JP3254566B2 - Method for stabilizing glycidyl quaternary ammonium salt aqueous solution - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for stabilizing an aqueous glycidyl quaternary ammonium salt solution. Glycidyl quaternary ammonium salts are used as cationizing agents for cellulose, starch, polyamine and the like.

[0002]

2. Description of the Related Art Known techniques relating to a method for producing an aqueous solution of a glycidyl quaternary ammonium salt are summarized in the following (1) to (4). In the manufacturing method in consideration of the above.

(1) After reacting epihalohydrin with a tertiary amine in the presence of an excess amount of epihalohydrin or in the presence of a non-polar solvent, the resulting glycidyl quaternary ammonium salt is separated, dried and dried in the form of crude crystals. Production method (J. Org.
Chem., Vol. 35, No. 6, 2059 (1970)].

(2) Water is added to the crude crystal of glycidyl quaternary ammonium salt obtained by the above method (1) to separate it into an organic layer and an aqueous layer. A method for producing a glycidyl quaternary ammonium salt in the form of an aqueous solution (JP-A-55-082973).

(3) Hydrohalic acid or a redox addition product of glycidyl quaternary ammonium salt and hydrohalic acid is added to an aqueous glycidyl quaternary ammonium salt solution,
A method for improving the storage stability of a glycidyl quaternary ammonium aqueous solution (JP-A-59-253225).

(4) In the above method (1), in the reaction using an excessive amount of epihalohydrin, a small amount of 1,3-dihalohydrin is added to carry out the reaction, and the resulting glycidyl quaternary ammonium salt is converted into an aqueous solution. For improving storage stability during storage (Japanese Patent Publication No. 4-53864)

[0007]

The glycidyl quaternary ammonium salt obtained by the above method (2) is easy to handle because it can be obtained in the form of an aqueous solution. And its purity decreases with time.

The stabilization method (3) is difficult to handle because the hydrohalic acid used is a strong acid. Also, its addition must be added to the purified aqueous solution of the glycidyl quaternary ammonium salt.

In the above method (4), it is difficult to remove unreacted dihalohydrin from the obtained crude crystals of glycidyl quaternary ammonium salt.

An object of the present invention is to improve the storage stability of a glycidyl quaternary ammonium salt aqueous solution.
The glycidyl quaternary ammonium salt aqueous solution is a basic aqueous solution, and therefore the glycidyl group is hydrolyzed by water, and its purity decreases with time. Therefore, it is an object of the present invention to develop a method for reducing the basicity of an aqueous solution and improving the stability of a glycidyl quaternary ammonium salt aqueous solution by a simple operation without producing by-products.

[0011]

SUMMARY OF THE INVENTION The present invention improves the storage stability of a glycidyl quaternary ammonium salt aqueous solution by treating an aqueous glycidyl quaternary ammonium salt solution with halohydrin to reduce the basicity of the aqueous solution. It is.

That is, the present invention provides a method for stabilizing an aqueous glycidyl quaternary ammonium salt solution, which comprises subjecting an aqueous solution containing a glycidyl quaternary ammonium salt to treatment by adding halohydrin, followed by degassing. is there.

[0013]

DETAILED DESCRIPTION OF THE INVENTION The aqueous solution of glycidyl quaternary ammonium salt used in the present invention may be any solution containing glycidyl quaternary ammonium salt, such as crude crude liquid obtained by a known method and purified product. For aqueous solutions. That is, a tertiary amine is reacted with epihalohydrin in the presence of an excess epihalohydrin or in the presence of an inert solvent, water is added to the obtained slurry, and a reaction crude solution containing epihalohydrin extracted and separated into an aqueous layer is added. The aqueous solution obtained by purifying the crude reaction solution by topping, the slurry after the reaction was washed with a solvent, the aqueous solution to which water was added, the slurry after the reaction was washed with the solvent, and then dried under reduced pressure, and the aqueous solution to which water was added. Aqueous solution obtained by drying the slurry under reduced pressure and then adding water.

The glycidyl quaternary ammonium salt is obtained by reacting epihalohydrin with a tertiary amine.
Epihalohydrin, which is a raw material of glycidyl quaternary ammonium salt, includes epichlorohydrin, epibromhydrin, epiiodohydrin and epifluorohydrin, but from the viewpoint of price, reactivity, usefulness of the product, etc., epichlorohydrin Is preferred.

Examples of the tertiary amine serving as a raw material of the glycidyl quaternary ammonium salt include those containing a linear or branched alkyl group having 1 to 20 carbon atoms and a cycloalkyl group having 3 to 6 carbon atoms. In addition, as a heterocycle,
It is a 5- to 6-membered ring, and may further contain O and S.

Specifically, for example, trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-hexylamine, dimethylethylamine, dimethylisopropylamine, dimethyl-n-butylamine, dimethyl-n-butylamine Dodecylamine, dimethyl-
n-octadecylamine, methylethyl-n-propylamine, methylethyl-n-butylamine, N-methylpiperidine, N-ethylpiperidine, Nn-propylpiperidine, pyridine, α-picoline, β-picoline, γ-picoline,
Dimethylpentylamine and the like are used.

The halohydrin added to the glycidyl quaternary ammonium salt aqueous solution is represented by the following structural formula. Intramolecular cyclization readily occurs, thereby releasing the halogen acid, which itself becomes a low boiling ring compound.

[0018]

Embedded image Here, X 1 is Cl, Br, I or F ² , R ¹ and R ² are each independently H ² or an alkyl group, and the sum of the single prime numbers of R ¹ and R ² is 4 or less.

Examples of such halohydrins include, for example, ethylene chlorohydrin, ethylene bromohydrin, ethylene iodohydrin, ethylene fluorohydrin, propylene chlorohydrin, 2-chlorocyclohexanol, 2-chloro-1-hydroxy Butanol, 3-chloro-2-butanol and the like.

The amount of halohydrin to be added is 0.01 to 0.1 mol, preferably 0.03 to 0.06 mol, per mol of glycidyl quaternary ammonium salt, but the amount of addition depends on the pH of the aqueous solution. It can be determined appropriately. The method of addition is optional, and the halohydrin may be added to the glycidyl quaternary ammonium salt aqueous solution at a time or in portions.

After the addition of the halohydrin, the aqueous solution
Aging is performed at a temperature of 80 ° C, preferably 30 to 50 ° C, for 1 to 10 hours, preferably 1 to 5 hours. If the aging time is too short, the reaction of the halohydrin will be insufficient, and if it is too long, the hydrolysis of the target product will easily occur. If sufficient heat is applied during degassing after aging, this aging can be omitted.

The aged aqueous solution is subjected to a degassing treatment to remove ring-closed products converted from halohydrin. The deaeration process is
Either normal pressure topping or reduced pressure topping may be used, and bubbling with an inert gas such as nitrogen, air, or argon may be used together.

[0023]

[Effect] In glycidyl quaternary ammonium salt aqueous solution,
Glycidyl quaternary ammonium hydroxide (I) is included as a by-product of the reaction. This is strongly basic, and the aqueous solution shows basicity. For this reason, the glycidyl group of the target substance reacts with water to cause a ring-opening reaction of the glycidyl group, and the purity of the target substance gradually decreases.

In the present invention, glycidyl quaternary ammonium hydroxide (I), which is considered to promote hydrolysis of glycidyl quaternary ammonium salt in an aqueous solution,
The added halohydrin (II) neutralizes (I) by the following reaction formula, and cyclizes itself to form an epoxide. As a result, the basicity of the treated aqueous solution of glycidyl quaternary ammonium salt decreases, and the decrease is only about 1 to 1.5 as measured by a pH value of a 5% aqueous solution. Is reliably suppressed. Further, the added halohydrin becomes a cyclized product having a low boiling point, and is easily removed from the system by degassing.

[0025]

Embedded image

The reaction of halohydrin does not involve side reactions,
The product does not contain impurities.

[0027]

【Example】

Example 1 7.60 kg of epichlorohydrin and 11.71 kg of 1,2-dichloroethane were charged into a 30-liter autoclave equipped with a thermometer, a gas inlet tube, and a stirrer, and 2.41 kg of trimethylamine was supplied with stirring at a system temperature of 30 ± 5 ° C. . After supplying trimethylamine, the mixture was aged at the same temperature for 8 hours. Water to the reaction product
2.05 kg was added to dissolve crude glycidyltrimethylammonium chloride crystals. After standing, the upper and lower layers were separated to obtain 8.41 kg of an aqueous layer and 15.31 kg of an organic medium layer.

In a 20-liter autoclave equipped with a fractionating tube for simple distillation, 8.41 kg of the aqueous layer and 52.6 g of ethylene chlorohydrin were added, and 0.51 kg of water was added thereto. An aqueous solution of trimethylammonium chloride was obtained. Decompression topping pressure is 48-30mmH
g, final can solution temperature is 60 ℃ (30mmHg), topping time is 4
It was time. The pH of the obtained glycidyltrimethylammonium chloride measured in a 5% aqueous solution was 8.90.

The change in the residual epoxy ratio when the storage stability of this aqueous solution was maintained at 20 ° C. for 60 days was measured by the analysis of the HCl-CaCl method, and the results are shown in Table 1.

Example 2 The same autoclave with a fractionating tube as in Example 1 was used.
8.44 kg of an aqueous layer and 61.8 g of propylene chlorohydrin obtained in the same manner as described above were added, and 0.52 kg of water was added thereto.
In the same manner as in the above, under reduced pressure to obtain a glycidyltrimethylammonium chloride aqueous solution. The pressure for the reduced pressure topping was 48 to 30 mmHg, the final bottom liquid temperature was 65 ° C (30 mmHg), and the topping time was 3.5 hours. Table 1 shows the pH and storage stability of the obtained 5% aqueous solution of glycidyltrimethylammonium chloride.

Comparative Example 1 Using the same autoclave with a fractionating tube as in Example 1, 0.52 kg of water was added to 8.44 kg of the aqueous layer obtained in the same manner as in Example 1.
Topping under reduced pressure was performed in the same manner as in Example 1 to obtain an aqueous solution of glycidyltrimethylammonium chloride. The decompression topping pressure is 48-30mmHg, and the final can liquid temperature is 65 ℃ (30mmH
In g), the topping time was 3.5 hours. Table 1 shows the pH and storage stability of the obtained 5% aqueous solution of glycidyltrimethylammonium chloride.

Example 3 To 6.00 kg of the aqueous solution of glycidyltrimethylammonium chloride obtained in Comparative Example 1 was added ethylene chlorohydrin.
6 g was added thereto, and 0.41 kg of water was added thereto, followed by performing vacuum topping in the same manner as in Example 1 to obtain an aqueous glycidyltrimethylammonium chloride solution. The pressure for the reduced pressure topping was 48 to 30 mmHg, the final bottom liquid temperature was 63 ° C (30 mmHg), and the topping time was 3 hours. Table 1 shows the pH and storage stability of the obtained 5% aqueous solution of glycidyltrimethylammonium chloride.

Example 4 7.69 kg of epichlorohydrin and 11.69 kg of 1,2-dichloroethane were charged into a 30-liter autoclave equipped with a thermometer, a gas inlet tube and a stirrer, and triethylamine was stirred at a system temperature of 35 ± 5 ° C. 4.10 kg was supplied. After supplying triethylamine, the mixture was aged at the same temperature for 8 hours. 2.05 kg of water was added to the reaction product to dissolve crude glycidyltriethylammonium chloride crystals. After standing, the upper and lower layers were separated to obtain 10.22 kg of an aqueous layer and 15.31 kg of an organic medium layer.

In a 20-liter autoclave equipped with a single distillation distillation tube, 10.22 kg of the aqueous layer obtained above and 53.0 g of ethylene chlorohydrin were added, and 0.50 kg of water was added thereto. Thus, an aqueous glycidyltriethylammonium chloride solution was obtained. The pressure of the reduced pressure topping was 48 to 30 mmHg, the final bottom liquid temperature was 65 ° C (30 mmHg), and the topping time was 4 hours. Table 1 shows the pH and storage stability of the obtained 5% aqueous solution of glycidyltriethylammonium chloride.

Comparative Example 2 To 10.24 kg of the aqueous layer obtained in the same manner as in Example 4, 0.50 kg of water was added, and topping was carried out under reduced pressure as in Example 4, to obtain an aqueous glycidyltriethylammonium chloride solution. The decompression topping pressure is 48-30mmHg, and the final can liquid temperature is 65 ℃ (3
0 mmHg) and the topping time was 3.5 hours. Table 1 shows the pH and storage stability of the obtained 5% aqueous solution of glycidyltriethylammonium chloride.

[0036]

[Table 1]

[0037]

The glycidyl quaternary ammonium salt aqueous solution having good storage and storage stability can be obtained by the halohydrin addition treatment and deaeration treatment according to the present invention. Also,
Since the aqueous solution to be treated may be a reaction crude liquid containing epihalohydrin, an inert solvent or the like, or a produced product, the present invention can be incorporated in the middle of the production process, or the present invention can be further carried out after the production process is completed. Good. The additives used are easy to handle. The added halohydrin cyclizes by itself and is removed from the system by degassing, so that it does not remain in the product as an impurity.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-61-130281 (JP, A) JP-A-50-62917 (JP, A) JP-A-61-134383 (JP, A) JP-A 55-129 89273 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C07D 303/36 C07D 301/27 CA (STN)

Claims (1)

(57) [Claims] 1. A method for stabilizing an aqueous solution of glycidyl quaternary ammonium salt, which comprises subjecting an aqueous solution containing glycidyl quaternary ammonium salt to treatment by adding halohydrin thereto, followed by degassing.