Patent Office Tia S

Paterated June 13, 1933 1,913,367 UNITED STATEs PATENT OFFICE TIA S. CACOTT AND wILLIAM A. Doug LAss, of PENNS GROVE, NEW JERSEY, AND HERBERT W. WALKER, OF WILMINGTON, DELAWARE, ASSIGNORS TO E. E. DO PONT OE NEORS & COMPANY., oE WILMINGTON, DELAWARE, A CORPORATION OF DEAWARE PRESERVATION of or LS, FATs, FATTY or LS, FATTY ESTERS, FATTY ACIDS, FATTY ACID SALTs, AND RELATED COMPOUNDS w No Drawing. Application filed December 18, 1929. Serial No. 415,04. This invention relates to the treatment of ringer in D.R.P. 308,408 discloses alkalilac auto-oxidizable substances such as oils, fats, tates as suitable stabilizers for margarine, fatty oils, fatty esters, fatty acids and salts butter and lard. Many of the compounds of fatty acids to retard deterioration and heretofore employed, however, have been 5 development of rancidification. More par open to the objection that they either dis 55 ticularly it pertains to the addition of or color the product to be preserved or form ganic compounds to such substances in compounds that have this objectionable order to accomplish these results. Specifi property. Certain compounds of the prior cally, the incorporation of diaryl or diaral art impart to the product in which they 10' kyl compounds, such as hydroxy diaryl al are incorporated a distinctive odor. Other 60 kanes into the material to be preserved is proposed preventives are actually ineffectual contemplated. or are effective only for a short time. Butter, lard, cocoanut oil and other an This invention has as an object the pres imal and vegetable fats and fatty oils, to ervation of fats, fatty oils, fatty esters, fatty 15 gether with soap, the sodium or potassium acids, fatty acid salts and the like. A fur salts of the fatty acids contained in these ther object of this invention is to insure the fats and fatty oils, tend to develop an ob retention of the original odors of these ma jectionable rancid odor and taste on ex terials for indefinite periods. Still further posure to, air under ordinary conditions. objects are to prevent or retard the auto-oxi 20 This deterioration is due to the oxidation dation of materials of this nature, to keep 70 of the fatty acid part of the fat or soap the materials sweet (in the sense of the odors molecule by atmospheric oxygen. The ox given off), for a long period, to maintain the ide derivatives which are first formed be original chemical and physical states for ex come decomposed or altered and produce tended periods, to prevent reaction of these 25 substances having a rancid odor and taste. substances or their constituent parts with 75 Some work has been done in the fat pres the atmosphere or its constituent parts such ervation field as shown by U.S. P. 1,542,438 as oxygen, to insure retention of the origi to Divine, wherein aniline, alpha naphthyl nal properties of these substances, without amine, para phenylene-diamine, diphenyl discoloring or imparting objectionable odors 30 amine and hexamethylenetetramine are thereto, to prevent oxygen absorption by the 80 . added to soap. In U. S. P. 1,575,529 to Boll materials to be preserved and generally man soya bean lecithin is added to edible overcome the objectionable features of the oils. Other improvements in the keeping prior art. Other objects will appear herein quality of auto-oxidizable substances are after. 35 claimed in U. S. P. 1,672,657 to Powell ac These objects are accomplished by the in 85 cording to which the condensation product vention herein disclosed which is related to of an aromatic amine and an aliphatic alde the invention of application E391706 filed hyde is added to the material to be pre September 10, 1929, by the same inventors served. The foreign patent art also dis in that it involves further work in the same 40 closes work along this line as evidenced by field. In that application the preservation 90 B. P. 181,365 to Moureu and DuFraisse who of oils, fats, etc., by the addition thereto of employ the phenols such as pyrogallol, guai diaryl compounds is disclosed and in the ex acol, and hydroquinone as stabilizers for amples set forth the aryl groups are directly auto-oxidizable substances. In B. P. 208,189 connected. It has now been found that 45 to Lever Bros. the phenols of the types preservation may also be accomplished by 95 hydroquinone, guaiacol and resorcinol are compounds containing a plurality of aryl or used to prevent deterioration of whale oil. aralkyl groups connected through or to an Rechburg, Braun and Oetermann in D. R. P. intermediary, such as, for example, an al 254,303 disclose sulfur and pyrogallol for kane, amino or oxygen radical. In com 50 the preservation of oils and fats. Boeh pounds of this class, those having a hydroxy, OO 2 1,918,867 ethoxy, or amino radical attached to an aryl sorbed by the soap it will be found that the . group are particularly effective. treated soap absorbs oxygen at a very much According to this invention members of slower rate than an untreated sample of the the hydroxy diaryl alkane class of com same soap. An inhibition of oxidation is pounds are incorporated into the substances secured by the use of p-hydroxy diphenyl 70 to be preserved. These incorporated mate methane in the soap resulting in an improve rials act as anti-oxidants to prevent or re ment in the aging qualities of the soap, tard the decomposition and rancidification which otherwise would have shown consid and prevent combination with or absorption erable deterioration and a development of O of oxygen. The general formula of the pre rancidity. 5 : ferred compounds used is . Eacample IV HO-R-Alkyl-R'-Y Cocoanut oil treated with 0.01% di-2- naphthol methane and exposed to the air at in which R and R' are aryl or aralky nuclei room temperature remainso stable, sweet ins 5 which may be alike or different and Y is odor, and essentially, unchanged for a cont. 80 either hydrogen, hydroxy or E. The siderably longer period than untreated oil retarding agents may be incorporated in the as determined by the sense of smell and the oilample, or fat by in mixing, any suitable and at manner any time as, forfound ex Kreis test. 30 preferable as, for instance, before or during Such compounds as di-2-naphthol meth 85. preparation or in the natural or ordinary ane, state. By way of illustrating our invention the following selected examples are given. ; : y : : Eacample I On OO 90. One tenth of 1% of di-2-naphthol en thane was incorporated into ordinary com p : p-dihydroxy diphenylmethane, mercial lard and the sample exposed to the action of the atmosphere at room tempera 30 ture along with an untreated control sample 95 of the same lard. After 7 days the control mm'-dihyroxy triphenylmethane, sample possessed a rancid odor and aWe a BO . OR positive test for rancidity with the phloro glucinol Kreis reagent. On the other hand, 35 the stabilized lard containing di-2-naph thol methane remained sweet to smell and gave no indication of rancidity by the Kreis. color reaction with phloroglucinol. For the 3 succeeding days the treatedlard remained o-hydroxy diphenylmethane, 40 stable and free from any rancid condition to 05 the extent that it was essentially unchanged after the ten day test. p-hydroxy diphenylmethane, Eacample II p-hydroxy diphenylmethane was added to 0 a sample of lard up to a concentration of 0.1% and its effect on the development of p-hydroxy diphenyl ether rancidity observed, as in Example I. While the control sample underwent deterioration with attendant rancidity after 7 days ex p:p'-diethoxy diphenylamine 15 posure as determined by odor and chemical test using the Kreis color reagent, the lard containing p-hydroxy diphenylmethane was distinctly sweet to smell and gave a negative p : p'-diamino diphenyl amine Kreis test, indicating stabilization of the 120 lard by the antioxidant with protection against spoilage and the development of have been used in lard and it was found that rancidity. lard treated with these agents remained Eacample III unaltered and free from rancidification for a considerably extended period over the time 25 If 0.05% of p-hydroxy diphenylmethane required for ordinary lard containing no be incorporated in soap, for example, white anti-oxidant to become deteriorated and olive castile soap, and the soap exposed to rancid. These substances may also be used the action of atmospheric oxygen at 60° C. with the same advantages in other animal 85 in such a way as to measure the oxygen ab- fats, vegetable oils, and soap. 30 1,918,367 3 The description of the Kreis color reac The aryl groups which may be substituted tion phloroglucinol test may be found in are not limited to phenyl, naphthyl, and bi J. I. E. C. 15, 1051 (1923). Briefly it is as phenyl groups, but tolyl, xylyl, or any other follows. One tenth of a gram of fat dis aryl group may be used with effectiveness in solved in 5 cc. ether is shaken with 5 cc. con compounds of the general type. It will, of 70 centrated HCl. The mixture is then shaken course, be obvious that when the aryl groups with 5 cc. 1% ether solution of phloroglu have substituents other than hydroxy or cinol. The development of a typical red alkoxy groups that the same must be of color in the HCl is regarded as a positive such nature as not to neutralize the hydroxy 0.

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