Patented Oct. 21, 1952 2,615,160 UNITED STATES PATENT OFFICE ; 2,615,160 MIXED-TRIGLYCERIDEs ; Fredric J. Baur, Wyoming, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Application May 28, 1949, . Serial No. 96,143 19. Claims. (CI. 260-410.8) This invention relates to mixtures of high mo : I have found that mixtures of diacetyltriglyc i.lecular diacetyl triglycerides in-aiwaxy translu ... erides the non-acetyl acyl, radicals of which are cent form-and-to-ways of making them. of high molecular weight (i. e. those offatty-acids ; : In copendings application-Serial No. 96;150. of : of 12 to 22 carbon atoms) are capable of crystals * Frank L. Jackson, bearing even date herewith, 5. lizing in Waxy translucent form, and that when synthetically prepared high-molecular triglycer- . at least ten per cent by weight of the diacetyl sides are'. described, having in their molecular triglycerides, in such mixtures are different in structure two acetyl groups attached to adjacent composition, or structure from the remainder of s' carbon atoms, of... the glyceryl radical...and...one ... the diacetyl triglycerides, this waxy translucent 's high molecular acyl group. (i.e.: containing: 12 to 0 form is of great, thermodynamic stability, being -22-carbon atoms)., attached to the third-glyceryl capable of existing for long periods of time or carbon. These tasymmetrical diacetyl-triglycer- indefinitely without transforming into the opaque sides are capable of solidifying in waxy...translu- ... solid-form in which conventional fats-exist at -cent-form, in which form they possess novel and itemperatures below their melting point. I have ruseful properties which distinguish them-from 15 furthermore discovered an inexpensive and com previously known fats. These -diacetyl.com.- ... mercially practicable process whereby such mix :-pounds' possess limitedi stability. .in, the waxy tures of diacetyl triglycerides may be prepared st translucent form, sufficient to make them service- in a purity which makes them suitable for cook - able for some purposes but limiting their serv- ling and other purposes. riceability for others; since they eventually lose 20. In a favored variant of my process of prepar - 'their waxy, translucent properties. Further- 'ing Such mixtures of: diacetyl triglycerides, the rimore, although Jackson has proposed methods first. Step is to rearrange molecularly the acyl of preparing diacetyl fats capable of assuming ... groups. in a mixture of triacetin and a conven the waxy translucent form, no-methods prior to ...tional fat, For this purpose the mixture is con my invention have been entirely satisfactory-for 25 tacted with a .rearrangement catalyst., Many i commercial practice. For example, chemical Such catalysts are known and may be used, such synthesis involving-reaction of -acetyl-lehloride "for example as water, alone at high temperature with an unsymmetrical-high molecular mono- ... and pressure, or the Soaps of alkali metals, zinc, '...' glyceride is undesirably costly. aluminum, tin or magnesium...However, I prefer It is an object of this invention to provide fats 30 low temperature: rearrangement... catalysts, by rt which may be solidified in waxy, translucentform. which I mean catalysts which are effective below - Another object is to provide such triglycerides 3.20 C., such as alkali metals or compounds whose which are either wholly-stable in waxy-trans cation is an alkali metal or a tetrasubstituted am i-lucent form or are stable in that form for long monium radical and whose anion is: the result of periods of time. ... Another object is to previde 35 removal of acidic hydrogen from any substance such triglycerides in the alpha-3 or the subalpha less, acidic than phenol. Thus finely divided me ... 3-polymorphics forms, to obes described sherein tallic Sodium or potassium in xylene, organhy - after.' Another object is to provide-mixtures of drolls Suspension of potassium hydroxide, in un - such...triglycerides;... Said mixtures containing a is decane may be used, or alkalimetal hydrides. : ; plurality. of combined high-molecular acyl- grOlipS. 40. Also, Suitable for this purpose are various alkox -c.Another-object is to provide mixtures of symmet vides Such as sodium, potassium and lithium meth rical and unsymmetrical: high molecular diacetyl oxides, ethoxides, propoxides and butoxides, as ... triglycerides. Another object is to...provide such ... are: also the corresponding alkoxides made from is mixtures.Which are 'substantially free from mono '... alcoholic compounds in general such as lauryl al . glycerides, diglycerides, glycerol, fatty acids, tri 45 Cohol, ethylene glycol, glycerol, oleic acid mono it... acetin, or... triglycerides , containing...not acetyl glyceride and many others. Also suitable are al ... groups. Another object is to provide a novel-kind *:koxides in which the cation is the tetrasubstitut of edible fat. Another objectiisi to provide an ed ammonium radical such as: tetramethylam '...inexpensive and commercially practicable: proc monium. methoxide and lauryl benzyl dimethyl - ess whereby mixtures of symmetrical and unsym 50 ammonium methoxide, and alkali-metal-organic ... metrical high-molecular. diacetyl triglycerides Compounds. Containing the alkali metal: atom, di nay, be prepared linSynaetrical triglycerides be rectly, bound-to a carbon atom as in Striphenyl sing in predominant amount in Said mixtures and methyl sodium or to a nitrogenatom: as in po ...said mixtures being substantially-free from mono - tassium. pyrrole. Sodium alkoxides of monohy ... glycerides, diglycerides, glycerol, fatty acids, tri 55. dric alcohols of less than 5 carbon atoms (for ex aceting or triglycerides-containing .no-acetyl ample, Sodium methoxide and sodium, ethoxide) igroups. Other objects will appear hereinafter. -- are especially Satisfactory catalysts. The amount 2,615,160 3. 4 of Such low-temperature catalyst required in crystallize readily in waxy translucent form, the creases With the inoisture content of the fat. In rearranged mixture requires purification. Tri the case of Sodium methoxide or ethoxide the acetin is especially objectionable because it low- . amount commonly ranges from about 0.05 per ers the temperature at which the product smokes cent to about 0.5 per cent, based on the weight 5 When used for cooking purposes; it also softens of the fat, about 0.3 per cent being an average the product and expands the temperature range figure according to my experience. Such cata over which it melts. I therefore remove by lysts are usually suspended in xylene or other distillation substantially all unreacted triacetin low-boiling hydrocarbon which is miscible with or other low-boiling constituents which may re fats, the amount of Suspending liquid being non G main in the rearranged mixture after inactivat critical. ing the catalyst and washing, as previously de The low temperature catalyst is added to the Scribed. In order to avoid high temperatures dried fat (usually refined and bleached pre Which might cause decomposition, I carry out viously) or to the dry triacetin or to the mix this distillation under reduced pressure, pref ture of the two. Rearrangement is allowed to erably while passing a stream of inert gas, such proceed at a temperature So high that at east for example as nitrogen or steam, through the a substantial part of the fat is liquid, since Solid molten fat. Under a pressure of 2 or 3 mm. of fat does not readily undergo rearrangement with mercury, triacetin steam-distills readily before triacetin. As the reaction proceeds, the acetyl a temperature of 40° C. is reached. containing fats which are formed tend to dis I next isolate a distillation fraction consisting Solve any remaining Solid fats and thus enable predominantly of high molecular diacetyl tri them to take part in the reaction. However, in glycerides. in Order to do this, the temperature order to attain more rapid rearrangement, the of the Stearin distillation or other distillation is mixture is commonly heated to above the con raised and/or the pressure is reduced until diace plete melting point of the fat or until the mix 2 tyl triglycerides distill, but conditions drastic ture is completely liquid, although temperatures enough to cause distillation of substantial above 120° C. are avoided lest the activity of the amounts of tiriglycerides containing less than 2 catalyst be impaired. Under these preferred acetyl groups are avoided as much as possible. conditions, more than one half hour is rarely The exact temperature of distillation, at a given required for substantially complete rearrange 30 preSSure, varies With the particular fat used in ment of acyl groups, although longer periods are the rearrangement and With the speed of dis not harmful. Furthermore, while a substantiai tillation which is desired. Thus in the case of degree of rearrangement should be effected, it unhydrogenated cottonseed oil, distillation has is not imperative that the reaction go to final been practiced at about 205 to 250° C. at a pres completion. Sure of about 2 mm. Imercury, while in the case The rearranged mixture is of complex conm of unhydrogenated rapeseed oil, temperatures stitution, the relative proportions of the con of about 220' to 270° C. have been required. One stituents depending upon the proportions of skilled in the art is of course guided by the shape triacetin and of fat initially used. It Will con of the distillation curve (temperature vs. amount prise triacetin, high molecular