US2127567A

US2127567A - Sulphated aliphatic compounds

Info

Publication number: US2127567A
Authority: US
Publication date: 1938-08-23
Anticipated expiration: 1955-08-23

Description

Patented Aug. 23, 1938 UNITED ,STATES PATENT OFFICE 2,127,567 SULPHATED ALIP HATIC COMPOUNDS No Drawing. Application April 29, 1936,

Serial No. 17,044

15 Claims. (o1. zoo-400) This invention relates to certain new chemical products and a method for their commercial preparation. The products fall within the general class of sulphated aliphatic materials and are particularly useful as wetting, detergi foaming or emulsifying agents.

Numerous compounds are already known, even within the class of sulphated aliphatic materials, that possess to a more or less marked degree the properties which are necessary to make them good foaming, emulsifying, wetting and deterging agents. The products hereinafter described are generally similar to these known compounds in this respect, but have the advantage of being relatively inexpensive to manufacture and of being readily formed into bars, beads, flakes,

chips or powders, that may be used to advantage to replace ordinary bars, beads, flakes, chips or powders of soap.

The new material may also replace ordinary soap in detergent solutions such as mouth washes and shampoos, in tooth paste, face creams and similar preparations, and may even be used in many instances in combination with ordinary soaps or other sulphated or sulphonated materials. For these purposes the new materials are especially suited by reason of their high deterging efliciency, total lack of alkalinity, easily masked odor, taste and color, and their ability to-act in hard or even sea water with little, if any, diminishing of their efllciency.

The new materials are made from fatty oil or fatty acids,- fuming sulphuric acid and anhydrous beta methyl glycerine or anhydrous beta methyl glycidol. The last two mentioned compounds are obtainable from isobutylene, a product of the petroleum industry, and hence are relatively inexpensive and can be obtained in large quantities. Glycerine, a similar compound that might be considered for use according to this invention, has an economic disadvantage in that it is a by-product of the'soap-industry and would become relatively scarce if the" present type of products began. to replace soap to a substantial extent. Then, too, glycerineis a base for the manufacture of explosives and'in war times the priceis greatly increased. Neither beta methyl glycerine nor beta methyl glycidol is useful for this purpose.

According to this invention, the fatty oil or fatty acid is reacted with beta methyl glycerine or beta methyl glycidol by heating in the presence of a catalyst and the resulting product, in a substantially anhydrous state, is thereafter sulphated with fuming sulphuric acid and finally neutralized.

When a fatty oil is used, approximately one molecular proportion is reacted with two molecular proportions of the isobutylene derivative to give a mixture of the mono fatty acid esters of glycerine and the mono fatty acid esters of the beta methyl glycerine in the ratio :of about one to two. The glycerine that forms the 'glycerine ester comes from the fatty oil. a

If fatty acid is used instead of fatty oil, the ratio of molecular proportions is approximately one to one, and the result is a mono fatty acid ester of beta methyl glycerine without admixed glycerine ester. Also, when the fatty acid is used, a certain amount of water is formed in the esterification which must be removed as the esterification proceeds.

The mono esters so formed are entirely soluble in ten times their volume of alcohol, but

will produce a slight cloudiness in ten volumes of carbon tetrachloride if there is any excess of the isobutylene derivative. Sulphation may be accomplished by treating the mono esters with fuming sulphuric acid, preferably of around 103% concentration (about l2 /2%- free $03), at a temperature around 35 C.- This concentration used according to the examples hereinafter given will produce a final concentration of sulphuric acid,

after reaction with the monoglyceride, of around 99.3%. It has been found that this final concentration is preferable for the production of the desired completely water-soluble products.

The sulphated product may be cooled and diluted before neutralization by pouring it, with agitation, into a mixture of ice and water, but preferably this is not done, for it results in considerable difllculty later in the process when it is necessary to concentrate or dry the final product. At that time, the presence of an excess of water'no't only entails a large heat loss in evaporation, but requires considerable equipment and endangers the purity of the product, for decomposition has a tendency to occur during the concentration. A

Instead of diluting the sulphated product before neutralization, it has been discovered that by maintaining a considerable body of the neutralized material and adding the sulphated product and a rather concentrated solution of a neutralizing agent to this body of material, agitating and cooling somewhat meanwhile, the neutralization can be accomplished rapidly, easily, without greatly diluting the material, and without decomposition or other injury to the product.

The neutralization has also been found to be greatly facilitated and the product improved by continuously controlling the amount of neutralizing solution added in accordance with the hydrogen ion concentration (pH) of the product. Preferably, the amount of neutralizing solution added is Just sufficient to give the product a pH of 6.0 to 7.0.

From the neutralization the product may be taken directly for use; may be further concentrated or dried by any of the methods used for soap such as spray drying or drying over rolls; or may be further treated, to remove the byproduct sulphate formed by the neutralization, or to change, in the product, the metal or other radical inserted by the neutralization, or both.

In the final product there is usually around 60% of the by-product sulphate. When this is to be removed, lim'e will ordinarily be used as the neutralizing agent so that the by-product sulphate will be calcium sulphate which is relatively insoluble. From this material the neutralized reaction product can be removed simply by washing with water. The calcium combined in the product can thereafter be replaced by other metals or radicals by an exchange reaction in which a salt of the desired metal or radical, that will precipitate calcium, is used. Examples of such salts are sodium oxalate, carbonate or phosphate or the same salts of ammonia, triethanolamine, potassium, or magnesium. Triethanolamine or ammonia and carbon dioxide gas may be added with the same eifect. The mercury or silver salts of the newproducts can also be formed in similar manner and are soluble and have valuable germicidal properties.

A somewhat different way of eliminating the by-product sulphate consists in extracting the reaction product either before or after neutralization with an organic solvent, Butyl'alcohol, toluol. benzene or petroleum ether or other water immiscible solvent can be used prior to neutralization, in which case the neutralization will usually be carried out in the solvent to avoid decomposition of the unneutralized product by the heat necessary to drive ofi the solvent. After the product is neutralized it is more stable to heat and the solvent can be removed without danger of decomposing the product. If the product is extracted after being neutralized and dried, water miscible solvents such as ethyl alcohol may be used, as well as water immiscible solvents.

In order to illustrate the principles of thisinvention and more particularly point out the details that contribute to its successful practice on a commercial scale, reference will be made to several specific examples of the process of making the new products. According to one of these examples, cocoanut oil was reacted with beta methyl glycerine in the presence of caustic soda, and in the substantial absence of water, and the resulting product sulphated and neutralized with caustic soda. The proportions entering the first step of the process were:

Parts by weight Cocoanut oil 102.9 Beta methyl glycerine (theory +5%)' 33.3 Caustic soda (granular) 0.5

This mixture was heated with agitation. At

' 155C. it became homogeneous and after an hour ble with 95% alcohol and exhibiting only a slight cloudiness with carbon tetrachloride. To this 5 material 246.2 parts by weight of 102.8% sulphuric acid (mi free 80:) were added slowly and with agitation at a temperature of about 35 C. and after a short time the product was found to be miscible with water without turbidity. It took approximately 380 parts by weight of a 50 Beaum caustic solution to neutralize the product so that the pH of a 1% solution was 7.0. This particular product was then'dried over a heated roll forming flakes that generally resembled soap and were easily moldable into bars by ordinary soap molding machinery.

This process has been described as though it were a batch process, but it can be accomplished continuously in the same manner, particularly if the neutralization is performed as suggested in a preceding paragraph, that is, by maintaining a body of the substantially neutralized product, agitating and cooling this body and adding thereto unneutrali'zed reaction product and neutraliz-' ing agent, the proportions of these materials added being controlled by a continuously operating hydrogen ion concentration (pH) testing device that continuously tests the pH of the'substantially neutralized product and adjusts the proportions of the materials being added so as to keep the pH of the product at the desired point or withinthe desired range.

In another instance, a product of the type contemplated by this invention was made from cocoanut oil fatty acids instead of cocoanut oil itself. In this case the following proportions were used in the first reaction:

Parts by weight Cocoanut oil fatty acids 82. 1 Beta methyl glycerine (theory 5%) 42.4 Caustic soda (granular) 0.4

This mixture was heated with agitation to around 1'75 to 185 C. and a current of carbon di-' oxide passed thereover to remove the water of reaction. The product was then sulphated, as before, using 212.4 parts by weight of 102.8% suiphuric acid, and neutralized with around 325 parts of 50 Beaum caustic soda solution.

As an example of the use of beta methyl glycidol according to this invention, the following materials were mixed:

7 Parts by weight Cocoanut oil fatty acid 126. 6 Beta methyl glycidol (theory 5%) 54. 8

- Caustic soda 0. 4

This mixture was reacted by heating to its refluxing point, which rose as the reaction proceeded to about 175 C." The mixture was held at that temperature for about an hour, after which an analysis showed less than 1% fatty acid to be present. The material thus formed was sulfated and neutralized as before.

In the foregoing examples, cocoanut oil and cocoanut oil fatty acids have been used. Other fatty oils or acids can be used instead, however, due allowance being made for the difference in their molecular weights. The fatty oils and fatty acids that are most likely to be useful for this purpose are cocoanut, palm kernel, palm, tallow or mixtures thereof.

I claim:

1. A process of the character described that comprises reacting a fatty material of the class consisting of fatty oils and fatty acids with a derivative of isobutylene of the class consisting of beta-methyl glycerine and beta-methyl glycidol and thereafter treating the product with fuming sulphuric acid.

2. A process of the character described that comprises reacting a fatty material of the class consisting of fatty oils and fatty acids with a derivative of isobutylene of the class consisting of beta-methyl glycerine and beta-methyl glycidol, thereafter treating the product with fuming sulphuric acid of such strength that the concentration of sulphuric acid, after reaction, is around 99.3% and finally neutralizing the product.

3. A process of the character described that comprises reacting approximately one molecular proportion of fatty oil with two molecular proportions of a derivative of isobutylene of the class consisting of beta-methyl glycerine and betamethyl glycidoi and treating the resultant product with an excess of fuming sulphuric acid.

4. A process of'the character described that comprises reacting approximateiymne molecular line hydroxide.

5. A process of the character described that comprises reacting approximately one molecular proportion of fatty acid with one molecular pro portion of a derivative of isobutylene of the class consisting of beta-methyl glycerine and betamethyl glycidol and thereafter treating the resultant product with an excess of fuming sulphuric acid.

6. A process of the character described that comprises reacting approximately one molecular proportion of fatty acid with one molecular proportion of beta-methyl glycerine and thereafter treating the resultant product with an excess of fuming sulphuric acid.

7. As a new compofltion of matter the sulphated reaction product obtained by reacting a fatty material of the class consisting of fatty oils and fatty acids, with a derivative of isobutylene of the class consisting of beta-methyl glycerine and beta-methyl glycidol and treating the product so obtained with sulphuricacid.

8. As a new composition of matter the neutralized reaction product obtained by reacting a fatty matErial of the class consisting of fatty oils and fatty acids. with a derivative of isobutylene of, the class consisting of beta-methyl glycerine and beta-methyl glycidol. treating the product so obtained with fuming sulphuric acid and then neutralizing.

9. As a new composition of matter the sulphated reaction product'pbtained by reacting approximately one molecular proportion of fatty oil with two molecular proportions of a derivative ofiso- A butylene of the class consisting of beta-methyl glycerine and beta-methyl glycidol and treating the product so obtained with an excess over three molecular proportions of fuming sulphuric acid, of such strength that the concentration of sulphuric acid, after reaction, is around 99.3%.

10. As a new composition of matter the neutralized reaction product obtained by reacting approximately one molecular proportion of fatty acid with one molecular proportion of a deriva1 tive of isobutylene of the class consisting of betavmethyl glycerine and beta-methyl glycidol, treating the product so obtained with an excess over three molecular proportions of turning sulphuric acid and neutralizing.

11. As a new composition of matter the suiphated reaction product obtained by reacting approximately one molecular proportionoffatty acid with one molecular proportion of betamethyl glycerine and treating the product so ob.- tained with an excess over three molecular proportions of fuming sulphuric acid.-

12. As a new composition of matter the sulphated reaction product obtained by reacting approximately one molecular proportion of fatty acid with one molecular proportion of betamethyl glycerine and treating the product so obtainedwith an excess over three molecular proportions of fuming sulphuric acid containing around 12 /4% free sulphuric trioxide.

13. As a new composition of matter the sulphated reaction product formed by first reacting approximately one molecular proportion of fatty oil with two molecular proportions of a derivative of isobutylene of the class consisting of betamethyl glycerine and beta-methyl glycidoi and thereafter treating the intermediate product with an excess of fuming sulphuric acid.

14. As a new composition of matter the sodium salt of the sulphated reaction product formed by first reacting approximately one molecular proportion of fatty oil with two molecular proportions of a derivative of isobutylene of the class consisting of beta-methyl glycerine and betamethyl glycidol, thereafter treating the intermediate product with an excess of fuming sulfuric acid and finally neutralizing the product with caustic soda.

15. As a new composition of matter the sul-' phated reaction product formed by first reacting approximately one molecular proportion of fatty acid with one molecular proportion of betamethyl glycidol and thereafter treating the intermediate product with an excess of sulphuric acid containing around 12%% free sulphuric trioxide.

meow. mmcm.