JPH06306041A - Process for producing monoglyceride disulfate and monoglyceride sulfate containing the disulfate - Google Patents

Abstract

(57) [Summary] [Object] To provide a method for producing a monoglyceride sulfate containing a monoglyceride disulfate, which is industrially available, inexpensive, less by-product, and efficient. [Structure] The α-monoglyceride represented by the general formula (2) is reacted with a sulfating agent at 10 ° C to -60 ° C, and then neutralized with a basic substance to give the monoglyceride represented by the general formula (1). A monoglyceride sulfate containing sulfate is prepared. [Chemical 1] M is alkali metal, alkaline earth metal, ammonium,
Indicates alkyl ammonium or alkanol ammonium. )

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a monoglyceride disulfate useful as a cleaning base which is mild and excellent in biodegradability, and a process for producing a monoglyceride sulfate containing the monoglyceride disulfate.

[0002]

BACKGROUND OF THE INVENTION Monoglyceride sulfate has a fatty acid and glycerin skeleton in its molecular structure and is useful as a detergent base having low irritation and excellent biodegradability.
It has also attracted attention because of the effective use of glycerin, which is a by-product of the recent worldwide increase in production of natural alcohol.

Monoglycerides and monosulfates are known,
Although it is a compound that is out of the standard for cosmetic ingredients, that is, a compound that is outside the standard of cosmetics, it is hard to say that its manufacturing method has been thoroughly studied. That is, as a method for producing monoglyceride monosulfate, a method of sulfating fat and oil and 2 mole times glycerin with a large excess of sulfuric acid (German Patent No. 702598,
German Patent No. 689511), a method of sulfating α-monoglyceride with a suitable sulfating agent (U.S. Pat.No. 2023387, Japanese Patent Publication No. 58-52989), sulfation of glycerin to obtain glycerin trisulfate, Then, a method of performing esterification (US Pat. No. 2868812, US Pat. No. 4832876) and the like are known.

However, in any of the methods described in any of the documents, it is mysterious that an excessive amount of the sulfating agent is required in excess of the theoretical amount to produce a large amount of inorganic sulfate, and the ester group is not preferable under acidic conditions. Since transfer and hydrolysis occur and glycerin, diglyceride, and triglyceride are by-produced, purification steps such as solvent extraction and washing are indispensable and the production cost of monoglyceride sulfate, which is the target product, is low, which avoids an increase in manufacturing costs. I can't.

Further, in the method of sulfating α-monoglyceride, various attempts have been made to use a milder sulfating agent in order to avoid transfer of ester groups and hydrolysis.
For example, in JP-A-54-5919, sulfamic acid,
J. Am. Oil Chemists' Soc., Volume 37, p.171 (1960) uses an excess amount of sulfur trioxide-pyridine complex. Further, JP-A-63-135367 proposes that sulfation with sulfur trioxide is carried out in an amine solvent. However, the sulfur trioxide / amine complex is a mild sulfating agent, but in this case it has poor reactivity and is suitable for industrialization in that it is difficult to remove the odor and color peculiar to amine. It's hard to say.

[0006]

DISCLOSURE OF THE INVENTION It is an object of the present invention to provide a method for industrially utilizing a monoglyceride sulfate which is inexpensive, has few by-products, and is highly efficient. Furthermore, the present invention aims at providing a monoglyceride disulfate which has not been reported until now.

[0007]

Means for Solving the Problems The present inventors have conducted extensive studies on a method for producing a monoglyceride sulfate and found that α
-By sulphating monoglyceride in a specific temperature range, it is almost a theoretical amount of a sulfating agent, and there are almost no inorganic salts such as sodium sulfate and by-products of glycerin, diglyceride and triglyceride, and it is directly used for commercial use without purification operation. The present invention has been completed by discovering that a monoglyceride sulfate that can be used in the present invention can be produced, and that a monoglyceride disulfate that has not been reported so far can also be produced. That is, the present invention provides a monoglyceride disulfate represented by the general formula (1).

[0008]

[Chemical 4]

M: Alkali metal, alkaline earth metal, ammonium, alkylammonium or alkanolammonium. Further, the present invention is represented by the general formula (2)

[0010]

[Chemical 5]

The α-monoglyceride represented by the formula (1) is reacted with a sulfating agent and then neutralized with a basic substance to give a compound represented by the general formula (3):

[0012]

[Chemical 6]

The present invention provides a method for producing a monoglyceride sulfate, which comprises reacting a sulfating agent at 10 ° C. to −60 ° C. when producing the monoglyceride sulfate represented by: In the above general formulas (1) to (3),

[0014]

[Chemical 7]

Specifically, palm fatty acid residue, palm oil fatty acid residue, palm kernel oil fatty acid residue, beef tallow fatty acid residue or hardened fatty acid residue thereof, or the like, or a simple substance constituting these fatty acid residues. One fatty acid residue, that is, a residue of lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid or the like, or a mixed fatty acid residue thereof may be mentioned.

M is an alkali metal, alkaline earth metal, ammonium, alkylammonium or alkanolammonium, preferably an alkali metal, more preferably Na or K.

The monoglyceride sulfate represented by the general formula (3) containing the monoglyceride disulfate represented by the general formula (1) can be easily produced by the above-mentioned method. An outline of an example of the reaction is shown below. For example, the reaction formula 1 is as follows.

[0018]

[Chemical 8]

The general formula (2) as a raw material of the production method of the present invention
The α-monoglyceride represented by can be obtained, for example, by subjecting a corresponding fatty acid or a lower alkyl ester of a fatty acid and glycerin to a dehydration reaction under conditions of an appropriate molar ratio. At this time, a small amount of β-monoglyceride, diglyceride or triglyceride is contained, but even if these remain, there is no problem in the subsequent sulfation reaction. However, if necessary, it is of course possible to purify by a method such as distillation.

In the present invention, any known sulfating agent may be used, but sulfur trioxide, sulfur trioxide and amine and ether are preferable from the viewpoint of suppressing transfer of ester group and hydrolysis. Or a complex with an amide,
Chlorosulfonic acid, fuming sulfuric acid and the like, with sulfur trioxide being most preferred.

Examples of the basic substance used in the neutralization reaction in the present invention include alkali metal or alkaline earth metal hydroxides, carbonates, bicarbonates, ammonia, alkylamines and alkanolamines. , Preferably NaOH, KOH, Na ₂ CO ₃ , NaHCO ₃ .

According to the method of the present invention, the α-monoglyceride represented by the general formula (2) is added with a sulfating agent in an amount of 0.8 to 3 mol, preferably 1.6 to 2.2 mol, per 10 mol of α-monoglyceride. -60 ℃, preferably 10 ~ -40 ℃, 0.5 ~
After reacting for 5 hours, preferably 1 to 2 hours, and then neutralizing with a basic substance in an approximately equimolar amount with the sulfating agent, preferably at 0 to 40 ° C, the monoglyceride sulfate represented by the general formula (3) is obtained. It can be obtained in high yield.

When the reaction temperature is higher than 10 ° C., hydrolysis of the monoglyceride disulfate progresses, resulting in defects such as decrease in yield and increase of by-products such as Na ₂ SO _4, and when lower than −60 ° C., reaction rate Is slow and cooling energy is required, which is industrially uneconomical. After the reaction with the sulfating agent, the reaction mixture is preferably poured into ice-cold water to stop the reaction, and then neutralized with a basic substance.

Examples of the reaction solvent include carbon halides such as methylene chloride, chloroform, carbon tetrachloride and 1,2-dichloroethane, with methylene chloride and chloroform being particularly preferred.

Further, the present inventors have made a detailed study on the temperature dependence of the sulfation reaction at a low temperature of 10 ° C. or lower. As a result, at the temperature of −10 ° C. or lower, monoglyceride disulfate is the main, regardless of the amount of sulfating agent. It was found that the product, the neutralization of which resulted in monoglyceride disulfate. Monoglyceride disulfate is described, for example, in J. Am.
Oil Chemists' Soc., Vol. 67, p. 8 (1990) describes the acid-type structure, but there has never been an isolated case as a neutralized salt.

Further, by heating and aging the reaction mixture containing monoglyceride disulfuric acid in the range of 10 ° C to -10 ° C, the monoglyceride disulfuric acid can be converted into monoglyceride monosulfuric acid. The ratio of monosulfate / disulfate in the neutralized product can be freely selected. This is J. Am. Chem. Soc., Vol. 81, p. 1620 (19
It is considered that the acyl group is involved in the elimination of sulfuric acid as described in (1959) (see reaction formula 2 below).

[0027]

[Chemical 9]

The monoglyceride sulfate obtained by the method of the present invention contains a small amount of by-products derived from inorganic salts, β-monoglyceride, diglyceride, triglyceride and their sulfates, etc. There is no problem at all. However, if necessary, purification can be performed by methods such as recrystallization, electrical shutoff, solvent extraction, etc. to obtain a higher purity product.

[0029]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. The composition of the reaction product in the examples is monoglyceride disulfate, monoglyceride monosulfate and monoglyceride by liquid chromatography, fatty acid and soap by acid value analysis, and diglyceride and triglyceride the amount of ether-soluble matter. Sodium sulfate was determined from the amount of ash.

Example 1 585.3 g (2.13 mol) of α-monolaurin was stirred at −30 ° C. in 3 kg of chloroform. 341.3 g of liquid SO ₃ (4.26 mol, 2 mol times relative to monoglyceride) was added dropwise over 1 hour, and the mixture was further stirred at −30 ° C. for 1 hour, and then the reaction mixture was poured into ice-cooled water 4 kg to stop the reaction. After neutralization with 373.3 g (4.48 mol) of 48% sodium hydroxide aqueous solution, the solvent was distilled off to obtain 1 kg of α-monolaurin sulfate. The reaction conditions and the composition of the product are summarized in Table 1.

Example 2 585.3 g (2.13 mol) of α-monolaurin was stirred at −30 ° C. in 3 kg of chloroform. Chlorosulfonic acid 496.3 g
(4.26 mol, 2 mol times relative to monoglyceride) was added dropwise over 1 hour, and the mixture was further stirred at -30 ° C for 1 hr. During this time,
The generated hydrochloric acid gas was completely removed by blowing nitrogen into the reaction system. The reaction mixture was poured into ice-cooled water (4 kg) to stop the reaction. 48% sodium hydroxide aqueous solution 373.3g (4.48mol)
After neutralizing with, the solvent was distilled off to obtain 1 kg of α-monolaurin sulfate. The reaction conditions and product composition are summarized in Table 1.
Shown in.

Example 3 300 g of α-monoglyceride of cured palm fatty acid (monoglyceride content 61%, α-monoglyceride content 53%) (hydroxyl group
1.72 mol) was stirred in 1500 g of chloroform at -30 ° C. Liquid SO ₃ 138.1 g (1.72 mol) was added dropwise over 1 hour, and the mixture was further stirred at −30 ° C. for 2 hours, and then the reaction mixture was poured into ice-cooled water (4 kg) to stop the reaction. After neutralizing with 233.5 g (1.7 mol) of 29% aqueous sodium hydroxide solution, the solvent was distilled off to obtain 449 g of α-monoglyceride sulfate of a cured fatty acid. The reaction conditions and the composition of the product are summarized in Table 1.

Comparative Example 1 184.2 g (0.61 mol) of α-monomyristin was stirred with 1000 ml of chloroform at 20 ° C. Into it, liquid SO ₃ 146.4
g (1.83 mol) was added dropwise while maintaining at 40 ° C. The reaction mixture was stirred at 60 ° C. for 2 hours under reflux. The reaction mixture was poured into 1 kg of ice-cold water to stop the reaction. After neutralizing with 271 g (3.25 mol) of 48% aqueous sodium hydroxide solution, the solvent was distilled off and α
458 g of a mixture containing monomyristin sulfate were obtained. The reaction conditions and the composition of the product are summarized in Table 2.

Comparative Example 2 106.9 g (0.39 mol) of α-monolaurin was added to chloroform.
Stirred in 500 ml at 20 ° C. Chlorosulfonic acid 136.3 g
(1.17 mol) was added dropwise at 30 ° C or lower over 1 hour. During this time,
The generated hydrochloric acid was completely removed by blowing nitrogen into the reaction system. Furthermore, the mixture was stirred at 60 ° C. for 3 hours under reflux. The reaction mixture was poured into 500 g of ice-cold water to stop the reaction. After neutralizing with 173 g (2.08 mol) of 48% aqueous sodium hydroxide solution, the solvent was distilled off to obtain 282 g of a mixture containing α-monolaurin sulfate. The reaction conditions and the composition of the product are summarized in Table 2.

Comparative Example 3 166.3 g (0.61 mol) of α-monolaurin and 58.5 g (0.61 mol) of sulfamic acid were stirred and mixed at 130 ° C. for 2 hours.
The pure content of the activator (acidic Epton method) in the reaction mixture was 0%. The reaction conditions and the composition of the product are summarized in Table 2.

[0036]

[Table 1]

[0037]

[Table 2]

Example 4 An α-monolaurin sulfate salt was obtained in exactly the same manner as in Example 1, except that 1.6 mol times of liquid SO ₃ was used with respect to the monoglyceride. The reaction conditions and product composition are summarized in Table 3.

Example 5 An α-monolaurin sulfate salt was obtained in exactly the same manner as in Example 1 except that liquid SO ₃ was used in an amount 1.3 times that of monoglyceride. The reaction conditions and product composition are summarized in Table 3.

Example 6 An α-monolaurin sulfate salt was obtained in exactly the same manner as in Example 1, except that liquid SO ₃ was used in an amount of 1 mol per mol of the monoglyceride. The reaction conditions and product composition are summarized in Table 3.

[0041]

[Table 3]

The results of Examples 1 to 6 show that the amount of the pure activator (monoglyceride disulfate) was small in comparison with the comparative example in which the conventional technique of high temperature reaction was additionally tested. It can be seen that a monoglyceride sulfate having a large amount of (+ monoglyceride monosulfate) can be obtained.

Example 7 82.3 g (0.3 mol) of α-monolaurin was added to methylene chloride 400
Stir in g at -30 ° C. SO ₃ and an air mixed gas (SO ₃ concentration 7% by volume) were blown into the reaction mixture. The bubbling of 0.6 mol SO ₃ was completed in 3 hours. After further stirring at -30 ° C for 1 hour, about 1/4 of the reaction mixture was poured into 150 g of ice-cold water to stop the reaction. 27% 25% aqueous sodium hydroxide solution
After neutralizing with (0.17 mol), the solvent was distilled off to obtain 32.4 g of α-monolaurin sulfate. The reaction conditions and product composition are summarized in Table 4.

Example 8 After heating the remaining reaction mixture of Example 7 to -10 ° C and stirring for 1 hour, about 1/3 of the reaction mixture was poured into 150 g of ice-cold water to stop the reaction. 25% aqueous sodium hydroxide solution 20.3
After neutralizing with g (0.13 mol), the solvent was distilled off to obtain 28.4 g of α-monolaurin sulfate. The reaction conditions and product composition are summarized in Table 4.

Example 9 The reaction mixture remaining in Example 8 was heated to 0 ° C. and stirred for 1 hour, and then about ½ of the reaction mixture was poured into 150 g of ice-cold water to stop the reaction. 25% aqueous sodium hydroxide solution 25.6
After neutralizing with g (0.16 mol), the solvent was distilled off to obtain 35 g of α-monolaurin sulfate. The reaction conditions and product composition are summarized in Table 4.

Example 10 After heating the remaining reaction mixture of Example 9 to 10 ° C. and stirring for 1 hour, the whole reaction mixture was poured into 150 g of ice-cold water to stop the reaction. 25% aqueous sodium hydroxide solution 42.7 g (0.27
Mol) and then the solvent was distilled off to obtain 49.2 g of α-monolaurin sulfate. The reaction conditions and product composition are summarized in Table 4.

[0047]

[Table 4]

From the results of Examples 7 to 10, it can be seen that the ratio of the monoglyceride disulfate and the monoglyceride monosulfate in the α-monolaurin sulfate produced by changing the aging temperature of the reaction can be selected.

Example 11 The compound of the formula (A) obtained by purifying the reaction product obtained in Example 1 by recrystallization.

[0050]

[Chemical 10]

The infrared absorption spectrum, mass spectrum, and ¹³ C-nuclear magnetic resonance spectrum of α-monolaurin disulfate represented by are shown in FIGS. 1, 2 and 3, respectively, and their major peaks are shown in Table 5. It was Further, the compound of the formula (B) obtained by purifying the reaction product obtained in Comparative Example 1 by recrystallization was used.

[0052]

[Chemical 11]

The infrared absorption spectrum, mass spectrum, and ¹³ C-nuclear magnetic resonance spectrum of α-monomyristin monosulfate represented by are shown in FIGS. 4, 5 and 6, respectively, and their major peaks are shown in Table 5. Indicated. 2 and 5
Among them, MGDS-Na shows a peak of monoglyceride disulfate and MGS-Na shows a peak of monoglyceride monosulfate. Further, in FIG. 3, MGS shows the peak of the mixed monoglyceride monosulfate, and MG shows the peak of the mixed monoglyceride.

From a comparison between the two, it can be seen that α-monoglyceride disulfate can be obtained by the sulfation according to the present invention.

[0055]

[Table 5]

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum of α-monolaurin disulfate obtained by purifying the reaction product obtained in Example 1 by recrystallization.

FIG. 2 is a mass spectrum of α-monolaurin disulfate obtained by purifying the reaction product obtained in Example 1 by recrystallization.

FIG. 3 is a ¹³ C-nuclear magnetic resonance spectrum of α-monolaurin disulfate obtained by purifying the reaction product obtained in Example 1 by recrystallization.

FIG. 4 is an infrared absorption spectrum of α-monomyristin monosulfate obtained by purifying the reaction product obtained in Comparative Example 1 by recrystallization.

FIG. 5 is a mass spectrum of α-monomyristin monosulfate obtained by purifying the reaction product obtained in Comparative Example 1 by recrystallization.

FIG. 6 ¹³ C of α-monomyristin monosulfate obtained by purifying the reaction product obtained in Comparative Example 1 by recrystallization.
-Nuclear magnetic resonance spectrum.

Claims (6)

[Claims] 1. A monoglyceride disulfate represented by the general formula (1). [Chemical 1] M: alkali metal, alkaline earth metal, ammonium,
Indicates alkyl ammonium or alkanol ammonium. ] 2. A general formula (2): The α-monoglyceride represented by the formula (3) is reacted with a sulfating agent and then neutralized with a basic substance to give a compound represented by the general formula (3): In producing the monoglyceride sulfate represented by
A method for producing a monoglyceride sulfate, which comprises reacting a sulfating agent at 0 ° C to -60 ° C. 3. The method for producing a monoglyceride sulfate according to claim 2, wherein the reaction temperature is 10 to −40 ° C. 4. The method for producing a monoglyceride sulfate according to claim 2, wherein the sulfating agent is sulfur trioxide, a complex of sulfur trioxide and an amine, an ether or an amide, chlorosulfonic acid, or fuming sulfuric acid. 5. The sulfating agent is sulfur trioxide.
Alternatively, the method for producing the monoglyceride sulfate according to 3 above. 6. The method according to claim 2, wherein after the reaction with the sulfating agent, the reaction mixture is poured into ice-cold water to stop the reaction and then neutralized with a basic substance. Method for producing monoglyceride sulfate of.