JPH0341461B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing hydroxyalkanesulfonic acid derivatives.

More specifically, the present invention relates to a manufacturing method that facilitates reaction control in manufacturing the compound and separates the compound with high purity.

Hydroxyalkanesulfonic acid derivatives are useful as raw materials for amidoalkanesulfonic acid derivatives, which have various uses such as lime soap dispersants and water-soluble polymer raw materials. As a method, the general formula (However, R represents a lower alkyl group having 1 to 10 carbon atoms.) Reacting the hydroxyalkanesulfonic acid represented by the formula and its derivatives, and α-alkylstyrene with hydrogen sulfite ions in an aqueous medium in the presence of oxygen. An application has been filed for a method of manufacturing the same.

The present inventors conducted a detailed study on a method for producing hydroxyalkanesulfonic acid derivatives by reacting an oil layer of α-alkylstyrene with an aqueous solution layer in which bisulfite ions are dissolved in suspension according to the production method described above. When I was doing it, I mainly found the following 3 things.
One problem became clear. That is, the first problem is that the pH of the reaction solution decreases as the reaction progresses. This is due to an increase in hydrogen sulfite ions produced as a by-product in the reaction, resulting in a decrease in the concentration of hydrogen sulfite ions and a decrease in the reaction rate. Therefore, in order to make the reaction proceed quickly, it is necessary to adjust the pH by adding an alkali or the like, but this operation is often complicated.

The second problem is that the solubility of α-alkylstyrene in water is low, and in order to make the reaction occur quickly, it is necessary to disperse it in water finely, or to
It is necessary to add substances to improve the solubility of the alpha-alkylstyrene in aqueous media. Generally speaking, this method involves adding a surfactant or a phase transfer catalyst to carry out the reaction, or carrying out the reaction in a mixture of water and an organic solvent that is miscible with water. However, new problems arise such as an increase in manufacturing costs due to the addition of the third component, separation of the third component from the target compound, and recovery of the added solvent.

The third problem is the separation of the target compound, since hydrogen sulfite ions and by-product hydrogen sulfate ions are present in the reaction solution and are nonvolatile.
When separating target compounds, contamination with these substances occurs. Possible methods for minimizing the contamination include purification by recrystallization or purification by ion exchange resin.

However, in the recrystallization method, since there is no extreme difference in solubility between the contaminant and the target compound, it is necessary to repeat recrystallization, resulting in a poor product yield. Furthermore, in the method using an ion exchange resin, since both the contaminant and the target compound are ionic substances, a huge amount of ion exchange resin is required, leading to an increase in manufacturing costs.

As mentioned above, even if attempts are made to solve the problems associated with the production of the compound by using general methods, there are advantages and disadvantages, and the method is not always satisfactory.

As a result of intensive studies to solve the above problems, the present inventors found that in a method for producing hydroxyalkanesulfonic acid derivatives by reacting α-alkylstyrene with hydrogen sulfite ions in an aqueous medium in the presence of oxygen, By using bisulfite of an alkaline earth metal as a hydrogen sulfite ion supplying material and starting the reaction under suspension of the alkaline earth metal sulfite, the pH of the reaction solution can be easily adjusted, and α-alkyl The present invention was achieved by discovering that it is possible to maintain good dispersion of styrene in an aqueous medium and to separate the target compound with high purity.

In other words, by suspending alkaline earth metal sulfite in the reaction solution, hydrogen sulfate ions, which cause a decrease in pH, react with the sulfite to form sulfate with low solubility in water. Precipitates from the liquid,
On the other hand, as a result of the reaction, hydrogen sulfite ions are regenerated, and as a result, the loss of hydrogen sulfite ions accompanying the by-production of hydrogen sulfite ions is compensated for.

In addition, by suspending the alkaline earth metal sulfite in the reaction solution, the α-alkylstyrene oil layer can be very well dispersed, and if no sulfite was present, it would immediately separate into two layers, but
By suspending the sulfite, the separation of the two layers becomes extremely slow, and the suspension stabilizes the α-alkylstyrene oil droplets.

Furthermore, calcium or barium ions are used as alkaline earth metal ions, and their oxides, hydroxides, or carbonates are added to adjust the pH of the reaction solution.
When stopping the reaction by neutralizing the reaction solution, the hydrogen sulfite ions and hydrogen sulfate ions in the reaction solution become sulfites and sulfates with low solubility in water, and can be separated as precipitates from an aqueous solution. You can obtain products with high purity.

Next, the present invention will be explained in more detail.

As the α-alkylstyrene that can be applied to the present invention, the α-alkylstyrene has 1 to 1 carbon atoms at the α-position of the double bond of styrene.
styrene derivative substituted with 10 lower alkyl groups,
Examples include α-methylstyrene, α-ethylstyrene, α-n-propylstyrene, α-isopropylstyrene, and the like.

Further, as the oxygen to be supplied to the reaction system, pure oxygen gas or an oxygen-containing gas such as air may be supplied. However, a higher oxygen concentration in the supplied gas is advantageous in that the reaction can proceed more quickly.

As the aqueous medium, it is preferable to use various types of water such as well water, tap water, industrial water, and ion exchange water. Alternatively, a mixture of water and an organic solvent miscible with water may be used as the reaction solvent, but in the method of the present invention, the purpose can be sufficiently achieved by using water alone. It is also possible to carry out the reaction by adding various surfactants or phase transfer catalysts, but according to the method of the present invention, the purpose can be sufficiently achieved without adding these third components. I can do things.

Although any alkaline earth metal ion may be employed in the method of the present invention, calcium and barium ions are particularly preferred.

Alkaline earth metal bisulfites exist only in the presence of free sulfite in aqueous solution. Therefore, methods for preparing bisulfite of alkaline earth metals include a method of adding sulfite to an aqueous solution in which sulfite is dissolved, and a method of blowing sulfur dioxide gas into an aqueous solution in which sulfite is suspended. There is.

On the other hand, to make a part of the sulfite suspended, the amount of sulfite added is usually less than 10 times the amount of sulfite, although it depends on the type of alkaline earth metal ion and the concentration of sulfite. It is preferable to do so.

In addition, the raw material sulfite can be produced by neutralizing an alkaline earth metal hydroxide or oxide with sulfite, by reacting an alkaline earth metal carbonate with sulfite, or Any method such as a method for producing by double decomposition of an alkali metal sulfite and an alkaline earth metal chloride may be used. Especially in the former case, even if the neutralization of hydroxide or oxide with sulfite is not completed, after adding a predetermined amount of sulfite, α
-The reaction can also be carried out by adding an alkyl styrene.

The reaction can also be promoted by adding transition metal ions such as F ³ _l ⁺ and C ² _u ⁺ that form a redox system with hydrogen sulfite ions.

The pH of the reaction solution in the method of the present invention is usually 0.2
It is adjusted to a range of 6 to 6. Generally, alkaline earth metal bisulfite coexists with sulfurous acid, so the pH of the solution is between 1 and 2, and the pH of the solution decreases as the reaction progresses. If the pH is below 0.5, it can be easily adjusted by adding alkaline earth metal oxides, hydroxides, carbonates, or sulfites.

Also, the reaction does not need to be carried out at high temperatures, usually -20
-70°C, preferably -10 to 60°C, and the reaction time varies depending on the reaction temperature, but is in the range of 20 minutes to 10 hours.

In the method of the present invention, the quantitative relationship between hydrogen sulfite ions and α-alkylstyrene is as follows:
Since the hydrogen sulfite ion concentration in the reaction solution cannot be determined unambiguously, the sulfite added to the sulfite and α-
Expressed in terms of quantitative relationship with methylstyrene, the molar ratio is in the range of 0.5-30.0, preferably 1.0-20.0.

Further, the ratio of addition of α-alkylstyrene to be reacted with the aqueous medium is not particularly limited, but is in the range of 5/95 to 70/30 in terms of volume ratio.

To suitably carry out the method of the present invention, first, an alkaline earth metal sulfite, carbonate, hydroxide, or oxide is suspended in an aqueous medium, and sulfur dioxide gas or sulfite water is added thereto. α-methylstyrene is added to an aqueous solution of hydrogen sulfite ions produced by a method of suspending an alkaline earth metal sulfite, carbonate, hydroxide, or oxide in sulfite water, and then The reaction is started by introducing an oxygen-containing gas. At this time, it is preferable to start the reaction with the alkaline earth metal sulfite suspended in the reaction solution in order to improve the dispersion of the α-alkylstyrene and to allow the reaction to proceed rapidly.

Oxygen may be supplied by blowing oxygen or an oxygen-containing gas under flow, or may be supplied under pressure in a closed system. However, the latter closed system reaction is more convenient in that the reaction can be carried out more quickly.

In order to further speed up the reaction, the stirring speed may be increased to facilitate the absorption of oxygen gas into the reaction solution, and the α-alkylstyrene may be finely dispersed.

After performing the reaction for a predetermined time while tracking the reaction,
The desired 2-phenyl-2-hydroxyalkanesulfonate salt can be separated according to conventional methods. The reaction can be monitored by detecting the supply of oxygen, the disappearance of α-alkylstyrene, the production of the target product, etc. using a gas flowmeter, gas chromatograph, high-performance liquid chromatograph, or the like.

Next, to separate the target product, the suspension in the reaction solution is separated and the alkaline earth metal oxide,
Add hydroxide or carbonate to bring the pH of the solution to 4~
After the concentration is reduced to 10%, insoluble matters are separated and the aqueous medium is distilled off from the liquid, whereby the target compound can be obtained in high purity from the remainder. Furthermore, in the above method, an alkaline earth metal oxide, hydroxide, or carbonate may be added without separating the reaction solution.

The target compound thus separated can be used as it is as a raw material for the synthesis of amidoalkanesulfonic acid, or if a highly purified product is to be used after further purification, it can be recrystallized from a polar solvent such as water or aqueous alcohol. or a method in which the solution is passed through an ion exchange resin such as an H-type strongly acidic cation exchange resin, and the effluent is purified by adding an alkaline earth metal hydroxide or carbonate.

In addition, in the method of the present invention, the counter cation of the target sulfonate is an alkaline earth metal ion, but when changing to an alkali metal ion, an alkali metal ion is added as a basic substance to be added at the time of reaction termination. It can be changed by adding hydroxides, oxides, carbonates, etc. In addition, when changing to other ions including alkali metal ions, there is a method of passing the liquid through H-type strongly acidic cation exchange resin and neutralizing the effluent with a specified alkali, or cation exchange with the cation to be exchanged. This can be carried out by exchanging the resin and passing liquid through the cation exchange resin, or by double decomposition with a sulfate.

The hydroxyalkanesulfonate produced according to the above method may contain 2-phenyl-2-sulfate-alkanesulfonate as a by-product. However, this compound can be converted to the desired compound by hydrolysis with acid or alkali, and when used as a raw material for producing amidoalkanesulfonic acid derivatives, one containing the above-mentioned by-products can be used. The desired amidoalkanesulfonic acid derivative can be produced without any problem.

The compounds produced by the method of the present invention are useful as raw materials for amidoalkanesulfonic acid derivatives, which have uses as limestone dispersants, water-soluble polymer raw materials, fiber modifiers, etc. A hydroxyalkanesulfonic acid derivative serving as a raw material can be produced with good yield and purity, and an amidoalkanesulfonic acid derivative can be efficiently produced using it as a raw material.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 364 g of calcium sulfite in 2 round bottom flasks
and 1 part of 6% sulfite water, and after replacing the atmosphere in the flask with oxygen while stirring, 105 g of α-methylstyrene was added, and the mixture was stirred at a stirring speed of 1.000 rpm.
The reaction was started at 30°C under suspension of calcium sulfite and continued for 5 hours. The reaction was carried out in a closed system, and oxygen was supplied so that the pressure inside the flask was increased to 10 mmHg.

During this time, the pH of the reaction solution decreased to 0.5 or less, so calcium hydroxide was added to maintain the PH at 0.5 or higher. This operation was repeated three times until the reaction was completed.

After separating the reaction solution to remove insoluble matter, calcium hydroxide was added to adjust the pH of the solution to 5. Insoluble matter was again separated and water was distilled off from the liquid to obtain 184 g of calcium 2-phenyl-2-hydroxypropanesulfonate (yield: 88%).

Comparative Example 1 11 g of calcium sulfite and 1 part of 6% sulfite water were added to the round bottom flask of 1 and 2, and the atmosphere inside the flask was replaced with oxygen while stirring. Then, 30 g of α-methylstyrene was added, and the mixture was stirred at a stirring speed of 1.000 rpm. 0
The reaction was carried out at ℃ for 5 hours. The reaction solution consisted of two layers, a transparent oil layer and a water layer, and the reaction was carried out in a closed system with the oil layer suspended while oxygen was supplied so that the pressure inside the flask was increased to 10 mmHg.

During this time, the pH of the reaction solution decreased to 0.5 or less, so calcium hydroxide was added to maintain the PH at 0.5 or higher. This operation was repeated 7 times until the reaction stopped.

Add calcium hydroxide to the reaction solution and adjust the pH of the solution.
was set as 5.

When the insoluble portion was separated and water was distilled off from the liquid, the yield of calcium 2-phenyl-2-hydroxypropanesulfonate was 44 g (yield 61%).
It was hot.

Example 2 209g of calcium hydroxide in 2 round bottom flasks
After adding 1 part of ion-exchanged water and replacing the atmosphere in the flask with oxygen while stirring, 240 g of sulfur dioxide was blown into the flask. After blowing, add 105 g of α-methylstyrene and stir at 1.000 rpm.
The reaction was carried out at 30°C for 5 hours.

The reaction was carried out in a closed system, with a pressure inside the flask of 10 mm.
Oxygen was supplied to achieve Hg pressurization.

During this time, the pH of the reaction solution decreased from 2 to 0.8.
Since the pH was 0.5 or higher during the reaction, the pH was not adjusted.

The subsequent treatment was carried out in exactly the same manner as in Example 1, and the target compound, calcium 2-phenyl-2-hydroxypropanesulfonate, was 188 g (yield 90%).
I got it.

Reference Example 1 In Example 1, the pH of the reaction solution was adjusted to 0.15 with sulfuric acid, and then the reaction was carried out in the same manner as in Example 1 without adjusting the pH. The yield of the target compound was 15 g. (yield 7%).

Example 3 One drop of 10% copper sulfate aqueous solution was added and the reaction was carried out for 3 hours in the same manner as in Example 1, and 194 g (yield 92%) of the target compound was obtained.

Example 4 612 g of barium sulfite and 1 portion of ion-exchanged water were added to the round-bottomed flask in Step 2, and the atmosphere inside the flask was replaced with oxygen while stirring, and then sulfur dioxide gas was added.
Inject 72g, then 105g of α-methylstyrene.
was added, and the reaction was carried out at 30°C for 5 hours at a stirring speed of 1.000 rpm. Thereafter, the same procedure as in Example 1 was carried out to obtain 227 g (yield: 90%) of barium 2-phenyl-2-hydroxypropanesulfonate.

Example 5 The reaction was carried out in exactly the same manner as in Example 2. i.e. 30
After carrying out the reaction for 5 hours at °C, 65 g of 50% sodium hydroxide solution and 10 g of calcium carbonate were added,
It was confirmed that the pH of the reaction solution was 4 or higher, and the insoluble portion was separated. Distill water from the liquid to obtain 2-phenyl-
Sodium 2-hydroxypropanesulfonate
192g (yield 91%) was obtained.

Claims (1)

[Claims] 1. By reacting α-alkylstyrene with hydrogen sulfite ions in an aqueous medium in the presence of oxygen, the general formula (R represents a lower alkyl group having 1 to 10 carbon atoms.)
A method for producing a sulfonic acid derivative represented by the above, characterized in that an alkaline earth metal bisulfite is used as a hydrogen sulfite ion supplying substance, and the reaction is initiated under suspension of the alkaline earth metal sulfite. A method for producing a hydroxyalkanesulfonic acid derivative. 2. The method according to claim 1, wherein the alkaline earth metal is calcium or barium. 3 Hydroxyalkanesulfonic acid derivative is 2-
Claim 1 or 2, which is phenyl-2-hydroxypropanesulfonic acid and its salts.
The method described in section.