JP2907521B2 - Production method of surfactant - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing an aqueous solution or paste of O-long-chain acylisethioic acids useful as a surfactant.

[Conventional technology]

As a method for producing O-long-chain acyl isethionic acids,
A method of reacting an isethionic acid alkaline solution with a fatty acid chloride or a fatty acid is known.

There is also a method of reacting chloroethanesulfonic acid or ethionic acid with a fatty acid (German Patent No. 652410).

Industrially, a method of reacting isethionic acids with fatty acid chlorides is generally used (BIOS Report, 11). At this time, the fatty acid chloride as a raw material is obtained by reacting phosphorus trichloride with a fatty acid.

By the way, when the O-long-chain acyl isethionic acids thus produced are used as a surfactant as an aqueous solution or paste, turbidity or precipitation, which may be caused by a trace amount of an inorganic or organic phosphorus compound contained therein, is caused. And significantly lower the product value of the surfactant.

Therefore, it has been attempted to avoid such a phenomenon by adding various ion sequestering agents (US Pat. Nos. 2,239,284, 2,240,957, 2,542,385).
No. 3760668).

However, these are not essential solutions and require a large amount of ion sequestering agent, which has a great influence on the quality of the surfactant.

In addition, from an industrial viewpoint, there is a disadvantage that the number of steps is increased.

[Problems to be solved by the invention]

An object of the present invention is to provide a method for producing an O-long-chain acyl isethionic acid aqueous solution or paste that does not cause turbidity or precipitation.

[Means for solving the problem]

The object of the present invention is achieved by obtaining O-long-chain acyl isethionic acids by reacting fatty acid chlorides obtained by reacting carbonyl chloride with fatty acids and isethionic acids in the presence of an alkali.

The obtained O-long-chain acyl isethionic acids can be used as a raw material for a surfactant in an aqueous solution or paste state without isolation.

The method for producing the O-long-chain acylisethioic acids of the present invention is as follows.

First, a fatty acid chloride is obtained by reacting a fatty acid with carbonyl chloride in the presence of a solvent and / or a catalyst if necessary.

Fatty acids used as raw materials are saturated or unsaturated fatty acids having 8 to 20 carbon atoms. In addition to those having a single composition such as lauric acid, palmitic acid, myristic acid, oleic acid, and stearic acid, coconut oil fatty acids, cattle Mixed fatty acids such as fatty acids can be used as well.

Various inert solvents can be used as the solvent. For example, aromatic hydrocarbons such as toluene and xylene; halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene; ethers such as tetrahydrofuran;
It is an aliphatic hydrocarbon such as cyclohexane.

The amount of the solvent is not particularly limited, but a large amount is not industrially preferable.

As the catalyst, dimethylformamide, dimethylacetamide, formamide, dimethylformanilide, pyridine, triethylamine and the like can be used.

The amount of the catalyst is 0.01 to 10 mol%, based on the raw material fatty acid.
, But is preferably 0.1 to 3 mol%.

When the amount is less than 0.01 mol%, the effect of the catalyst is low, and when it exceeds 10 mol%, the amount of impurities contained in the fatty acid chloride increases, which is not preferable.

The carbonyl chloride can be reacted with the fatty acid in an equimolar amount or more. Preferably, it is about 1.05 to 1.5 times mol, and if it is used more than that, there is no effect on the yield, but it is not industrially preferable.

The reaction can be performed at a temperature ranging from room temperature to around the boiling point of the solvent, but is preferably 40 to 100 ° C.

 The reaction is usually completed in about 5 hours.

After completion of the reaction, the fatty acid chloride can be obtained with high purity by completely performing the degassing or desolvation operation.

Next, the above-mentioned fatty acid chloride and isethionic acid are reacted in an aqueous solution or a water-containing solvent in the presence of an alkali to obtain the desired O-long-chain acyl isethionic acid as an aqueous solution or paste.

Examples of the isethionic acid used as a raw material include sodium isethionate, potassium isethionate, calcium isethionate, ammonium isethionate, isethionic acid, and the like.

Examples of the alkali include inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, and sodium carbonate; and organic bases such as pyridine and triethylamine. Sodium and potassium hydroxide are useful.

These are used in an amount of 0.5 to 1.5 equivalents of isethionic acids and 1 to 4 equivalents of alkali relative to 1 equivalent of the fatty acid chloride.

Examples of the solvent for the water-containing solvent include dimethoxyethane, acetone, tetrahydrofuran, toluene, and ethyl acetate.

The reaction can be carried out at a temperature between -20 ° C and the reflux temperature of the reaction solution, and particularly preferably at -10 to 50 ° C.

If the temperature is lower than −20 ° C., the reaction rate becomes slow, and if the temperature exceeds the reflux temperature of the reaction solution, fatty acids produced as a by-product of hydrolysis increase.

 The reaction is usually completed in about 5 hours.

The resulting O-long chain acyl isethionic acids include O
-Long chain acyl isethionate, sodium O-long chain acyl isethionate, potassium O-long chain acyl isethionate and the like.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to examples. In the following, “%” is based on weight unless otherwise specified.

The purity of the desired O-long-chain acylisethioic acids was determined by phase separation titration or HPLC.

Further, the obtained aqueous solution or paste of O-long-chain acyl isethionic acids was subjected to the following solubility test and storage stability test, and the results are shown in Tables 1 and 2, respectively.

-Solubility test The sample was heated and melted at 60 ° C, and the transparency was visually evaluated in four stages.

-Storage stability test The sample was stored in a 40 ° C constant temperature bath for one month.

Thereafter, the sample was heated and melted at 60 ° C., and the transparency was visually evaluated in four stages.

Example 1 A reactor (with a thermometer, a stirrer and a condenser) was charged with 120 g (0.06 mol) of lauric acid, and 64 g (0.65 mol) of carbonyl chloride was introduced over 3 hours while maintaining the temperature at 80 ° C.

After completion of the reaction, excess carbonyl chloride was removed under reduced pressure to obtain 129 g of crude lauroyl chloride.

185 g of a 40% aqueous solution of sodium isethionate (0.50
Mol), 62.2 g of 45% aqueous sodium hydroxide solution (0.70
Sodium isethionate aqueous solution was prepared from 300 ml of acetone.

While maintaining the above aqueous solution at 15 ° C, 129 g of the above crude lauroyl chloride was added dropwise.

After completion of dropping, the mixture was aged at 15 ° C for 2 hours, and then concentrated hydrochloric acid to pH 7.
2 and remove acetone under reduced pressure
-An aqueous solution of sodium lauroylisethionate was obtained.

The content of sodium O-lauroylisethionate is 17
With 6 g, the yield was 96 mol%.

Example 2 A crude cocoyl chloride was obtained in the same manner as in Example 1, except that lauric acid was replaced with coconut oil fatty acid.

To 24.8 g (0.11 mol) of this crude cocoyl chloride, 16.4 g (0.10 mol) of potassium isethionate and 3 g of potassium carbonate
(0.02 mol) was added slowly at 30-40 ° C. When the amount of generated hydrogen chloride gas was reduced, the temperature was increased to 110 ° C. to cause a reaction. After the completion of the reaction, hydrogen chloride gas was removed under reduced pressure, and the pH was adjusted to 7.1 with an aqueous potassium carbonate solution to obtain a target paste of potassium O-cocoylisethionate.

The content of potassium O-cocoylisethionate is 34.6
g, the yield was 98 mol%.

Example 3 A crude oleoyl chloride was obtained in the same manner as in Example 1, except that lauric acid was replaced with oleic acid.

14.8 g (0.10 mol) of sodium isethionate is suspended in 100 ml of dimethoxyethane, and while maintaining the temperature at 10 ° C., 33.1 g (0.11 mol) of the above crude oleoyl chloride and 22.0 g (corresponding to 0.11 mol) of a 20% aqueous sodium hydroxide solution are added. It was dropped at the same time.

After completion of the dropwise addition, the mixture was aged at 25 ° C. for 3 hours, and then the solvent was separated to obtain a target aqueous solution of sodium O-oleoylisethionate.

The content of O-oleoyl sodium isethionate is
In 39.2 g, the yield was 95 mol%.

Comparative Example 1 The procedure of Example 1 was repeated except that crude lauroyl chloride was synthesized from lauric acid and phosphorus trichloride.
-An aqueous solution of sodium lauroylisethionate was obtained.

Comparative Example 2 The same operation as in Example 2 was carried out except that crude cocoyl chloride was synthesized from coconut oil fatty acid and phosphorus trichloride.
A paste of potassium cocoylisethionate was obtained.

Comparative Example 3 The procedure of Example 3 was repeated except that the crude oleoyl chloride was synthesized from oleic acid and phosphorus trichloride.
-An aqueous solution of sodium oleoyl isethionate was obtained.

〔The invention's effect〕

According to the present invention, by using fatty acid chlorides obtained by reacting carbonyl chloride with fatty acids, it is possible to produce O-long-chain acylisethioic acids useful as surfactants without causing turbidity or precipitation. it can.

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C11D1 / 28 C11D1 / 28 (56) References JP-A-56-110639 (JP, A) JP-A-59-108737 (JP, A) JP-A-60-115549 (JP, A) JP-A-2-235840 (JP, A) JP-A-2-1454 (JP, A) JP-A-63-227561 (JP, A) (58) (Int.Cl. ⁶ , DB name) C07C 309/12 C07C 303/22 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A method for producing an aqueous solution or paste of O-long-chain acyl isethionic acids by reacting fatty acid chlorides obtained by reacting carbonyl chloride and fatty acids with isethionic acids in the presence of an alkali.