- if 3 {: 3 S ; 4 £, A2) g f sub. Patented Sep 8, 1938 2,128,946 care." UNITED STATES PATENT OFFICE 2,128,946 TETRAPHOSPHORCAC) ESTERS Morris B. Katzman, Chicago, Ill. No Drawing. Application April 9, 1937, Serial No. 135,931 23 (Claims. (C. 260-46) My invention relates to a new class of chemi More specifically, the most preferable of the cal substances. It relates more in particular to compounds of my invention may be defined as . a class of chemical, substances having the prop tetraphosphoric acid esters of polyhydroxy sub erties of interface modifiers as, for example, when stances wherein at least one hydroxy group of employed in a treating bath containing textile, the polyhydroxy substance has its hydrogen sub leather or ores. Many of the compounds of my stituted by a lipophile group. The lipophile group 5 invention are also effective to decrease the spat- nay include any organic acid group, particular tering of margarine, to increase the oiliness of ly fatty acid groups having preferably at least lubricating oils and greases, such as are derived four carbon atoms such as the fatty acid radi O from mineral oils, to act as emulsifying agents calls of the following acids: caproic acid, capric, O for cosmetic and other emulsions, to reduce vis- caprylic, valeric, butyric, abietic, naphthenic, hy cosity of chocolate and the like, to retard the droxystearic, benzoic, benzoylbenzoic, naphthoic, rancidification of oils, fats, and vitamin prepara- toluic, higher molecular weight saturated and tions which are subject to deterioration by oxi- unsaturated fatty acids including palmitic acid, dation, to act as assistants in the textile and re- Stearic, lauric, melissic, oleic, myristic, ricinoleic, 5 5 lated industries and, in general, to function linoleic acid or mixed fatty acids derived from wherever interface modification is sought or de- animal or vegetable fats and fish oils such as sired. lard, oleo oil, coconut oil, corn oil, cottonseed The substances of my invention have many oil, partially or completely hydrogenated vege useful application in the arts where frothing, table oils such as cottonseed oil, corn oil, sesame 20 20 foaming, wetting, penetrating, detergent, emul- oil and fatty acids of various waxes such as bees sifying, and other interface modifying functions Wax and carnauba waX; or the lipophile group. are required. They are in general possessed of may be an alkyl radical derived from an t at least two groups, one having a hydrophile corresponding to any of the preceding acids, such function and the other having a lipophile func- as , , , oleyl 25 tion in the molecule. The hydrophile function alcohol, lauryl alcohol, higher saturated and un- 25 is performed primarily by a tetra-phosphoric Saturated aliphatic derived from natural acid or tetraphosphate group, giving the mole- fats and oils, cholesterol, Sperm oil, etc. cule as a whole an affinity for aqueous materials. Specific examples of polyhydroxy substances, The lipophile group is any radical having a defl- the residues of which may serve as linkages be 30 nite affinity for oils and fats and may comprise tween the lipophile groups, and the hydrophile 30 radicals such as acyl or alkyl derived from a fatty tetraphosphate groups, besides those previously acid or its corresponding alcohol. The hydro- mentioned, are as follows: mucic acid, tartaric phile tetraphosphate group may be and prefer- acid saccharic acid, gluconic. acid, glucuronic ably is linked to the lipophile group by means acid, gulonic acid, mannoic acid, trihydroxyglu 35 of a polyhydroxy substance. I have found poly- taric acid, glyceric acid, and the like, as well as 35 hydroxy substances such as sugars, sugar alco- carboxylic oxidation products of polyglycerols hols, glycols, polyglycols, , polyglycerols, which may be represented by the formulae: and hydroxycarboxylic acids to be particularly QH OE. O. 40 substancesuitable. Anand ester the linkagetetraphosphate joins the polyhydroxygroup. The Ho-Cio-Cio-Cio-C-OH 40 linkage between the polyhydroxy substance and gh OE O. O. the lipophile group may be either an ester or Ho-CII-bil-CH-O-CH-CH-CH-0-cr-en-3-oh ether linkage. cated,All ofare the esters products of tetraphosphoric of my invention, acid, as which indi- Ho-Chi-CH-CH-OH Ho-CH-CH-6-OH 45 acid may be represented by the following struc tural formula: CH, ch, rO > O N / O -C-OH E-C-OE 50 Ho-r o=d-OH Hid-oh 50 go O OB pH 9 Ho-r Ho-5-bH-CH-O-CH-bH-E-OH p (Jo O OH OE OH. O 55 O) HO-PN HO-C-CH-CH-O-CH-CH-CH-O-C-C-C-OH8-d &H-CH: bH s go O OH OH O . t HO-P/ IO-C-CH-CH-O-C-CH-CH-O-C-C-OI and sugars such as: xylose, galactose, fructose, 60 2 2,128,946 maltose, glucose, , dulcitol, arabitol and 28. Tetraphosphoric acid ester of octyl alcohol. other sugar alcohols such as hexahydric alco 29. Tetraphosphoric acid ester of lauryl alcohol. hols derived from sugars, and other substances 30. Tetraphosphoric acid ester of . having free hydroxy groups. The above poly 31. Tetraphosphoric acid ester of steary and their oxidation products are pro alcohol. duced by polymerizing glycerine, preferably by 32. Tetraphosphoric acid esters of mixture of heating with about 1% of alkali at temperatures alcohols derived from reduction of sperm from 250 C. to 260 C. for about three hours in oil. the presence of an inert gas. This reaction mix 33. Tetraphosphoric acid esters of mixture of O ture will give a mixture of various polyglycerols, alcohols derived from reduction of cocoa O the size of the molecules depending upon the nut oil. time of polymerization. The mixture of poly 34. Tetraphosphoric acid ester of ricinoley glycerols is then oxidized with mild oxidizing alcohol. agents to convert at least one of the primary hy 35. Tetraphosphoric acid ester of butyl alcohol. 5 droxy groups to a carboxylic group, 36. Tetraphosphoric acid ester of cholesterol. Examples of Substances of my invention are as The procedural details of the methods by follows: means of which the materials of my invention 1. Tetraphosphoric acid ester of mono-olein, may be made may be varied. The exact method ammonium salt. employed should be determined primarily by con 2. Tetraphosphoric acid ester of diethylene Sidering the type of reacting constituents and 20 glycol mono-ricinoleate, triethanolamine the final Substance to be produced. In introduc salt. & ing the tetraphosphate radical, for example, a Tetraphosphoric acid ester of mono-aurin, material containing an esterifiable hydroxy group SOdium salt. is reacted with tetraphosphoric acid. Either one 25 Tetraphosphoric acid ester of mono-acetin, or more tetraphosphate radicals may be intro 25 Sodium salt. duced, depending upon the Substance desired. Tetraphosphoric acid ester of di-butyrin, Furthermore, the molal ratios of the reacting Sodium salt. constituents may be varied to produce products Tetraphosphoric acid ester of cetyl ether of having varied properties. A condensing agent 30 SOrbitol. and/or a solvent may be added where required. 30 Tetraphosphoric acid ester of ethylene gly In order that those skilled in the art may even Col. In Ono-Stearate. more fully understand the scope of my invention, 8. Tetraphosphoric acid ester of ethyl ether of I shall describe various specific embodiments of . my invention in detail. It is to be understood, 35 9. Tetraphosphoric acid ester of octanoic acid however, that the following examples are given ester of diethylene glycol. dnly by Way of illustration and are not to be con 10. Tetraphosphoric acid ester of mixed cocoa strued as limitative of the true scope of my in nut oil fatty acid estér of diethylene glycol, vention which is set out in the appended claims. ammonium salt. W It is evident that proportions of reacting in 40 11. Tetraphosphoric acid ester of butyl ether of gredients, temperatures of reaction, time of re diethylene glycol, Sodium salt. action, and the like represent factors which may 40 12. Tetraphosphoric acid ester of sucrose mono be varied, all Within the skill of those versed in the Oleate, Sodium salt. art in the light of my teachings herein. 13. Tetraphosphoric acid ester of mixed cocoa Eacample I 45 nut oil fatty acid mono- or diglycerides or mixtures of mono- and diglycerides, am 50 parts by weight of monostearin were heated monium or triethanolamine Saits. to 90 degrees C. and to Said monostearin was 14. Di-tetraphosphoric acid ester of sucrose di added slowly, while stirring, 50 parts by weight stearate, ammonium salt. of tetraphosphoric acid, previously heated to 90 50 15. Tetraphosphoric acid ester of mono-oleic degrees C. The temperature rose to about 115 acid ester of diglycerol, sodium salt. degrees C. and the mass became viscousand light 50 16. Tetraphosphoric acid ester of mono-octyl brown in color. Stirring was continued for sev ether of glycerol, potassium salt. eral minutes until the product cooled down to ap 17. Tetraphosphoric acid ester of di-caproin, proximately 90 degrees C. When the reaction 55 SOdin Salt. mixture begins to drop in temperature, it is an 18. Di-tetraphosphoric acid ester of mono indication that at least the major portion of the 55 cetylglycerol, potassium salt. reaction has proceeded to completion. The final 19. Tetraphosphoric acid ester of lauryl ether product, which was practically odorless, very sub of diethylene glycol, sodium salt. stantially reduced the spattering of margarine 60 20. Tetraphosphoric acid ester of mono-melis and likewise reduced the Surface tension of water. sic acid ester of , ammonium salt. 30 21. Tetraphosphoric acid ester of di-cetyl ether Eacample II of Sorbitol, monoethanolamine salt. To 69 parts by weight of tetraphosphoric acid, 22. Tetraphosphoric acid ester of di-stearic previously heated to 90 degrees C., 27 parts by acid ester of triglycerol, potassium salt. Weight of commercial stearic alcohol, also pre 23. Tetraphosphoric acid ester of mono-butyric viously heated to 90 degrees C., were slowly add acid ester of tartaric acid. ed with vigorous stirring. The temperature rose 24. Tetraphosphoric acid ester of mono-propi to about 100 degrees C. and, at that temperature, onic acid ester of mucic acid, sodium salt. the reaction product was a viscous mass, light 70 25. Tetraphosphoric acid ester of monoabietic brown in color and odorless. The resulting prod acid ester of glycerol, ammonium salt. uct was water soluble and foamed copiously when 26. Tetraphosphoric acid ester of mono-benzoic Shaken in Water. The product was then neutral acid ester of glycerol, sodium salt. ized with sodium hydroxide. The resulting prod 27. Tetraphosphoric acid ester of di-oleic acid uct markedly reduced the spattering of marga 5 ester of diethylene glycol. rine when used in percentages of less than 1%. 5 2,128,946 3. Eacample III erol, previously heated to 90 degrees C., were 26.8 parts by weight of oleic alcohol, previously slowly added, with vigorous stirring, to 34.8 parts heated to approximately 90 degrees C., were add by Weight of tetraphosphoric acid, also previously ed slowly, with stirring, to 34.8 parts by weight of heated to 90 degrees C. After a few minutes the 5 tetraphosphoric acid, also previously heated to 90 temperature rose to 15 degrees C. and at this 5 degrees C. The temperature rose to 125 degrees temperature' the product was a medium brown C. and, at this temperature, the reaction product paste. As in the previous examples, stirring was was a viscous mass, medium brown in color. At continued until the product cooled down to 90 room temperatures, the product became a heavy, degrees C. O nearly solid paste. Eacample IX 0. 62 parts by weight of diolein, previously heated Eacample IV to 90 degrees C., were added slowly with stirring 27 parts by weight of stearyl alcohol, previously to 34.8 parts by weight of tetraphosphoric acid. heated to approximately 90 degrees C., were add The temperature rose after a few minutes to 126 ed slowly, with vigorous stirring, to 34.8 parts by degrees C. At 120 degrees C. the reaction prod weight of tetraphosphoric acid, also previously uct was a red-brown liquid. On cooling, it be heated to approximately 90 degrees C. The ten came Substantially thicker. perature rose during the reaction to 100 degrees C. at which point 18.2 parts by weight of pow Eacample X 20 - dered mannitol were slowly added. The mass be 37 parts by weight of diethylene glycol mono came thick and, upon stirring for several min oleate, at 90 degrees C., were slowly added, with utes, the reaction naSS became nuch thinner. stirring, to 34.8 parts by weight of tetraphos The product was then heated to 125 degrees C. phoric acid, also at a temperature of about 90 for several minutes with vigorous stirring. The degrees C. The temperature rise during the re 25 final product had many of the properties which action was 55 degrees C. The resulting product have been described hereinabove. In place of Was a chocolate-brown paste. By carrying out mannitol, other polyhydroxy substances such as the reaction at lower temperatures, lighter dextrose could be employed. colored reaction products are obtainable. 30 Eacample V Eacample XI 30 26 parts by weight of 2-ethyl hexanol-1 (beta 30.8 parts by weight of mixed coconut oil mono ethyl hexyl alcohol), previously heated to 90 de fatty acid esters of diethylene glycol, at a tem grees C., were slowly added, with vigorous stir perature of about 90 degrees C., were mixed with ring, to 34.8 parts by weight of tetraphosphoric 34.8 parts by weight of tetraphosphoric acid, the 35 acid, also previously heated to about 90 degrees ester being added to the acid as described in the 35 C. The temperature rose to approximately 125 above examples. The temperature rose to 136 degrees C. The reaction product was a liquid degrees C., at which temperature the reaction having a medium brown color. product Was a liquid of medium brown color. On cooling, it became a paste. This product was 40 Eacample VI then neutralized in one case with triethanol 40 21 parts by weight of laury alcohol, previously amine and in another case with mono- heated to 90 degrees C., were slowly added with amine. In each case, products resulted having stirring to 69.6 parts by weight of tetraphos excellent foaming properties rendering them phoric acid, also previously heated to 90 degrees especially adaptable for shampoos and deter C. The tenperature rose to 10 degrees C. The gents. reaction product was a yellow paste, soluble in Eacample XII water, and had excellent foaming properties. 20 s parts by Weight of the resulting product were dis 31 parts by weight of castor oil were slowly Solved in ether, the insoluble material filtered off, added, with stirring, to 34.8 parts by weight of and ammonia gas passed into the filtrate. The tetraphosphoric acid at 50 degrees C. The addi 50 resulting product, the ammonium salt of tetra tion of the castor oil reduced the temperature of phosphoric acid ester of lauryl alcohol, was an the mixture to about 25 degrees C. and this tem excellent foaming agent and possessed many of perature shortly rose to 70 degrees C. The mass the other desirable properties described herein Was then heated for several minutes to 125 de 5 5 above. grees C. The resulting product was a semi-vis Eacample VII cous red-brown liquid when Warm. 42 parts by weight of lauryl alcohol, previously Eacample XIII heated to 90 degrees C., were slowly added, with 7 parts by weight of amylene and 34.8 parts 60 stirring, to 69.6 parts by weight of tetra phos by weight of tetraphosphoric acid were mixed at 60 phoric acid. The temperature rose to 125 de room temperature (25 degrees C.), the amylene grees C. and the reaction product, at room ten being slowly added with stirring to the tetra peratures, was a yellow paste. 32 parts by weight phosphoric acid. The temperature rose to 65 de of triethanolamine were dissolved in 60 parts by grees C. The reaction product was a viscous, weight of water and 20 parts by weight of the red-colored liquid, very soluble in water. above prepared reaction product were added with While all of the substances of my invention fall stirring at room temperature. The final Solu into the category of interface modifiers, they tion was neutral to litmus, was clear and trans modify an interface in various ways and to vari parent, and had excellent foaming properties ous extents, depending upon the relative poten O rendering it especially adaptable for shampoos, cies of the hydrophile and lipophile groups, the 70 detergents and the like. resultant of the two representing the interfacial function of the molecule as a whole. Eacample VIII While the illustrative examples listed herein 42 parts by weight of a product consisting es above represent in some cases single substances, 5 Sentially of the mono stearic acid ester of diglyc it must be understood that the invention is by 75 4. 2,128,946 no means limited to single substances. Indeed, tetraphosphate ester, by the generai procedure in practice, it is frequently more convenient to : described in the examples listed hereinabove. prepare a mixture of the substances of my inven Eacample.-Potassium cetylate tion and to use such a mixture, For example, I may prepare mixtures of monoglycerides and di (CH3-(CH2)4-CH2-OK) glycerides of higher fatty acids by any convenient is reacted with excess ethylene glycol chlorhydrin method, as, for example, by direct esterification by the procedure described in the above example of glycerol with higher fatty acids or by re to form the glycol mono cetyl ether. This is esterification of a triglyceride oil or fat with then treated with tetraphosphoric acid to form 0 glycerol, preferably in the presence of a catalyst, a tetraphosphoric acid ester of cetyl glycol ether. O and then introduce into each member of this This may be neutralized with annonia or some mixture of monoglycerides and d-glycerides a other alkaline or potentially alkaline material to tetraphosphate radical. Moreover, in place of give salts of the cetyl glycol ether tetraphos pure mono stearin, I may use a commercial prod phate. 5 uct which contains small proportions of mono It must not be inferred that all of my con palmitin and mono-olein, or small proportions of pounds possess a polyhydroxy residue linking the the di-fatty acid esters of glycerin. tetraphosphate radical with the lipophile radi It is evident that I may prepare the ethers or cal. Although, for most purposes, I find such the esters of the polyhydroxy substances in any compounds to be most efficacious, I wish also to 20 desired or known ways and subsequently esterify include within the broader aspects of my inven one or more of the remaining hydroxy groups of tion the tetraphosphoric acid esters of the the polyhydroxy substance to introduce therein straight or branched chain alphatic alcohols, the tetraphosphoric acid radical or, alternatively, particularly the higher molecular weight sat I may first esterify the polyhydroxy Substance urated and unsaturated aliphatic alcohols prefer 25 with tetraphosphoric acid to form a tetraphOS ably containing at least six carbon atoms such as phoric acid ester and I may then esterify or are derivable from natural oils, fats and waxes etherify one or more of the remaining hydroxy such as lauryl alcohol, myristyl alcohol, oleyl, groups of the polyhydroxy substance by esterify palmity, Stearyl; branched chain octyl alcohols ing or etherifying procedures well known in the like 2-ethylhexanol-l; the alcohols derived from 30 art. wool fat such as cholesterol; alcohols such as 3. The polyhydroxy substances which are the abletol, etc. Among these compounds are tetra linking substances between the lipophile group or phosphoric acid ester of lauryl alcohol, tetra groups and the hydrophile tetraphosphate group phosphoric acid ester of oleyl alcohol (sodium may be conveniently considered as falling into salt), cholesterol tetraphosphate, etc. These two groups. The first of these groups includes compounds have been fully described herein 3 5 compounds containing less than four esterifiable above and further elaboration appears to be un hydroxy groups and is exemplified by glycerine, neceSSary. glycol and polyglycols. The second group con While my preferred compounds are tetraphOS tains those substances which have more than phoric acid derivatives of polyhydroxy substances 40 three esterifiable hydroxy groups, examples of wherein at least one hydroxy group of the poly O which are the sugars and sugar alcohols, the hydroxy substance is esterified or etherified With polyglycerols such as di- and tri-glycerol, etc. a group containing at least four carbon atoms, It will be understood that my compounds may and more desirably at least eight carbon atoms, have one or more lipophile radicals and One or still, for some-purposes, the last mentioned group 45 more hydrophile tetraphosphate radicals at may contain less than four carbon atoms as, for tached to the polyhydroxy substance. Thus, for example, in the case of the tetraphosphoric acid example, I may have the mono-tetraphosphate ester of mono-acetin (sodium Salt), number 4 of the diioleic acid ester of sucrose, or the di in the list of compounds mentioned above. tetraphosphate of the diolelic acid ester of Sucrose. Propionic acid and such lower fatty acids may Similarly, I may have the di-stearic or other fatty be employed in partially esterifying the poly 50 acid ester of di- or tri-glycerol mono- or di hydroxy substance which may then be reacted tetraphosphate. In a similar way, as described to form the tetraphosphoric acid ester. above, instead of the acyl derivatives of the poly It will be noted, from the examples listed hydroxy substances I produce the corresponding above, that the tetraphosphoric acid reacts with 5 5 alkyl derivatives. one or more hydroxy groups to form the tetra 5 5 As I have described above, my compounds may phosphoric acid ester. It is within the broader contain either ester or ether linkages. Any confines of my invention, however, and as is known methods of etherifying polyhydroxy Sub evident in the light of the examples described stances may be employed. The following ex above, to produce other types of compounds GO amples are illustrative: containing a tetraphosphoric acid group. For 60 Eacample.-Sodium octylate example, in tri-olein, the tetraphosphoric acid radical adds on to the double bond of the oleic acid portion of the molecule. Other compounds of east(NaO-HC-HC-HC the same character which react to add tetra 35 phosphoric acid at a double bond are mono-olein is treated with a 25% molal excess of glycerine di-stearate, corn oil, olive oil, cocoa, butter, lard, alpha bronhydrin. The mixture is heated under unsaturated hydrocarbons such as amylene, etc. reflux with exclusion of moisture and with stirring In castor oil, for example, double bonds and until the anticipated amount of Sodium bronide esterifiable hydroxy groups are both present. has formed. The Sodium bromide is filtered out Other compounds within the scope of my in O of the hot reaction mixture and the product, vention are tetraphOSphoric acid esters of higher namely, glycerol alpha octyl ether, is separated molecular weight hydroxycarboxylic acids. Ex from the excess mono bromhydrin by fractional amples of such acids are ricinoleic acid (pre distillation under reduced pressure. The ether viously mentioned), di-hydroxy stearic acid pre is treated with tetraphosphoric acid to form the pared by hydroxylation of oleic acid, and tri 75 2,128,946 5 hydroxy stearic acid prepared by hydroxylation Wherever the prefix "poly' is employed, it will of ricinoleic acid. be understood to mean more than one. In the neutralization of the tetraphosphate The term "residue', as used throughout the group or groups, considerable latitude and modi Specification and claims, is employed in its ordi fication may be employed. While the tetraphos narily understood chemical significance. For phate group may be left unneutralized, I find example, where one of the hydroxyl groups of 5 that, in general, the products are more Suited glycerine is esterified with a fatty acid or to the purpose for which they are intended if etherified with an alcohol and another of the they are treated with a suitable inorganic or hydroxyl groups of the glycerine is esterified with organic anti-acid agent to form the neutral or tetraphosphoric acid, that which remains of the acid salt. Examples of inorganic and Organic glycerine molecule, for example O anti-acid agents which may be used satisfactorily are bicarbonates of the alkali metals, potassium CE hydroxide, potassium carbonate, metallic sodium, & Hoh 5 sodium hydroxide, sodium oxide, sodium car 5 bonate, ammonium hydroxide, ammonda gas, and is the "residue' of the polyhydroxy substance, other anti-acid materials of the alkaline earth in this case glycerine. group, sodium stearate, calcium stearate, ali The term "higher", as used hereinabove and in phatic and aromatic amines including tertiary the appended claims, will be understood to cover 20 amines, pyridine, quinaldine, alkylolamines, such at least six carbon atoms unless otherwise spe 20 as mono-, di- and triethanolamine and mixtures cifically indicated. thereof, quaternary ammonium bases such as What I claim as new and desire to protect by tetramethyl and tetra-ethyl ammonium hydroX Letters Patent of the United States is: ide, and also other anti-acid materials in which l. A tetraphosphate of an aliphatic polyhy case hydrogen of the tetraphosphate group Or droxy Substance wherein the hydrogen of at groups is replaced by a cation such as sodium, least one hydroxy group of the aliphatic poly potassium, ammonium, calcium, magnesium, hydroxy Substance is replaced by a radical se aluminum, zinc, amines, alkylolamines, etc. It lected from the group consisting of alkyl and will be understood that by the term "cation', as acyl radicals. 30 used throughout the specification and claims, is 2. A tetraphosphate of an aliphatic polyhy 30 meant such elements as are mentioned herein droxy Substance wherein the hydrogen of at and, in general, atoms or radicals which are least one hydroxy group of the aliphatic poly regarded as bearing a positive charge. The tetra hydroxy substance is replaced by a radical se phosphoric ester may be neutralized to methyl lected from the group consisting of alkyl and orange, litmus, or phenolphthalein. acyl radicals containing at least four carbon 35 The products above described may be added atons. in suitable proportions to a treating bath con 3. A tetraphosphate of an aliphatic polyhy taining an aqueous medium, with or without an droxy substance wherein the hydrogen of at least additional substance, such as for example alkalis, one hydroxy group of the aliphatic polyhydroxy mordants, dyes, color discharging reagents, H2O2, Substance is replaced by a radical Selected from color reducing agents, oils, sulphonated oils, the group consisting of alkyl and acyl radicals, mordanting salts, and other reagents or Sub said polyhydroxy Substance being a member of stances used in treating baths, and the treating the group consisting of glycerol, glycols, poly bath so formed can be employed with Satisfaction glycerols, polyglycols, sugars, Sugar alcohols, and 45 in the arts in which interface modification is hydroxycarboxylic acids. 45 desired. For example, dyeing, bleaching, Scouring, 4. A tetraphosphate of an aliphatic polyhy leather stuffing, and otherwise treating fabrics, droxy substance wherein the hydrogen of at least fibers and other materials in a treating bath of one hydroxy group of the aliphatic polyhydroxy this character is productive of good results. Also substance is replaced by a radical Selected from 50 in the stuffing of leather, dyeing, and otherwise the group consisting of alkyl and acyl radicals 50 treating furs, and in many other arts, a treat containing at least four carbon atoms, said poly ing bath employing the materials of my inven hydroxy substance being a member of the group tion may be used. In flotation of ores it may consisting of glycerol, glycols, polyglycerols, poly be used by itself or in connection with other glycols, Sugars, Sugar alcohols, and hydroxycar 58 reagents such as oleaginous agents of vegetable boxylic acids, 55 or mineral origin, collecing agents such as fatty 5. A tetraphosphate of a polyhydroxy sub acids, depressants, etc., to modify the interface stance wherein the polyhydroxy substance has between the finely divided ore and the adueous only one hydroxy group in which the hydrogen medium. Various of the compounds of my in has been replaced by an acyl group containing 80 vention also serve to increase the stability and at least four carbon atoms. 80 modify the character of egg white foam made 6. A tetraphosphate of an aliphatic polyhydric by beating egg whites or egg albumin. alcohol wherein at least one hydroxy group of While I have described various examples for the alcohol has its hydrogen replaced by an the preparation of the materials of my invention, acyl group containing at least four carbon atoms. 85 it must be understood that the scope of the 7. A tetraphosphate of an aliphatic polyhydric 65 invented class of substances is by no means alcohol wherein at least One hydroxy group of limited by these methods. Other convenient the alcohol is esterified by a fatty acid contain methods may be used. This also applies, and ing at least four but less than eighteen carbon particularly so, to supplementary procedures of atoms. purification or isolation which lie strictly within 8. A tetraphosphate of a fatty acid monoglyc 70 the province of skill of any qualified chemist eride, the fatty acid radical containing at least whose procedures in each instance must be four carbon atons. governed by the properties of the materials con 9. A tetraphosphate of a fatty acid monoglyc cerned, and by the degree or the character of eride. s the purity desired. 10. A tetraphosphate of a fatty acid glyceride, s 6 2,128,946 the fatty acid radical of which contains at least phatic alcohol containing at least six carbon six carbon atoms. atoms. 11. A tetraphosphate of an aliphatic dihy 18. A tetraphosphate of an aliphatic alcohol droxy substance, where the hydrogen of One derived from naturai fats and oils and contain s 5 hydroxy group is replaced by an acyl radical ing at least six carbon atoms. containing at least four carbon atoms. i9. A chemical compound represented by the 12. A tetraphosphate of an aliphatic polyhy general formula droxy substance with at least four carbon atoms R-Mo-Y and with at least two esterifiable hydroxy groups, wherein R represents a radical containing a hy 10 0. wherein the hydrogen of one hydroxy group is drocarbon chain of at least eight carbon atoms, replaced by an acyl radical which contains at M is a tetraphosphoric acid group, Y is a cation, least four carbon atoms. and u) is a small whole number. 13. A tetraphosphate of a polyhydroxy sub 20. A chemical compound represented by the stance having not less than four esterifiable hy general formla, droxy groups, the hydrogen of at least one hy 5 5 droxy group being replaced by a radical Selected from the group consisting of alkyl and acyl wherein R represents the radical of an aliphatic radicals. polyhydroxy substance wherein the hydrogen of 14. A poly-tetraphosphate of a polyhydroxy at least One hydroxy group is replaced by an 20 substance, the hydrogen of at least One of Said aliphatic radical containing at least eight carbon 20 hydroxy groups being replaced by a radical se atoms, M is a tetraphosphoric acid group, Y is lected from the group consisting of alkyl and acyl a cation, and u) is a small whole number. radicals. 21. A reaction product of a tetraphosphate 15. A tetraphosphate of a polyglycerol, the hy with an alkyl or acyl derivative of a polyhy 25 drogen of at least one hydroxy group of the droxy substance, said derivative having at least polyglycerol being replaced by a radical selected One hydroxy group in its molecule. from the group consisting of alkyl and acyl 22. Tetraphosphates of mixed cocoanut oil radicals. mono-fatty acid esters of a glycol. 16. A tetraphosphate of an alcohol containing 23. The product of claim 22 wherein the glycol 80 at least six carbon atoms. is diethylene glycol. 30 17. A tetraphosphate of a straight chain all MORRIS B. KAZMAN.