US2015500A

US2015500A - Process for preparing wetting agents

Info

Publication number: US2015500A
Application number: US708075A
Authority: US
Inventors: Schrauth Walther
Original assignee: UNICHEM CHEMIKALIEN HANDELS A
Current assignee: "unichem" Chemikalien Handels A-G; UNICHEM CHEMIKALIEN HANDELS A
Priority date: 1933-01-30
Filing date: 1934-01-24
Publication date: 1935-09-24
Anticipated expiration: 1952-09-24

Description

Patented Sept. 24, 1935 UNITED STATES PATENT orrics WalthenSchrauth, Berlin-Dahlem, Germany, as-

signor, by mesne assignments, to Unichem Ohemilralien Handels A.-G., Zurich, Switzerland, a corporation of Switzerland No Drawing.

Application January 24, 1934,

Serial No. 708,075. In Germany January 30,

The present invention has for an object the production of washing-, cleansing-, wetting-out and emulsifying agents by conjoint sulfonation of fat like substances and aromatic or hydroaromatic hydrocarbons or mixed aromatic-hydroaromatic hydrocarbons respectively. 1

As everybody knows, the sulfonates of aromatic hydrocarbons and particularly of naphthalene and of tetrahydronaphthalene, possess the property of converting substances insoluble in water into aqueous solutions (hydrotropic properties). They are therefore not merely app ied as admixtures to soaps of all kinds, but also as diluents for soap-like substances such as are found 18 in the sulfates and sulfonates of waxes fats, oils and especially of higher molecular fatty alcohols and the like. Now, as a'rule, the conditions under which the sulfonating process'le'ads to the production of sulfonates of aromatic hydrocar- 20 bons are different from those under which an exhaustive suifonation, of for example the higher molecular fatty alcohols. is obtained. While in sulfonating the latter one employs the lowest possible temperatures, the production of arcmatic sulfonic acids occurs as a rule at temperatures of more than 100 C. Therefore it could not be expected without ado, that e. g. higher molecular alcohols might be conjointly sulfonated with aromatic hydrocarbons in such a manner that sulfates and sulfonates of higher molecular alcohols are obtained simultaneously with the sulfonates of aromatic hydrocarbons.

Now it has been found that materials of both groups can be conjointlysulfonated at low temperatures and in such a manner that even the aromatic hydrocarbons, which otherwise can be sulfonated only at higher temperatures, produce sulfonic acids even if the sulfonation is performed at the lowest possible temperatures. It is also possible to employ chlor sulfonic acid andsimilar sulfonating agents. One employs advantageously chloro sulfonic acid in a proportion that ex,- ceeds by about 10 to 20% the theoretically necessary proportion, the degreeof purity being considered when determinating the respective, proportion. The aromatic hydrocarbon which at the beginning is still unsulfonated, acts as a solvent and insures even at very low temperatures a perfect sulfonation of the reaction mixture. The sulfonation, under the aforesaid condltions, is performed with quite surprising completeness so that there is no need of any separate treatment of the single components. In only a single operation one obtains a mixture of sul- 55 fonates similar to that which otherwise results 24 Claims. (01. as-1) by a mechanical mixing, conjoint grinding and the like of the single components; thus one saves the cost of the machines which would be necessary for the latter operations.

Compared with the well-known method of sul- 5 fonation of higher molecular alcohols in the presence of solvents which makes possible a sulfonation at low temperatures the procedure of this invention is distinguished not only by making it possibletosulfonate the applied hydrocar- 1o bons at low temperatures but also by the simulsulfonate higher molecular fatty or wax alcohols. 20

their esters and ethers, fatty acids, their esters with monoor polyhydric alcohols, particularly glycerides, and furthermore waxes, fat-like substances and the like, but the alcohols or fatty acids respectively on which the said compounds 25 are based, should contain no less than 8 carbon atoms in the molecule. Among the alcohols to be c'onsideredthere may be mentioned first of all the-dodeyh, myristyl-, cetyl-, octadecyland the oleyl alcohol; among the fatty acids thebleic 30 and ricinolic acid are particularly recommendable. The hydrocarbons suitable for the'performing of the present procedure must have a low pointofsolidiflcation and-they must themselves be sulfonable, thus to secure a thorough 35 sulfonation even at low temperatures. The sulfonates made of them areto be fit for converting substances insoluble in-water into aqueous solutions.

The products obtained according to the pres- 40 ent method distinguish themselves by an extraordinary stability ahd are superior to the preparations obtained by mixing the single components. The degree of sulfonation is considerably higher than that obtained by the separate sulfonation of the single components. They are fast toboiling in hard water of (German hardness degreeiand-form solutions which are clear even at very low temperatures. Their fastness 50 to acids is excellent. Owing to the low reaction temperatures which are applied, the reaction of the sulfonating agents is very mild and, therefore, the thus obtained products are of a very light colour.

Example 1 1400 g. of oleyl alcohol of the iodine number and of a congealing-point of +2 are mixed with 500 g. of tetrahydronaphthalene. Into this mixture 1120 g. of chlorosulfonic acid are gradually stirred in the course of about 5 hours at a temperature of -5 to +5 under constant cooling. By the neutralizing with a diluted solution of caustic soda one obtains about 4500 g. of a reaction product containing approximately 30% of fat. The clarification point of 2% solutions is at about 20.

Example 2 To a mixture consisting of 420 parts by weight of sperm oil and 260 parts by weight of tetrahydrophenanthrene (or weight parts of cymol respectively), one adds gradually under stirring 280 parts by weight of chlorosulfonic acid at a temperature of -3 to +5 C. taking care for a good cooling and then one continues to stir for three hours. The further treatment is carried out as per Example 1. The thus obtained reaction product suits well for the production of emulsifying and wetting-baths.

Example 3 1500 g. of dioleylether of theiodine number 92 are mixed with 500 g. of tetrahydronaphthalene and cooled down to about 0 C. Into this mass 1050 g. of chlorosulfonic acid are gradually dropped in the course of about 4-5 hours while continuing the constant cooling and under a re ular stirring. The reaction being terminated one neutralizes with a diluted solution of caustic soda and the thus obtained product shows excellent capillary-active properties. It is also allowed to substitute other ethers for the dioleylether. particularly mixed ones such as lauryl-mono-glycolether, cetyl-mono-glycerineether and the like.

Example 4 1000 g. of oleic acid of a iodine number of 85 are mixed with 400 g. of tetrahydromethylnaphthalene, whereupon the mixture is cooled down to a temperature lying between 5 and +5 C. Into this mixture, which is kept at the said temperature, one gradually drops 700 g. of chlorosulfonic acid. The reaction product obtained after terminating the reaction and after neutralization is. advantageously applied for washingand cleansing baths.

The term "sulfonation" as found in the claims is used in the broad sense to include both true sulfonation and sulfation.

The terms "sulfona "sulfonation" and the like are used in the broad sense to define the formation of sulfuric acid esters as well as the formation of true sulfonic acid, except where it is clear that the true sulfonation is intended.

What I claim is:

1. As a product of manufacture the composition of sulfonated sperm oil with tetrahydrophenanthrene sulfonic acid, applicable as wetting-out-, washing-, cleansingand emulsifying agent.

2. 'As a. product of manufacture the composition of" sulfonated dioleyl ether with tetrahydronaphthalene sulfonic acid, applicable as wettingout-, washing-, cleansingand emulsifying agent.

3. As a. product of manufacture the composition of sulfonated oleic acid with tetrabydromethylnaphthalene sulfonic acid, applicable as wetting-out-, washing-, cleansingand emulsifying agent.

ucts between both components.

4. The manufacture of washing, cleansing, wetting-out and emulsifying agents characterized by the conjoint sulfonation of an aliphatic compound selected from the group consisting of the primary aliphatic alcohols having 8 or more 5 carbon atoms in the molecule, the ethers of these alcohols with the same or other primary aliphatic alcohols, the esters of these alcohols with primary aliphatic carboxylic acids, primary aliphatic carboxylic acids having 8 or more car- 10 bon atoms in the molecule and the esters of. these acids with primary monoand poly-hydric aliphatic alcohols, and of an aromatic hydrocarbon without the formation of condensation prod- 5. The manufacture of washing, cleansing, wetting-out and emulsifying agents characterized by the conjoint sulfonation of a primary aliphatic alcohol having 8 or more carbon atoms in the molecule and of an aromatic hydrocarbon go without the formation of condensation products between both components.

6. The manufacture of washing,v cleansing, wetting-out and emulsifying agents character ized by the conjoint sulfonation of primary alig5 phatic alcohol having 12 to 18 carbon atoms in the molecule and of an aromatic hydrocarbon at a temperature of the order of 5 to +5 C. without the formation of condensation products between both components. 30

7. The manufacture of washing, cleansing, wetting-out and emulsifying agents characterized by the conjoint sulfonation of primary aliphatic unsaturated alcohol having 12 to 18 carbon atoms in the molecule and of an aromatic 35 hydrocarbon at a temperature'of the order of 5 to +5 C. without the formation of condensation products between both components.

8. The manufacture of washing, cleansing, wetting-out and emulsifying agents character- 40 ized by the conjoint sulfonation of oleyl alcohol and of an aromatic hydrocarbon without the formation of condensation products between both components.

9. The manufacture of washing, cleansing, 45 wetting-out and emulsifying agents characterized by the conjoint sulfonation of an ether of primary aliphatic alcohols, at least one of which alcohols has 8 or more carbon atoms in the molecule and of an aromatic hydrocarbon with- 50 out the formation of condensation products between both components.

10. The manufacture of washing, cleansing, wetting-out and emulsifying agents characterized by the conjoint sulfonation of ethers of pri 5 mary aliphatic alcohols both of which have 8 or more carbon atoms in the molecule and of an aromatic hydrocarbon without the formation of condensation products between both components.

11. The manufacture of washing, cleansing, wetting-out and emulsifying agents characterized by the conioint sulfonation of di-oleyl ether and of an aromatic hydrocarbon without the formation of condensation products between both components.

12. The manufacture of washing, cleansing, wetting-out and emulsifying agents characterized by the conjoint sulfonation of an ester of a primary aliphatic alcohol and a primary all-- 70 phatic acid at least one of which components has 8 or more carbon atoms in the molecule without the formation of condensation products between both components.

13. The manufacture of washing, cleansing, 75

wetting-out and emulsifying agents characterized by the conjoint sulfonation of esters of primary aliphatic acid having 8 or more carbon atoms in the molecule with primary aliphatic alcohol and of an aromatic hydrocarbon without the formation of condensation products between both components.

14. The manufacture of washing, cleansing, wetting-out and emulsifying agents characterized by the conjoint sulfonation of esters of primary aliphatic alcohol having 8 or more carbon atoms in the molecule with primary aliphatic acid and of an aromatic hydrocarbon without the formation of condensation products between both components.

15. The manufacture of washing, cleansing, wetting-out and emulsifying agents characterized by the conjoint sulfonation of esters of primary aliphatic alcohol having 8 or more carbon atoms in the molecule with primary aliphatic acid having 8 or more carbon atoms in the molecule and of an aromatic hydrocarbon without the formation of condensation products between both components.

16. The manufacture of washing, cleansing, wetting-out and emulsifying agents characterized by the conjoint sulfonation of an unsatu rated wax ester and of an aromatic hydrocar- -bon without the formation of condensation products between both components.

17. The manufacture of washing, cleansing, wetting-out and emulsifying agents characterized by the conjoint sulfonation of sperm oil and of an aromatic hydrocarbon without the formation of condensation products between both components.

18. The manufacture of washing, cleansing, wetting-out and emulsifying agents characterized by the conjoint sulfonation of an aliphatic compound selected from the group consisting of the primary aliphatic alcohols having 8 or more carbon atoms in the molecule, the ethers-of these alcohols with the same or other primary aliphatic alcohols, the esters of these alcohols with primary aliphatic carboxylic acids, primary aliphatic carboxylic acids having 8 or more carbon atoms in the molecule and the esters of these acids with primary monoand poly-hydric aliphatic alcohols, and of hydrocarbons of the group consisting of naphthalene, tetrahydronaphthalene, tetra hydro phenanthrene,-tetrahydro methyl naphthalene and cymol at low temperatures without the formation of condensation products between both components.

19. The manufacture of washing, cleansing, wetting-out and emulsifying agents characterized by the conjoint sulfonation of an aliphatic compound selected from the group consisting of the primary aliphatic alcohols having 8 or more carbon atoms in the molecule, the ethers of these alcohols with the same or other primary aliphatic alcohols, the esters of these alcohols with primary aliphaticcarboxylic acids, primary aliphatic carboxylic acids having 8 or more carbon atoms in the molecule and the esters of these acids with primary monoand poly-hydric aliphatic alcohols and of aromatic hydrocarbons of the naphthalene series at a temperature of the order of 5 to +5 C. without the formation of condensation products between the compm nents.

20. The manufacture of washing, cleansing, wetting-out and emulsifying agents characterized by the conjoint sulfonation of an aliphatic compound selected from the group consisting of the primary aliphatic alcohols having 8 or more carbon atoms in the molecule, the ethorsof these a'cohols with the same or other primary aliphatic alcohols, the esters of these alcohols with primary 5 aliphatic carboxylic acids, primary aliphatic carboxyhc acids having 8 or more carbon atoms in the molecule and the esters of these acids with primary monoand poly-hydric aliphatic alcohols and of hydronaphthalene hydrocarbons 1 without the formation of condensation products between both components.

21. The manufacture of washing, cleansing, wetting-out and emulsifying agents character-, ized by the conjoint sulfonation of an aliphatic 15 compound seiected from the group consisting of the primary aliphatic alcohols having 8 or more carbon atoms in the molecule, the ethers of these alcohols with the same or other primary aliphatic alcohols, the esters of these alcohols with pri- 20 mary aliphatic carboxylic acids, primary aliphatic carboxylic acids having 8 or more carbon atoms in the molecule and the esters of these acids with primary monoand poly-hydric aliphatic alcohols and of aromatic hydrocarbons capable of 25 being sulfonated to form emulsifying agents with out the formation of condensation products between both components.

22. The manufacture of washing, cleansing, wetting-out and emulsifying agents character- 30 ized by the conjoint sulfonation ofan aliphatic compound selected from the group consisting of the primary aliphatic alcohols having 8 or more carbon atoms in the molecule, the ethers of these alcohols with the same or other primary aliphatic 35 alcohols, the esters of these alcohols with primary aliphatic carboxylic acids, primary aliphatic carboxylic acids having 8 or more carbon atoms in the molecule and the esters of these acids with primary monoand poly-hydrlc aliphatic alco- 40 hols and of tetrahydronaphthalene without the formation of condensation products between both components.

23. The manufacture of washing, cleansing, wetting-out and emulsifying agents character- 45 ized by the conjoint sulfonation of an aliphatic compound selected from the group consisting of the primary aliphatic alcohols having 8 or more carbon atoms in the molecule, the ethers of these alcohols with the same or other primary aliphatic 60 alcohols, the esters of these alcohols with primary aliphatic carboxylic acids, primary aliphatic carboxylic acids having 8 or more carbon atoms in the molecule and the esters of these acids with primary monoand poly-hydric aliphatic alco- 55 hols and of tetrahydro phenanthrene without the formation of condensation products between both components.

24. The manufacture of washing, cleansing, wetting-out and emulsifying agents character- 60 ized by the conjoint sulfonation of an aliphatic compound selected from the group consisting of the primary aliphatic alcohols having 8 or more carbon atoms in the molecule, the ethers of these alcohols with the same or other pri mary aliphatic alcohols, the esters of these aicohols with primary aliphatic carboxylic acids, primary aliphatic carboxylic acids having 8 or more carbon atoms in the molecule and the esters of these acids with primary monoand poly- 70 hydric aliphatic alcohols and of tetrahydro methyl naphthalene without the formation of condensation products between both components.

WALTHER SCI-IRAU'HI,