JP3471442B2 - Method for producing high-purity choline carbonate or choline bicarbonate - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing choline carbonate or choline bicarbonate, and more particularly to a method for producing high-purity choline carbonate or choline bicarbonate from choline containing by-products. Regarding

[0002]

2. Description of the Related Art The present inventors have already described in the description of "inclusion complex of quaternary ammonium hydroxide or a salt thereof and a method for producing the inclusion complex" (Japanese Patent Application No. 6-38894). An inclusion complex of hydroxide or a salt thereof and a method for producing the inclusion complex are proposed.

Although choline is a strongly basic substance and is used as a photoresist developing solution, it is impossible to remove by-products produced as a by-product during the production of choline, and it has been conventionally used in the presence of by-products. There is.

[0004]

Choline is generally produced according to formula (1).

[0005]

[Chemical 1]

As a by-product of this reaction, the compound of formula (2) is presumed.

[0007]

[Chemical 2]

This by-product is obtained by sequentially adding ethylene oxide to choline, and n = 1 and 2
Is the main one. The above-mentioned by-product is contained in the conventional choline aqueous solution in an amount of about 2 to 3% by weight based on choline.

This by-product cannot be practically suppressed or removed by general chemical and physical operation treatments such as improvement of choline reaction conditions, distillation, recrystallization and adsorption. If high-purity choline containing no by-products can be produced, not only will it lead to further expansion of applications as a photoresist developer, but it can also be expected to open up new applications in fields such as pharmaceuticals, agricultural chemicals and functional materials.

The inventors of the present invention have proposed the above-mentioned Japanese Patent Application No. 6-38.
As a result of repeated intensive research after No. 894, a method for producing high-purity choline carbonate or choline bicarbonate was found, and the present invention was accomplished.

That is, an object of the present invention is to provide a method for producing high-purity choline carbonate or choline bicarbonate that does not contain by-products. The high-purity choline carbonate or choline bicarbonate obtained in the present invention can be provided as high-purity choline by an electrolysis method using an ion exchange membrane as a diaphragm.

[0012]

According to the present invention, a high-purity choline carbonate or heavy-carbon choline carbonate is produced by reacting a molecular inclusion complex of choline with carbon dioxide gas. A method for producing choline carbonate is provided.

According to the present invention, an aqueous choline solution containing impurities is reacted with 1,1'-bis-β-naphthol,
A process for producing high-purity choline carbonate or choline bicarbonate, which comprises reacting the obtained molecular inclusion complex of choline with carbon dioxide to produce high-purity choline carbonate or choline bicarbonate.

[0014]

When a compound incorporates another molecule to form a complex, this complex is called a molecular inclusion complex, the former compound is called a host molecule, and the latter molecule is called a guest molecule.

The present invention is novel in that only choline in an aqueous solution of choline forms a molecular inclusion complex with a host molecule such as 1,1'-bis-β-naphthol and does not form a molecular inclusion complex with a by-product. Based on such findings, an aqueous solution of choline is reacted with a host molecule such as 1,1′-bis-β-naphthol to obtain a choline inclusion complex containing no by-products, and then the choline inclusion complex is added to water. By dispersing and blowing carbon dioxide gas, high-purity choline carbonate or choline bicarbonate is obtained in the form of an aqueous solution.

That is, the choline incorporated in the choline inclusion complex reacts with carbon dioxide gas to become water-soluble choline bicarbonate or choline carbonate, and is dissolved in water to obtain an aqueous solution of choline bicarbonate or choline carbonate. . This reaction is represented by the following equations (3), (4) and (5).

[0017]

[Chemical 3]

[0018]

[Chemical 4]

[0019]

[Chemical 5]

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION As the host compound used in the present invention, for example, a phenol compound described in Japanese Patent Publication No. 6-21017 can be mentioned, and particularly preferable one is 1,1'-bis. -Β-naphthol, that is, the compound of the following formula (6) is used.

[0021]

[Chemical 6]

The guest compound used in the present invention is choline, and the choline aqueous solution produced by the method of the formula (1) can be used as a raw material.

The high-purity choline carbonate or choline bicarbonate of the present invention can be produced by the following simple method.

The 1,1'-bis-β-naphthol and choline aqueous solution was diluted with pure water in a ratio such that 1,1'-bis-β-naphthol / choline = 1/1 or 1/2 (molar ratio). Along with this, it is charged into a reactor and heated to dissolve. The aqueous choline solution used is produced by the method of formula (1), and generally contains the by-product of formula (2) in an amount of about several wt% with respect to choline.

After dissolution by heating, crystals of a molecular inclusion complex of 1,1'-bis-β-naphthol and choline are immediately precipitated.
After stirring for about 1 hour, cooling to room temperature, filtration or centrifugation, washing with water and drying, a high-purity molecular inclusion complex containing no by-products can be obtained in a high yield of 80 mol% or more.

Pure water was added to the obtained high-purity molecular inclusion complex, carbon dioxide gas was blown into it, and 1,1'-bis-β-naphthol was removed as an insoluble crystal by filtration or centrifugation to remove by-products. It is possible to obtain a highly pure choline carbonate or choline bicarbonate aqueous solution that does not contain it. The host compound 1,1'-bis-β-naphthol was not mixed in this aqueous solution.

The recovered 1,1'-bis-β-naphthol can be reused, and the recovery rate is almost quantitative.

[0028]

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The molecular inclusion ratio of 1,1′-bis-β-naphthol / choline of the inclusion complex was determined by NMR (60 MH
In step z), the choline content in the aqueous choline solution is determined by hydrochloric acid neutralization titration, and the by-product described in the formula (2) in the aqueous choline solution, the choline inclusion complex, the aqueous choline carbonate solution or the aqueous choline bicarbonate solution and the separated mother liquor is an ion. It was quantified by chromatography.

Example 1 Synthesis of 1,1′-bis-β-naphthol / choline inclusion complex 1,1′-bis-β-naphthol 1.145 g (4.0)
mmol) and 47.75 wt% choline aqueous solution 2.030
g (8.0 mmol) was added to 10 g of pure water and dissolved by heating. The by-product in the choline aqueous solution is 1.8 with respect to choline.
It was 4% by weight. Crystals precipitated immediately after heating and dissolution. Furthermore, after adding 20 g of pure water, filtering, washing with water and drying,
1.460 g (yield 89.60 mol%) of 1,1′-bis-β-naphthol / choline inclusion complex was obtained. In melting point measurement, it melted while decomposing at 210 to 213 ° C. Also,
From NMR, the molecular ratio of the inclusion complex was 1,1′-bis-β.
-Naphthol / choline = 1/1. When choline in the inclusion complex was analyzed by ion chromatography,
By-products were below the detection limit. In addition, the total amount of choline in the inclusion complex separation mother liquor and the washing liquid was 0.535 g.
(4.4 mmol).

(Example 2) Synthesis of choline carbonate or choline bicarbonate from 1,1'-bis-β-naphthol / choline inclusion complex 1,1'-bis-containing no by-product obtained in Example 1 β-
Naphthol / choline inclusion complex 1.246 g (3.2 mm
ol) was added to 30 g of pure water, and carbon dioxide gas was blown in while stirring. The insoluble crystals were filtered and washed with water to obtain 50.939 g of a highly pure choline carbonate or choline bicarbonate aqueous solution (choline equivalent weight: 0.37 g, 3.1 mmol). Yield 9
It was 5.40 mol%. This high-purity choline carbonate or choline bicarbonate aqueous solution contained no by-products. In addition, the insoluble crystals were dried and dried at 0.850 g (3.0 mmo).
l) was recovered. This insoluble crystal is 1,1'-
It was confirmed to be bis-β-naphthol. The recovery rate was 92.80%.

Example 3 Synthesis of 1,1′-bis-β-naphthol / choline inclusion complex 1,1′-bis-β-naphthol 1.145 g (4.0)
mmol) and 47.75 wt% choline aqueous solution 1.014
g (4.0 mmol) was added to 10 g of pure water and dissolved by heating. The by-product in the choline aqueous solution is 1.84 with respect to choline.
% By weight. Crystals precipitated immediately after heating and dissolution.
Furthermore, after adding 20 g of pure water, filtering, washing with water and drying, 1,
1'-bis-β-naphthol / choline inclusion complex was added to 1.0
90 g (yield 78.40 mol%) was obtained. In melting point measurement, it was dissolved while decomposing at 105 to 110 ° C. NMR
Therefore, the molecular ratio of the inclusion complex was 1,1′-bis-β-naphthol / choline = 2/1. This inclusion complex contained no by-products. Further, 0.260 g (2.0 mmol) of choline remained in the separated mother liquor.

Example 4 Synthesis of 1,1′-bis-β-naphthol / choline inclusion complex 1,1′-bis-β-naphthol 42.90 g (0.1
5 mmol) and 47.75 wt% choline aqueous solution 76.1
Add 3 g (0.30 mmol) to 350 g of pure water and add 50
Melted at ° C. The by-product in the choline aqueous solution was 1.84% by weight based on choline. Crystals precipitated immediately after heating and dissolution. After stirring at 50 ° C. for 1 hour, 450 g of water was added and the mixture was cooled to room temperature. After cooling, the crystals were washed twice with pure water and dried to obtain 53.0 g (yield 88.2 mol%) of 1,1′-bis-β-naphthol / choline inclusion complex. From the NMR, the molecular ratio of the inclusion complex was 1,1′-bis-β-naphthol / choline = 1/1. This inclusion complex was free of by-products. The total amount of choline in the separated mother liquor and washing water was 20.18 g (0.16 g).
6 mmol).

(Example 5) Synthesis of choline carbonate or choline bicarbonate from 1,1'-bis-β-naphthol / choline inclusion complex 1,1'-bis-containing no by-product obtained in Example 4 β-
Naphthol / choline inclusion complex 48.90g (0.12m
ol) was added to 400 g of pure water, and carbon dioxide gas was blown in while stirring. Insoluble crystals were filtered and washed with water to give 500 g of choline carbonate or choline bicarbonate aqueous solution (choline equivalent weight: 12.
60 g, 0.104 mol) was obtained. The yield was 86.70 mol%. By-products in the aqueous solution of choline carbonate or choline bicarbonate were analyzed by ion chromatography, but the detection limit was reached. The insoluble crystals were dried to give 1,
It was confirmed to be 1'-bis-β-naphthol. The recovery rate was almost quantitative.

(Comparative Example 1) 2,1'-bis (4-hydroxyphenyl) -cyclohexane 2.680 g (10.
00 mmol) and 47.75 wt% choline aqueous solution 2.5
4 g (10.00 mmol) was added to 10 g of pure water and dissolved by heating. The by-product in the choline aqueous solution was 1.84% by weight based on choline. After dissolution by heating, the mixture was left overnight at room temperature. Then, add 20 g of pure water, filter and dry,
3.20 g (yield 97.3 mol%) of 1,1'-bis (4-hydroxyphenyl) -cyclohexane / choline inclusion complex was obtained. From NMR, the molecular ratio of this inclusion complex is
It was 1,1'-bis (4-hydroxyphenyl) -cyclohexane / choline = 2/1. Melting point is 119-1
It was not sharp at 51 ° C. Impurities in this inclusion complex were 1.84% by weight with respect to choline and were not purified at all. This inclusion complex 3.17 g (4.80
(mmol) was added to 30 g of pure water, and carbon dioxide gas was blown in while stirring. The insoluble crystals were filtered and washed with water to obtain 70.60 g of choline carbonate or choline bicarbonate aqueous solution (choline equivalent weight 0.501 g, 4.10 mmol). By ion chromatography, the by-product in the choline carbonate or choline bicarbonate aqueous solution was 1.82% by weight based on the choline-converted weight.
And was not purified at all.

[0035]

INDUSTRIAL APPLICABILITY According to the present invention, a by-product obtained by reacting a choline aqueous solution containing a compound obtained by further adding ethylene oxide to choline as a by-product with a host molecule such as 1,1′-bis-β-naphthol. It is possible to obtain a highly pure choline carbonate or choline bicarbonate aqueous solution by reacting a choline inclusion complex containing no with carbon dioxide gas.

High-purity choline carbonate or choline bicarbonate can be converted into high-purity choline by an electrolysis method using an ion exchange membrane as a diaphragm. Choline is a strongly basic compound and is extremely useful as a photoresist developer.

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Claims (3)

(57) [Claims] 1. A method for producing high-purity choline carbonate or choline bicarbonate, which comprises reacting a molecular inclusion complex of choline with carbon dioxide gas to produce high-purity choline carbonate or choline bicarbonate. 2. The production method according to claim 1, wherein the molecular inclusion complex of choline uses choline as a guest molecule and 1,1′-bis-β-naphthol as a host molecule. 3. A choline aqueous solution containing impurities and 1,
1'-bis-β-naphthol is reacted, and the obtained molecular inclusion complex of choline is reacted with carbon dioxide gas to produce high-purity choline carbonate or choline bicarbonate. Method for producing choline bicarbonate.