US2020998A - New composition of matter - Google Patents

Description

' Patented Nov.

,UNlTED s rAr s amass I NEW courgsmonor Mama Melvin Dc Groote', St. Louis, and Bernhard Keilei',

Webster Groves, M were to 'lrctolite Company, Webster. Groves, Mo a corporation Jo: Missouri No pplidation December :1, 19:4,

sulfonatable" fatty body and to a method oi pro-' ducing'the same. .One object of our invention is to provide. a 3 new material, composition of matter or chemical compound, that is capable, of various industrial uses, but particularly adapted for use as a'raw material in the manufacture of various sultonated ,products intended to be-used for the purpose for 10 which ordinary Turkey red oils and similar materials are employed:- Said new material, composition of matter or chemical compound may properly be described as a sulfonatable fatty acid, or glycerides thereof, having less than 16,carb on atoms and more than 5 carbon atoms in the molecule, and derived by the pyrolytic 'or thermal. decomposition or splitting oi? a body obtained by oxidation .of arelatively highly unsaturated nonhydroxylated fatty body. It is akin to hende whole or its glycerides and may be considered asisologue or homologue of oic acid or its glycerides.

- Hendecenoic acid or undecylenic acid, as it e sometimes termed, is obtained by distilling recin- -oleic acid or the glyoeride thereof (castor oil) under diminished or atmospheric pressure. .The method ofproducing this acid is well known and is described in the publication Dictionary of Applied Chemistry, by Thorpe, 1922. In volume 4, pages 630 and .631 or the said publication, the

reaction of hendecenoic acid is properly indiso but in the text. the term hendecatoiciacid is erroneously used to refer to the product cannot. However, volume a, page5l5 or the" .atoms. It is understood that the expression- "fatty" is here used because the split acid thus obtained is a -lower homologue of ,oleic acid. Ho'wever, so far as we are aware, this acid does not occur naturally in any fat or'oiLas is true of fatty acids in the usual sense. We will herein referto-hendecjenoic acidderived from castdr oil asf'normal hendeoenoic'acid. Y 1 p U. S. Patent No. 1,749,463, to Bertsch, dated March .4, 1930 relates to the sulfonation of cer- "tain pyrolytie decomposition products of caster '55 oil, which ,are'knowmin view or the abovemen- (cur-1n This invention relates toa .new unsaturated,

tioncd publication by Thorpe, consist essen-' tially of hendecenoic acid or a g yceride thereof;

- The valueIof normal hendecenoic acid as a raw material for producing valuable sulfonated products, is well recognized, in view-ofsa'id Bertsch 5 patent. The ability of castor oil or its acid, ricinoleic acid, to undergo thermal or pyrolytic decomposition soas to yield a sulfonatable fatty acid or glyceride of lower molecular weight, is unique.- This property does not appear to be en- 10 ioyed by any other commercially available natural fat or fatty oil. As indicated by the reaction referred to above, it appears that decomposition takes place at the hydroxyl radical and that the fatty acid or glyceride thereof which is split air, is

contains the ethylene linkage, and thus is capa-- bio of sulfonation, although presumably the presence of an hydroxyl radical would give the same effect. The sulfonation of such material is d'escribed not only in the Bertsch patent previously 9 referred to, but also in our co-pending application for patent Serial No. 760,024, filed December. 31, 1934.

Due to the relatively high cost r oaatoifoii,

and also to the fact that the pyrolytic decomposi- 25 tion reactioh yields an aldehyde and perhaps some hydrocarbon or limited commercialvalue, normal 4 hendecenoic acid .is somewhat expensive, and then even though valuable sulfonated products may be derived therefrom, the cost of the latterismarlr- :ediy higher than the cost of ordinary Turkey red oils or substitutes therefor. We have attempted to producematerials similariin chemical proper-. ties to hendecenoic acid or its ester, and in such a manner that t e productss'o obtained will com- 35 pare favorably in cost with ordinary, fatty materials employed in sulfonation processes, or .for

other purposes, The new composition of matter herein described may be used in the form of an acid, salt or ester to break petroleum emulsions of the water-in-oil type.'

In producing omnew material or composition 'of matter, weemploy a relatively highly unsaturated fatty body as e raw material. By relatively highly unsaturated .body we mean those materials whose iodine number is distinctly-high- 'er than 0160 acid, and arethus characterized as havingamore'than one ethylene linkage present in the hydrocarbon, chain of the characteristic fatty acid'or acids present as such or in the form of glycerides. It is well known that various dry-' ing and semi-drying oils, and various marine oils are characterized by an iodine number greatly in excess of oleic acid, varying in a general man-.

= pet from approximately to 180 or-190, ton l,

relatively with water to produce two hydroxyl groups.

Whether or not this is the correct explanation, it is known that hydroxyl groups are formed. For

instance, Chemistry of-the Oil Industry",- by

Southcombe, 1926, page 181,'in speaking of blown (oxidized) oils, states as follows:

"Hydroxyl groups are unquestionably formed, as the considerable rise in acetyl value proves If one uses airor oxygen to blow a fatty material having'a single ethylene linkage, the resultant hydroxylated body has no particular analogy to ricinoleic acid, but is analogous, perhaps, to hydroxystearic acid. We have found by blowing a hly unsaturated fatty acid or oil of the kind p viously referred to, that the resultant product is characterizedby the presence of fatty bodies having both a ,hydroxyl radical and an ethylene linkage. I These particular'materials are analogous to castoroil and may be subjected to thermalor pyrolytic decomposition in the same manner that castor oil or ricinoleic acid is subradicals, so that the unsaturated acid obtained by pyrolytic decomposition, may vary in molecular size, depending, in part, upon the position of the split hydroxyl radical. Thus, one may obtain various unsaturated acids having a different a number of carbon atoms as a result of the process ,hereindescribed. In some instances itis even possible that the split fatty acids may have a hydroxyl group attached to the hydrocarbon chain. These split acids appear to be homologues'lo or isologues of oleic acid. The lowest homologue of oleic acid which is known to'occur naturally, appears to be tiglic acid, which has four carbon atoms. Lower homologues of oleic acidhaving 6 to 10 atoms appear to be unknown in nattn'al l5 coils. The lower homologue of oleic acid, hende- -cenoic acid, previously referred. to, is obtained most conveniently by the pyrolytic decomposition of castor oil. Also homologues of oleic acid, said to have 12 to 14 carbon atoms, have sometimes 20 been stated to occur in the fat of cochineal;.-

' if this be true, they are only laboratorycm'iosi- .ties' and are unknown commercially or in the trade. We have characterized our new composition of matter as containing more than five car'- 25 bon atoms and less than 16 carbon atoms and being derived by the thermal or pyrolyticdecomposition of oxidized '(blown) relatively highly rmsaturated fatty bodies, so as to clearly define the metes and bounds of our present invention. 30

jected. The resultant product obtained, 1. e., an It is substantially free from or does not containunsaturated fattyacid or glyceride, having fewer carbon atoms, of course, than the original fatty body from which it-is derived,is acheap and suitable substitute for hendecenoic acid or'its.

glycerides. Thereis, of course, an aldehyde, such as heptaldehyde (heptoic aldehyde) or somewhat similar bodies formed which may be used for the same pin-pose as heptaldehyde. For instance, these aldehydesm'ay be combined with 'bisulfltes,

such as sodium or potassiumbisulfltes, to produce' addition products having the-same valuable properties enjoyed by heptaldehyde sodium blsulflte addition products. For instance, Watts Dictionary of Chemistry (1919) Muirand Morley,- volume 2, page 680, contains the following in re-' to heptoic aldehyde bisulflteaddition prod lution of heptoic' aldehyde containing potash,

soda, or NHs'.--CsH1:.CH(QH-).SO:NA no: brillian't unctuous' scales; vsol.water,v.e.s0l. hot, nearly insol. cold, alcohol."

The alddiydes obtained in the manufacture of our, compositionof-matter, whether composed of' heptoic aldehyde alone or similar materials or a mixture, may be employed in the same manner aspureheptoic aldehydetoproduce bisulflte addition products.

It is not intended to infer that the use 'of hendecenoic acid is limited to its useas a raw niaterial in sulfonation The ammonium We desire to'point-out that the P tics: of the fethylene'linkagesinvarious highly fatty oils or acids may vary and=that, due to variation in condition of oxidation, various ethylene'linkages maybe oxidized to produce hydroxyl an appreciable amount of hendecenoic acid of the kind obtained from castor oil.

Since the bl0wing' (oxidation) of various oils is a welf known commercial process, and since the thermal decomposition 0f castor oil is a well known process, it is hardly n to give an elaborate description of a procedure suitable-for producing our newcompositionof matter, invlew of .what hasbeen said previously as to the .40 sarychemical reactions involved. Briefly stated, a a suitable of selecting 'a suitable, relatively highly oil or acid,-or mixture of the same, blowing said oil,-

acid or mixture with dry, or prerersf lr. moist 4s air or'with any other suitable oxidising agent.

-astopsoduceahydroxylatedoroxy material in-whichtherearepresentmbstanees presentinthesamechamso linkage and then subjecting this oxidised (on) unsaturatedmaterialtopyrolyticorthermaldecomposition in the manner employed for the then. mail decomposition of eastor oil. The usual procedimeistoheattoapproximatelyilmtowc u' withalossin weightofnbtover12%.\mderatmospheric ordiminished 0n acoount'oftheirlow 0st, and we-particnlarly prefer touse American sardine 'ofltbeealle 00 it is frequently available at a cost of .matelyone-halforlessofthecostoloaltoroll. We m'efertoconducttheblowimproosandthe thermal decomposition in tbesamevelehpurely as a matter of convenience. Our preferred cedureinvolvesusingmoripwlbs. oILandbIowingthesame thmoist 'proximately 150-to 250 C. untiltliere is iodine number toapproximately original iodine value, and a rise or vofoxygencorrespondingtothedrop inthe value. Atthecompletion'ofthe blowingprocessfliemoistairisshutofl the temperatureraisedwimslightlyreduced pressme, so-asto'thermaliy-the oxidised 7;

hydrox'ylradiealandan'etbylenepross acetv v e oil. The aldehyde-like materials which over, are condensed and employed for any suitable purpose. The loss in weight of the residue during thermal decomposition should not exceed, as a rule, or 12% by weight of the original oxidized sardine oil. The final product which appears to represent homologues or isologues of oleic acid, but not to contain any hendecenoic acid,

may be saponifled in any suitable manner. so as to give salts suitable for use in the same manner that ammonium salt of normal hendeeenoic acid is employed. As previously indicated, such materials may be employed in resolution of petrolemn emulsions. If desired, the unsaturated materials obtained, may be sulfonated in the manner described in U. S. patent to Bertsch, previously referred to, so as to yield valuable produtts which may be employed for various purposes in the same mannerthat Turkey redoil is employed. It is to be noted that it is immaterial whether the final product be an acid or ester, or whether it be converted into a. water-soluble salt, such as the sodium salt; or a water-insoluble salt, such as the calcium salt. It is immaterial whether the raw material prior to oxidation be an acid, or whether 1 it be a naturally-occurring ester, such as sardine oil.

Since the exact decomposition of the materials herein contemplated is not known, but since they appear to be isologues or homologues of hendecenoic acid, and exhibit the property of an'ung saturated fatty acid, such as hendecenolc acid,

mal decomposition of a body obtained by oxidation of a relatively highly unsaturated fatty body; said fatty body, prior to oxidation, being characterinedbyaniodinenumberotnotlessthan and not more than 190, said oxidation being'conducted at a temperature range of from 1509 C. to 250 C.,by means ofairuntii thereisadropin theiodinenumbertoavalueofnotovertwod thirds the original iodine number and a corresponding increase in the aoetyl 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 unsaturated, saponiflable, fatty acid-material having at least S'carbon atoms and less than 16 carbon-atoms in the molecule and derived by the thermal decomposition of a body obtained by 18 oxidation of a relatively highly unsaturated fatty glyceride; said fatty glyceride, 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 $0 of from C. to 250 (2., by means of air until there is a drop in the iodlnenumber to a'value of not over two thirds the original iodine number and a corresponding increase in theacetyl value; and said thermal decomposition being conducted 25 ata temperature range of from 270 C. to 330 0., with a loss in weight of not over 12%.

3. A new composition of matter, consisting of an unsaturated, saponifiable, fatty acid material having at least 6 carbon atoms and less than is 80 carbon atoms in the molecule and derived by therinal decomposition of a body obtained by oxidation of sardine oil, said oxidation being conducted at a temperature range of from 150 C. to 250 0., bymeansof air-until thereis adropin iodine number to a value of not over two-thirds the original iodine number and a corresponding increase in the acetyl value; and said thermal decomposition being conducted at a temperature range oi from 270 c. to 330 C., with a loss in weight of not over 12%.

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