JP2002105068A - Method for producing sulfoalkylating agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a sulfoalkylating agent having a high production efficiency capable of efficiently reducing a halogenated salt being a by-product by a simple method in the case of carrying out a reaction by using a hydroxy group- containing haloalkanesulfonic acid or its salt as a sulfoalkylating agent and to efficiently obtain a sulfoalkylated substance of a hydroxy compound having a reduced halogenated slat. SOLUTION: This method for producing an epoxy group-containing sulfonate comprises reacting a hydroxy group-containing 2-5C haloalkanesulfonic acid or its salt with an alkali compound to give an epoxy group-containing alkanesulfonate and a halogenated salt and then separating the halogenated salt. This method for producing a sulfoalkylated substance of a hydorxy compound comprises reacting a sulfoalkylating agent with a hydroxy compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sulfoalkylating agent used in the production of cosmetics, toiletries, external medicines, water-soluble paints, thickeners for building materials, activators, gelling agents, emulsions and the like. The present invention relates to a method for producing a sulfoalkylating agent capable of performing an efficient reaction with little by-product salt. Further, the present invention relates to a method for producing a sulfoalkylated product by reacting the sulfoalkylating agent with a hydroxyl compound.

[0002]

BACKGROUND OF THE INVENTION When a sulfoalkylated product is obtained from a hydroxyl compound,
As the sulfoalkylating agent, a haloalkanesulfonic acid optionally having a hydroxyl group or a salt thereof (hereinafter, referred to as “haloalkanesulfonic acid”) is often used. When these are used as sulfoalkylating agents, the reaction is carried out by allowing an alkali compound to coexist in the reaction system.

However, when the sulfoalkylation reaction is carried out by this method, a halide salt of approximately the same mole as the haloalkanesulfonic acid used is by-produced. When the sulfoalkylation reactant is blended into a product or the like, the halogenated salt contained in the sulfoalkylation reactant causes problems in freedom of blending, performance, viscosity, stability and the like depending on the use.

[0004] Therefore, in order to remove the halide salt from the sulfoalkylation reaction, extraction, electrodialysis, crystallization,
It is necessary to use a purification method such as ultrafiltration. However, these methods have a problem in that the purification load is large, resulting in an increase in capital investment and an increase in production cost.

[0005] An object of the present invention is to provide a method for producing a sulfoalkylating agent with high production efficiency which can efficiently reduce by-products of halide salts by a simple method.

It is another object of the present invention to provide a method for efficiently producing a sulfoalkylated hydroxyl compound having a reduced halide salt by reacting the sulfoalkylating agent with a hydroxyl compound.

[0007]

SUMMARY OF THE INVENTION The present invention provides a method for reacting a haloalkanesulfonic acid having 2 to 5 carbon atoms having a hydroxyl group or a salt thereof with an alkali compound to obtain an alkanesulfonic acid salt having an epoxy group and a halogenated salt. After getting
The present invention relates to a method for producing an alkane sulfonate having an epoxy group (hereinafter referred to as a “sulfoalkylating agent”) for separating the halogenated salt. The present invention also relates to a method for producing a sulfoalkylated product of a hydroxyl compound by reacting the sulfoalkylating agent thus obtained with a hydroxyl compound.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION C 2 having a hydroxyl group
Examples of the haloalkanesulfonic acid (hereinafter referred to as “halohydroxyalkanesulfonic acid”) or salts thereof include those represented by the following formula (1).

[0009]

Embedded image

Wherein A: halogen atom, preferably chlorine atom, M: hydrogen atom, alkali metal atom, alkaline earth metal atom or ammonium, preferably hydrogen atom, sodium atom or potassium atom, n: 1-3 When the number of carbon atoms is 5 or less, the hydrophobicity becomes appropriate and the separation from the halide salt becomes easy.

The alkali compound is not particularly limited but is preferably an alkali metal hydroxide from the viewpoint of reactivity, and more preferably sodium hydroxide and potassium hydroxide.

When a halohydroxyalkanesulfonic acid is used, the amount of the alkali compound is preferably 1.5 to 2.1 moles, more preferably 1.8 to 2.05 moles, based on the halohydroxyalkanesulfonic acid. It is twice. 1.
When it is 5 mol times or more, the yield of the sulfoalkylating agent and the removal rate of the halide salt increase. On the other hand, when the molar ratio is less than 2.1 moles, the sulfoalkylating agent hardly reacts with water and decomposes due to excess alkali compound.

When a halohydroxyalkanesulfonate is used, the amount of the alkali compound is preferably from 0.5 to 1.1 times, more preferably from 0.8 to 1 mol, per mol of the halohydroxyalkanesulfonate. .05 molar times.
When the amount is 0.5 mol times or more, the yield of the sulfoalkylating agent and the removal rate of the halide salt increase. On the other hand, when the molar ratio is less than 1.1 mol, it is unlikely that the sulfoalkylating agent reacts with water and decomposes due to excess alkali compound.

When a sulfoalkylating agent is prepared by reacting a halohydroxyalkanesulfonic acid or a salt thereof with an alkali compound, the amount of water is preferably from the viewpoint of precipitating a halide salt. Is preferably 0.1 to 1.2 times by weight, and more preferably 0.2 to 0.8 times by weight. When it is 0.1 weight times or more, the concentration of the slurry in which the halide salt is precipitated is appropriate, so that there is no operational problem and the yield of the sulfoalkylating agent is improved. Further, when the weight is 1.2 times by weight or less, the amount of the dissolved halide is reduced, and the amount of the precipitated halide is increased. In the present invention, the concept of the aqueous solution is also included in the slurry, since the precipitation amount of the halide salt may be small to form an aqueous solution.

The method of reacting the halohydroxyalkanesulfonic acid or a salt thereof with an alkali compound is not particularly limited, but it is preferable to drop the alkali compound into an aqueous solution of the halohydroxyalkanesulfonic acid or a salt thereof. The dropping time is preferably 0.5 to 5 hours, and then 0.5 hours.
The aging reaction is preferably performed for 1 to 3 hours.

The halohydroxyalkanesulfonic acid or a salt thereof is preferably handled as an aqueous solution. When the amount of water contained is larger than the above amount, it is preferable to remove the water outside the system by distillation or the like. . In this case, the water may be removed first and the alkali compound added, or the water may be removed after the alkali compound is added first, or the alkali compound may be divided and added before and after the water is removed. Is also good.

After the reaction, if the halide salt is precipitated by cooling or standing, a mixture of the sulfoalkylating agent dissolved in water and the halide salt as a precipitate is obtained.

The method for separating the precipitated halide salt is not particularly limited, but centrifugation, filtration, extraction, electrodialysis, crystallization, ultrafiltration and the like can be used to obtain the sulfoalkylating agent of the present invention. .

The temperature for the addition, precipitation and separation of the alkali compound is -10 to 40 ° C, preferably 0 to 20 ° C.
It is desirable to perform at. When the temperature is higher than −10 ° C., the aqueous solution does not thicken, and the yield of the sulfoalkylating agent is improved. When the temperature is lower than 40 ° C., the decomposition of the generated sulfoalkylating agent tends to be reduced.

Further, the hydroxyl compound is sulfoalkylated using the sulfoalkylating agent obtained by this method, and a part or all of the hydrogen atoms of the hydroxyl group of the hydroxyl compound is substituted with a sulfoalkyl group or a salt thereof. A sulfoalkylated compound of the compound can be obtained.

Examples of the hydroxyl compound include polysaccharides.

Examples of the polysaccharide include those described in JP-A-9-110901, column 3, line 4, lines 39 to 50. Among them, cellulose, hydroxyethylcellulose, methylcellulose, ethylcellulose, hydroxypropyl Cellulose such as cellulose and compounds having a cellulose structure are preferred. 10 to 10 carbon atoms which may have an oxycarbonyl group or an ether bond inserted
A polysaccharide derivative in which a hydrogen atom of a hydroxyl group is substituted with 43 linear or branched alkyl groups, alkenyl groups or acyl groups may be used. The degree of substitution is preferably 0.
0001 to 0.1.

The amount of the sulfoalkylating agent used in the reaction depends on the amount of the sulfoalkyl group introduced into the hydroxyl compound, but is preferably 0.01 to 5 relative to the hydroxyl compound (per polysaccharide for the constituent monosaccharide). A molar amount, preferably 0.05 to 2 molar times, is desirable. In addition, as the addition method, batch, division, or drop addition may be mentioned, but the division or drop method is preferable.

The sulfoalkylation reaction is preferably carried out in the presence of an alkali compound. As the alkali compound, sodium hydroxide and potassium hydroxide are preferable,
It is preferable to use the alkaline compound used in preparing the aqueous sulfoalkylating agent solution without removing it. The amount of the alkali compound to be present in the system is preferably 0.01 to 5 moles per mol of the hydroxyl compound (per polysaccharide for the constituent monosaccharide).

Examples of the solvent for the sulfoalkylation reaction include lower alcohols having 3 to 5 carbon atoms, such as isopropyl alcohol and tert-butyl alcohol.
The amount used is 0.05 to 2 with respect to the hydroxyl compound.
It can be performed at 5 times the weight. In order to improve the reactivity, the reaction may be carried out by adding water to the lower alcohol in an amount of 0.01 to 2.0 times by weight.

The reaction temperature is preferably in the range of 10 to 80 ° C, more preferably 20 to 50 ° C. The reaction is preferably performed for 1 to 30 hours, and after completion, the alkali compound is neutralized using an acid compound. As the acid compound to be used, inorganic acids such as sulfuric acid, hydrochloric acid and phosphoric acid, and organic acids such as acetic acid can be used.

The sulfoalkylated product thus obtained can be subjected to filtration, drying and the like, if necessary.

[0028]

【Example】

Synthesis Example 1 A 35% aqueous sodium bisulfite solution 17 was placed in a 500 mL glass reaction vessel equipped with a stirrer, thermometer and vacuum equipment.
8.4 g and 1.5 g of a 48% aqueous sodium hydroxide solution were charged, and the temperature was raised to 60 ° C. while stirring. 54.4 g of epichlorohydrin was added dropwise over 1 hour at a temperature in the range of 55 to 65 ° C., and then the temperature was raised to 70 ° C. and the reaction was carried out for 2 hours. Was confirmed by gas chromatography to be 10 ppm or less, and cooled to 10 ° C to obtain a slurry containing sodium 3-chloro-2-hydroxypropanesulfonate.

Example 1 In a reaction vessel containing the slurry containing sodium 3-chloro-2-hydroxypropanesulfonate obtained in Synthesis Example 1, 13.2 g of a 48% aqueous sodium hydroxide solution was taken for 0.3 hours. And dropped. Reduce the pressure to 9-10 kPa,
At 40 to 50 ° C., 78.8 g of water was distilled out of the system. Then, at 10 to 15 ° C., 48% aqueous sodium hydroxide solution 3
4.0 g was added dropwise over 0.5 hours, and the reaction was carried out for 1 hour to obtain a slurry containing sodium 2,3-epoxypropanesulfonate and a precipitate of sodium chloride.

The slurry was filtered at 10 to 12 ° C. using a filter paper No. 2 with Nutsche, and 143.6 g of an aqueous solution containing sodium 2,3-epoxypropanesulfonate was filtered.
As a filtrate and a cake containing sodium chloride 50.
1 g was obtained as filtration residue. The analysis results and the desalting ratio of the filtrate are shown in Table 1. The desalting rate (%) is calculated according to the equation (2).

[0032]

(Equation 1)

Example 2 A slurry containing sodium 3-chloro-2-hydroxypropanesulfonate separately synthesized by the method of Synthesis Example 1 was dried in a 300 mL glass reaction vessel equipped with a stirrer and a thermometer. 70.5 g of the powder obtained and 13.3 g of water.
After adding 1 g and adjusting the temperature to 5 ° C., 41.8 g of a 48% aqueous potassium hydroxide solution was added dropwise at 10 to 12 ° C. over 0.5 hours, and the reaction was carried out at 5 ° C. for 1 hour. A slurry containing sodium epoxypropanesulfonate and potassium chloride precipitate was obtained.

The above slurry was filtered at 15 ° C. using a filter paper No. 2 at Nutsche, and 95.6 g of an aqueous solution containing sodium 2,3-epoxypropanesulfonate was used as a filtrate and a cake containing potassium chloride 29. 8 g were obtained as filtration residue. The analysis results and the desalting ratio of the filtrate are shown in Table 1.

[0035]

[Table 1]

Example 3 Hydroxyethylcellulose (average molecular weight 250 per constituent monosaccharide, manufactured by Union Carbide Co., Ltd.) was placed in a 1000 mL glass reaction vessel equipped with a stirrer, thermometer, and cooling tube.
Product name: QP15000H LOT. NO W8077
P) 40 g, isopropyl alcohol 178.0 g, and ion-exchanged water 31.4 g were added to prepare a slurry. 2.7 g of 48% aqueous sodium hydroxide solution under a nitrogen atmosphere
Was added and the temperature was raised to 40 ° C. The aqueous solution of sodium 2,3-epoxypropanesulfonate obtained in Example 1 there
(48.9 wt%) 52.4 g (1.0 mol times, relative to hydroxyethyl cellulose) was added, and a sulfoalkylation reaction was carried out at 40 ° C. for 12 hours. Then cool to 30 ° C,
Neutralization was performed using 1.5 g of 5% phosphoric acid. The obtained polysaccharide sulfoalkylated slurry was filtered with Nutsche using filter paper 2 and filtered at 70 ° C. under a reduced pressure of 1 kPa or less.
After drying for 2 hours, the mixture was pulverized to obtain 65.4 g of a polysaccharide sulfoalkylated product as a yellowish white powder. The analytical values are shown in Table 2.

Synthesis Example 2 178.4 g of 35% aqueous sodium bisulfite solution was placed in a 500 mL glass reaction vessel equipped with a stirrer and a thermometer, and 48
A 0.4% aqueous sodium hydroxide solution was charged, and the temperature was raised to 60 ° C. while stirring. There epichlorohydrin 5
4.4 g was added dropwise over 1 hour at a temperature in the range of 55 to 65 ° C., then the temperature was raised to 70 ° C. and the reaction was carried out for 2 hours to obtain sodium 3-chloro-2-hydroxypropanesulfonate. It was confirmed by gas chromatography that unreacted epichlorohydrin was 10 ppm or less. After cooling to 45 ° C., 152.2 g of water was added and 30.0 wt% of uniform and transparent was added.
Of sodium 3-chloro-2-hydroxypropanesulfonate was obtained.

Comparative Example 1 In place of 52.4 g (1.0 mol times, based on hydroxyethyl cellulose) of the aqueous solution of sodium 2,3-epoxypropanesulfonate (48.9 wt%) obtained in Example 1, Synthesis Example 2 was used. Of the aqueous solution of sodium 3-chloro-2-hydroxypropanesulfonate (30.0 wt%) obtained in
9 g (1.0 mol times, relative to hydroxyethyl cellulose),
In the same manner as in Example 3 except that 13.3 g of a 48% aqueous sodium hydroxide solution was added, 71.0 g of a polysaccharide sulfoalkylated product as a yellowish white powder was obtained. The analytical values are shown in Table 2.

[0039]

[Table 2]

Test Example Each of the sulfoalkylated products obtained in Example 3 and Comparative Example 1 was added to a concrete agent (methacrylic acid / methoxypolyethylene glycol methacrylate (8/2) copolymer Na salt 20% aqueous solution) at a concentration of 0.1%. As a result of conducting a dispersion stability test at 40 ° C. by mixing 5%, there was no problem such as stability of the drug using the sulfoalkylated product obtained in Example 3. However, the drug using the sulfoalkylated product obtained in Comparative Example 1 was poor in stability and separated.

[0041]

According to the present invention, it is possible to obtain a sulfoalkylating agent capable of efficiently reducing the by-product halogenated salt by a simple method and performing an efficient reaction. Further, the sulfoalkylating agent can be reacted with a hydroxyl compound to efficiently obtain a sulfoalkylated compound having a reduced halide salt.

Claims (4)

[Claims] An alkanesulfonic acid salt having an epoxy group and a halogenated salt are obtained by reacting a haloalkanesulfonic acid having 2 to 5 carbon atoms having a hydroxyl group or a salt thereof with an alkali compound, and then obtaining the halogenated salt. Alkane sulfonate having an epoxy group to separate salts
(Referred to as "sulfoalkylating agent"). 2. The method according to claim 1, wherein the step of separating the halide salt comprises filtration and / or
The method according to claim 1, further comprising a centrifugation operation. 3. A method for producing a sulfoalkylated product, wherein a part or all of the hydrogen atoms of a hydroxyl group is substituted with a sulfoalkyl group or a salt thereof, by reacting a hydroxyl compound with a sulfoalkylating agent. Using an alkane sulfonate having an epoxy group obtained by the production method according to claim 1 or 2, as a sulfoalkylating agent,
A method for producing a sulfoalkylated product. 4. The method for producing a sulfoalkylated product according to claim 3, wherein the hydroxyl compound is a polysaccharide.