JPS5928599B2 - Method for manufacturing surfactant - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a light-colored polyoxyalkylene derivative and a method for producing a mild sulfo-citrate type anionic surfactant using the same as a raw material.

Polyoxyalkylene derivatives of higher fatty acid alkanolamides are used as surfactants for detergents, emulsifiers, and wetting agents in liquid kitchen detergents, powdered laundry detergents, and Jump I products.

It is also useful as a raw material for various surfactants derived from this product. Conventionally, the production method involved reacting higher fatty acid methyl ester with approximately equimolar amounts of alkanolamine in the presence of an alkali catalyst, and then reacting with 120
Polyoxyalkylene derivatives were produced by adding alkylene oxide at ~220°C, but the polyoxyalkylene derivatives produced in this way were highly colored, which was undesirable from the viewpoint of their intended use, and the by-product of amine components such as ester amines was observed. Many have drawbacks such as poor skin irritation.

Further, although this coloring can be temporarily removed by treatment with an oxidizing agent such as hydrogen peroxide, the coloring reappears over time and cannot be essentially improved. Other known methods include reacting higher fatty acids with alkanolamines and then adding alkylene oxides, and adding alkylene oxides to higher fatty acid amides, but in both cases the products are of poor purity and have a pale color. It has been impossible to obtain polyoxyalkylene derivatives that are In addition, USP 252O38L describes a method of adding ethylene oxide to higher fatty acid alkanolamide in the presence of an amine catalyst such as triethylamine, but in this case, it is difficult to completely remove the amine catalyst after the reaction, and the formation of There was a drawback that things had a strange smell. Furthermore, surfactants derived from alkanolamides containing these colored impurities often have more severe coloring and are highly irritating to the skin and mucous membranes, causing problems in their use as surfactants. The inventors of the present invention have conducted repeated research to improve these drawbacks, and as a result, by strictly selecting the reaction conditions for the lower alcohol ester of higher fatty acid and alkanolamine and the conditions for the subsequent addition of alkylene oxide, extremely high purity was achieved. However, it was discovered that a light-colored, low-odor polyoxyalkylene derivative could be obtained, and the present invention was achieved.

That is, the present invention involves reacting a lower alcohol ester of a higher fatty acid with an equimolar amount or more of alkanolamine in the presence of an alkali metal or an alkali metal compound, then removing excess alkanolamine, and then reacting 60 to 10
A method for producing a light-colored polyoxyalkylene derivative represented by the general formula (1), which comprises reacting an alkylene oxide at 0°C.

General formula (1) [wherein, R is a residue of a higher fatty acid having 6 to 22 carbon atoms,
R2 represents hydrogen or a methyl group, AO represents an oxyalkylene group having 2 to 3 carbon atoms, and n represents an integer of 1 to 50.

] and a method for producing a sulfosuccinate type anionic surfactant derived therefrom.

In the lower alcohol esters of higher fatty acids (hereinafter simply referred to as esters) used in the present invention, the higher fatty acids that are one of the components constituting the ester include caproic acid, chifururic acid, chipuric acid, lauric acid, palmitic acid, Saturated fatty acids with linear and side chains having 6 to 22 carbon atoms such as stearic acid, isostearic acid, and behenic acid; unsaturated fatty acids such as oleic acid, linoleic acid, and linoleic acid; fatty acids with hydroxyl groups such as ricinolenic acid; Examples include fatty acids having a carbon distribution such as beef tallow fatty acid, hydrogenated beef tallow fatty acid, apricot oil fatty acid, and palm oil fatty acid.

Examples of the lower alcohol, which is the other component constituting the ester, include methanol, ethanol, n-propanol, and isopropanol. The ester may be a mixture of two or more types, and preferred among the above esters are methyl esters of higher fatty acids,
Particularly preferred are lauric acid methyl ester, oil fatty acid methyl ester, and stearic acid methyl ester. The alkanolamine used in the method of the present invention includes monoethanolamine and isopropanolamine, and mixtures thereof may also be used.

The alkali metal catalyst used as a catalyst in the present invention is sodium, potassium lithium metal or its hydroxide, or an alcoholade such as methanol, ethanol or propanol. Particularly preferred is sodium methylate. Examples of the alkylene oxide include ethylene oxide and propylene oxide, which may be added alone or mixed in blocks or randomly.

In the process of the invention, the molar ratio of ester to alkanolamine may be from 1.00:1.02 to 2.00, preferably from 1.00:1.05 to 1.00:1.50. The reaction between the ester and the alkanolamine can be carried out by mixing the two and heating the mixture, and the reaction temperature is 60 to 150°C, preferably 80 to 130°C.

A solvent may be used, but is not particularly required. In order to facilitate the distillation of the lower alcohol produced as a by-product during the reaction and to prevent coloration during the reaction, it is preferable to flow an inert gas such as nitrogen gas into the reaction liquid phase or gas phase, or to carry out the reaction under reduced pressure. . Although the reaction can be carried out under reduced pressure, care must be taken not to distill off the alkanolamine while it is not reacting, so a method using an inert gas at normal pressure is preferable. The amount of catalyst added is 0.05% to 0.5% by weight (based on the total weight of ester and alkanolamine), preferably 0.1 to 0.3% by weight.

The reaction time is usually 3 to 15 hours. After the reaction, excess alkanolamine can be easily removed under reduced pressure. Next, alkylene oxide is introduced and the reaction is carried out at a temperature of 60 to 100°C, preferably 70 to 9°C.
0°C'(' is there.

When the temperature exceeds 100°C, the higher the temperature, the more likely an amide and ester exchange reaction will occur and free amines will be produced.

The pressure is 0-10kg/Cd, preferably 1-5k
g/Cd. As the catalyst for alkylene oxide addition, the catalyst used for the above amidation can be used as is, but the same type or a different catalyst may be added and reacted. After the reaction, these catalysts do not need to be removed in particular and can be used as they are by adjusting the pH of the product at the time of use. Further, when the next step is added and the derivative is further used as a derivative, it may be used without being removed, or it may be removed by performing acid clay treatment or the like. Usually, it is treated by adding inorganic acids such as sulfuric acid or phosphoric acid, or organic acids such as toluenesulfonic acid or acetic acid to neutralize it. The polyoxyalkylene derivative thus obtained can then be sulfated, phosphorylated, or reacted with sulfosuccinic acid to produce a more hydrophilic anionic surfactant. The anionic surfactant obtained in this way can be used as a very light-colored product, and because it contains few impurities, mucous membrane and skin irritation is greatly alleviated, making it particularly suitable for use in kitchen detergents, Jump 1, cosmetics, etc. It becomes a base material.

The reaction for forming an anion activator can be carried out by adding a conventionally known anionization reaction to the above polyoxyalkylene derivative. For example, the polyoxyalkylene derivative itself or an anion activator that is difficult to solidify at low temperatures in the presence of a non-reactive solvent or Concentrated sulfuric acid, mixed with the raw material of the agent (for example, synthetic higher alcohol or its alkylene oxide adduct),
A sulfating agent such as chlorosulfonic acid, sulfuric anhydride, or sulfamic acid is gradually added at a low temperature that prevents coloring and reacted, and then an alkaline solution such as caustic soda, caustic potash, ammonia, or ethanolamine is added to neutralize. A sulfated anion activator may be produced.

In addition, in the case of forming a phosphate type activator, phosphoric acid, phosphoric anhydride, phosphorus trichloride, or phosphorus pentachloride may be reacted in place of the above-mentioned sulfating agent, but this reaction can be carried out at room temperature to 70°C. It is performed at a somewhat high level. Neutralization can be carried out in the same manner, but in this case, it can also be carried out by directly adding an alkaline solution to the phosphorylation reaction product. It can also be derived from sulfo-citrate type anionic active agents, which are superior in that they are less irritating to mucous membranes.

This anionic activator has the general formula (2) and/or (3
) [wherein, R1 is a residue of a higher fatty acid having 6 to 22 carbon atoms, R2 is hydrogen or a methyl group, AO is an oxyalkylene group having 2 to 3 carbon atoms, n is an integer of 1 to 50, M1, M2 is an ion selected from the group consisting of hydrogen, alkali metals, ammonium, and hydroxyalkylammonium.

], and the production method is not particularly limited as long as the above compound can be obtained. First, obtain sulfosuccinic acid,
The polyoxyalkylene derivative of the present invention can then be reacted with the polyoxyalkylene derivative of the present invention to obtain the product, but from the viewpoint of obtaining inexpensive raw materials and reducing impurities, about 70 to 100 molar amounts of maleic anhydride are added to the polyoxyalkylene derivative of the present invention. It is preferable to produce it by reacting at 40 to 80°C for 2 to 5 hours, and then reacting about equimolar amount of sodium sulfite in the presence of water for 2 to 5 hours at 40 to 80°C.

In the method of the present invention, polyoxyalkylene derivatives can be produced with extremely high purity, light color, and low odor by strictly selecting the reaction conditions for lower alcohol esters of higher fatty acids and alkanolamines and the subsequent addition conditions for alkylene oxide. can get.

Furthermore, the anionic active agent obtained starting from this derivative is also very pale in color and exhibits the feature of being extremely low in irritation to the skin and mucous membranes. Examples will be described below. Example 1 Methyl ester laurate (1 mol), monoethanolamine (shown in the table below), and catalyst shown in the table below (0.01 mol) were charged, and all the methanol was distilled off at 100 to 110°C under a nitrogen stream. The reaction was continued until no decrease in the amine value was observed, and then the remaining monoethanolamine was distilled off at 130 to 140°C under reduced pressure.

Next, ethylene oxide (3 mol) was gradually added (pressure 2 to 3 kg/CrA) at the temperature shown in the table below, and the mixture was aged at the same temperature until no decrease in pressure was observed. Various conditions (
The hue (APHA method), odor, and total amine value of the polyoxyalkylene derivatives obtained under Black 1 to 7) were as shown in Table 1. In addition, for Black 7, after reaction aging, 8 under reduced pressure
The test was carried out by topping at 0 to 90°C for 3 hours. Example 2 An oil fatty acid methyl ester 219y (1 mol), isopropanolamine 90y (1.2 mol), and sodium methylate 0.67 (pure content) were prepared and heated for 120 y under a nitrogen stream.
The reaction was carried out for 8 hours while methanol was distilled off at ~130°C, and then the remaining isopropanolamine was distilled off at 130-140°C under reduced pressure.

The total amine value at this time was 7.8. Next, ethylene oxide 4407 (10 mol) was gradually added at 70-80°C (pressure 2-3 kg/leak), and then aged at the same temperature for 2 hours. When the obtained compound was analyzed, the hue (APHA method)
120, the total amine value was 4.3, and the compound had a good odor. Example 3 Isostearic acid methyl ester 2987 (1 mol) and isopropanolamine 112.5 t (1.5 mol),
1.17 (pure) of sodium methylate was charged, and while distilling off methanol at 110 to 120°C under a nitrogen stream, 1.
The reaction was carried out for 0 hours, and then the remaining isopropanolamine was distilled off at 130 to 140° C. under reduced pressure.

Next, add ethylene oxide 8807 (20 mol) to 90~
It was gradually added at 100° C. (pressure: 4 to 5 kg/Cd) and then aged at the same temperature for 1 hour. When the obtained compound was analyzed,
The compound had a hue (APHA method) of 120, a total amine value of 5.1, and a good odor. Example 4 Anolyte fatty acid methyl ester 2197 (1 mol), monoethanolamine 73.37 (1.2 mol), and sodium methylate 0.9 V (pure content) were charged and heated under a nitrogen stream for 1 mol.
The reaction was carried out at 00 to 110°C while methanol was distilled off, and then the remaining monoethanolamine was distilled off at 130 to 140°C under reduced pressure.

Next, add 80% of propylene oxide 5807 (10 mol)
It was gradually added at ~90°C (pressure: 1-2 kg/Cni) and then aged at the same temperature for 4 hours. Analysis of the obtained compound revealed that it had a hue (APHA method) of 100, a total amine value of 4.5, and a good odor. Example 5 Maleic anhydride 98.17 (1 mol) was added to the compound 3757 (1 mol) obtained in Step 3 of Example 1, and after reaction at 80 to 90°C for 4 hours under a nitrogen stream, 126 y of sodium sulfite was added.
(1 mol) and 1,400 f7 of water were added, and the reaction was carried out at 60 to 70°C for 4 hours.

Claims (1)

[Claims] 1. A lower alcohol ester of a higher fatty acid is reacted with an equivalent molar amount or more of an alkanolamine in the presence of an alkali metal or alkali metal compound catalyst, then excess alkanolamine is removed, and then the reaction is carried out at 60 to 100°C. A method for producing a light-colored polyoxyalkylene type surfactant represented by the general formula (1), which comprises reacting an alkylene oxide. General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) [In the formula, R_
1 represents a residue of a higher fatty acid having 6 to 22 carbon atoms, R_2 represents hydrogen or a methyl group, AO represents an oxyalkylene group having 2 to 3 carbon atoms, and n represents an integer of 1 to 50. ]. 2. The production method according to claim 1, wherein the lower alcohol ester of higher fatty acid is lauric acid methyl ester, coconut oil fatty acid ethyl ester, or stearic acid methyl ester. 3. The manufacturing method according to any one of claims 1 to 2, wherein the alkali metal compound catalyst is sodium methylate. 4 The molar ratio of lower alcohol ester of higher fatty acid and alkanolamine is 1.00:1.05 to 1.00:1
．． 50. The manufacturing method according to any one of claims 1 to 3, wherein the manufacturing method is 50. 5. The manufacturing method according to any one of claims 1 to 4, wherein the alkylene oxide is ethylene oxide. 6. In the presence of an alkali metal or alkali metal compound catalyst, a lower alcohol ester of a higher fatty acid is reacted with an equivalent mole or more of alkanolamine, then excess alkanolamine is removed, and then an alkylene oxide is reacted at 60 to 100°C. General formula (1) obtained
A method for producing a sulfosuccinate type anionic surfactant represented by the general formula (2) and/or (3), which comprises reacting a polyoxyalkylene derivative represented by the formula with maleic acid or a derivative thereof and a sulfite. General formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1) [In the formula, R_
1 represents a residue of a higher fatty acid having 6 to 22 carbon atoms, R_2 represents hydrogen or a methyl group, AO represents an oxyalkylene group having 2 to 3 carbon atoms, and n represents an integer of 1 to 50. ] General formula (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2) [R_1, R
_2, AO, and n have the same meanings as in general formula (1) above, and M_1 and M_2 are ions selected from the group consisting of hydrogen, alkali metals, ammonium, and hydroxyalkylammonium. ] General formula (3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) [R_1, R
_2, AO, n, M_1, and M_2 have the same meanings as in general formula (2). ].