US2280118A

US2280118A - Process of sulphonation

Info

Publication number: US2280118A
Application number: US189892A
Authority: US
Inventors: Bernard A Dombrow
Original assignee: National Oil Products Co
Current assignee: National Oil Products Co
Priority date: 1938-02-10
Filing date: 1938-02-10
Publication date: 1942-04-21
Anticipated expiration: 1959-04-21

Description

Patented Apr. 21,

raocass orsuLrnoNA'rros Bernard A. Dombro w, New York,- N.

or to National Oil Products Company, Harrison, N. 1., a corporation of NewJersey Y., assign- No Drawing. Application February 10,1938.

Serial No. 189,892

14 Claims. (Cl. 260-400) The invention relates, in general, to sulphonated fatty materials and, in particular, to an improved process for producing sulphonated fatty oils and waxes and to correlated improvements in the products thus produced.

According to the usual procedure in producing sulphonated fatty oils and waxes, the. fatty material is subjected to sulphonation with any suitable sulphonating agent such as sulphuric acid,

conventional processes contain not more than about 10% organically combined SO: and in most cases the 80: content lies within the range of about 4%. to 9%. While these ordinary sulphonated fatty oils and waxes have found extensive 'use in many fields, they are characterized by be- They' ing unstable under certain conditions. tend to separate and decompose on standing 'or in the presence of aqueous acid or salt solutions, thereby resulting in a sludge formation. Where such sulphonated. products are used in textile treatments:foryexample, the separation and decomposition lead to spotting or staining of the fibers.

The general, object of the present invention is v.to obviate the foregoing and other disadvantages.

A specific object of the invention is to provide improved sulphonated fatty oils'and waxes having an enhanced stability when subjected to nor- 5 mal use. Another object of the invention is to provide improved sulphonated fatty oil and waxcswhich fare'substantially resistant to decomposition in the presence of acid or salt solutions.

A further object of the invention is to provide an improved process of producing highly stable sulphonated' fatty oils and waxes. I Other objects of the invention will in part be obvious and. will in part appear hereinafter.

, It has been found that the stability of sulpho- 'nated fatty oils and waxes may be greatly im- I proved by increasing the organically combined SOs-content to avalue above 10%.

Such productsareal so particularly resistant to the formation of sludge or the separation of greasy or fatty deposits upon standing or in the presence of acids orsaits. "These products of increased 80:

content are not, however, readily produced by direct sulphonatiom 1 0 In order to obtain highlysulphonated products it'has even been proposed in some instances 'to oxidize and hydroxylate the aliphatic chains of the high molecular weight fatty materials to provide more places for attachment of SO; groups and thus enable the compounds to be sulpho- I nated to a higher degree, but these oxidation and hydroxylation methods do not produce high yields of the desired materials. In any case. it is not readily possible directly to increase the 30: content of these fatty materials to above 10% without extended and difficult procedures involving substantial increased cost in raw materials and more expensive apparatus with decreased yields of the desired sulphonated product.

It appears that the usual sulphonated fatty oils or waxes containing less than 10% of So; contain substantial quantities of unsulphonated materials which 'tend to give rise to the instability of the products. It further appears that when these unsulphonated materials are partly removed to give a product of increased SO: content, the stability of the sulphonated material will be greatly enhanced. I

According to the invention. the pr'ocess comprises subjecting a sulphonated fatty oil or wax.

to agitation with a water-miscible aliphatic organic solvent. After admixture of the solvent and suifonated product two. distinct layers are formed upon standing, the upper layer containing the solvent and high 80: fraction and the lower layer'containing the lower SO: fraction. The solvent employed must be miscible with the sulphonated fraction and substantially immiscible with the unsulphonated fraction in the presence of each other and moisture. The acid value of the sulphonated product may be adjusted according to. the particular solvent to be employed. In the usepf a solvent such as acetone or acetone alcohol, bettcrrcsults are obtained if a product of a low acid value is used whereas a product of disclosure, and the scope a relatively higher acid value is more suitable when a solvent such as mesityl oxide is employed.

The relationship beween any suitable solvent indicated in the claims.

' of the fractions.

The process of the invention is directed particularly to the treatment of sulphonated fatty oils and waxes, a few examples of which may be given as follows: castor 'oil, olive oil, neats-foot oil, cottonseed oil, rapeseed oil, corn oil, cod oil, fish oils in general, tallow, sperm oil, etc.

Any suitable water-miscible, aliphatic organic solvent or mixture of the such solvents, may be used, such for example, as ketones, such as acetone, ethyl propyl ketone, mesityl oxide, etc., alcohols, such as methyl, ethyl, isopropyl etc., ethers, such as dioxane, amines, such as trimethylamine, ketone-alcohols, such as diacetone-alcohol, etc. Solvents such as methanol, ethanol and and acetone arepreferred in view of their efllcient extraction, ease of handling, low cost, etc. A relatively small amount of water may be used with the solvent but in most cases addition of water will not be necessary as the quantity of water normally present in the sulphonated product will be suflicient to insure proper separation The amount of solvent used may be varied to obtain the desired results. The ratio of solvent to be used depends upon the extraction or split desired. The less solvent employed, the higher theSOa content of the oil extracted, but the lower the yield of high SO; material. extracted product is inversely proportional to the yield obtained. This relationship will be more fully described hereinafter.

In carrying out the process, the solvent is preferably used in amounts equal to or greater than that of sulphonated fatty oil or wax to be treated. After thorough agitation of. the solvent and sulfonated material, the mixture is allowed to settle whereupon two layers will be formed, one layer containing most of the solvent and the suifonated product of increased SO: content and the other layer containing the unsulphonated or sulphonated material of low 80: content. The extraction may be repeated several times if desired. The temperatur under which the extraction step is carried out may be varied within wide limits, it being highly preferable, however, to carry out this step within a range between room temperature to C. or lower. After separation of the layers, they may be subjected to distillation to drive off the solvent which may be recovered for subsequent use. The fraction bearing the un-- sulphonated or low S0: products may be used as such or they may be utilized as raw material for further sulphonation.

While use of the terms extracting and "extraction has been made herein with respect to the separation of the fractions containing high and low S03 contents, these terms are not used according to their usual meaning inasmuch as the action of the solvent is not essentiallyone of extraction but one of partition. Some of the solvents recommended are, in their substantially anhydrous forms, solvents for the unsulphonated or low SO: fractions as well as possessing solvent powers for the fraction having a high $03, It appears, however, that the solvents in the presence of moisture have a greater aflinity for the high SO: fraction than that of the low SO; fraction, thus giving rise to the unexpected results. In view of this condition, the aforementioned terms are used to describe the partitioning action of the solvent with respect to the high and low S03 fractions.

For a fuller understanding of the nature and objects of the invention, reference should be had to the following examples which are given merely In other words, the S03 content of the to further illustrate the invention and which are not to be construed in a limiting sense.

Example I Example II t By carrying out the same procedure as outlined in Example Iusing 600 cc. of acetone (twice the amount) the following yield was obtained: 149 I grams of extracted oil with an $03 content of 11.3% and 113 grams of residual oil having an S0: content of 7.1%.

From a comparison of the aboveexamples, it may be noted that the use of a smaller quantity of solvent, as in Example I, gave a smaller yield but of a higher S03 value than that obtained by rising a larger quantity of solvent (as in Example Example III 380 grams of sulphonated olive oil (about 30% moisture) containing 8.8% organically combined S0; was agitated with 380 grams of methyl alcohol. After separation of the two layers which resulted on standing and removal of the solvent, the oil in the upper layer had an organically combined content of 13.9% and the oil in the lower layer showed an S0: content of 6.4%.

Example IV In carrying out the same process outlined in Example III, using ethyl alcohol in lieu of methyl alcohol, the oil in the upper layer showed an organically combined S03 value of 10.4%.

The expression "sulphonated naturally occurring fatty materials is employed in the appended claims to connote the water-soluble salts of sulphated fatty acids, fatty triglycerides and fatty waxes. Likewise the expression "sulphonated" 18 used to define the water-soluble salts of the sulphuric acid esters produced on sulphonation of fatty materials,

Since certain changes may be made in carrying out the above process without departing from the scope of the invention, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

.specific features of the invention herein described,

and all statements of the scope of the invention, which as a matter of language might be said to fall therebetween.

Having described my invention, what I claim as new and desire to secure by Letters Patent is:

1. In a process for increasing the SO: content of sulphonated naturally occurring fatty materials, the step which comprises subjecting the sulphonated material to extraction with an organic, water-miscible solvent, in an amount at least equal to the volume ofthe sulphonated fatty material.

2. A process for increasing the SO: content of sulphonated naturally occurring fatty materials which comprises mixing such sulphonated materialswith an organic water-miscible solvent,

allowing the mixture to settle whereby two layof sulphonated cod oil, the step which comprises subjecting a sulphonated cod oil to extraction with a water-miscible organic solvent selected from the group consisting of low molecular weight alcohols and ketones.

11. In a process for increasing the S03 content of sulphonated cottonseed oil, the step which comprises subjecting a sulphonated cottonseed oil to extraction with a water-miscible organic solvent selected from the group consisting of low molecular weight alcohols and ketones.

12. In a process for increasing the S03 content of sulphonated olive oil, the steps which comprise mixing the sulphonated olive oil with a low subjecting a sulphonated olive oil to extraction with a water-miscible organic solvent.

6.- In a process for increasing the SO; content of sulphonated cod oil, the step which comprises subjecting a sulphonated cod oil to extraction with a water-miscible organic solvent.

7. In a process for increasing the SO: content of sulphonated cottonseed oil, the step which comprises subjecting a sulphonated cotton seed oil to extraction with a water-miscible organic solvent.

8. In a process for increasing the S03 content of sulphonated triglycerides, the step which com prises subjecting a sulphonated triglyceride to extraction with a water-miscible organic solvent selected irom the group consisting of low molecular weight alcohols and ketones. A

9. In a process for increasing the S03 content or sulphonated olive oil, the step which comprises subjecting a sulphonated olive oil to extraction with a water-miscible organic solvent selected from the group consisting of low molecular weight alcohols and ketones.

10. In a process for increasing the S0: content molecular weight ketone, permitting the mixture to settle whereby two layers form, one containing sulphonated material dissolved in said low molecular weightketone and the other. containing unsulphonated material; and separating the respective layers.

13. In a process forincreasing the S03 content of sulphonated cod oil, the steps which comprise mixing the sulphonated cod oil with a low molecular weight ketone, permitting the mixture to settle whereby two layers form, one containing sulphonated material dissolved in said low molec ular weightketone and the other containing un- ..sulphonated material, and separatingthe respecrating the respective layers.

BERNARD A. DOMBROW.