JP2001026575A - Sulfonic derivative of chained polyphenol sulfide and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a novel chained polyphenol sulfide sulfonic derivative that is soluble in water and is useful as a dispersant or a surfactant by sulfonation of a chained polyphenol sulfide that can be simply synthesized from inexpensive raw materials using sulfuric acid. SOLUTION: This is a novel sulfonic derivative of a chained polyphenol sulfide represented by formula I (R1 is H, an alkyl, sulfonic acid group, or the like; (n) is 1-20; in the case of n=1, (a) and (b) are each 0 or 1 and a+b≠0; in the case of n>=2, (a) and (b) are each 0 or 1; (m) is 1 or 2-7). The derivative of formula I is prepared, for example, by allowing a chained polyphenol sulfide of formula II (R2 is an alkyl; (q) is 1-20; in the case of q=1, (d) and (e) are each 0 or 1 where d+e≠0; in the case of q>=2, (d) and (e) are each 0 or 1; (p) is 1 or 2-7) to react with sulfuric acid. When the derivative of formula I is used as a dispersant or surfactant, insoluble or slightly soluble organic compounds can be readily dispersed or dissolved in water clearly without emulsification.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a water-soluble sulfonic acid derivative of a linear polyphenol sulfide useful as a dispersant or a surfactant, and a method for producing the same.

[0002]

2. Description of the Related Art Phenol sulfides are widely used as lubricating oil additives because of their high lipophilicity. However, their production is mainly limited to oil-soluble substances, and water-based No phenol sulfide-based dispersant or surfactant that can be used has been known so far.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a simple method for reacting a linear polyphenol sulfide synthesized from an inexpensive raw material with sulfuric acid to form a sulfonate, which is useful as a dispersant or a surfactant. An object of the present invention is to provide a water-soluble sulfonic acid derivative of a linear polyphenol sulfide and a method for producing the same.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that a linear polyphenol sulfide having a phenol having an alkyl group as a constitutional unit is reacted with sulfuric acid. To find a method for efficiently producing a novel water-soluble sulfonic acid derivative of a linear polyphenol sulfide into which a sulfonic acid group has been introduced, and salting out the sulfonic acid derivative of this linear polyphenol sulfide. As a result, a method for efficiently producing a novel water-soluble sulfonic acid derivative of a linear polyphenol sulfide into which a sulfonic acid salt has been introduced has been found, and the present invention has been completed. That is, the present invention relates to the general formula
(1)

[0005]

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(Wherein R ¹ is a hydrogen atom, an alkyl group, a sulfonic acid group, or a salt of a sulfonic acid group represented by SO ₃ M, and M is a metal, ammonium, lower alkyl ammonium, lower alkanolamine, Or pyridiniums, a plurality of R ¹ may be the same,
Although they may be different, at least one R ¹ is a sulfonic acid group or a salt of a sulfonic acid group, and when there are a plurality of salts of a sulfonic acid group, M may be the same or different. May be. When n = 1, a and b are 0 or 1,
a + b ≠ 0, and when n is 2 or more, a and b may be 0 or 1 and may be the same or different, and m is 1 or an integer of 2 to 7, M may be the same or different. n is an integer of 1 or more and 20 or less. The present invention provides a sulfonic acid derivative of a linear polyphenol represented by the following formula: Further, the present invention provides a compound represented by the general formula (2)

[0007]

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(Wherein R ² is an alkyl group;
² may be the same or different, and when q = 1, d and e are 0 or 1, and d + e ≠
0 and q is 2 or more, d and e may be 0 or 1 and may be the same or different;
Is 1 or an integer of 2 to 7, and a plurality of p's may be the same or different. q is 1 or more and 20
It is the following integer. ) Is reacted with sulfuric acid to obtain the general formula (1)

[0009]

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Wherein R ¹ is a hydrogen atom, an alkyl group, a sulfonic acid group, or a salt of a sulfonic acid group represented by SO ₃ M, wherein M is a metal, ammonium, lower alkyl ammonium, lower alkanolamine, Or pyridiniums, a plurality of R ¹ may be the same,
Although they may be different, at least one R ¹ is a sulfonic acid group or a salt of a sulfonic acid group, and when there are a plurality of salts of a sulfonic acid group, M may be the same or different. May be. When n = 1, a and b are 0 or 1,
a + b ≠ 0, and when n is 2 or more, a and b may be 0 or 1 and may be the same or different, and m is 1 or an integer of 2 to 7, M may be the same or different. n is 1 or more 2
It is an integer less than or equal to 0. The present invention provides a method for producing a sulfonic acid derivative of a linear polyphenol sulfide, which comprises producing a sulfonic acid derivative of a linear polyphenol represented by the following formula: Further, the present invention provides a compound represented by the general formula (2)

[0011]

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(Wherein R ² is an alkyl group;
² may be the same or different, and when q = 1, d and e are 0 or 1, and d + e ≠
0 and q is 2 or more, d and e may be 0 or 1 and may be the same or different;
Is 1 or an integer of 2 to 7, and a plurality of p's may be the same or different. q is 1 or more and 20
It is the following integer. The present invention provides a sulfonic acid derivative of a linear polyphenol sulfide produced by reacting the linear polyphenol sulfide represented by the formula (1) with sulfuric acid. Further, the present invention provides a water-soluble dispersant comprising a sulfonic acid derivative of the linear polyphenol sulfide represented by the general formula (1). Hereinafter, the present invention will be described in detail.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), R ¹ is a hydrogen atom, an alkyl group, a sulfonic acid group, or a salt of a sulfonic acid group represented by SO ₃ M. The alkyl group preferably has an average carbon number of 1 or more and 20 or less, particularly preferably 1 or more and 12 or less. Further, as the alkyl group, a tertiary hydrocarbon group is preferable, and particularly preferable is tert-But.
yl group, tert-Octyl group and the like. In a salt of a sulfonic acid group represented by SO ₃ M, M is a metal, ammonium,
Lower alkyl ammonium, lower alkanolamine,
Or pyridiniums. Specific examples of metals include, for example, alkali metals such as sodium and potassium,
Examples include alkaline earth metals such as calcium and magnesium.

Specific examples of lower alkyl ammonium include, for example, methyl ammonium, ethyl ammonium, n-butyl ammonium, iso-butyl ammonium, sec-butyl ammonium, tert-butyl ammonium, n-propyl ammonium, iso-propyl Ammonium, dimethyl ammonium, diethyl ammonium, di
-n-butylammonium, di-iso-butylammonium,
Di-sec-butyl ammonium, di-tert-butyl ammonium, di-n-propyl ammonium, di-iso-propyl ammonium, trimethyl ammonium, triethyl ammonium, tri-n-butyl ammonium, tri-iso-butyl ammonium, tri- n-propylammonium and the like. In the general formula (1), there are a plurality of R ¹
R ¹ may be the same or different,
At least one R ¹ is a sulfonic acid group or a salt of a sulfonic acid.

In the general formula (1), when there are a plurality of salts of a sulfonic acid group represented by SO ₃ M, M may be the same or different. In the general formula (1), when n = 1, a and b are 0 or 1, and a + b ≠ 0. When n is 2 or more, a and b are 0 or 1, even if they are the same. Good or different. In the general formula (1), m is 1 or an integer of 2 to 7, and a plurality of m may be the same or different. In the general formula (1), n is 1 or more and 20
In the following integers, n may contain a sulfonic acid derivative of a linear polyphenol sulfide exceeding 20.
The sulfonic acid derivative of the linear polyphenol sulfide represented by the general formula (1) of the present invention may be a single type of linear polyphenol sulfide or a sulfonate of two or more types of linear polyphenol sulfide. It may be a mixture composed of an acid derivative, but preferably contains at least one kind of chain polyphenol sulfide in which n is an integer of 2 to 20.

The sulfonic acid derivative of the linear polyphenol sulfide of the present invention can be produced by reacting the linear polyphenol sulfide of the general formula (2) with sulfuric acid. General formula
The alkyl group of (2) is an alkyl group having an average carbon number of 1 or more and 20 or less, preferably 1 or more and 12 or less, and this alkyl group is the same as the alkyl group described in the general formula (1). In the general formula (2), R ² there are a plurality, each R ² may be the same or may be different. General formula (2)
When q = 1, d and e are 0 or 1, and d + e ≠ 0. When q is 2 or more, d and e are 0 or 1, which may be the same or different. Is also good. In the general formula (2),
p is 1 or an integer of 2 to 7, and a plurality of p may be the same or different. In the general formula (2), q is
It is an integer of 1 or more and 20 or less, but q may contain a chain polyphenol sulfide exceeding 20 or more. In the production method of the present invention, the chain polyphenol sulfide represented by the general formula (2) as a raw material may be a single chain polyphenol sulfide or two or more chain polyphenol sulfides. Although it may be a mixture composed of various substances, it is preferable that at least one kind of chain polyphenol sulfide in which q is an integer of 2 or more and 20 or less is contained.

The raw material chain polyphenol sulfide is
It may be manufactured by any manufacturing method. For example, those produced by the reaction of halogenated phenols with alkali metal sulfide reagents, those produced by the reaction of phenols with sulfur halides, phenols,
Manufactured by the method of using elemental sulfur and molecular halogen as the reaction raw materials, manufactured by the method of using phenols and elemental sulfur as the reaction raw materials, manufactured by reacting phenols and elemental sulfur in the presence of an acid catalyst Those produced by reacting phenols with elemental sulfur in the presence of a base catalyst, or those produced by a method of reacting phenols with aryl disulfides under a base catalyst, etc. Can be used. The present applicants have already disclosed several methods for producing a chain polyphenol sulfide (JP-A-9-227503, JP-A-10-81680 and Japanese Patent Application No. 11-75747).
etc). One of these chain polyphenol sulfides may be used alone, or two or more thereof may be used in combination.

In the present invention, when the above-mentioned raw material is converted into a sulfonic acid derivative of a linear polyphenol sulfide by the method of the present invention, when the raw material contains metal ions, it is preferable to remove the metal ions in advance. The removal of metal ions is preferably performed by neutralizing the raw material with an aqueous solution of a mineral acid, filtering off metal sulfate as required, and extracting and washing the organic component with an organic solvent. It is preferable that the organic solvent used for the extraction is distilled off in advance. Sulfuric acid, hydrochloric acid, nitric acid and the like can be used as the mineral acid used for neutralization, but sulfuric acid is preferred for suppressing a secondary chemical reaction. The concentration of mineral acid is
The aqueous solution is desirably 10 N or less so as not to be in a homogeneous phase with the organic component. Although a dilute solution does not cause a problem in the reaction, it has disadvantages in operation such as a remarkably large amount of the solution. Therefore, the range of 1 to 6 N is preferable. The amount of the mineral acid used is, when the raw chain polyphenol sulfide is obtained by the reaction of a phenol with an alkali metal reagent or an alkaline earth metal reagent and elemental sulfur, the specific amount of the alkali metal reagent used in the reaction or An amount (equivalent) for neutralizing the alkaline earth metal reagent is required, and preferably 1.2 to 2 equivalents based on the alkali metal reagent or alkaline earth metal reagent used.

The organic solvent for extraction can be arbitrarily selected as long as it dissolves the linear polyphenol sulfide and is not uniformly miscible with water.
Aromatic hydrocarbons such as benzene and toluene, ethers such as diethyl ether, and halogenated hydrocarbons such as chloroform can be used. The amount of the organic solvent used for extraction is optional.However, if the amount is too small, the viscosity of the solution becomes high, which makes it difficult to perform operations such as washing with water.If the amount is too large, the apparatus and equipment become large and the process becomes inefficient. For the sake of simplicity, it is preferable to use a minimum amount that does not cause a problem in the washing operation. Specifically, 50 ml per 1 mol of the total amount of the phenol skeleton units constituting the phenols and chain polyphenol sulfide contained in the raw material
By using the above organic solvent, suitable workability can be obtained. The sulfonic acid derivative of the linear polyphenol sulfide can be synthesized by suspending and heating and stirring the thus-produced linear polyphenol sulfide represented by the general formula (2) in sulfuric acid. . That is, the general formula
In the reaction between the chain polyphenol sulfide represented by the formula (2) and sulfuric acid, at least one of the alkyl groups of the chain polyphenol sulfide represented by the general formula (2) is converted to a sulfonic acid group.

The concentration of the sulfuric acid used may be 80% or more, preferably 90% or more, and fuming sulfuric acid may be used. The amount of sulfuric acid to be used is not particularly limited, but is usually preferably 2 to 200 ml per 1 g of polyphenol sulfide. The reaction temperature is preferably at least 70 ° C, more preferably at least 80 ° C. The upper limit of the reaction temperature is not particularly limited, but is preferably 150 ° C. or lower. When fuming sulfuric acid is used, the reaction temperature may be at least 10 ° C, more preferably 50 ° C.
That is all. The reaction time is not particularly limited, but may be generally 2 hours to 48 hours. However, in this reaction, since the decomposition reaction of the raw materials is also proceeding at the same time, it is not preferable to carry out the reaction for an excessively long time. In the present invention,
The sulfonic acid of the linear polyphenol sulfide obtained by the above reaction may be taken out as a product, or the sulfonic acid salt of the linear polyphenol sulfide may be taken out as a product. In the general formula (1), when a plurality of salts of a sulfonic acid group represented by SO ₃ M exist, M may be the same or different.

As a preferred method for producing a sulfonic acid salt of a linear polyphenol sulfide, a sulfonic acid of a linear polyphenol sulfide, which is a reaction product, is diluted with water after completion of the above-mentioned reaction, and alkali metal or alkaline earth is used. Salting out using a metal salt such as a similar metal, an ammonium salt, a lower alkylammonium salt, a lower alkanolammonium salt or a pyridinium salt, etc., yields a sulfonic acid of the linear polyphenol sulfide represented by the general formula (1). And a method for obtaining crystals such as metal salts, ammonium salts, lower alkyl ammonium salts, lower alkanol ammonium salts or pyridinium salts. Examples of the alkali metal salt include alkali metal halides such as alkali metal carbonate and alkali metal chloride. Examples of the alkaline earth metal salt include an alkali earth metal halide such as an alkali metal carbonate and an alkaline earth chloride. Specific examples of lower alkyl ammonium salts include, for example, methylamine hydrochloride, ethylamine hydrochloride, n-butylamine hydrochloride, iso-butylamine hydrochloride, sec-butylamine hydrochloride, tert-butylamine hydrochloride, n-propylamine hydrochloride , Iso-propylamine hydrochloride, dimethylamine hydrochloride, diethylamine hydrochloride, di-n-butylamine hydrochloride, di-iso-butylamine hydrochloride, di-sec-butylamine hydrochloride, di-tert-butylamine hydrochloride, -n-propylamine hydrochloride, di-iso-propylamine hydrochloride,
Trimethylamine hydrochloride, triethylamine hydrochloride, tri-n-butyl hydrochloride, tri-iso-butylamine hydrochloride, tri-n-propylamine hydrochloride and the like. Specific examples of the lower alkanol ammonium salt include, for example, ethanolamine hydrochloride, diethanolamine hydrochloride, triethanolamine hydrochloride and the like. Specific examples of the pyridinium salt include pyridine hydrochloride, an N-methylpyridinium halogen compound, and the like.

When the reaction product contains unreacted raw materials, it can be separated by a usual method, for example, by utilizing the difference in recrystallization or solubility. The water-soluble, novel sulfonic acid derivative of a linear polyphenol sulfide of the present invention is useful as a dispersant and a surfactant, and specifically, emulsifies an organic compound insoluble or hardly soluble in water. It can be easily dispersed and dissolved in water while maintaining transparency without performing. Further, an organic compound insoluble or hardly soluble in water can be stably present in water. In the present invention, the water-soluble, novel sulfonic acid derivative of a linear polyphenol sulfide is used as a dispersant / surfactant in contact with an organic compound in various forms such as solid, liquid, gas, and solution. This is a form in which these organic compounds are dispersed and dissolved in water.

As a preferred specific example of contacting the water-soluble novel sulfonic acid derivative of a linear polyphenol sulfide with an organic compound, for example, a sulfonic acid derivative of a linear polyphenol sulfide or a solution prepared by dissolving the same is preferred. There is a method in which an aqueous solution is brought into contact with an organic compound or a solution in which the organic compound is dissolved by various stirring operations such as shaking and stirring. The conditions for the shaking and stirring operations are not particularly limited, and they may be allowed to stand after contact. The concentration of the sulfonic acid derivative of the linear polyphenol sulfide represented by the general formula (1) in the aqueous solution is not particularly limited except that the upper limit is limited by the solubility of the sulfonic acid derivative of the linear polyphenol sulfide. Absent. When the form of the organic compound to be brought into contact with the sulfonic acid derivative of the novel linear polyphenol sulfide showing a water solubility of the present invention is a solution, the concentration of the organic compound contained in the solution is not particularly limited. . The temperature at which the sulfonic acid derivative of the novel water-soluble linear polyphenol sulfide of the present invention is brought into contact with the organic compound is not particularly limited, but may be usually from about room temperature to about 80 ° C. The time for contacting the water-soluble sulfonic acid derivative of the novel linear polyphenol sulfide with an organic compound according to the present invention is not particularly limited. The field of application of the novel water-soluble sulfonic acid derivative of a linear polyphenol sulfide as a dispersant / surfactant in the present invention includes application to analytical techniques and use to additives.

[0024]

EXAMPLES The present invention will be described in more detail with reference to production examples and examples below, but the present invention is not limited thereto. (Production Example 1) Mantle heater, distillation head, thermometer,
150 g (1.0 m) in a 500 ml flask equipped with a nitrogen gas inlet tube
ol) 4-tert-butylphenol, 34.0 g (0.2 mol) of diphenyl ether and 31.0 g of ethylene glycol at room temperature (about 20 ° C.) and stirred.
The solution was heated to 60 ° C. under normal pressure to obtain a homogeneous solution. Here 14.0g
(0.25 g-atom) of calcium oxide was added, and the mixture was stirred and heated under nitrogen gas aeration, and then heated to 120 ° C. after about 30 minutes. 1
After stirring at 20 ° C. for 2 hours, a water pump and ethylene glycol were distilled off under reduced pressure by connecting a vacuum pump. To the remaining reaction mixture, sulfur (48.1 g, 1.5 mol) was added, and the mixture was heated under stirring and nitrogen gas flow. After about 30 minutes, the temperature was raised to 200 ° C. After stirring was continued at 200 ° C. for 3 hours, the heating was stopped, the mixture was allowed to cool to 90 ° C., and diluted with 100 ml of toluene. 250 ml of 4N sulfuric acid was added to this toluene solution and stirred, and calcium ions were precipitated as calcium sulfate. After cooling to room temperature, the mixture was stirred for 1 hour, and the precipitate of calcium sulfate was filtered. The filtrate was washed twice with 100 ml of distilled water, anhydrous magnesium sulfate was added, and the mixture was stirred and filtered again to remove water. The obtained chain polyphenol sulfide mixture solution was concentrated using a rotary evaporator to obtain 185 g of a brown tar-like chain polyphenol sulfide mixture. The obtained chain polyphenol sulfide mixture is represented by d in the general formula (2).
= E = 0~1, p = 1~2 , q = 1~12, R 2 = tert-Butyl
Group.

(Production Example 2) d = e = 0 obtained in Production Example 1
1, p = 1~2, q = 1~12, R 2 = tert-Butyl a is linear polyphenol sulfide mixture 180 g of acetic acid 700 ml was added to the group, under stirring, to room temperature after heated to about 70 ° C. Upon cooling, most of the liquid became a light brown solid. This was filtered to remove a solid, and the solid component on the funnel was washed with 500 ml of acetic acid and then with 200 ml of n-hexane. The washed solid was dried under reduced pressure at 60 ° C. and 0.1 mmHg to obtain 104 g of a linear polyphenol sulfide mixture. The acetic acid adduct of the solid chain polyphenol sulfide mixture obtained here is d = e = 0 to 1, p = 1 to 2, q = 5 to 1 in the general formula (2).
2, R ² = corresponds to a tert-Butyl group. Fig. 1 shows the FD-MS spectrum as a result of FD-MS analysis of the chain-like polyphenol sulfide mixture obtained from the acetic acid adduct and trimethylsilylation.
It was shown to. In FIG. 1, one group having a mass number of 1739 as a representative peak is a component of q = 7, and 1486 is a component of q = 7.
6, 1992 is q = 8, and 2244 is q = 9. It is suggested that substantially no components having q = 5 or less are contained.

(Example 1) In the general formula (2), d = e = 0 to 1,
p = 1~2, q = 5~12, the R ² = tert-Butyl-chain polyphenol sulfide mixture 10g obtained in Production Example 2 is a group was suspended in concentrated sulfuric acid 100 ml, 6 hours at 80 ° C. The mixture was heated and stirred.
While cooling the reaction solution, gradually add 50 ml of distilled water,
A sulfonic acid derivative of a linear polyphenol sulfide was precipitated. The precipitate was filtered and dissolved in 200 ml of distilled water, and 60 g of sodium chloride was added to the aqueous solution to carry out salting out to obtain a brown powder. This was recrystallized from distilled water-ethanol to obtain 5 g of a brown powder.

When ¹ H NMR of the powdery linear mixture of polysulfonic acid sulfonate and sodium sulfonate obtained here was measured in deuterated water, no proton peak corresponding to the tert-Butyl group was measured, and the For the hydroxyl group of
The peak of the multiplet corresponding to the proton located at the m-position was measured, and it is clear that the compound in which R ¹ = tert-Butyl was not contained in this mixture. ¹ HN
FIG. 2 shows the MR spectrum. The mixture was subjected to elemental analysis. Elemental analysis value of the linear polyphenol sulfide mixture obtained in Production Example 2 was C; 59.1, H; 6.4,
S; 14.7, whereas in the case of a mixture of powdered linear polyphenol sulfide and sodium sulfonate,
27.6, H; 3.0, Na; 12.0, S; 23.5, and this elemental analysis value indicates that the sulfonic acid group was substituted and introduced in this powdery mixture of sodium sulfonate of chain polyphenol sulfide. It is clear from. Furthermore, the infrared absorption spectrum (KB
When r) was measured, strong absorption characteristic of a sulfonic acid group was observed at around 1190 and 1144 cm ^-1 . FIG. 3 shows the infrared absorption spectrum. The mixture obtained from these results has the general formula (1) (where a = b = 0 to 1, m = 1 to 2, n
= 5-12, a sulfonic acid sodium salt of linear polyphenol sulfide represented by R ¹ = SO ₃ Na).

(Example 2) In the general formula (2), d = e = 0 to 1,
20 g of the linear polyphenol sulfide mixture obtained in Production Example 1 in which p = 1 to 2, q = 1 to 12, and R ^{2 is a} tert-butyl group was suspended in 100 ml of concentrated sulfuric acid, and the suspension was stirred at 80 ° C. for 5 hours The mixture was heated and stirred.
While cooling the reaction solution, gradually add 50 ml of distilled water,
A sulfonic acid derivative of a linear polyphenol sulfide was precipitated. The precipitate was filtered and dissolved in 300 ml of distilled water, and 100 g of sodium chloride was added to the aqueous solution to carry out salting out to obtain a brown powder. This was recrystallized from distilled water-ethanol to obtain 9.3 g of brown powder.

[0029] The sodium sulfonate mixture here obtained powdery chain polyphenol sulfide, deuterium ¹ H NMR (FIG. 4) and infrared absorption spectrum (KBr)
As a result of measuring (FIG. 5), the obtained mixture was represented by the general formula (1) (where a = b = 0 to 1, m = 1 to 2, n = 1 to 12, R = 1 to 12)
¹ = SO ₃ Na) Among the sodium sulfonate salts of linear polyphenol sulfide represented by SO ₃ Na), some of R ¹ are tert-B
It was confirmed to be a sodium sulfonate of a chain polyphenol sulfide which is a utyl group.

(Application Example) A 5% heavy aqueous solution of a mixture of the sulfonate of the linear polyphenol sulfide synthesized in Example 1 was prepared. Each 3 ml of this heavy aqueous solution was placed in a 10 ml vial bottle, and n-hexane, toluene, methylene chloride, and 1,1,2-trichloroethane were added in an amount of 3 ml each, followed by stirring at room temperature for 5 hours. The solubility of the organic compound in heavy water was determined by separating the heavy water phase and the organic phase and measuring the ¹ H NMR of the heavy water phase. The concentration of organic compounds in heavy water was determined by adding a standard sample (3- (Trime
thylsilyl) propionic-2,2,3,3-d ₄ acid, sodium salt)
Was calculated by comparing the integral ratio with the trimethylsilyl group. Further, for comparison, the same operation was performed using heavy water containing no chain polyphenol sulfide. Table 1 shows the results.

[0031]

[Table 1] For any of the organic compounds, the solubility in heavy water was improved by adding the sulfonate of chain polyphenol sulfide to heavy water. It was also found that the mixture of the sulfonate of the linear polyphenol sulfide synthesized in Example 1 had the performance of a surfactant.

[0032]

The chain polyphenol sulfide sulfonic acid derivative of the present invention is a compound useful as a dispersant and a surfactant. Further, according to the method of the present invention, a sulfonic acid derivative of a linear polyphenol sulfide can be efficiently and easily produced by reacting a linear polyphenol sulfide with sulfuric acid.

[Brief description of the drawings]

FIG. 1 shows an FD-MS spectrum of a linear polyphenol sulfide.

FIG. 2 shows a ¹ H NMR spectrum of sodium sulfonate of a linear polyphenol sulfide in heavy water.

FIG. 3 shows an infrared absorption spectrum of a sodium sulfonate of a linear polyphenol sulfide.

FIG. 4 shows a ¹ H NMR spectrum of sodium sulfonate of a linear polyphenol sulfide in heavy water.

FIG. 5 shows an infrared absorption spectrum of a linear polyphenol sulfide sodium sulfonate.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (Reference) B01F 17/40 B01F 17/40 (72) Inventor Haruhiko Takeya 1134-2 Gongendo, Satte City, Saitama Kosmo Research Institute (72) Inventor Hitoshi Kumagai 1134-2 Gongendo, Satte City, Saitama Prefecture Cosmo Research Institute R & D Center

Claims (4)

[Claims] [Claim 1] The general formula (1) (In the formula, R ¹ is a hydrogen atom, an alkyl group, a sulfonic acid group, or a salt of a sulfonic acid group represented by SO ₃ M, M is a metal,
Ammonium, lower alkyl ammonium, lower alkanolamine, or pyridiniums, and a plurality of R ¹ may be the same or different, but at least one R ¹ is a sulfonic acid group or a sulfonic acid group. When there are a plurality of sulfonic acid group salts, M may be the same or different. When n = 1, a and b are 0 or 1 and a + b ≠ 0, and when n is 2 or more, a and b may be 0 or 1 and may be the same or different. Good, m is 1 or 2-7
And a plurality of m may be the same or different. n is an integer of 1 or more and 20 or less. ) A sulfonic acid derivative of a chain polyphenol sulfide represented by). (2) The general formula (2) (In the formula, R ² is an alkyl group, and a plurality of R ² may be the same or different, and q
When = 1, d and e are 0 or 1, d + e ≠ 0, and q
Is 2 or more, d and e may be the same as 0 or 1, respectively, or may be different, p is an integer of 1 or 2 to 7, and a plurality of p are each the same They may be different or different. q is an integer of 1 or more and 20 or less. ) Is reacted with sulfuric acid to give a general formula (1) (In the formula, R ¹ is a hydrogen atom, an alkyl group, a sulfonic acid group, or a salt of a sulfonic acid group represented by SO ₃ M, M is a metal,
Ammonium, lower alkyl ammonium, lower alkanolamine, or pyridiniums, and a plurality of R ¹ may be the same or different, but at least one R ¹ is a sulfonic acid group or a sulfonic acid group. When there are a plurality of sulfonic acid group salts, M may be the same or different. When n = 1, a and b are 0 or 1 and a + b ≠ 0, and when n is 2 or more, a and b may be 0 or 1 and may be the same or different. Good, m is 1 or 2-7
And a plurality of m may be the same or different. n is an integer of 1 or more and 20 or less. ). A method for producing a sulfonic acid derivative of a linear polyphenol sulfide, which comprises producing a sulfonic acid derivative of a linear polyphenol represented by the following formula: (3) The general formula (2) (In the formula, R ² is an alkyl group, and a plurality of R ² may be the same or different, and q
When = 1, d and e are 0 or 1, d + e ≠ 0, and q
Is 2 or more, d and e may be the same as 0 or 1, respectively, or may be different, p is an integer of 1 or 2 to 7, and a plurality of p are each the same They may be different or different. q is an integer of 1 or more and 20 or less. A) a sulfonic acid derivative of a linear polyphenol sulfide produced by reacting the linear polyphenol sulfide represented by the formula (1) with sulfuric acid. 4. A compound of the general formula (1) (In the formula, R ¹ is a hydrogen atom, an alkyl group, a sulfonic acid group, or a salt of a sulfonic acid group represented by SO ₃ M, M is a metal,
Ammonium, lower alkyl ammonium, lower alkanolamine, or pyridiniums, and a plurality of R ¹ may be the same or different, but at least one R ¹ is a sulfonic acid group or a sulfonic acid group. When there are a plurality of sulfonic acid group salts, M may be the same or different. When n = 1, a and b are 0 or 1 and a + b ≠ 0, and when n is 2 or more, a and b may be 0 or 1 and may be the same or different. Good, m is 1 or 2-7
And a plurality of m may be the same or different. n is an integer of 1 or more and 20 or less. A) a water-soluble dispersant comprising a sulfonic acid derivative of a linear polyphenol sulfide represented by