JP3164693B2 - Method for producing monoglyceride sulfate - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing monoglyceride sulfate, and more particularly to a method for producing monoglyceride sulfate by a sulfation reaction of monoglyceride in a solvent containing an amide group or a sulfoxide group.

[0002]

2. Description of the Related Art Monoglyceride sulfate has a fatty acid and glycerin skeleton in its molecular structure, is useful as a cleaning base with low irritation and excellent biodegradability.
In recent years, attention has been paid to the effective use of glycerin, which is a by-product of the worldwide production of natural alcohol.

[0003] Monoglyceride sulfate is known and is a compound listed in the standard of non-standard ingredients of cosmetics, so-called extra-cosmetic standard, but it is hard to say that its production method has been sufficiently studied. That is, as a method for producing monoglyceride sulfate, a method of sulfating fats and oils and glycerin at a molar ratio of 2 with a large excess of sulfuric acid (German Patent No. 702598, German Patent No. 689511); (US Patent No. 2023387, JP-B-58-1983)
No. 52989), a method in which glycerin is sulfated to obtain glycerin trisulfate, and then esterified (US Pat. No. 2,688,812, US Pat. No. 4,832,876).

However, in any of the methods described in the literatures, a surprisingly large amount of a sulfating agent is required in excess of the theoretical amount, and a large amount of inorganic sulfate is formed. Since the transfer and hydrolysis occur and glycerin, diglyceride, and triglyceride are produced as by-products, purification steps such as solvent extraction and washing are indispensable, and the yield of monoglyceride sulfate, which is the target product, is low. Can not do.

Further, in the method of sulfating α-monoglyceride, various attempts have been made to use milder sulfating agents in order to avoid the transfer of ester groups and hydrolysis.
For example, in JP-A-54-5919, sulfamic acid,
J. Am. Oil Chemists' Soc., Vol. 37, p. 171 (1960) uses an excessive amount of sulfur trioxide / pyridine complex. JP-A-63-135367 proposes that sulfuration with sulfur trioxide be carried out in an amine solvent. However, sulfur trioxide / amine complex is a mild sulfating agent, but in this case, it has poor reactivity, and it is difficult to remove the odor and coloring peculiar to amine. Is not good.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a process for producing monoglyceride sulfate which is industrially available, is inexpensive, has few by-products, and is efficient.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies on a method for producing monoglyceride sulfate.
-When a monoglyceride is sulfated, by using a specific solvent, the required minimum amount of sulfating agent is used, and there are almost no by-products of inorganic salts such as sodium sulfate and unreacted oil, and the product is used as it is without purification. It has been found that a monoglyceride sulfate which can be subjected to the present invention can be produced, and the present invention has been completed. That is, the present invention relates to the general formula
(1)

[0008]

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The α-monoglyceride represented by the formula (1) is reacted with a sulfating agent, and then neutralized with a basic substance.

[0010]

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M is an alkali metal, an alkaline earth metal,
Indicates ammonium, alkyl ammonium or alkanol ammonium. A) providing a high-quality and inexpensive method for producing a monoglyceride sulfate, characterized in that a solvent having an amide group or a sulfoxide group is used as a solvent for sulfation in producing the monoglyceride sulfate shown in (1). It is.

Hereinafter, the production method of the present invention will be described in detail. In the present invention, α-monoglyceride is sulfated with a sulfating agent in a solvent containing an amide group or a sulfoxide group to obtain an acid type monoglyceride sulfate, which is neutralized to obtain a target salt thereof. An outline of an example of such a reaction of the present invention is represented by the following reaction formula 1.

[0013]

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In the sulfation of the present invention, the reaction solvent is important. That is, when sulfation is carried out in a solvent other than a solvent having an amide group or a sulfoxide group in the molecule, good results such as sulfation in a solvent containing an amide group or a sulfoxide group cannot be obtained. The solvent having an amide group or a sulfoxide group used in the present invention may be any solvent having an amide group or a sulfoxide group, but is preferably an amide compound represented by the general formula (3) or a compound represented by the general formula (4). Sulfoxide compounds shown

[0015]

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(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different and represent H or an alkyl group having 1 to 20 carbon atoms. Note that R ¹ and R ³ , R ² are R ³ , R ⁴ and R ⁵ may be combined to form a ring.), More preferably N-methylformamide, N, N-dimethylformamide (DMF), N , N-dimethylacetamide (DM
A), N-methylpyrrolidone, N, N-dimethyllauramide, N, N-dimethylimidazolidinone, and the like, and sulfoxide compounds such as dimethylsulfoxide and the like, particularly preferably N, N-dimethylformamide (D
MF).

As the solvent other than the amide group or sulfoxide group-containing solvent, the most common solvents used for the sulfation reaction include halogenated hydrocarbon solvents, specifically, chloroform and methylene chloride. In the case of performing sulfation using these solvents, an excessive amount of a sulfating agent is required, and undesired transfer of ester groups under acidic conditions, hydrolysis occurs, and a large amount of fats and oils are produced as by-products. Both the purity and the yield of the target monoglyceride sulfate significantly decrease.

As described above, it is conceivable to use an amine as a solvent. However, a complex formed by mixing a sulfurating agent such as sulfur trioxide or chlorosulfonic acid with an amine is stable, poor in sulfation ability, and poor in sulfation ability. It is not preferable as a solvent used for sulfation. In addition, ether solvents may be used as the solvent for the sulfation reaction, but in this case, similarly to the halogenated hydrocarbon solvents, undesired transfer and hydrolysis of the ester group occur, and the desired monoglyceride sulfate Is not preferred because both the purity and the yield of the compound significantly decrease.

On the other hand, in the sulfation reaction of α-monoglyceride in the amide group or sulfoxide group-containing solvent of the present invention, the sulfation reaction proceeds quantitatively without side reactions such as transesterification, and the required minimum amount By using a sulfating agent, it is possible to produce a monoglyceride sulfate which has almost no inorganic salts such as sodium sulfate and by-products of oil and can be used for commercial purposes without purification.

Under the conditions of the sulfation reaction of the present invention,
Monoglyceride monosulfuric acid and monoglyceride disulfuric acid are produced, and the neutralization gives the corresponding sulfate. The ratio of monosulfate and disulfate can be adjusted by the ratio of the raw material α-monoglyceride and the sulfating agent, but by raising the temperature of the reaction mixture containing monoglyceride disulfate and aging,
Monoglyceride disulfate can also be converted to monoglyceride monosulfate. By utilizing this, the ratio of monosulfate / disulfate in the neutralized product can be freely selected.
This is described in J. Am. Chem. Soc., Volume 81, p.1620 (1959)
It is considered that the acyl group is involved in the elimination of sulfuric acid as described in (2) (see the following reaction formula 2).

[0021]

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Such an advantage of the sulfation reaction of the present invention is that the solvent containing an amide group or a sulfoxide group forms a complex with a sulfating agent, so that the sulfation conditions are mild, and the sulfation is formed by sulfation. It is considered that neutralizing the sulfate and sulfuric acid has an effect of trapping free acids in the reaction system. That is, although amines and ethers are more likely to form a complex with a sulfating agent than amides, the sulfation of the present invention is possible only when a solvent containing an amide group or a sulfoxide group is used.

As the sulfating agent used in the sulfation reaction of the present invention, any known one may be used, but from the viewpoint of reactivity, sulfur trioxide, chlorosulfonic acid, fuming sulfuric acid and the like are preferable. Sulfur is most preferred. The amount of the sulfating agent to be used is 0.3 to 3.
It is preferably 0 mole times, more preferably 0.5 to 2.0 mole times. When a mixture containing diglyceride or the like is used as a raw material, correction may be made based on the hydroxyl value of the mixture. Use of an excessive amount of the sulfating agent is not only unnecessary, but also causes an increase in the content of inorganic sulfate in the neutralized product, which is not preferable.

The reaction temperature of the sulfation reaction of the present invention is from -20 ° C to 80 ° C, preferably from 0 ° C to 60 ° C. Further, as described above, when it is desired to change the composition ratio of monoglyceride monosulfate and monoglyceride disulfate in the monoglyceride sulfate generated, besides adjusting the ratio of the sulfating agent to monoglyceride, adjusting the reaction temperature You can do it. That is, monoglyceride disulfate is predominantly produced at the reaction temperature on the low temperature side (-20 to 20 ° C), and conversely, monoglyceride monosulfate is produced at the reaction temperature on the high temperature side (20 to 80 ° C).

Although the reaction time of the sulfation reaction of the present invention varies depending on the reaction temperature and the strength of the sulfating agent, it is generally sufficient for several hours, preferably 0.1 to 5 hours. In the α-monoglyceride represented by the general formula (1) which is a starting material of the present invention,

[0026]

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[0027] Any of a mixture or a single composition may be used. Specifically, coconut oil fatty acid residues, palm oil fatty acid residues, palm kernel oil fatty acid residues, tallow fatty acid residues or their hardened fatty acid residues, or the like, or Single fatty acid residues constituting those fatty acid residues, that is, residues of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, or the like, or And mixed fatty acid residues.

Further, even if α-monoglyceride contains β-monoglyceride which is a by-product in the production of α-monoglyceride, or diglyceride or triglyceride, it does not affect the sulfation reaction. In addition, a sulfated product having a structure derived from these components may be contained in the sulfated product.

Examples of the basic substance used in the neutralization reaction in the present invention include hydroxides, carbonates, bicarbonates and the like of alkali metals or alkaline earth metals, ammonia, alkylamines and alkanolamines. , preferably NaOH, KOH, an Na ₂ CO _3, NaHCO _3, in particular NaO
H and KOH are preferred.

After the completion of the above-mentioned sulfation reaction, a basic substance is preferably added as a high-concentration aqueous solution for neutralization, and the solvent is removed to obtain the desired product. The monoglyceride sulfate obtained by the method of the present invention described above contains a small amount of an inorganic salt and the like, but is of high purity such that it can be used as it is depending on the use. However, if necessary, a higher purity can be obtained by purification by a method such as recrystallization, electrodialysis, or solvent extraction.

[0031]

According to the production method of the present invention, a small amount of a sulfating agent is used, inorganic salts such as sodium sulfate and unreacted oil are hardly produced as by-products as compared with the prior art, and there is no purification operation. A monoglyceride sulfate which can be used for commercial purposes can be produced.

[0032]

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

Example 1 240 g of liquid SO ₃ (3 mol, 1.2 mol based on α-monolaurin)
Mol) at 10 ° C with N, N-dimethylformamide (DMF) 17
The resulting mixture was added dropwise to 00 g to prepare a DMF solution containing sulfur trioxide / DMF complex. 686 g (2.5 mol) of α-monolaurin and DMF
1 kg was stirred at 10 ° C. The DMF solution containing the sulfur trioxide / DMF complex was dropped into the solution over 40 minutes while maintaining the temperature at 10 ° C. After completion of the dropwise addition, the mixture was aged at 30 ° C. for 1 hour. The reaction mixture was poured into 3.5 kg of ice water to stop the reaction. After neutralization with 390 g (3.41 mol) of a 35% aqueous sodium hydroxide solution, the solvent was distilled off to obtain 1 kg of α-monolaurin sulfate. Table 1 summarizes the reaction conditions and the composition of the product.

Example 2 68.6 g (0.25 mol) of α-monolaurin was stirred in 240 g of N, N-dimethylacetamide (DMA). SO ₃・ at 0 ℃
Air mixed gas (SO ₃ concentration, 4.4% by volume) was blown.
In 1 hour, 0.33 mol (1.3 mol times of α-monolaurin) of SO ₃ was blown. After heating to 40 ° C,
Stirring was continued for hours. After pouring the reaction mixture into ice water, 25
Neutralized with 55 g (0.34 mol)
The solvent is distilled off and the desired α-monolaurin sulfate 109
g was obtained. Table 1 summarizes the reaction conditions and the composition of the product.

Example ₃ 20 g of liquid SO ₃ at 140 ° C. in 140 g of N-methylpyrrolidone
(0.25 mol) was added dropwise over 15 minutes and stirred. After the temperature was raised to 10 ° C., 68.6 g (0.25 mol) of α-monolaurin was added, and stirring was continued at 30 ° C. for 3 hours. The reaction mixture was poured into ice water, neutralized with a 48% aqueous sodium hydroxide solution, and the solvent was distilled off to obtain the desired α-monolaurin sulfate. Table 1 summarizes the reaction conditions and the composition of the product.

Example 4 Liquid SO ₃ 20 at 13 ° C. in 137.2 g of N-methylformamide
g (0.25 mol) was added dropwise over 15 minutes.
68.6 g (0.25 mol) was added at 10 ° C. and stirred. The temperature was raised to 40 ° C., and stirring was continued for another 3 hours. After pouring the reaction mixture into ice water, the mixture was neutralized with 25 g (0.3 mol) of a 48% aqueous sodium hydroxide solution, and the solvent and water were distilled off to obtain 96.0 g of the objective α-monolaurin sulfate. Table 1 summarizes the reaction conditions and the composition of the product.

Example 5 In 109.8 g of DMF, 23.3 g (0.2 mol) of chlorosulfonic acid was added dropwise at 10 ° C. over 5 minutes and stirred. α-monolaurin 54.9g
(0.2 mol) was added at 10 ° C. and stirred. The temperature was raised to 30 ° C., and stirring was continued for another hour. The reaction mixture was poured into ice water, neutralized with 34.2 g (0.41 mol) of a 48% aqueous sodium hydroxide solution, and the solvent and water were distilled off to obtain 87.6 g of the target α-monolaurin sulfate. Table 1 summarizes the reaction conditions and the composition of the product.

Example 6 In 1 kg of DMF, 141.2 g (1.76 mol, 0.5 equivalent to hydroxyl group) of liquid SO _{3 was} added dropwise at 40 ° C. in 40 minutes, and monoglyceride (monoglyceride) of coconut oil fatty acid (C6-18) was added. Content 67%, α / β ratio = 8/2) 500 g (hydroxyl value 396)
It was added at 10 ° C and stirred. The temperature was raised to 40 ° C., and stirring was continued for another 30 minutes. After pouring the reaction mixture into 1.5 kg of ice water, the mixture was added with 154.2 g (1.85 mol) of a 48% aqueous sodium hydroxide solution at 0 to 30 ° C.
The solvent and water were distilled off to obtain 682 g of monoglyceride sulfate of palm oil fatty acid as a target. Table 2 summarizes the reaction conditions and the composition of the product.

EXAMPLE 7 16 g (0.2 mol) of liquid SO ₃ was added dropwise to 150 g of N, N-dimethyllauramide at 20-30 ° C. in 15 minutes, and 54.9 g (0.2 mol) of α-monolaurin was added at 25 ° C. Added and stirred.
The temperature was raised to 30 ° C., and stirring was continued for another 4 hours. After pouring the reaction mixture into ice water, a 48% aqueous sodium hydroxide solution 17.1 was added.
g (0.205 mol), and the solvent and water were distilled off to obtain 75.4 g of the objective α-monolaurin sulfate. Table 2 summarizes the reaction conditions and the composition of the product.

Example 8 Liquid S at 9 ° C. in 95.3 g of N, N-dimethylimidazolidinone
After 13.8 g (0.174 mol) of O ₃ was added dropwise over 5 minutes, 47.7 g (0.174 mol) of α-monolaurin was added at 10 ° C. and stirred. The temperature was raised to 30 ° C., and stirring was continued for another 3 hours. 15.9 g of 48% aqueous sodium hydroxide solution at 10-30 ° C. in the reaction mixture
(0.191 mol) and neutralized, and the solvent and water were distilled off to obtain 65.7 g of the target α-monolaurin sulfate. Table 2 summarizes the reaction conditions and the composition of the product.

Example 9 16.0 g (0.2 mol) of liquid SO _{3 was} added dropwise to 109.8 g of dimethyl sulfoxide (DMSO) at 20 to 25 ° C. in 10 minutes, and 54.9 g (0.2 mol) of α-monolaurin was added at 10 ° C. Added and stirred. The temperature was raised to 30 ° C., and stirring was continued for another 2 hours. After pouring the reaction mixture into ice water, a 48% aqueous sodium hydroxide solution
The mixture was neutralized with 17.1 g (0.205 mol), and the solvent and water were distilled off to obtain 75.4 g of the objective α-monolaurin sulfate. Table 2 summarizes the reaction conditions and the composition of the product.

Comparative Example 1 106.9 g (0.39 mol) of α-monolaurin was added to chloroform.
Stir at 500C in 500 ml. 136.3 g of chlorosulfonic acid
(1.17 mol) was added dropwise at 30 ° C. or lower over 1 hour. During this time,
Nitrogen was blown into the reaction system to completely remove the generated hydrochloric acid. Further, the mixture was stirred under reflux at 60 ° C. for 3 hours. 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 a 48% aqueous sodium hydroxide solution, the solvent was distilled off to obtain 282 g of a mixture containing α-monolaurin sulfate. Table 3 summarizes the reaction conditions and the composition of the product.

Comparative Example 2 166.3 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 activator (acidic Epton method) in the reaction mixture was 0%. Table 3 summarizes the reaction conditions and the composition of the product.

Comparative Example ₃ 20 g of liquid SO ₃ (0.degree. C.) in 140 g of triethylamine at 0.degree.
25 mol) was added dropwise over 15 minutes and stirred. After heating to 10 ° C,
68.6 g (0.25 mol) of α-monolaurin was added, and 30
Stirring was continued at 4.5 ° C. for 4.5 hours. After the reaction mixture was poured into ice water, the mixture was neutralized with a 48% aqueous sodium hydroxide solution, and the solvent was distilled off to obtain the desired α-monolaurin sulfate. Table 3 summarizes the reaction conditions and the composition of the product.

Comparative Example 4 68.6 g (0.25 mol) of α-monolaurin was added to 240 g of dioxane, and 24 g (0.3 mol) of liquid SO ₃ was added at 15 ° C.
The mixture was dropped in 15 minutes and stirred. The temperature was raised to 40 ° C., and stirring was continued for another hour. The reaction mixture was poured into ice water, neutralized with 64.4 g (0.32 mol) of a 20% aqueous sodium hydroxide solution, and the solvent was distilled off to obtain 111 g of the desired α-monolaurin sulfate. Table 3 summarizes the reaction conditions and the composition of the product.

[0046]

[Table 1]

[0047]

[Table 2]

[0048]

[Table 3]

Example 10 20 g (0.25 mol) of liquid SO ₃ were added to 140 g of DMF at 5 ° C.
The mixture was dropped in minutes and stirred. After the temperature was raised to 10 ° C, 68.6 g (0.25 mol) of α-monolaurin was added, and stirring was continued at 30 ° C for 2 hours. The reaction mixture was poured into ice water, neutralized with a 48% aqueous sodium hydroxide solution, and the solvent was distilled off to obtain the desired α-monolaurin sulfate. Table 4 summarizes the reaction conditions and the composition of the product.

Example 11 In 140 g of DMF, 16 g (0.2 mol) of liquid SO _{3 was} added dropwise at 5 ° C. over 10 minutes and stirred. After the temperature was raised to 10 ° C, 68.6 g (0.25 mol) of α-monolaurin was added, and stirring was continued at 30 ° C for 2 hours. The reaction mixture was poured into ice water, neutralized with a 48% aqueous sodium hydroxide solution, and the solvent was distilled off to obtain the desired α-monolaurin sulfate. Table 4 summarizes the reaction conditions and the composition of the product.

Example 12 To 137.2 g of DMF, 12 g (0.15 mol) of liquid SO ₃ was added dropwise at 10 ° C., and 68.6 g (0.25 mol) of α-monolarin was added and stirred. The temperature was raised to 30 ° C., and stirring was continued for 2 hours. The reaction mixture was poured into ice water, neutralized with a 48% aqueous sodium hydroxide solution, and the solvent was distilled off to obtain the desired α-monolaurin sulfate. Table 4 summarizes the reaction conditions and the composition of the product.

[0052]

[Table 4]

Note) * 1: Amount per mole of monoglyceride The results of Examples 1 to 12 provide a monoglyceride sulfate having a larger amount of the active agent compared to Comparative Examples 1 to 4 in which the prior art was additionally tested. It is understood that it is done.

Example 13 19.2 g (0.24 mol) of liquid SO _{3 was} added at 10 ° C. to 220 g of DMF.
The mixture was dropped in 10 minutes and stirred. 54.9 g of α-monolaurin (0.2
Mol) was added and stirred for 1 hour. A part of the reaction mixture was poured into ice water and neutralized with a 48% aqueous sodium hydroxide solution to obtain a neutralized product. The remaining reaction mixture was further stirred at 30 ° C. for 2 hours. This was poured into ice water, neutralized with a 48% aqueous sodium hydroxide solution, and the solvent was distilled off to obtain the desired α-monolaurin sulfate. The composition of the product at 10 ° C. and 30 ° C. is summarized in Table 5.

[0055]

[Table 5]

The results of Example 13 show that the ratio of monoglyceride disulfate to monoglyceride monosulfate in α-monolaurin sulfate produced by changing the aging temperature of the reaction can be selected.

Continuation of front page (56) References JP-A-63-135367 (JP, A) JP-A-58-113165 (JP, A) JP-A-55-11525 (JP, A) JP-B-44-25767 (JP, A) , B1) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 305/00 C07C 303/00 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] [Claim 1] General formula (1) Α-monoglyceride, sulfur trioxide,
A sulfonating agent selected from rosulfonic acid or fuming sulfuric acid is reacted and then neutralized with a basic substance to obtain a compound of the general formula (2). M is an alkali metal, alkaline earth metal, ammonium,
Indicates alkyl ammonium or alkanol ammonium. A method for producing a monoglyceride sulfate, wherein a solvent having an amide group or a sulfoxide group is used as a solvent for sulfation in producing the monoglyceride sulfate represented by the formula (1). 2. The monoglyceride sulfate according to claim 1, wherein the solvent having an amide group is an amide compound represented by the general formula (3), and the solvent having a sulfoxide group is a sulfoxide compound represented by the general formula (4). Manufacturing method. Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different and represent H or an alkyl group having 1 to 20 carbon atoms. Note that R ¹ and R ³ , R ²
And R ³ , and R ⁴ and R ⁵ may form a ring together. ) 3. The method according to claim 1, wherein the solvent having an amide group is N-methylformamide, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N, N-dimethyllauramide or N, N-dimethylimidazolide. 2. The method for producing monoglyceride sulfate according to claim 1, wherein the solvent which is non and has a sulfoxide group is dimethyl sulfoxide. 4. The reaction temperature is adjusted to a low temperature (−20 to 20).
℃) at the reaction temperature of monoglyceride disulfate, high temperature side (20
The method for producing a monoglyceride sulfate according to any one of claims 1 to 3 , wherein a monoglyceride sulfate having an increased proportion of the monoglyceride monosulfate is obtained at a reaction temperature of about 80 ° C.