JPH0742255B2 - Method for producing quaternary ammonium bicarbonate - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a quaternary ammonium bicarbonate.

The quaternary ammonium bicarbonate is widely used as a surfactant and a raw material for the surfactant, or is also useful as a raw material for pharmaceuticals and cosmetics.

In recent years, quaternary ammonium hydroxide derived from quaternary ammonium bicarbonate has been widely used as a cleaning solution for wafers, an etching solution, a developing solution in the manufacturing process of IC, LSI, etc. in the electronic industry and the semiconductor industry. Has been done.

[Prior art and its problems]

The quaternary ammonium bicarbonate according to the present invention generally, for example, (1) carbonates quaternary ammonium hydroxide, or (2) causes quaternary ammonium chloride to react with carbon dioxide gas and aqueous ammonia. Can be obtained.

However, the above method (1) is not industrially practical, and the method (2) has problems that the reaction process is complicated and many by-products are produced.

In view of the above situation, the present invention provides a method for producing a highly pure quaternary ammonium bicarbonate.

[Means for using the low problem as a solution]

As a result of various studies to solve the above-mentioned problems, the present inventors have developed a novel quaternary ammonium bicarbonate by reacting a tertiary amine with a dialkyl carbonate or diaryl carbonate in the presence of water. A method for producing salt has been found.

That is, the present invention relates to a method for producing a quaternary ammonium bicarbonate, which comprises reacting a dialkyl carbonate or diaryl carbonate with a tertiary amine in the presence of water.

The method of the present invention is represented by the following formula.

The tertiary amine used in the present invention has the general formula (R ₁ , R ₂ ,
R ₃ ) ₃ N (in the formula, R ₁ , R ₂ and R ₃ represent C _{1 to} C ₈ alkyl groups, alkenyl groups, phenyl groups and benzyl groups), and specifically, trimethylamine and triethylamine , Tripropylamine, tributylamine, trioctylamine, dimethylethylamine, diethylmethylamine, N,
N'-dimethylbenzylamine, N, N'-dimethylaniline, N, N'-dimethylcyclohexylamine, N, N'-diethylbenzylamine N, N'-dimethylethanolamine, N, N'-diethylethanolamine, Examples include N-methyldiethanolamine, triethanolamine, N, N'diethylethanolamine, N-ethyldiethanolamine and the like.

Further, the dialkyl carbonate or diaryl carbonate used in the present invention has the general formula And (wherein R ₄ and R ₅ represent a C _{1 to} C ₈ alkyl group or aryl group), specifically, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, dibenzyl carbonate. , Dicyclohexyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, and the like.

In the present invention, water is an essential component for the reaction and also has a function as a solvent, and it may be used in excess of the theoretical amount.

In the present invention, the amount of the above-mentioned dialkyl carbonate or diaryl carbonate and the tertiary amine used is appropriately selected in consideration of the type of the dialkyl carbonate or diaryl carbonate or tertiary amine used, the reaction conditions, etc. Specifically, the molar ratio of the dialkyl carbonate or diaryl carbonate and the tertiary amine is in the range of 0.05 to 20, preferably 0.
Used in the range of 1-10. The amount of water may be basically added in a stoichiometric amount or more with respect to the dialkyl carbonate, diaryl carbonate or tertiary amine, but if it is too large, it takes a lot of time for separation and removal after the reaction. It is not economically advantageous.

In the method of the present invention, alcohols, nitriles,
Polar solvents such as acid amides can be used. By using a polar solvent, the reaction rate at the initial stage of the reaction can be increased and the entire reaction can be carried out in a short time.
Furthermore, the use of such a polar solvent also has the effect of increasing the reaction yield.

Examples of such a polar solvent include aliphatic lower alcohols such as methanol, ethanol, propanol, and the like,
Monohydric aromatic alcohols such as benzyl alcohol, glycols such as ethylene glycol, acid amides such as N, N-dimethylformamide, and nitriles such as acetonitrile are exemplified, but these polar solvents are It is preferable that the boiling point is not too high, and it is preferable that the boiling point is in the range of 50 to 200 ° C., preferably methanol, ethanol,
Propanol, acetonitrile and the like are preferable from the viewpoint of separation operation after the reaction.

The amount of these polar solvents used is 0.5 to 30 times (weight) with respect to the raw material dialkyl carbonate, diaryl carbonate or tertiary amine, and is usually 1 to 20 times, preferably 2 to 10 times. It

The reaction temperature in carrying out the process of the invention is generally 30.
Although it is in the range of ~ 300 ° C, it is necessary to consider the reaction rate, decomposition of the starting material dialkyl carbonate, diaryl carbonate and the desired product quaternary ammonium bicarbonate, etc. It is preferably 50 to 200 ° C.

In the present invention, the reaction may be carried out under an inert gas atmosphere that does not affect the reaction of nitrogen, argon helium, hydrogen gas or the like, if necessary. Further, the present invention can be carried out by any of batch, semi-batch and continuous methods.

〔The invention's effect〕

The present invention is a novel method of obtaining a quaternary ammonium bicarbonate in a high yield by reacting a dialkyl carbonate or diaryl carbonate with a tertiary amine and water, which is of great industrial significance. That's the method.

Examples of the present invention will be shown below.

Example 1 Dimethyl carbonate 60.4 was placed in an autoclave having an inner volume of 300 ml.
g, trimethylamine 39.4g, water 60.0g introduced, heating,
It was stirred. After the temperature in the reactor reached 100 ° C, the reaction was continued at that temperature for 3 hours. After the reaction was completed, the product was analyzed and as a result, tetramethylammonium bicarbonate was found to be 86.8%.
The yield was (mol) (based on trimethylamine).

Example 2 A reactor similar to that used in Example 1 was charged with 60.4 dimethyl carbonate.
g, trimethylamine 39.4g, water 30.0g and methanol 5
Example 1 was repeated except that 0.0 g was introduced. As a result, tetramethylammonium bicarbonate was obtained in a yield of 90.3% (mol) (based on trimethylamine).

Example 3 Diethyl carbonate 63. in a reactor similar to that used in Example 1.
g, triethylamine 63.4 g, and water 50.0 g were introduced, and the mixture was heated and stirred. After the temperature in the reactor reached 140 ° C, the reaction was continued at that temperature for 5 hours. After the reaction was completed, the product was analyzed and found to contain 87.9% tetraethylammonium bicarbonate.
The yield was (mol) (based on triethylamine).

Example 4 Dibenzyl carbonate 10 was added to a reactor similar to that used in Example 1.
1.6g, trimethylamine 23.6g, water 60.5g, methanol 2
0.0g, was introduced and heated with stirring. The temperature in the reactor is 150
After reaching ℃, the reaction was continued at that temperature for 5 hours. After the reaction was completed, the product was analyzed and trimethylbenzylammonium carbonate was obtained in a yield of 81.0% (based on trimethylamine).

Example 5 Dimethyl carbonate 30.2 was added to a reactor similar to that used in Example 1.
g, tri-n-butylamine 62.1 g, water 30.0 g and methanol 15.0 g were introduced, and the mixture was heated and stirred. After the temperature in the reactor reached 140 ° C, the reaction was continued at that temperature for 7 hours,
Methyltributylammonium bicarbonate was obtained with a yield of 84.3% (based on tri-n-butylamine).

Example 6 Dimethyl carbonate 60.4 was added to a reactor similar to that used in Example 1.
g, trimethylamine 39.4 g, and water 25.0 g were introduced, and the mixture was heated and stirred. After the temperature in the reactor reached 100 ° C., the reaction was carried out at that temperature for 6 hours to obtain tetotimethylammonium bicarbonate in a yield of 90.1% (based on trimethylamine).

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References Japanese Patent Publication No. 317164 (JP, B1) US Patent 2635100 (US, A)

Claims (1)

[Claims] 1. A method for producing a quaternary ammonium bicarbonate, which comprises reacting a dialkyl carbonate or diaryl carbonate with a tertiary amine in the presence of water.