JPS6013751A - Production of sulfonic acid salt of unsaturated fatty acid ester - Google Patents

Abstract

PURPOSE:To obtain the light-colored titled compound suitable as a detergent, in high conversion, by sulfonating an unsaturated fatty acid ester using a specific amount of a saturated fatty acid ester as the reaction solvent. CONSTITUTION:A fatty acid ester mixture containing (A) a lower alkyl ester of a 8-22C unsaturated fatty acid and (B) a lower alkyl ester of a 8-22C saturated fatty acid at a weight ratio (A/B) of 90/10-5/95, preferably 80/20-10/90, is sulfonated at 30-120 deg.C with a sulfonation agent such as SO3. The sulfonation is carried out keeping the content of the component (A) in the unreacted fraction of the fatty acid ester mixture to >=0.3wt%, and the reaction product is neutralized and hydrolyzed to obtain the objective compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a method for obtaining a sulfonate by sulfonating an unsaturated fatty acid ester using a saturated fatty acid ester as a reaction solvent.

Sulfonation of saturated fatty acid esters was published in Japanese Patent Publication No. 39-208.
Publication No. 42, Special Publication No. 39-28635, Special Publication No. 4
This can be carried out by a known method such as that described in Japanese Patent No. 1-965, and by neutralizing and hydrolyzing this sulfonated product, a light-colored sulfonate can be obtained with a high reaction rate. On the other hand, even if the above method is applied to the sulfonation of unsaturated fatty acid esters, it is not possible to obtain a sulfonated product with a high reaction rate, and even if the molar ratio of the sulfonating agent such as SO8 is increased, it is not always possible to obtain a high reaction rate. Not only is the reaction rate unobtainable, but the amount of polysulfonated products into which two or more sulfonic acid groups have been introduced increases, resulting in a significant decrease in color tone.

By combining the sulfonate of unsaturated fatty acid ester with the sulfonate of NJJ & fatty acid ester, a cleaning agent with excellent foaming power, detergency, and penetration power, and good rinsing properties can be obtained. , is promising as a surfactant. Therefore, there is a need to develop a method for producing a sulfonate of a light-colored unsaturated fatty acid ester suitable for use as a cleaning agent at a cylinder reaction rate, and an object of the present invention is to provide this method.

The method for producing a sulfonate of an unsaturated fatty acid ester of the present invention comprises (A) unsaturated fatty acid (Cs~1.) lower alkyl ester and (B) saturated fatty acid (Cδ~11) lower alkyl ester. /(B)=90/l O~5/
A fatty acid ester mixture containing a fatty acid ester mixture with a weight ratio of 95% is used, and the content of the component (A) in the unreacted portion of the mixture is 0.3%.
It is sulfonated to be more than 100% pure, and then neutralized.
Characterized by hydrolysis.

The sulfonation reactivity of (A) unsaturated fatty acid ester and (B) unsaturated fatty acid ester is (A) >> (B). Therefore, when a mixture of components (A) and (B) is sulfonated, component (A) is first sulfonated preferentially to produce a 1-mole adduct of SO3. At this time,(
It has been found that the presence of component B) allows a sulfonated product of an unsaturated fatty acid ester to be obtained at a significantly higher reaction rate than when component (A) is used alone for sulfonation. This is considered to be because component (B) acts as a good reaction solvent. It has been found that when the reaction proceeds further, a polysulfonated product of component (A) and a sulfonated product of component (B) are simultaneously produced, resulting in significant deterioration of color tone. At this time, the polysulfonated product producing reaction of component (A) is faster than the sulfonation reaction of component (B).

In the present invention, the (A) component and the (B) component are expressed as (Δ)/(B).
=90/10~5/95. Preferably 80/20~
Sulfonation is performed on a fatty acid ester mixture containing a lo/900 weight ratio, and unsaturated fatty acid ester is sulfonated in the presence of saturated fatty acid ester.

If the above ratio is larger than 90/l O, the reaction rate will decrease because the solvent effect of the saturated fatty acid ester will not be sufficiently exhibited, while if it is smaller than 5/95, the yield of the sulfonate of the unsaturated fatty acid ester will decrease. However, it is not practical.
“Component (A) is a lower alkyl ester of an unsaturated fatty acid in which the fatty acid residue has 8 to 22 carbon atoms, and one in which the lower alkyl group has 1 to 6 carbon atoms is suitable. Generally, the group has 12 to 18 carbon atoms, and the lower alkyl group has 1 to 3 carbon atoms.

Component (B) is a lower alkyl ester of a saturated fatty acid in which the fatty acid residue has 8 to 22 carbon atoms, preferably one in which the lower alkyl group has 1 to 6 carbon atoms. Generally, the carbon number is 12 to 18, and the lower alkyl group has 1 to 3 carbon atoms.

Sulfonation is carried out at a SO8 molar ratio of 05 to 2.0, preferably 1
．． Using sulfonating agent at 0-1.5, temperature 30-120
C., preferably 40 to 90.degree. C., under normal sulfonation conditions, and methods such as thin film reaction and tank reaction can be employed. Also, as a sulfonating agent, liquid SO, ,
So, gas, oleum, chlorsulfone cough, etc. are used.

In the sulfonation, component (A) is preferentially sulfonated so that the content of the (Al component) in the unreacted portion of the fatty acid ester mixture is 0.3 wt% or more. ) The sulfonation reaction is stopped before the sulfonated product of the component is formed.

If the sulfonation is performed until the amount of the unreacted (Al component) is less than 0.3 wt%, the polysulfonation reaction etc. will proceed and the product will be colored. It is more preferable to carry out the sulfonation at an amount of 3 to 5 wt%, and if the sulfonation reaction is stopped at an amount exceeding 5 wt%, the reaction rate will decrease.Furthermore, (A)
When sulfonated until the component content reaches 0.3 to 5 wt%, saturated fatty acid ester containing this amount of unsaturated fatty acid ester can be recovered as unreacted oil, and by sulfonating this, the color tone can be improved. A sulfonated product containing a good sulfonate of saturated fatty acid ester as a main component can be obtained. Therefore, it is preferable to sequentially produce a sulfonate of an unsaturated fatty acid ester and a sulfonate of a saturated fatty acid ester using a mixed fatty acid ester containing a saturated fatty acid ester and an unsaturated fatty acid ester as a raw material. . Further, from the above viewpoint, it is even more preferable to sulfonate the unreacted portion so that the content of the Al component is 0.5 to 2 wt%.

After the sulfonation is completed, it is neutralized and hydrolyzed by a conventional method, and then the sulfonate of the unsaturated fatty acid ester is separated.

In addition, in the present invention, a hydroxyl sulfone salt that does not contain a sulfonated double bond by adding a hydroxyl group to a double bond is also produced, and this is also included in the sulfonate of an unsaturated fatty acid ester.

Neutralization can be carried out, for example, by oxides or hydroxides of alkali or alkaline earth metals such as sodium, potassium, lithium or magnesium, calcium, or organic bases such as ammonia, ethanolamine, jetanolamine, triethanolamine, etc. , 40~
It can be carried out at a temperature of 80°C. Hydrolysis is 60
It is generally carried out at ~200°C for 1 to 180 minutes.

Then, the unreacted oil is recovered by a conventional method such as hexane extraction, static separation by adding alcohol, or centrifugation.
A sulfonate of a saturated fatty acid ester is obtained.

Since the recovered unreacted oil mainly consists of the saturated fatty acid ester which is the component (B), it may be recycled and used in the sulfonation reaction and mixed with the component (A). Also,
The unreacted oil may be sulfonated by a conventional sulfonation method of saturated fatty acid esters to form a sulfonate of saturated fatty acid esters.

According to the method of the present invention, a light-colored sulfonate of an unsaturated fatty acid ester can be obtained at a high reaction rate by sulfonating an unsaturated fatty acid ester in the presence of a predetermined amount of a saturated fatty acid ester. .

Example - Zome oil fatty acid methyl ester (unhydrogenated ester, unsaturation content 42%, average molecular weight M 281 ) was prepared using a Hakumei reactor manufactured by Razekarasu at a molar ratio of 803 and a reaction temperature of 1.2. After sulfonation in urine at 80°C, 5% NaOH
Neutralized with an aqueous solution. A portion of the resulting neutralized product was taken, the unreacted product was isolated by extraction with petroleum ether, its iodine value was measured, and the content of unreacted unsaturated ester in the unreacted oil was recorded.
When I put it out, it was 0.7ch.

On the other hand, the sulfonation reaction rate of the unsaturated ester was calculated from the unsaturated ester content in the raw material before sulfonation and the unsaturated ester content in the unreacted oil, and was found to be 98.2.
% values were obtained.

Further, unreacted oil was removed from this neutralized product to obtain a sulfonate of unsaturated fatty acid ester, and the color tone of this 5-thi aqueous solution was measured using a KLETT-Summerson absorbance spectrometer.
When measured using a 40XIO+nm quartz cell, 3
,700.

Sulfonation was carried out using various sulfonation raw materials and sulfonation conditions in the same manner as described above, and the results are summarized in Section 1i.

(Left below) After adding ethanol IKP to each of the neutralized products IKg obtained in the above manner and mixing well, petroleum ether SO
oml, and extracted three times. Next, the petroleum ether layer was topped under reduced pressure using a rotary evaporator to recover unreacted oil.

This unreacted oil was collected in a glass thin film reactor in the same manner as above.
Sulfonated at a 803 molar ratio of 1.5 and a reaction temperature of 80°C,
After neutralizing with 5%-NaOH, the reaction rate and color tone were measured.

Next, the sulfonated product of the saturated ester and the water-ethanol layer (sulfonated product of the unsaturated ester) from which unreacted oil has been removed by petroleum ether extraction are mixed at a solid content pace to obtain an isotropic compound. , a saturated/unsaturated ester sulfonation mixture. The reaction rate of this mixture was calculated and the color tone was measured. The above results are summarized in Table 2.

(Margin below)

Claims (1)

[Claims] 1, 0. ) Unsaturated fatty acid (Ca~! lower alkyl ester and (B) saturated fat e (Cs~2 lower alkyl ester) (A) / (B) = 90 / 10 ~
A fatty acid ester mixture containing the fatty acid ester mixture in a weight ratio of 5/95 is used when the content i of the component (A) in the unreacted content of the mixture is 0.
．． A method for producing a sulfonate of an unsaturated fatty acid ester, which comprises sulfonating to a concentration of 3% by weight or more, followed by neutralization and hydrolysis.