wherein, R ¹ and R ² are the same or different and each have 8 to 8 carbon atoms.
36 represents an alkyl group or an alkenyl group. R ³ represents an alkyl group having 1 to 3 carbon atoms or an alkyl group or alkenyl group having 8 to 36 carbon atoms. ]