US2020999A - Sulpho fatty body - Google Patents

Description

Patented Nov 12, 19 35 v UNITED s ArEs' SULPHO ram nonY Melvin De Groote, St. Louis, and Bernhard new.

Webster Groves. Mo., as'signors to lite Company, Webster Groves, Mo a corpora on of Missouri a No Drawing. ApplicatiomDecember 31, 1934, I

. Serial No. 769,026

,7 Claims. (01. iii-1e) This invention relates to a new'sulpho-fatty body and to a method of producing the same.

One object of our invention is to provide a new material, composition of matter, or chemical com- 8 pound, that is capable of various industrial uses, but particularly adapted for use as a substitute for Turkeyred oil and the like. Said new material, composition of matter, or chemical compound, may properly be described as a sulphofatty body derived by'sulphonation of a split unsaturated fatty acid material having at least 6 carbon atoms and less than 16 carbon atoms in the molecule and derived by the thermal decomposition of a body obtained by oxidation of a rel atively highly unsaturated fatty body. Briefly, said new material may be described as a sulphofatty body derived by the sulphation or sulphonation of certain isologues or homologues of normal hendecenoic acid. The substance or substances sulphonated or sulphated to produce our new material are described in our co-pending application for Patent Serial No. 760,025, flied December 31, 1934. The raw material employed'in the sulphonation process and the method of pre-' l paring the same are best described by reference to its homologues or isologues, such as normal hendecenoic acid and oleic acid.

Hendecenoic acid is obtained by distilling rlcinoleic acid or the glyceride thereof (castor oil) under diminished or atmospheric pressure. It is sometimes known as undecylenic acid.- The method of producing this acid is 'well known and is described in the publlcation "Dictionary of Applied, Chemistry", by Thorpe, 1922. 111 volume 4, pages 630 and 631 of the said publication the'reaction of hendecenoic 'acid is properly indicated as follows:

but in the text the term hendecatolc-acid" is erroneously used to refer to the product CnHzoOa. However,-volume 3, pape 515 of the said publication properly identifies hendecatoic acid is u'ndecyclic acid (CuHaeOz). In otherwords, the pyrolytic decomposition of ricinolelc acid or castor oil causes the molecule. to break at the hydroxyl position and yields a sulphonatable unsaturated "fatty" acid having 11 carbon atoms. It is understood'that the expression fatty ishere used because the split acid thus obtained is a lower homologue of oleic-acid. However, so far as we are aware, this acid does not occur naturally in 1 any fat or oil. For reasons which will be subsequently obvious, we shall. refer to hendecenoic yea.

acid derived from castorpil as normal hendecenoic acid. 9 In our aforementioned co-pending application we have described the production of materials similar to ricinoleic acid insofar that they con- 5 tain an ethylene linkage and. a hydroxyl radical in the hydrocarbon fatty chain. Briefly stated, the process there described -consists in subjecting a relatively highly unsaturated fatty acid or fatty body having an iodine number of 120, or higher, 10

and derived from the class of semi-drying, drying e I and marine oils to oxidation or blowing with air, particularly moist air, so as to decrease the iodine number to or of its original value, with a subsequent increase in acetyl value, or at least 15,

with the fori nation of bay bodies. Unsaturated oxidized bodies, so produced, are then subjected- ,to thermal decomposition to yield homologues or isologues of normal hendecenoic acid in the same manner essentially that normal hendecenoic acid is derived from ricinoleic acid or from castor oil.

It is immaterial whether the products thus obtained are in the form 'of fatty acids, or in the form of glycerides or a mixture of the same,

and it is immaterial whether the relatively highly unsaturated material, prior to oxidation; be in the form of a fatty acid or a glyceride or, a mixture of same.

The raw material that we prefer to use in producing the new sulpho-fatty bodies that consti- 80 .tute the subject-matter of our present application for patent, is derived by the thermal decomposition of oxidized or blown marine oils, particularly sardine oil. In order that said raw material may be readily prepared without reference to any other source of information, we give the following procedure for preparing said raw material: The blowing process and the thermal decomposition are preferably conducted in the same vessel, pure-'- ly as a matter of convenience. Our preference. is i to employ 500 or 1,000 lbs. of sardine oil, blow the same with moist air at approximately 150 to 250 9 until there is a drop in iodine number to approx- 7 imately or $9 of the original iodine value, and

.a rise in acetyl value or. absorption of oxygen corresponding to the drop in the iodine value. .At

the completion of the blowing process the moist air'is shut ofl and the temperature I with slightly reduced pressure, so as to thermally-de- 5o compose the oxidized sardine oil. The aldehyde q like materials which'distill over are condensed and employed for any suitable purpose. 'Ihe loss in-weight of the residue during thermal decomposition should not exceed, as a rule, 10% or acid can be subjected to sulpho ation in the various manners applied in the its higher homologue, oleic acid. 0

Itgis well known that oleic acid may be sulphonated at a relatively low temperature, for instance, or less, with66 Baum sulphuric acid to yield a fatty acid sulphate, i. e. oleic acid hydrogen hydrogen sulphate. It also known phonation of that oleic acid may be sulphonated at or near the boiling point of water with sulphuric acid, or at a lower temperature with an onium compound of sulphuric acid to yield a true sulphonic acid. Such true'sulphonic acids are differentiated from fatty acid sulphates above referred to by the fact that they do not decompose on boiling with dilute hydrochloric acid. Another-well known procedure for sulphonating oleic acid, is to sulphonate in the presence of a suitable aromatic compound, such as benzene, phenol, naphthalene beta naphthol, etc., so as to produce a sulpho aromatic fatty" acid.

tached to the aromatic nucleus and not directly to the hydrocarbon fatty chain 'of the fatty ,acid. Although one can produce pure sulpholeicfacid,

i. e., oleic acid hydrogen hydrogen sulphate,- yet.

the expression sulpholeic acid is most commonly employed in the arts to indicate the commercial product obtained by sulphation or sulphonation of oleic acid which contains, for example, not

. tones may be present.

only oleic acid hydrogen sulphate, but also the hydrolytic decomposition product, i. e., lrvdroxystearic acid, and also products obtained by the auto-esteriflcation of hydrox ystearic acid, such as hydroxystearyl hydroxystearic acid. Unreacted oleic acid or its ester derived by reaction 'with hydroxystearic acid may be present. Lac- Sulphonated poly acids may be present. Sulpholeic acid may be almost free from sulphur-containing constituents. Similarly, the sulphonation employed in the manu- 'facture of a true sulphonic acid or asulphoaromatic fatty acid, is accompanied by similar hydrolytic decomposition products and other products obtained by the esterification of or etherization of the hydronla'ted bodies present. In the same manner that the expression sulpholeic acid has been used broadly to indicate sulpho derivatives obtained by all three of these processes, together with the accompanying materials, similarly the expression "normal sulphohendecenoic acid" is herein employed in the same analogous manner to indicate the analogous products obtained from normal hendecenoic acid alone or in presence of such reactive aromatic compounds as benzene, phenol, naphthalene. beta naphthol, etc.

The unsaturated fatty acids employed as raw materials to produce the sulpho-fatty acids herein described} are characterized by having "at least 6 carbon atoms and less than 16 carbon atoms,

'and being free or substantially so from -hende--' cenoic acid. As previously stated, they represent isologues or homologues of normal hende-- cenoic acid and enter into the above three types of sulphonation or sulphation which has been described in respect to oleic acid and normal Such sulphonation products are. characterized by the presence of a sulphonic acid radical, but said sulphonic .acid radical is atpho isohomohendecenoic acid.

hendecenoic acid. Sin'e the exact composition of the raw materials are unknown except to the extent that they are unsaturated fatty acids having less than 16 carbon atoms and more than I 5 6 carbon atoms-in the molecule, one cannot exactly state their chemical composition, except as noted that they may be sulphated or sulphonated to'produce sulphonic acids, fatty acid sulphates or sulpho-aromatics. Furthermore,- there are certain hydrolytic reactions which take place during sulphonation with the formation of hydroxy acids, and said-hydroxy acids react further to' give lactones, poly acids, etc.- In the same analogous manner as is true in the sulphbnation or sulph'ation of normal'hend'ecenoic acid or oleic acid. Various salts, esters, etc. may be formed from the sulpho bodies in the usual manner, i. e., one may produce water-soluble salts, such as sodium salts, potassium salts, ammonium salts, or salts derived dro'm basic amines, such as; triethanolamine, water-insoluble calcium' salts, etc. Esters may be formed, such as ethyl ester, methyl ester, propyl'ester, butyl ester, etc. a

Purely for-the sake of convenience wewill refer to the raw material, prior to sulphonation, as

"isohomohendecenoic acid, because, in view of the method of preparation, and in view of the chemical reactions which these raw materialsso undergo, they appear to be isologues or homologues of hendecenoic acid, and therefore, in the absence of more suitable nomenclature, the coined word isohomohendecenoic acid will be employed. Similarly, the new composition of 85 matter forming the subject-matter ofthe present application for patent will be referred to as "sulpho-isohomohendecenoic acid". The word "sulpho is employed in the same manner that the word "sulpholeic acid is commonly employed 40 in the arts, 1. e., to mean theproduct obtained by sulphonation in any of the various manners described, plus the accompanying produQtPand not to mean the fatty acid sulphate derived at low temperature, which might also be'termed sul- What is said in our co-pendlng application for patent Serial No. 760,024, filed Dec. 31, 1934, in

; regard to the sulphonation of normal hendecenoic acid, applies in an analogous manner to the sulphonation of isohomohendecenoic acid herein contemplated. In the said co-pending application-there appears the following statement in regard to the sulphonation of normal hendecenoic acid: L

Thesulphbnation of-hendecenoic acid must behandled cautiously so as to prevent polymeramount of a readily sulphonatable aromatic compound, such as phenol, is also a suitable pro- Whenthe sulphonated mass obtained by sulphonation in absence of an aromatic compound, isdiluted with water there is a decomposition or hydrolysis of some of the, fatty acid sulphate if present. The fatty acid sulphate referred tois hendecenoic acid,hydrogen hydrogen sulphate,

whichmayalsobechatacmlM-aumbstih-IS and may be considered hydrogensulphate hendecoic acid, i. e., an acid in which one hydrogen of hendecoic acid (undecylic acid). has been re- I placed by a hydrogen sulphate radical. Thus,

the decomposition product obtained by hydrol ysis of hydrogen sulphate hendecoic acid is hydroxy hendecoic acid, and the poly acid obtained by autoesteriflcation. of two moles, of hydroxy hendecoic acid is' hydroxyhendecoyl hydroxy hendecoic acid. Thefanalogyto the formation of hydroxyste'aric acid, poly acids, lactones, sulphated poly acids, etc. therefrom is evident".

What has been saidin the above-mentioned excerpt from our co-pending application for patent Serial No. 760,024, filed December 31, 1934, in regard to the 'sulphatlon or sulphonation of normal handecenoic acid or itsKesters, applies with equal force and effect to the "sulphationor sulphonation of isohomohendecenoic acid, as is herein described. The same analogous sulphation or sulphonation reactions take place; the same analogous hydrolytic reactions take place;

the same analogous esterification or polymerization reactions take place: and the same anal gous compounds are formed, but are different isomerically and probably different in the number of carbon atoms present also.

It is well known that when reagents such as sulphoisohomohendecenoic 'acid are prepared and have both a carbon] hydrogen and a sulphonic hydrogen that only the sulphonic hydrogen need be neutralized if desired. Thus, one

5 may produce ahalf salt in which the carbon! 7 hydrogen is unneutralized; but one may also produce mixed salts, in which the sulphonic hydrogen is replaced by one metallic tom, such as Turkey red oil, as previously stated, and they may. also be used as a demulsifying agent in the reso-,

- lution of crude petroleum emulsions of the water- I in-oil type. It has been so common to use a... demulsifying agent derived from an ester in the form of a salt, or in the form of an est'er,-that the expression acid body isjrequently used to mean the acid itself or an ester thereof, or a salt thereof. The word body is herein employed in this same sense in conformity with its'prior usage in the art. v It is to be understood, that isohomohendecenoic acid, i. e., the product which is subjected to sulphonation or sulphation, need not. be derived from rdine oil, but may be derived from" any 18 marln oil of commerce or from any semi-drying or drying fatty oil or the corresponding. fatty acid. Sardine oil is preferably employed because of its low cost, uniformity and easeof oxidation. It should also be understood that the sulphona- 20 tionof the isohomohendecenoic'acid or the split acid derived from oxidized sardine oil,.'need not be conducted in the manner above described togive fatty acid sulphates, but it may be conducted in a mannerso that the sulpho derivative 25' is in the. form of a true sulphonic acid or in the formof a sulpho-aromatic fatty acid. D Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A new composition of matter, .consisting of 'a sulpho derivative of an unsaturated,'saponiilable, fatty acid material, said unsaturated, 'sa-' .poniflable, fatty acid material having at least 6 I carbon atoms and less than 16 carbon atoms in 85 the molecule, and derived by thermal decomposodium atom, and the carboxylic drogen isre- 40 placed by some dissimilar atom or radical, such as an ammonium radical. Similarly; one may produce a mixed ester, etc.

'Since isohomohendecenoic acid is-sulphated or sulphonated in the same manner as oleic acid.

or normal hendecenoic acid, the sulphation or sulphonation' of which incidentally is described in our first. mentioned co-pending application, and also in U. S. Patent No. 1,749,463, to Bertsch, dated May 4, 1930, it hardly appears necessary to desEribe the manufacture of the newcomposltion of a body. obtained by the oxidation of a relatively highly unsaturated ,fatty body; said fatty body, prior to oxidation, being characterized by an iodine number of not less than 120 and 40 not more than 190, said oxidation being conducted at a temperature range of from 150 C. to 250 C.,'by means of air until there is a drop inthe iodine number to a value of not over two-thirds the original iodine number anda corresponding 4! sltion of matter, because it is only, necessary to applysuch conventional processes to. the raw material described in our last mentioned co-pending application and which has previously been briefly summarized. However, as an example, we

will state that we prefer to obtain 500 lbs. of

isohomohendecenoic acid derived by the thermaldecomposition of oxidized sardine oil, prepared sis-previously described, and mix the same with 150 lbs. of acetic anhydride, and then sulphonate the same with 500 lbs. of concentrated sulphuric acid at a temperature of not over 10 C. The reaction mixture resulting from said sulphonation 5 or sulphation process is-washed in the cold with twice its volume of concentrated Glauberls salt solution, and after complete separation, the uptralized with .ammonium hydroxide, so that the 70 final mixture is an ammonium sodium .salt'of a kind wherein'the sulphonic hydrogen is replaced by a sodium ato'm'and the carboxylic hydrogen increasein the acetyl value; and said thermal decomposition being conducted at a temperature range of from 270 C. to 330 C., with a loss in weight of not over 12%.

2. A new composition of matter, consisting of, an acidic, sulpho derivative of an unsaturated," saponifiable, fatty acid material; said unsaturated, saponifiable, fatty acid material having. at least 6 carbon atoms, and less than 16 carbon atoms in the molecule, and derived by thermal decomposition of a body obtained by the oxida-' tion' of a relatively highly unsaturatedfatty body; said-fattybody, prior to oxidation, being characterized by an iodine number of not less than 120 and not-more than .190, said oxidation being conducted at a temperature range offrom 150 C. to 250 0., by means of air until there is a drop in'the iodine number toa valueof not over two-thirds the original iodine number and a corresponding increase in the acetyl value: and

said thermal decomposition being conducted at a a O 9 per layer is withdrawn and at least partially neuwtemperamre range of from 270 to 330 rated, saponiilable, fatty acid material:v said 1111- at least partially replaced by an ammonium radical.

Such may be used assubstitutes for I saturated, saponiflable, fatty acid material having v at least 6 carbon atoms andJess than-'16 carbon atoms in the molecule, and derived by thermal decomposition oi abody obtained by the oxidation 76 l of a relatively highly unsaturated fatty bodya said fatty body, prior to oxidation, bein'g char--' 'acterized by an iodine number of notless than 120 and not more than 190, said oxidation bein conducted at a temperature range of from 150 C. to 250. (2., by means ofair=until'there is a drop inthe iodine number to.a value-pf not over, twothirds the original iodine number and a corresponding increase in the acetyl- -value;- and said V k a drop in the iodine numberto a value of notover two-thirds the original iodine number and a corresponding increase in the acetyl value; and said thermal decomposition being conducted at a temperature range of from 270 C. to 330 0., with s a loss in weight of not over 12%, neutralization being accomplished by means of an inorganic 6. A newcomposition' of matter, consisting of a 5- 150; C. to 250 C; by means of air until there-is thermal decomposition being conducted at a'temperature range of from 270 C;-to-330--C.,'with a loss in weight of not over 12%;

4. A new. composition of matter, consisting of' a neutralized sulpho-derivat-ive of anunsaturated, saponiflable, fatty acid-material; said-.un- Y saturated, saponifiable, fatty acid material having oxidation of sardine 0 S id Oxidation being at least 6 carbonatoms and less*than 1 6 carbon 1- conductedat a temperature range of from 150 C. atoms in the molecule, and derived by thermal 250" Q, by means of air until there is a drop decomposition of abodypbtainedby the oxidationin iodin, number to a value of not over twoof a relatively highlyun'saturated fatty body; sa d fatty body. prior-to oxidation, being characterized by an iodine number of not less than '120 andrnot more than ,l9 0, =said oxidation being. conducted; at a temperature range of from 150 C. to 250 6.; by means of air until there is a drop in the-iodine number -to a value of not over twoehhfdS-the original iodine number and a corresponding in creaseiin the acetyl value; and said thermal decomposition being conducted at a temperature 30" range of' from 270 C. .to 330 C.,' with a loss in weight 'bf not over 12%, neutralization being accomplished by means of an inorganic base. 5. A new composition of matter, consisting of a neutralized'sulphate compound of an unsaturated, saponifiable, fatty acid material, said unsaturated, saponiflable, fatty acid 'material having at least fi carbon atoms and less than 16 carf bon atomsin' the molecule, and derived by thermal decomposition of a body obtained by: the oxidation of a relatively highly unsaturated, fatty body; said fatty body prior-to oxidation, being characterized byan iodine number of not less than-120 and not more than 190, said oxidation being conducted at a; .temp erature range of from rated, saponiflable, fatty acid material, said unsaturated, saponiiiable, fatty acid material having at least 6 carbon atoms and less than 16 carbon atoms in the molecule, and derivedby therspog msl ar ase in h tvl value d said thermal decomposition beingconducted at a temperaturerangefof from 270 C. to 330 C.', with a 7, A new composition of matter, consisting of a sulphate compound of an unsaturated, saponiflable, fatty acid material having at least 6 carbon molecule, and'derived bythermal decomposition of 'a body obtained by the oxidation of sardine oil, said oxidation beingvconducted at. a temper- .ature range of from 150 C. to 250 C. by means.

a value of not over two-thirds of the original iodine number anda corresponding increase in: A the acetyl value, and said thermaldecomposition being conducted at a temperature range offff m.

40' over 12%, neutralization being accomplished by means of ammonium hydroxide.

MELVIN GROOTE, BERNHABD xmsan.

neutralized sulphate compound of an unsatu- 10,;

mal decomposition of a body obtained by the is.

thirds oftlfe original iodine number and a corre- 20 loss-in weight-of not over 12%, neutralization oeing accomplished by means of .an inorganic atoms-andless than 16 carbon atoms in the 30.-

-of air untilthere is a drop in iodinefnumber to 270 Cato 330 0., with a loss in'weight of ot 40-