JPH083114B2 - Detergent manufacturing method - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION The present invention relates to the formula: RCONH (C ₂ H ₄ O) _n CH ₂ COOH, where R is a linear or branched chain having 5 to 21 carbon atoms. Of an aliphatic hydrocarbon group, wherein n is a number from 1 to 20], and a detergent containing one or more compounds represented by the formula: RCOOH, wherein R is By amidating, ethoxylating and / or carboxymethylating one or more fatty acids of the formula: and converting all or part of the ether carboxylic acid obtained to a salt thereof, if desired. It relates to a method of manufacturing.

PRIOR ART Such a method is known from EP-A-102118. The starting compounds, ie fatty acids of the formula RCOOH, are usually prepared from oils or fats, especially when R is an aliphatic radical having 10 to 20 carbon atoms. The oils and / or fats are saponified by generally known methods and the fatty acids formed are separated from the reaction mixture. As is generally known, oils and fats are composed to a large extent of glycerol esters of fatty acids, so that a significant amount of glycerol is present in the saponification product. Due to the high boiling point and high viscosity of glycerol, its separation from fatty acids is cumbersome and expensive. It was speculated that the presence of glycerol hindered the ethoxylation and carboxymethylation of fatty acids, or at least resulted in a product with less favorable properties.

Surprisingly, surprisingly, the aminolysis of oils or fats was carried out with monoethanolamine in the presence of alkali (earth) metal alkanolates, followed by ethoxylation and carboxymethylation of all reaction products. It has been found that by doing so, a mixture is obtained which has very advantageous properties as a cleansing agent in terms of detergency and acceptability for hair and skin. Therefore, such products are often used for detergents intended to come into contact with human skin or hair for extended periods of time, such as shampoos, shower and bath preparations, skin-care products such as creams, It is particularly suitable for use in dishwashing detergents and other chemicals for hand washing.

Within the scope of the present invention, aminolysis means converting the fatty acid ester to fatty acid monoethanolamide glycerol using monoethanolamine.

It has been found that coconut oil (a cheap product) yields excellent products. It is also within the scope of the present invention to produce the detergents obtainable by the process according to the invention and the washing or cleaning agents containing said detergents.

To produce the detergents according to the invention, it is possible to start with fats or oils, preferably coconut oil. If starting from coconut oil, this may be a refined or unrefined oil.

Aminolysis of oils is carried out with monoethanolamine in the presence of alkali (earth) metal alkanolates. Sodium methylate is preferably used. Preference is given to using monoethanolamine. The reason is,
This is because the product obtained by aminolysis already has a hydroxyethyl group attached to the amide nitrogen atom. Of course, the amidation can in principle also be carried out with ammonia, followed by the introduction of another ethoxy group in the subsequent ethoxylation, but from a technical point of view the use of monoethanolamine is Much easier than using toxic pressurized ammonia. The reaction can be carried out at an elevated temperature (for example 50 to 100 ° C.) for a relatively short time (1 to several hours). The physical state of the starting oil is not critical, as the process is preferably carried out at elevated temperature. This means that the oil may be solid or semi-solid at ambient temperature.

The reaction mixture obtained contains free glycerol and the monoethanolamide of coconut oil fatty acids, or alternatively free fatty acids, and additionally the by-products, which may or may not have been converted from the raw palm row.

Furthermore, this mixture is ethoxylated in a conventional manner. As is known, this results in reaction mixtures with varying numbers of ethoxy groups per molecule. This reaction is usually at 125 ° C
It is carried out at a moderate temperature (generally 100 to 150 ° C).

Ethoxylation can, of course, occur at the hydroxyl group of monomethanolamide and also at one or more hydroxyl groups of glycerol,
By-products present in relatively small amounts can also undergo ethoxylation.

The product thus obtained is again carboxymethylated at elevated temperature, usually with sodium chloroacetate, in a conventional manner as described, for example, in EP-A-102118. A crude reaction mixture is thus obtained in which the carboxymethyl group is of course present as the sodium salt. In addition, the crude reaction mixture can be treated in various ways, for example as follows: a) diluting the crude reaction mixture with water to 30% dry solids,
The pH is adjusted to 7, preferably with hydrochloric acid. In this case the product still contains NaCl and other impurities. NaCl
Is often used as a thickener in cosmetics. It is observed that the product thus obtained acts extremely well in shampoos and the like.

b) The product is washed with water and hydrochloric acid by heating a mixture of water and hydrochloric acid, for example to 90 ° C., then adding the crude reaction mixture, leaving the solution and separating the layers. The recovered oil layer contains carboxylated products in the free acid form. The product thus purified can be converted to the sodium salt with sodium hydroxide solution at about 50 ° C.

In addition, it is common to add preservatives to the final product, such as benzyl formal.

Many different hydrophilic compounds can form during ethoxylation and carboxymethylation. Although the starting composition is not well defined, reproducible results are obtained and, as already mentioned, the resulting mixture has excellent cleaning properties and is better tolerated by human skin and hair. It was found to be done.

Since the product of the invention contains a certain amount of carboxamide derivative pairs according to EP 0 102 108, when choosing the number of ethoxy units to be introduced,
The types of hydrophobic groups of the fatty acids that make up the oils and fats used as starting materials are considered. In general, higher fatty acids (eg C ₁₈ ) tend to require more ethoxy units than lower fatty acids (C ₁₂ -C ₁₄ ), but have a wide range of ethoxy units for all these hydrophobic groups. Can be used. Generally, the number of ethoxy units introduced is 0-19 (assuming the amidation was carried out with ethanolamine).

In the above general description of the process according to the invention, it has been mentioned that the sodium salt is optionally prepared in the part relating to carboxymethylation. Of course, other salts can also be prepared with alkali metals, alkaline earth metals (due to their high stability towards calcium) and ammonium and amines via the free acid.

The selection range of usable oils and fats is extremely wide,
In general all vegetable and animal oils are suitable as starting materials. Of course, for some substances, the presence of unpleasant-smelling impurities can be an obstacle, and this choice is often largely determined by price and availability. Finally, it is of course possible to mix different types of oils and / or fats and, if desired, use these mixtures as starting material.

As already mentioned, the products considered have a good cleaning action and a good acceptance on the skin and hair. Of course, quantitatively, these properties
Depending on the oil and / or fat combination selected and the average number of ethoxy units introduced by ethoxylation, one of ordinary skill in the art can readily determine the optimal combination by routine testing. You can

The present invention will now be described in detail with reference to some production and formulation examples.

Examples Example I Step A Crude (unrefined) coconut oil used as starting material 510.
Melt 6g at 35 ° C, then monoethanolamine 138.
8 g (calculated to be about 1.02 molar equivalents relative to coconut oil) and 5.1 g of a 30% NaOCH ₃ solution in methanol were added sequentially. The mixture was then heated at 60-70 ° C. under stirring for 2 hours and then left at 70 ° C. for 4 hours, after which the mixture became clear. Then, post-reaction was carried out at 75 ° C for a short time. The yield is
It was 654.2 g.

Step B An average of 3 ethoxy units was added to the product of Step A as follows: In 546.6 g of the product obtained by IA containing 89.4% monoethanolamide of coconut oil fatty acid. , 249 g of epoxyethane were introduced at a temperature of 117 to 127 ° C. and a pressure of 0 to 2.8 for about 15 minutes. The reaction proceeded easily, post-stirring was continued for another 30 minutes, and the mixture was cooled to 70 ° C. The yield of ethoxylated product was 790.3 g.

Step C 674.7 g of the product obtained from Step B were reacted with 281.7 g sodium monochloroacetate and solid NaOH. Carboxymethylation was performed for 6 hours in a conventional manner. This gave 1038.7 g of crude reaction mixture.

Step C-1 203.8 g of the crude reaction mixture obtained in Step C was dissolved in 400 g of water, and 0.9 g of preservative (benzyl formal) was added. The pH was lowered to 7.0 with 9.8 g of 10% HCl. The mixture was then diluted with water to 679.3 g (concentration 30%). The product thus obtained was ready for use.

Step C-2 834.9 g of the crude reaction mixture was treated with 754.7 g of water and 30% hydrochloric acid.
It was washed with 197.8 g. This was done in 3 glass beakers equipped with a thermometer and stirrer. After separating the layers, 438.9 g of product in the form of the free acid was obtained. In a two glass beaker equipped with a thermometer and a stirrer, 339.0 g of this product was added to a mixture of 600 g of water and 38.4 g of 50% NaOH and the mixture was heated at 50 ° C. After that, 50 more
% NaOH 2.3 g and endylformal 1.5 g were added. Finally, add 8.3 g of 10% HCl to bring the pH to 8.2 to 7.
Lowered to 1. The final product was diluted with water to 1055.9 g.

Example II Step A 1096.6 g of refined coconut oil was melted at 35 ° C. Then 315.9 g of monoethanolamine (1.02 eq calculated) and 11.0 g of 30% NaOCH _{3 in} methanol were added in that order. The mixture became clear after heating at 60-70 ° C for about 20 minutes. After that, the mixture is still at 90 ° C at 90 ° C.
It was made to react after an hour. A small portion of the mixture was post-reacted at 105 ° C, which was found to be a much faster method than expected. However, the after-reaction at 70 ° C. can actually be carried out in a temperature-controlled storage vessel without the need for any other work, so that the after-reaction at this temperature is for the moment only. Considered preferable.

Step B To the product obtained by Step A was added an average of 9 ethoxy units as follows: To 391.5 g of the product of Step A,
560 g of epoxyethane were introduced at a temperature of 112-130 ° C. and a gauge pressure of 0-2.8 atmosphere for 40 minutes. This gives the product 9
50 g were obtained.

Step C 402.2 g of the product of Step B are transferred to a glass beaker 1 equipped with a thermometer and stirrer and placed in a water bath, 109.8 g sodium monochloroacetate and solid NaOH 3
7.7 g was added. The reaction was carried out at 60 to 75 ° C for 6 hours.
This gave 543.2 g of product.

Step C-1 203.6 g of this product was dissolved in 400 g water, after which 0.9 g benzylformal was added and the pH was lowered to 7.0 with 4.9 g 30% HCl. After that, the mixture is 678.7 g with water.
Diluted to give a light brown liquid with a viscosity of 5.8 mPa.s at 22 ° C. and a pH of 7.0. The solids content was 30%.

Step C-2 339.6 g of the crude reaction mixture of carboxymethylation was treated with water in a glass beaker of 2 equipped with a stirrer and a thermometer.
It was neutralized with 225.6 g and 77.8 g of 30% HCl at a temperature of 85-90 ° C.

260 g of water and 18.0 g of 50% NaOH were transferred to a 2 glass beaker equipped with stirrer and thermometer and heated to about 50 ° C. Next, 164.5 g of the oil layer obtained by the above neutralization was added. Finally, a further 1.7 g of NaOH and 0.8 g of benzylformal were added and the mixture was diluted with 491.0 g of water to give 676.5 g of a solution with a solids content of 22%. The clear product obtained has a viscosity of 11.5 mPa.s at 20 ° C. and
It had a pH of 7.2.

Here are the following notes to the above example: 1. In step A, the average molecular weight of the fatty acids present was known because the saponification number of the oil was predetermined. Based on this, monoethanolamine can be dosed.

2. The reaction mixture obtained by step A still contained sufficient alkali to be used as an ethoxylation catalyst. For this reason no catalyst was added. If the use of SbCl ₅ as a catalyst is desired, this method is feasible, but not advantageous, because of course the mixture must first be neutralized.

Example III This example shows the production of a product similar to that in Example I on an industrial scale.

Step A 1000 kg of refined coconut oil used as a starting material is treated at 32 ° C.
It was heated to and melted. Monoethanolamine 283 kg 7
Added in minutes, then 30% sodium methylate 10 kg
Is added at once. The mixture was then heated to 60 ° C. for 10 minutes after which the temperature rose spontaneously and rapidly to 80 ° C. and was kept constant at this temperature for about 15 minutes by cooling. afterwards,
Cooling and stirring were discontinued and the mixture was left at 72-78 ° C. The reaction was complete after a total reaction time of 24 hours. The yield was 1250 kg (theoretical value 1293 kg: loss occurs during discharge, etc.).

Note: In this large scale test run, the entire amidation process was carried out in the reactor, but in practice the entire mixture was pumped to a heated storage tank when cooling was no longer needed, and It can also be reacted.

Step B 1246 kg of the product of Step A are placed under partial vacuum at a temperature of 85 ° C.
Transferred to a clean, dry reactor. After 20 minutes the mixture was further heated and when a temperature of 115 ° C. was reached after a further 20 minutes the metering of epoxyethane was started. The reaction temperature was 120 to 130 ° C. A total of 587 kg of epoxyethane (corresponding to an average loading of 3 ethoxy units) was added in 15 hours. After reacting the mixture for another 30 minutes,
The mixture was cooled to 78 ° C for 15 minutes. 16 ° C melting point and N _D
A product with 25 = 1.4469 was obtained. The product is distributed in various containers, the total yield being 1813 kg (theoretical 1833 k
g: loss occurs during filling the container).

Step C 1800 kg of the product of Step B is added to sodium monochloroacetate
762 kg were reacted in the presence of 4 kg of sodium chloride and 262 kg of solid NaOH. The reaction was carried out as follows: 1800 kg of product was transferred to a reactor and heated to 50 ° C. for 10 minutes.
After sampling the product, sodium monochloroacetate
62 kg and 4 kg sodium chloride were added in this order while heating was continued. After 10 minutes, the temperature rose to 66 ° C and heating was discontinued. At this point, the remainder of sodium monochloroacetate was added in small portions and at the same time the addition of NaOH particles was started. These substances are divided into 10 parts every 30 minutes (sodium chloroacetate 70 kg 10 times, NaOH 27 kg twice, 26 kg 8 times).
Times). Towards the end of the addition, the mixture clearly thickened. The temperature was kept between 65 and 75 ° C for the entire time. After the last addition, the mixture was post-reacted at 70 ° C. for another hour. After that, 3 kg of 30% hydrogen peroxide was added and the product was briefly heated at 90 ° C.

Step C-2 2780 kg of the crude reaction mixture obtained were acidified as follows: A mixture of 2536 kg of softened water and 780 kg of 30% HCl was heated to 90 ° C. The crude reaction mixture obtained as described above was added during 30 minutes, during which time some foaming initially occurred. After 20 minutes, the sample has a pH of 2.8.
It was found to have 30k HCl 50k at 15 minute intervals
It was observed that g was added in 3 portions and the pH finally dropped to 1.7. The stirring was discontinued and the layers separated. The upper organic phase is the desired product containing 10.6% residual water and having a melting point of 10 ° C. 1440 kg of this organic phase were transferred to the reactor and 2750 kg of water and 180 kg of 50% NaOH were added during 30 minutes. After that, the sample was found to have a pH of 7.1. After another 40 minutes, 170 kg of water was added and the mixture was mixed with 6
Heated to 0-70 ° C. After 30 minutes, the mixture, which now has a pale color, was gradually cooled to 50 ° C. Benzylformal 5 kg (3
0%) was added and the mixture was left overnight and then discharged into a container. A total of 4560 kg of neutral product is 1700 mP at 20 ° C
Obtained with a viscosity of as. The product had a light colour.

Example IV Liquid Soken Two liquid soap preparations were prepared: Instead of 11% of the product of Example II, 8% of the product of Example I can be used in these preparations with a correspondingly large amount of water.

Liquid soap was prepared by adding components 2, 3, 4 and 5 in that order to component 1 with stirring. NaCl
Was dissolved in water and added to the resulting premix. The mixture was stirred until homogeneous, colorants and fragrance were optionally added, and the balance of water was also added.

The two products had a concentration of surfactant of about 20%; the pH was adjusted to about 7-7.5 and the viscosity at 20 ° C was
> 3000 mPa.s for product a and 2000 mPa.s for product b. The obtained liquid soap has extremely good foaming property and bubble stability even in cold water,
And had good dermatological properties.

Note: Preparations with pearl concentrate should be at least 20 ° C.
It had a viscosity of 3000 mPa.s.

Example V Formulation formulation for foam bath% 1) Na laurylethylsulfate (2 ethoxy groups, concentration 28%) 52.00 2) Product of Example II (step 2) 10.00 (or of example I, step C-2) Product 8%) 3) Na alkyl ether carboxylate (same as in example I) 6.00 4) Thickener ^a 2.00 5) Akypoquat 132 ^b 2.50 6) Benzylformal 0.07 7) Perfume qs 8) Colorant a residue from the R, the synthetic C ₁₂ / C ₁₃ alcohol mixture; qs 9) supplementing to 100% water _{a) RO- (CH 2 CH 2} O) 1,5 CH 2 CO-NH-CH 2 CH 2 OH Yes; thickener according to Dutch patent application No. 8402893.

b) The reaction product of lauric acid and glycidyltrimethylammonium chloride; this quaternary product gives a better feel.

Example VI Ingredients for Shear Preparation Composition% 1) Sodium lauryl ether sulphate (same as Example IV ⁾ 40.00 2) Pearl concentrate (see Example IV) 6.00 3) The product of Example 1 14.00 (or Example II, Step C) -2 product 19.00%) 4) Thickener (see Example V) 2.00 5) Benzylformal 0.07 6) NaCl 0.60 7) Fragrance qs 8) Colorant qs 9) Supplement with 100% water Example VII Dry hair Composition of shampoo for use composition% 1) Sodium lauryl ether sulfate (see Example IV) 40.00 2) Product of Example I 7.00 (or product of Example II, Step C-2 9.00%) 3) Pearl concentrate (Example See IV) ^a 5.00 4) Akipoquat 132 ^b 0.50 5) Benzylformal 0.07 6) Fragrance qs 7) Colorant qs 8) NaCl 2.80 9) Water 100% a) Addition of this substance gives an emulsified shampoo If this ingredient is omitted, a clear shampoo It is.

b) This component has a conditioning effect (with regard to the "feel" of the hair and antistatic properties).

Example VIII The procedure was as in Examples I and II, except that
The starting material was castor oil and in step B an average of 10 ethoxy units were added.

Step A started with 203.3 g of castor oil (liquid at room temperature), 38.7 g of monoethanolamine and 2 g of 30% sodium methylate in methanol. Due to the reaction, the temperature of the mixture rises to 32 ° C, after which the mixture is placed in a storage container
Post-reaction was carried out at 0 ° C for 1 week. In step B, 204 g of the product obtained were reacted with 230 g of epoxyethane in the same manner as in Examples I and II. Further, the step C (carboxymethylation step) was also performed by the same method. The yield was 460 g of crude reaction mixture, which was acidified with hydrochloric acid and water according to step C-2. This yielded 410 g of oil, which was the final product in this case. This oil can be used as a component of any of Examples IV-VII, optionally with a neutralizing agent.

Claims (4)

[Claims] 1. A formula: RCONH (C ₂ H ₄ O) _n CH ₂ COOH [wherein R represents a linear or branched aliphatic hydrocarbon group having 5 to 21 carbon atoms, and n is 1 to 20] and a detergent containing one or more compounds represented by the formula: RCOOH, wherein R represents one of the above. Amidating, ethoxylating and carboxymethylating the fatty acids of, and optionally converting all or part of the ether carboxylic acids obtained to their salts, starting from oils or fats, Moreover, aminolysis of the oil or fat is carried out in the presence of an alkali (earth) metal, and the resulting reaction mixture is ethoxylated by a conventional method, carboxymethylated, and if desired, converted wholly or partially into a salt. Characteristic Process for the preparation of detergent. 2. The method according to claim 1, wherein the aminolysis is carried out in the presence of sodium methanolate. 3. The method according to claim 1 or 2, wherein the aminolysis is carried out at a temperature of 50 to 100 ° C. 4. A process as claimed in any one of claims 1 to 3 starting from coconut oil.