JPS58225057A - Preparation of hydroxyalkanesulfonic acid derivative - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as a raw material for amidoalkanesulfonic acid derivatives in high purity and yield, by reacting an alpha-alkylstyrene with a hydrogenbisulfite of an alkaline earth metal as a hydrogensulfite ion supply source. CONSTITUTION:An alpha-alkylstyrene is reacted with hydrogensulfite ions in the presence of oxygen in an aqueous medium at -20-+70 deg.C to give the aimed substance of the formula (R is 1-10C lower alkyl). In the process, a hydrogensulfite of an alkaline earth metal, e.g. calcium or barium, is used as the hydrogensulfite ion supply source, and the reaction is carried out in the suspension of the sulfite of the alkaline earth metal. According to the method, the pH of the reaction solution is easily adjusted, and the dispersion of the alpha-alkylstyrene in the aqueous medium is kept in a good state. The amidoalkanesulfonic acid derivative is useful as a dispersant for calcium soaps, a raw material for water- soluble high polymers, etc.

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 raw materials for water bathing polymers.
The present inventors have developed a hydroxyalkadisulfonic acid represented by the general formula % (where R represents a lower alkyl group having 1 to 10 carbon atoms) and its derivatives as a new compound and a new manufacturing method; A method for the production thereof has been filed, which comprises reacting α-alkylstyrene with bisulfite ions in an aqueous medium in the presence of oxygen.

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. As a result, the following six problems were identified. 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 speed up the reaction, i'H
It is necessary to make adjustments, but this operation is often complicated.

The second problem is that the solubility of α-alkylstyrene in water is low. In order to speed up the reaction, it is necessary to disperse the α-alkylstyrene finely in water, or to add a third substance to the α-alkylstyrene. There is a need to improve the solubility of alkylstyrenes 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 sixth component from the target compound, and recovery of the added solvent.

The third problem is separation of the target compound.Since hydrogen sulfite ions and by-product hydrogen sulfate ions exist in the reaction solution and are nonvolatile, contamination by these substances occurs when the target compound is separated. That's a thing. 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 the contaminants and the target compound are ionic substances, a huge amount of ion exchange resin is required, which increases the manufacturing cost.

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

As a result of intensive studies to solve the problem mentioned above, the present inventors produced hydroxyalkanesulfonic acid derivatives by reacting α-alkylstyrene with immediate acid hydrogen ions in the presence of oxygen in an aqueous medium. In the method, by using an alkaline earth metal bisulfite as a hydrogen sulfite ion supplying substance and starting the reaction under suspension of the alkaline earth metal sulfite, the pH of the reaction solution is adjusted to 91.
The inventors have discovered that it is possible to easily separate α-alkylstyrene in an aqueous medium, and to separate the target compound with high purity, thereby achieving the present invention.

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, while - as a result of the reaction,
Bisulfite ions are regenerated, and as a result, the loss of hydrogen sulfite ions due to 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 sulfite, the separation of the two layers becomes extremely slow, and the suspended matter causes α
- The alkylstyrene oil droplets are stabilized.

Furthermore, when using calcium or barium ions as alkaline earth metal ions and adding their oxides, hydroxides or carbonates to neutralize the pH of the reaction solution and stop the reaction, The hydrogen sulfite ions and hydrogen sulfate ions become sulfites and sulfates with low solubility in water, and can be separated as precipitates from the water bath solution, making it possible to obtain the target product with high purity.

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

Examples of the α-alkylstyrene applicable to the present invention include styrene derivatives substituted with a lower alkyl group having 1 to 10 carbon atoms at the α-position of the double bond of styrene, such as eva-α-methylstyrene, α-ethylstyrene, α- Examples include n-propylstyrene and α-isopropylstyrene.

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, the higher the oxygen concentration in the supplied gas, the
This is advantageous in that the reaction can proceed rapidly.

As the water repellent medium, it is preferable to use various types of water such as well water, tap water, industrial water, and ionized water. Alternatively, a mixture of water and an organic bath agent that is 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. In addition, although it is possible to react various surfactants by adding a phase transfer catalyst, the method of the present invention can sufficiently achieve the purpose without adding any third component. It can be achieved.

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

Alkaline earth metal bisulfites exist only in the presence of free sulfite in the bath solution. Therefore, the method for preparing bisulfite of alkaline earth metals is to add sulfite to a water bath solution in which sulfite is dissolved and to blow sulfur dioxide gas into a water bath solution in which sulfite is suspended. There is a way to go.

On the other hand, in order to make a part of sulfite suspended, the amount of sulfite added is usually 10% of the amount of sulfite, although it varies depending on the type of alkaline earth metal ion and the concentration of sulfite.
It is preferable to make it twice the mole or less.

The raw material, sulfite, can be produced by neutralizing an alkaline earth metal hydroxide or oxide with sulfite, or by reacting an alkaline earth metal carbonate with ll1i-sulfuric acid. , or a method of producing by bale decomposition of an alkali metal sulfite and an alkaline earth metal chloride. 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.

In addition, 1, which forms a redox system with hydrogen sulfite ions,
The reaction can also be accelerated by adding transition metal ions such as l=+ and cξ+.

The pH of the reaction solution in the method of the present invention is usually adjusted within the range of 02 to O. In general, alkaline earth metal bisulfite coexists with sulfite, so the Pl of the bath solution decreases.
(is between 1 and 2, and the pH of the bath solution decreases as the reaction progresses.↑If H becomes 0.5 or less, remove alkaline earth metal oxides, hydroxides, carbonates, or sulfites. It can be easily adjusted by adding.

In addition, the reaction does not need to be carried out at high temperatures, usually -20 to 70
°C1 is preferably in the range of -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, regarding the quantitative relationship between hydrogen sulfite ions and α-alkylstyrene, since the hydrogen sulfite ion concentration in the reaction solution cannot be determined unambiguously, the sulfite added to sulfite and α-methyl Expressed in terms of quantitative relationship with styrene, the molar ratio is 0.5-30.0, preferably 1
．． The range is 0-20.0.

Further, there is no particular restriction on the addition ratio of α-alkylstyrene to be reacted with the aqueous medium, but the volume ratio is 5/95 to 5/95.
The range is 70/30.

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. Add α-methylstyrene to the bath solution of sulfite aqueous ions produced by Method 1, or by suspending alkaline earth metal sulfites, carbonates, hydroxides, or oxides in sulfite water. Then, an oxygen-containing gas is introduced to start the reaction. 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 carrying out the reaction for a predetermined period of time while monitoring the reaction, the desired 2-phenyl-2-hydroxyalka/sulfo/acid salt can be separated according to a conventional method. As a method for monitoring the reaction, a method is used in which the supply of oxygen, the disappearance of α-alkylstyrene, the production of the target product, etc. are detected using a gas chromatograph or the like.

Next, to separate the target product, the suspended P in the reaction solution is separated, and an alkaline earth metal oxide, hydroxide, or carbonate is added to the r solution to adjust the pH of the solution to 4 to 10. After that, P is separated from the unbathed material, and the aqueous medium is distilled off from the liquid f, whereby the target compound can be obtained in high purity in 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 f-alkaline earth metal ion, but when changing to another ion, the solution is passed through an H-type strongly acidic cation exchange resin. This can be carried out by neutralizing the effluent with a predetermined alkali, or by replacing the cation exchange resin with the cations to be exchanged and then passing the liquid through the cation exchange resin.

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. However, the desired amidoalkanesulfonic acid derivative can be produced.

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, raw materials for water bathing polymers, 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 and 6
After adding 11% sulfite water and replacing the atmosphere in the flask with oxygen while stirring, 105g of α-methylstyrene was added.
was added, and the reaction was started at 30°0 with a stirring speed of 1.00 Or pm under suspension of calcium sulfite, and the reaction was 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 1 otrurqtg.

During this time, the pH of the reaction solution decreased to below 065, so
Calcium hydroxide was added to maintain PI at 0.5 or higher. This operation was repeated three times until the reaction was completed.

1. After the reaction solution was separated from each other to remove insoluble matter, calcium hydroxide was added to adjust the pH of the solution to 5.

The insoluble matter was separated again, water was distilled off from the P solution, and calcium 2-phenyl-2-hydroxypropanesulfonate 1
84 g (yield 88%) was obtained.

Comparative example 1 27? 11 g of calcium sulfite and 6
After adding 11% sulfite water and replacing the atmosphere in the flask with oxygen while stirring, α-methylstyrene 309 was added and the reaction was carried out at 30'O for 15 hours at a stirring speed of 1.000 rpm. 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 by 10 mm.

During this time, the pH of the reaction solution decreased to below 10.5, so calcium hydroxide was added to maintain the pH above 05. This operation was repeated 7 times until the reaction stopped.

Calcium hydroxide was added to the reaction solution, the unbathed part of the solution was separated, and water was distilled off from the F solution. The yield of calcium 2-phenyl-2-hydroxypropanesulfonate was 44 g (yield: 61 %)Met.

Example 2 209 g of calcium hydroxide and 11 ml of ion-exchanged water were added to a round bottom flask of No. 21, and the atmosphere inside the flask was replaced with oxygen while stirring, and then 240 g of sulfur dioxide was blown into the flask. After the blowing was completed, 105 g of α-methylstyrene was added, and the reaction was carried out at 30°G and a stirring speed of 11,000 rpm for 5 hours.

The reaction was carried out in a closed system, and the pressure inside the flask was jQmml (
g Oxygen was supplied so that the pressure was increased.

゛During this time, the pH of the reaction solution decreased from 2 to 08.

During the reaction, the pH was 0.5 or above, so P) 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 not adjusted. 188& (yield qo%) was obtained.

Reference Example 1 In Example 1, the pH of the reaction solution was adjusted to 015 with sulfuric acid, and after that, the pH was not adjusted and the rest was carried out in the same manner as in Example 1. The yield of the target compound was 15
g (yield: 7).

Example 3 The reaction was carried out in exactly the same manner as in Example 1 except that one drop of copper 10 sulfate water bath solution was added, and the reaction was carried out for 3 hours to obtain 194 II of the target compound (yield: 92 II).

Example 4 612 g of barium sulfite and 14 y of ion-exchanged water were added to the round bottom flask of No. 21, and after replacing the atmosphere in the flask with oxygen while stirring, 72 g of sulfur dioxide gas was blown in, and then 105 y of α-methylstyrene was added. and stirring speed t
The reaction was carried out at 3000 rpm for 5 hours. After that, mK was carried out exactly as in Example 1, and 2-phenyl-2-
227 g (yield: 90%) of barium hydroxyfuropanesulfonate was obtained.

Procedural amendment Written on July q, 1982 by Mr. Aio Wakasugi, Commissioner of the Patent Office1, Indication of the case Patent Application No. 106711 of 19832, Title of invention Process for producing hydroxyalkanesulfonic acid derivatives3, Amendment. ``Detailed explanation of the invention'' column (1) of the specification of the person who makes the claim: ``In the case of changing to another ion, ... omitted ... can be done'' on page 13 of the specification, lines 3 to 8. Correct it like this.

[When changing to all alkali ions, this can be done by adding hydroxides, oxides, carbonates, etc. of alkali metal ions as the basic substance added at the time of reaction termination F.

In addition, when changing to other ions including alkali metal ions, there is a method of passing the liquid through a type 1 strongly acidic cation exchange resin and neutralizing the effluent with a specified alkali, or using the cation to be exchanged. Attachment (2) Page 17, 21, which can be carried out by replacing the exchange resin and passing liquid through the cation exchange resin, and double decomposition with sulfate.
Insert the following example into the line.

[Reaction Example 5 The reaction was carried out in exactly the same manner as in Example 2. That is, after the reaction was carried out at 30°C for 5 hours, 50 sodium thihydroxide faW
After adding 65 g of calcium carbonate and 10 g of calcium carbonate, it was confirmed that the pH of the reaction solution was 4 or more, and the insoluble portion was separated by e. Water was distilled off from the r liquid to obtain 192 g (yield 91%) of sodium 2-phenyl-2-hydroxypropanesulfonate.

Patent applicant: Mitsui Toatsu Chemical Co., Ltd. :・

Claims (3)

[Claims] (1) A sulfonic acid derivative represented by the general formula (R represents a lower alkyl group having 1 to 10 carbon atoms) is produced by reacting α-alkylstyrene with hydrogen sulfite ions in an aqueous medium in the presence of oxygen. In the manufacturing method, an alkaline earth metal sub(f) is used as a salivary hydrogen sulfate ion supplying substance.
[A method for producing hydroxyalkanesulfonic acid derivatives, which uses a hydrogen salt and starts the reaction under suspension of an alkaline earth metal sulfite. (2) The method according to claim 1, wherein the alkaline earth metal is calcium or barium. (3) The method according to claims 1 and 2, wherein the hydroxyalkanesulfonic acid derivative is 72-phenyl-2-hydroxypropanesulfonic acid and a salt thereof.