JPS5938221B2 - Method for producing quaternary ammonium salt - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for synthesizing a bis(acylaminoalkyl) type 1 quaternary ammonium salt useful as a cation activator with high purity using an imidazoline derivative as an intermediate.

Quaternary ammonium salts, typified by di-long-chain alkyldimethylammonium salts, are used as cationic activators that are sparingly soluble in water, such as in fiber treatment agents and hair treatment agents.

On the other hand, bis-(acylaminoalkyl)-dialkylammonium salts, which are similar in structure to di-long-chain alkyl-type quaternary ammonium salts, can use fatty acids easily obtained from natural fats and oils directly as raw materials; Compared to di-long-chain alkyl type quaternary ammonium salts that use amines, it is a preferred cationic activator because it can be obtained at a lower cost and with higher purity.

However, until now, there was no known process for industrially producing this bis-(acylaminoalkyl)-dialkylammonium salt, and only a few
No. 375 briefly describes a method for quaternizing a bis-(acylaminoalkyl)-alkylamine obtained by an amidation reaction between a fatty acid and a bis-(acylaminoalkyl)-alkylamine; Because it uses a special triamine as a raw material, it is unsuitable as an industrial production method.

The present inventors have completed the present invention as a result of intensive studies on a method for industrially producing a highly pure bis-(acylaminoalkyl)-dialkylammonium salt.

Bis-(acylaminoalkyl)-dialkylammonium salts can be converted into quaternary ammonium salts directly from secondary amines, as in the case of di-long-chain alkyldimethylammonium salts.

A method for quaternizing a secondary amine in one alkylation reaction is described, for example, in Japanese Patent Publication No. 39-24786. Another widely known method is to carry out an alkylation reaction twice to convert a secondary amine into a tertiary amine and then into a quaternary ammonium salt. On the other hand, it is also well known that imidazoline derivatives can be obtained by reacting fatty acids with diethylenetriamine or hydroxyethylethylenediamine via secondary amines having an acylaminoalkyl group.

Furthermore, it is known that a secondary amine having the original amide bond can be obtained by hydrolyzing an imidazoline derivative. That is, bis-(acylaminoalkyl)-amine, which is an intermediate necessary to obtain the final product, is produced by the reaction of an acyl compound such as a fatty acid with a dialkylene triamine such as diethylenetriamine. be.

However, this reaction does not allow the required diamide to be obtained in high purity. This is because, in addition to the required diamide, this reaction also produces monoamides, imidazoline derivatives, triamides, and the like. In particular, when an acyl compound and a dialkylene triamine are reacted at a 2:1 (molar ratio), which is the stoichiometric equivalent for producing a diamide, to completely produce only diamide, most of the acyl compounds are in the amide type. It becomes an imidazoline derivative. In that case, it would be possible to generate the necessary diamide by hydrolyzing the amide-type imidazoline derivatives that are produced in large quantities in this reaction, but this is not easy.

This is because, in this hydrolysis reaction, the amide-type imidazoline derivative is hydrolyzed (ring-opened) to become diamide, but in addition to this ring-opening reaction of the imidazoline derivative, diamide is further hydrolyzed to monoamide and acyl compound. This is because the reactions naturally proceed at the same time. Therefore, if the imidazoline derivative is completely hydrolyzed (ring-opened), monoamide and acyl compounds will be produced as by-products, and as a result, the purity of the final product, bis-(acylaminoalkyl)-dialkylammonium salt, will decrease. I end up doing it. Due to these circumstances, a method for producing a highly pure bis-(acylaminoalkyl)-dialkylammonium salt using a dialkylene triamine and an acyl compound as raw materials has not been studied until now.

This invention was made in view of the above circumstances, and its purpose is to provide a method for producing highly purified bis-(acylaminoalkyl)-dialkylammonium salts from dianolekylene triamine and acyl compounds. It is to provide.

That is, the present invention provides the general formula R1-C-Y (where R
1 is a linear or branched aliphatic hydrocarbon group having 7 to 26 carbon atoms, and may be saturated or unsaturated.

Y is 0H or 0R2, R2 is a lower alkyl group having 1 to 3 carbon atoms), and an acyl compound represented by the general formula (H2N
-R3) 2NH (where R3 is a linear or branched alkylene group having 2 to 3 carbon atoms) is reacted with dialkylene triamine at a molar ratio of 2:1.05 to 1.25, and unreacted Amidation and imidazolination of the acyl compound are performed until the acyl compound is 3% by weight or less and the imidazoline derivative is 75% by weight or more, and then,
For reaction products mainly consisting of imidazoline derivatives,
Hydrolysis is carried out by adding 1 to 5 times the mole of water of the imidazoline derivative until the imidazoline derivative becomes 50% by weight or less, and the product of this hydrolysis is reacted with an alkylating agent to form a compound represented by the following general formula. This is a method for obtaining quaternary ammonium salts. (However, R1 is mentioned above.

R is the same as R1 above. R3 is mentioned above. R4 is an alkyl group having 1 to 2 carbon atoms. X represents an anion residue of the alkylating agent. ) Hereinafter, the present invention will be explained in detail based on a chemical reaction formula. (l) Reaction of acyl compound and dialkylene triamine (amidation and imidazolination): The molar charge of the acyl compound and dialkylene triamine is defined in the range of 1.05 to 1.25 for every 2 of the former.

The reason why the amount of amine charged is in excess of the chemical equivalent ratio is to suppress the remaining amount of unreacted acyl compound to 3% by weight or less.

If it exceeds 3% by weight, not only will the purity of the target product be reduced, but also the phenomenon of off-odor and discoloration will likely occur.

However, if the amount of amine is too large, the amount of monoamide produced will increase, which will not only reduce the purity of the desired product but also have an unfavorable effect on the subsequent quaternization reaction.
The molar ratio must be within the range specified above.

The reaction must be continued until the imidazoline derivative reaches 75% by weight or more.

If the cyclization rate of the derivative is low and does not reach 75% by weight, the amount of unreacted acyl compounds and monoamides will increase, making it impossible to obtain the target product with high purity.

Based on the above chemical reaction formula, unreacted [I
], [I], [V], and [] are reduced as much as possible, and the amount of imidazoline derivative [] produced is maintained at 75% by weight or more.

Note that [ ] is consumed in the quaternization reaction as described later. Regarding the reaction temperature, reaction time, selection of solvent, etc., there is no need to be particularly limited in the present invention, but in general, amidation is carried out at 80°C or higher in the absence of a solvent, so that the amidation reaction can be completed. Once it has progressed beyond a certain point,
Preferably the atmosphere is 100? Imidazolination is carried out under reduced pressure to NmHg or less, and if necessary, the reaction temperature is raised to produce by-products H2O and R5OH (however, R5 has 1 to 1 carbon atoms).
It is desirable to continuously remove the lower alkyl groups (3) etc. from the system.

Amidation and imidazolination do not necessarily proceed individually; rather, imidazoline is partially generated during amidation, and generally, during imidazolination, amidation of unreacted acyl compounds also proceeds. .

Next, the details of the raw materials will be explained. First, as the acyl compound, a linear or branched fatty acid or fatty acid ester having 8 to 27 carbon atoms is selected, but fatty acids are preferable.

Specifically, lactofuric acid, phosphoric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, α-methyllauric acid, α-methylpalmitic acid, α-methylstearic acid, beef tallow. These include fatty acids, apricot fatty acids, palm oil fatty acids, straight chain or branched chain fatty acids produced by a synthetic reaction from olefin and carbon monoxide, and methyl and ethyl esters of the same fatty acids.

These fatty acids can be used alone or as a mixture.

Further, as the dialkylene triamine which is the other raw material, there are diethylene triamine and diisopropylene triamine.

2) Hydrolysis of a reaction product mainly consisting of an imidazoline derivative: The hydrolysis here must be carried out until the imidazoline derivative becomes 50% by weight or less.

The specific reaction operation is generally to dissolve the reaction product containing the imidazoline derivative obtained in the previous section (1) in a low boiling alcohol such as methanol, ethanol, propanol, isopropanol, add water, and dissolve if necessary. Preferably, the hydrolysis is carried out in the presence of an alkaline catalyst. The appropriate amount of water required for the hydrolysis is 1 to 5 moles per mole of imidazoline derivative. If more than 5 moles of water is added, it will have an adverse effect on the quaternization reaction described below, so care must be taken.

In other words, if more than 5 moles of water is added, the hydrolysis reaction will occur too strongly, and the diamide produced by hydrolysis of the amide-type imidazoline derivative will be further hydrolyzed to produce a monoamide and an acyl compound as by-products. be.

Since the hydrolysis reaction is autocatalytic with amines, an alkaline catalyst is not necessarily required, but usable alkaline catalysts include sodium hydroxide, sodium hydrogen carbonate,
Examples include sodium carbonate, potassium hydroxide, mixtures of sodium hydroxide and sodium bicarbonate, and alkali metal hydroxides, carbonates, and bicarbonates.

In addition to being used as a catalyst during hydrolysis, this alkali catalyst can also be used as a neutralizing agent for the acid produced by tertiaryization of a secondary amine in the quaternization reaction described below.

The reason why the degree of hydrolysis is specified in the present invention so that the imidazoline derivative content is 50% by weight or less is that if it exceeds 50% by weight, the purity of the target product will be significantly reduced.

In other words, the smaller the residual amount of the imidazoline derivative, the better. If it exceeds 50% by weight, a large amount of imidazoline type quaternary salt [ ] will be produced as a by-product during the quaternization reaction described later, and secondary Several percent of the tertiary amine also remains.

As a result, the amount of colored substances and off-flavor-causing substances increases, which causes deterioration of the physical properties of the desired product.

In order to avoid this, it is possible to re-quaternize the amines that remain without being quaternized, but in that case, conditions suitable for quaternization must be set separately, and the settings are It is complicated and impractical in reality.

(3) Quaternization treatment of hydrolysis product: The hydrolysis product obtained in the previous section (2) is subjected to quaternization treatment by acting with an alkylating agent.

In other words, when a mixture of [] and [] in which the imidazoline derivative has been reduced to 50% by weight or less is subjected to quaternization treatment in the presence of sufficient water to completely hydrolyze [], [] is directly converted to Since hydrolysis of [] proceeds preferentially than alkylation, a highly purified target product [] can be obtained as a result.

In that case, a mixture of [] and [] is reacted with at least the same mole of alkylating agent to form a tertiary amine salt as an intermediate, and then an alkali substance is reacted to form a free amine, and then Furthermore, a quaternary ammonium salt may be produced by reacting with an alkylating agent, or by reacting with an alkylating agent in an amount of 2 times the mole or more in the presence of an alkaline substance as a neutralizing agent, the quaternary ammonium salt may be directly produced. Ammonium salts may also be produced.

As the alkali substance, as described above, the alkali catalyst used in the hydrolysis may be used as it is, or it may be newly added.

Regarding the amount used, the amount necessary for neutralizing the acid generated by tertiaryization of the amino group is sufficient.

The alkylating agent can be selected from alkyl halides and dialkyl sulfates, and preferred examples include methyl chloride, methyl bromide, and ethyl chloride. The amount used is preferably in excess of the chemical equivalent ratio. As described above, using an imidazoline derivative as an intermediate, a bis-(acylaminoalkyl)-dialkylammonium salt can be obtained with high purity, generally a purity of 9501) or higher, using industrially advantageous raw materials. I can do it.

Next, an example will be described.

In addition, in the following, "part" means "part by weight". Example 1 453 parts of stearic acid as an acyl compound and 95 parts of diethylenetriamine as a dialkylene triamine (
molar ratio of the former 2 and the latter 1.15), and under normal pressure, 18
The amidation reaction was carried out at 5° C. for 1 hour, and then the imidazolination reaction (cyclization dehydration) was carried out at 185 to 215° C. for 5 hours under reduced pressure and 30 ml of Hg.

Analysis of the reaction product revealed that it contained 81.9% imidazoline, 15.2% diamide, 1.8% monoamide, and 1.1% unreacted fatty acid.

Next, to 180 parts of this imidazoline, 110 parts of isofluoropanol, 15.8 parts of water, and 17.6 parts of sodium hydroxide were added.
1 part, add 24.6 parts of sodium hydrogen carbonate, and heat to 120°C.
, when hydrolyzed in a glass autoclave for 1.5 hours, 54% diamide, 43% imidazoline, remaining 3%
The composition was obtained.

Subsequently, excess methyl chloride was added to the contents,
As a result of performing quaternization treatment at 100° C. for 5 hours in a glass autoclave, a mixture with a solid content of 65% and the remainder being isopropanol was obtained.

Analysis of this solid content revealed that bis-(acylaminoalkyl)-dialkylammonium salt was 63.3% or more, unreacted diamide was 1(f) or less, unreacted fatty acid was 0.70f or less, and diamide-type The purity of quaternary salt is 97
It was %. Example 2 Charge molar ratio of stearic acid and diethylenetriamine 2:
The amidation reaction and cyclization dehydration reaction were carried out in the same manner as in Example 1, except that the concentration was 1.05.

The composition of the reaction product is 180 parts of the obtained imidazoline,
110 parts of isopropanol, 15.8 parts of water, 15.2 parts of sodium hydroxide, and 12.3 parts of sodium bicarbonate were added and hydrolyzed in the same manner, and then quaternized with methyl chloride. As a result, the purity was determined. 97% of screws (
Acylaminoalkyl)-dialkylammonium salt could be obtained.

Example 3 The charging molar ratio of stearic acid and diethylenetriamine was 2
Amidation and cyclization dehydration reactions were carried out in the same manner as in Example 1, except that: 1.2.

The composition of the reaction product was as follows: To 180 parts of the obtained imidazoline, 110 parts of isopropanol, 15.8 parts of water, 20 parts of sodium hydroxide, and 24.6 parts of sodium hydrogen carbonate were added, followed by hydrolysis and tetrahydrolysis in the same manner. The classification process was performed.

A bis-(acylaminoalkyl)-dialkylammonium salt with a purity of 97 (!) could be obtained. Example
As a 4-acyl compound, 408 parts of lauric acid and 118 parts of diethylenetriamine (molar ratio of the former to the latter 1.15) were mixed, and amidation and cyclization dehydration reactions were allowed to proceed in the same manner as in Example 1.

The composition of the reaction product is as follows: 180 parts of the obtained imidazoline, 1 part of isopropanol
10 parts, 21.3 parts of water, 23.6 parts of sodium hydroxide,
After adding 33.1 parts of sodium hydrogen carbonate and carrying out the same hydrolysis and quaternization treatment, the purity was 97.
A bis-(acylaminoalkyl)-dialkylammonium salt of 01) could be obtained.

Example 5 As acyl compounds, 533 parts of palmitic acid and 118 parts of diethylenetriamine (molar ratio of the former to the latter: 2:1.2)
were mixed, and the amidation and cyclization dehydration reactions were allowed to proceed in the same manner as in Example 1.

The composition of the reaction product is as follows: 180 parts of the obtained imidazoline, 1 part of isopropanol
10 parts of water, 16.7 parts of water, 21 parts of sodium hydroxide, and 26 parts of sodium hydrogen carbonate were added thereto, and thereafter, hydrolysis and quaternization treatments were performed in the same manner as in Example 1.

A bis-(acylaminoalkyl)-dialkylammonium salt with a purity of 95% or more could be obtained.

Comparative Example 1 The molar ratio of stearic acid and diethylenetriamine was 2:1.03, and the amidation and cyclization dehydration reactions were carried out in the same manner as in Example 1. The composition of the reaction product was imidazoline (amide type). 72.5%, diamide 9.9%,
Monoamide 7.9%, unreacted fatty acid 7.0%, balance 2.
It was 7%.

Thereafter, when hydrolysis and quaternization treatments were performed, only a low-purity bis-(acylaminoalkyl)-dialkylammonium salt was obtained.

Comparative Example 2 Amidation and cyclization dehydration reactions were carried out under the same conditions as in Example 1 using stearic acid and diethylenetriamine as raw materials.

The composition of the reaction product was: imidazoline 81.9% diamide 15.2% monoamide 1.8% unreacted fatty acid 1.1% After that, hydrolysis was carried out in the same manner at 120°C for 1 hour, resulting in imidazoline 58%. 3%, diamide 38.8C
I became fb.

When quaternization treatment was carried out in this state, unreacted amines were
6% remained, and several percent of imidazoline type quaternary salts were also produced, resulting in a decrease in the purity of the diamide type quaternary salts.

Claims (1)

[Claims] 1. General formula R^1-C-Y (where R^1 is carbon number 7
~26 linear or branched aliphatic hydrocarbon groups, whether saturated or unsaturated. Y is OH or OR^2, R_2 is a lower alkyl group having 1 to 3 carbon atoms), and an acyl compound represented by the general formula (
dialkylenetriamine represented by H_2N-R^3)_2NH (where R^3 is a linear or branched alkylene group having 2 to 03 carbon atoms) in a molar ratio of 2:1.05.
~1.25 to carry out amidation and imidazolination of the acyl compound until the unreacted acyl compound becomes 3% by weight or less and the imidazoline derivative becomes 75% by weight or more, and then this imidazoline derivative is used as the main component. To the reaction product, water is added in an amount of 1 to 5 times the mole of the imidazoline derivative, and a hydrolysis reaction is carried out until the imidazoline derivative becomes 50% by weight or less, and this hydrolysis product is reacted with an alkylating agent. A method for producing a quaternary ammonium salt represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R^1 is shown above. R is the same as R^1 above. R^3 is shown above. R^4 is alkyl having 1 to 2 carbon atoms. (X represents an anion residue of an alkylating agent.) 2. The method according to claim 1, wherein the hydrolysis reaction is carried out in a lower alcohol solution of a reaction product mainly containing the imidazoline derivative.