US2128946A - Tetraphosphoric acid esters - Google Patents

Description

Planes Sept: 6, 1938 Pram orrica TETRAPHOSPHORIC ACID ESTERS Morris B. Katzman, Chicago, Ill.

No Drawing. Application April 9, 1927,

' Serial No. 135,931

23 Claims.

r employed in a treating bath containing textile,

Cil

leather or ores. Many of the compounds of my invention are also effective to decrease the spattering of margarine, to increase the oiliness of lubricating oils and greases, such as are derived from mineral oils, to act as emulsifying agents for cosmetic and other emulsions, to reduce vis-- cosity of chocolate and the like, to retard the rancidification of oils, fats, and vitamin preparations which are subject to deterioration by oxidation, to act as assistants in the textile and related industries and, 'in general, to function wherever interface modification is sought or desired.

The substances of my invention have many useful application in the arts where frothing, foaming, wetting, penetrating, detergent, emulsifying, and other interface modifying functions are required. They are in general possessed of at least two groups, one having a hydrophile function and the other having a lipophile function in the molecule. The hydrophile function is performed primarily by a tetra-phosphoric acid or tetraphosphate group, giving the molecule as a whole an affinity for aqueous materials.

The lipophile group is any radical having a clefinite aflinity for oils and fats and may comprise. radicals such as acyl or alkyl derived from a fatty acid or its corresponding alcohol. The hydrophile tetraphosphate group may be and preferably is linked to the lipophile group by means of a polyhydroxy substance. I have found polyhydroxy substances such as sugars, sugar alcohols, glycols, polyglycols, glycerol, polyglycerols, and hydroxycarboxylic acids to be particularly suitable. An ester linkage joins the polyhydroxy substance and the tetra-phosphate group. The linkage between the polyhydroxy substance and the lipophile group may be either an ester or ether linkage.

All of the products of my invention, as indicated, are esters of tetraphosphoric acid, which acid may be represented by the following structural formula: I

More specifically, the most preferable of the compounds of my invention may be defined as tetraphosphoric acid esters of polyhydroxy substances wherein at least one hydroxy group of the polyhydroxy substance has its hydrogen substituted by a lipophile group. The lipophile group may include any organic acid group, particularly fatty acid groups having preferably at least four carbon atoms such as the fatty acid radicals of the following acids: caproic acid, caprlc, caprylic, valeric, butyric, abietic, naphthenic, hydroxystearic, benzoic, benzoylbenzoic, naphthoic, toluic, higher molecular weight saturated and unsaturated fatty acids including palmitic acid, stearic, lauric, melissic, oleic, myristic, ricinoleic, linoleic acid or mixed fatty acids derived from animal or vegetable fats and fishcils such as lard,-oleo oil, coconut oil, corn oil, cottonseed oil, partially or completely hydrogenated vegetable oils such as cottonseed oil, corn oil, sesame oil and fatty acids of various waxes such as beeswax and carnauba wax; or the lipophile group may be an alkyl radical derived from an alcohol corresponding to any of the preceding acids, such as octanol, cetyl alcohol, stearyl alcohol, oleyl alcohol, lauryl alcohol, higher saturated and unsaturated aliphatic alcohols derived from natural fats and oils, cholesterol, sperm oil, etc.

Specific examples of polyhydroxy substances,

the residues of which may serve as linkages between the lipophile groups and the hydrophile tetraphosphate groups, besides those previously mentioned, are as follows: mucic acid, tartaric acid, saccharic acid, gluconic acid, glucuronic acid, gulonic acid, mannoic acid, trihydroxyglutaric acid, glyceric acid, and the like, as well as carboxylic oxidation products of polyglycerols which may be represented by the formulae:

7 on on o ao-onl-dn-onr-o.oni-t in-i z-oa on on on o Ho-cm-dn-cm-o-om-dn-cnro-onz-cu-ti-on n I n lie-0-tin-on,-o-ora-on-cm-o-cm-o-oa and sugars such as: xylose, gaiactose, fructose,

maltose, glucose, sorbltol, dulcitol, arabitol and other sugar alcohols such as hexahydric alcohols derived from sugars, and other substances having free hydroxy groups. The above polyglycerols and their oxidation products are produced by polymerizing glycerine, preferably by heating with about 1% of alkali at temperatures from 250 C. to 260 C. for about three hours in the presence of an inert gas. This reaction mixture will give a mixture of various polyglycerols, the size of the molecules depending upon the time of polymerization. The mixture of polyglycerols is then oxidized with mild oxidizing agents to convert at least one of the primary hydroxy groups to a carboxylic group.

Examples of substances of my invention are as follows:

1. Tetraphosphoric acid ester of mono-olein,

ammonium salt. 2. Tetraphosphoric acid ester of diethylene glycol mono-ricinoleate, triethanolamine salt.

3. Tetraphosphoric acid ester of mono-laurin,

sodium salt.

4. Tetraphosphoric acid ester of mono-acetin,

sodium salt.

5. Tetraphosphoric acid ester of di-butyrin,

sodium salt.

6. Tetraphosphoric acid ester of cetyl ether of sorbitol.

'7. Tetraphosphoric acid ester of ethylene glycol mono-stearate.

8. Tetraphosphoric acid ester of ethyl ether of ethylene glycol.

9. Tetraphosphoric acid ester of octanoic acid ester of diethylene glycol.

10. Tetraphosphoric acid ester of mixed cocoanut oil fatty acid ester of diethylene glycol, ammonium salt.

11. Tetraphosphoric acid ester of butyl ether of diethylene glycol, sodium salt.

12. Tetraphosphoric acid ester of sucrose monooleate, sodium salt.

13. Tetraphosphoric acid ester of mixed cocoanut oil fatty acid'monoor diglycerides or mixtures of monoand diglycerides, ammonium or triethanolamine salts.

14. Di-tetraphosphorlc acid ester of sucrose distearate, ammonium salt.

15. Tetraphosphoric acid ester of mono-oleic acid ester of diglycerol, sodium salt.

16. Tetraphosphoric acid ester of mono-octyl ether of glycerol, potassium salt.

17. Tetraphosphoric acid ester of di-caproin,

sodium salt.

18. Di-tetraphosphoric acid ester of monocetyl glycerol, potassium salt.

19. Tetraphosphoric acid ester of lauryl ether of diethylene glycol, sodium salt.

20. Tetraphosphoric acid ester of mono-melissic acid ester of mannltol, ammonium salt.

21. Tetraphosphorlc acid ester of di-cetyl ether of sorbitol, monoethanolamine salt.

22. Tetraphosphoric acid ester of di-stearic acid ester of triglycerol, potassium salt.

23. Tetraphosphoric acid ester of mono-butyric acid ester of tartaric acid.

24. Tetraphosphoric acid ester of mono-propionic acid ester of mucic acid, sodium salt.

25. Tetraphosphoric acid ester of monoabietic acid ester ofglycerol, ammonium salt.

26. Tetraphosphoric acid ester of mono-benzoic acid ester of glycerol, sodium salt.

27. Tetraphosphoric acid ester of di-oleic acid ester of diethylene glycol.

28. Tetraphosphoric acid ester of octyl alcohol.- 29. Tetraphosphoric acid ester of lauryl alcohol. 30. Tetraphosphoric acid ester of oieyl alcohol. 31. Tetraphosphoric acid ester of stearyl alcohol. 32. Tetraphosphoric acid esters of mixture of. alcohols derived from reduction of sperm oil. 33. Tetraphosphoric acid esters or mixture of alcohols derived from reduction of cocoanut oil.

34. Tetraphosphoric acid ester of ricinoleyl alcohol. 35. Tetraphosphoric acid ester of butyl alcohol. 36. Tetraphosphoric acid ester of cholesterol. The procedural details of the methods by means of which the materials of my invention may be made may be varied. The exact method employed should be determined primarily by considering the type of reacting constituents and the final substance to be produced. In introducing the tetraphosphate radical. for example, a material containing an esterifiable hydroxy group is reacted with tetraphosphoric acid. Either one or more tetraphosphate radicals may be intro duced, depending upon the substance desired. Furthermore, the molal ratios of the reacting constituents may be varied to produce products having varied properties. A condensing agent and/or a solvent may be added where required.

In order that those skilled in the art may even more fully understand the scope of my invention, I shall describe various specific embodiments of my invention in detail. It is to be understood, however, that the following examples are given o'nly by way of illustration and are not to be construed as limitative of the true scope of my invention which is set out in the appended claims. It is evident that proportions of reacting ingredients, temperatures of reaction, time of reaction, and the like represent factors which may be varied, all within the skill of those versed in the art in the light of my teachings herein.

Example I 50 parts by weight of monostearin were heated to degrees C. and to said monostearin was added slowly, while stirring, 50 parts by'weight of tetraphosphoric acid, previously heated to 90 degrees C. The temperature rose to about degrees C. and the mass became viscousand light brown in color. Stirring was continued for several minutes until the product cooled down to approximately 90 degrees C. When the reaction mixture begins to drop in temperature, it is an indication that at least the major portion of the reaction has proceeded to completion. The final product, which was practically odorless, very substantially reduced the spattering oi margarine and likewise reduced the surface tension of water.

Example II To 69 parts by weight of tetraphosphoric acid,-

Example III 26.8 parts by weight of oleic alcohol, previously heated to approximately degrees C., were added slowly, with stirring, to 34.8 parts by weight of tetraphosphoric acid, also previously heated to 90 degrees C. The temperature rose to 125 degrees C. and, at this temperature, the reaction product was a viscous mass, medium brown in color. At room temperatures, the product became a heavy, nearly solid paste.

Example IV 27 parts by weight of stearyl alcohol, previously heated to approximately 90 degrees C., were added slowly, with vigorous stirring, to 34.8 parts by weight of tetraphosphoric acid, also previously heated to approximately 90 degrees C. The temperature rose during the reaction to degrees C. at which point 18.2 parts by weight of pow- -dered mannitol were slowly added. The mass became thick and, upon stirring for several minutes, the reaction mass became much thinner. The product was then heated to 125 degrees C. for several minutes with vigorous stirring. The final product had many of the properties which have been described hereinabove. In place of mannitol, other polyhydroxy substances such as dextrose could be employed.

Example V 26 parts by weight of 2-ethyl hexanol-1 (betaethyl hexyl alcohol), previously heated to 90 degrees C., were slowly added, with vigorous stirring, to 34.8 parts by weight of tetraphosphoric acid, also previously heated to about 90 degrees C. The temperature rose to approximately 125 degrees C. The reaction product was a liquid having a medium brown color.

Example VI 21 parts by weight of lauryl alcohol, previously heated to 90 degrees C., were slowly added with stirring to 69.6 parts by weight of tetraphosphoric acid, also'previously heated to 90 degrees C. The temperature rose to degrees C. The reaction product was a yellow paste, soluble in water, and had excellent foaming properties. 20 parts by weight of the resulting product were dissolved in ether, the insoluble material filtered on", and ammonia gas passed into the filtrate. The resulting product, the ammonium salt of tetraphosphoric acid ester of lauryl alcohol, was an excellent foaming agent and possessed many of the other desirable properties described hereinabove.

Example VII 42 parts by weight of lauryl alcohol, previously heated to 90 degrees C., were slowly added, with stirring, to 69.6 parts by weight of tetraphosphoric acid. The temperature rose to 125 degrees C. and the reaction product, at room temperatures, was a yellow paste. 32 parts by weight of triethanolamine were dissolved in 60 parts by weight of water and 20 parts by weight of the above prepared reaction product were added with stirring at room temperature. The final solution was neutral to litmus, was clear and transparent, and had excellent foaming properties rendering it especially adaptable for shampoos, detergents and the like.

Example vm 42 parts by weight of a product consisting essentially of the mono stearic acid ester of diglyc- 62 parts by weight of dlolein, previously heated to 90 degrees C., were added slowly with stirring to 34.8 parts by weight of tetraphosphoric acid. The temperature rose after a few minutes to 126 degrees C. At degrees C. the reaction prodact was a red-brown liquid. on cooling, it became substantially thicker.

Example X 37 parts by weight of diethylene glycol monooleate, at 90 degrees C., were slowly added, with stirring, to 34.8 parts by weight of tetraphosphoric acid, also at a temperature of about 90 degrees C. The temperature rise during the reaction was 55 degrees C. The resulting product was a chocolate-brown paste. By carrying out the reaction at lower temperatures, lighter colored reaction products are obtainable.

Example XI 30.8 parts by weight of mixed coconut oil mono fatty acid esters of diethylene glycol, at a temperature of about 90 degrees C., were mixed with 34.8 parts by weight of tetraphosphoric acid, the ester being added to the acid as described in the above examples. The temperature rose to 136 degrees C., at which temperature the reaction product was a liquid of medium brown color. On cooling, it became a paste. This product was then neutralized in one case with triethanolamine and in another case with mono-ethanol amine. In each case, products resulted having excellent foaming properties rendering them especially adaptable for shampoos and detergents.

Example XII Example XIII 7 parts by weight of amylene and 34.8 parts by weight of tetraphosphoric acid were mixed-at room temperature (25 degrees C.), the amylene being slowly added with stirring to the tetraphosphoric acid. The temperature rose to 65 degrees C. The reaction product was a viscous. red-colored liquid, very soluble in water.

While all of the substances of my invention fall into the category of interface modifiers, they modify an interface in various ways and to various extents, depending upon the relative potencies of the hydrophile and lipophile groups, the resultant of the two representing the interfacial function of the molecule as a whole.

While the illustrative examples listed hereinabove represent in some cases single substances,

it must be understood that the'invention is by no means limited to single substances. Indeed.

in practice, it is frequently more convenient to prepare a mixture of the substances of my invention and to use such a mixture. For example, I may prepare mixtures of monoglycerides and diglycerides of higher fatty acids by any convenient method, as, for example, by direct esterification of glycerol with higher fatty acids or by reesteriiication of a triglyceride oil or fat with glycerol, preferably in the presence of a catalyst, and then introduce into each member of this mixture of monoglycerides and di-glycerides a tetraphosphate radical. Moreover, in place of pure mono stearln, I may use a commercial product which contains small proportions of monopalmitin and mono-olein, or small proportions of the di-fatty acid esters of glycerin.

It is evident that I may prepare the ethers or the esters of the polyhydroxy substances in any desired or known ways and subsequently esterify one or more of the remaining hydroxy groups of the polyhydroxy substance to introduce therein the tetraphosphoric acid radical or, alternatively, I may first esterify the polyhydroxy substance with tetraphosphoric acid to form a tetraphosphoric acid ester and I may then esterify or etherliy one or more of the remaining hydroxy groups of the polyhydroxy substance by esterifying or etherifying procedures well known in the art.

The polyhydroxy substances which are the linking substances between the lipophile group or groups and the hydrophile tetraphosphate group may be conveniently considered as falling into two groups. The first of these groups includes compounds containing less than four esteriflable hydroxy groups and is exemplified by glycerine, glycol and polyglycols. The second group contains those substances which have more than three esterifiable hydroxy groups, examples of which are the sugars and sugar alcohols, the polyglycerols such as diand tri-glycerol, etc. It will be understood that my compounds may have one or more lipophile radicals and one or more hydrophile tetraphosphate radicals attached to the polyhydroxy substance. Thus, for example, I may have the mono-tetraphosphate of the dioleic acid ester of sucrose, or the ditetraphosphate of the dioleic acid ester of sucrose. Similarly, I may have the di-stearic or other fatty acid ester of dior tri-glycerol monoor ditetraphosphate. In a similar way, as described above, instead of the acyl derivatives of the polyhydroxy substances I produce the corresponding alkyl derivatives.

As I have described above, my compounds may contain either ester or ether linkages. Any known methods of etherifying polyhydroxy substances may be employed. The following examples are illustrative:

Example-Sodium octyiate (CHr-CHr-CHz-CHzCEhJ tetraphosphate ester, by the general procedure described in the examples listed hereinabove.

Example.Potassium cetylate (CH3(CH2) 14CH2-OK) is reacted with excess ethylene glycol chlorhydrin by the procedure described in the above example to form the glycol mono cetyl ether. This is then treated with tetraphosphoric acid to form a tetraphosphoric acid ester of cetyl glycol ether. This may be neutralized with ammonia or some other alkaline or potentially alkaline material to give salts of the cetyl glycol ether tetraphosphate.

It must not be inferred that all or my compounds possess a polyhydroxy-residue linking the tetraphosphate radical with the lipophile radical. Although, for most purposes, I find such compounds to be most eiilcacious, I wish also to include within the broader aspects of my invention the tetraphosphoric acid esters of the straight or branched chain aliphatic alcohols, particularly the higher molecular weight saturated and unsaturated aliphatic alcohols preferably containing at least six carbon atoms such as are derivable from natural oils, fats and waxes such as lauryl alcohol, myristyl alcohol, oleyl, palmityl, stearyl; branched chain octyl alcohols like Z-ethyl hexanol-l; the alcohols derived from wool fat such as cholesterol; alcohols such as abietol, etc. Among these compounds are tetraphosphoric acid ester of lauryl alcohol, tetraphosphoric acid ester of oleyl alcohol (sodium salt), cholesterol tetraphosphate, etc. These compounds have been fully described hereinabove and further elaboration appears to be unnecessary.

While my preferred compounds are tetraphcsphoric acid derivatives of polyhydroxy substances wherein at least one hydroxy group of the polyhydroxy substance is esterified or etherifled with a group containing at least four carbon atoms, and more desirably at least eight carbon atoms, still, for some-purposes, the last mentioned group may contain less than four carbon atoms as, for example, in the case of the tetraphosphoric acid ester of mono-acetin (sodium salt), number 4 in the list of compounds mentioned above. Propionic acid and such lower fatty acids may be employed in partially esterlfying the polyhydroxy substance which may then be reacted to form the tetraphosphoric acid ester.

It will be noted, from the examples listed above, that the tetraphosphoric acid reacts with one or more hydroxy groups to form the tetraphosphoric acid ester. It is within the broader confines of my invention, however, and as is evident in the light of the examples described above, to produce other types of compounds containing a tetraphosphoric acid group. For 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 the same character which react to add tetraphosphorlc acid at a double bond are monoolein di-stearate, corn oil, olive oil, cocoa butter, lard, unsaturated hydrocarbons such as amylene, etc. In castor oil, for example, double bonds and esteriilable hydroxy groups are both present.

Other compounds within the scope of my invention are tetraphosphoric acid esters of higher molecular weight hydroxycarboxylic acids. Ex-

amples of such acids are ricinoleic acid (previously mentioned), (ii-hydroxy stearic acid prepared by hydroxylation of oleic acid, and trihydroxy stearic acid prepared by hydroxylation of ricinoleic acid.

In the neutralization of the tetraphosphate group or groups. considerable latitude and modification may be employed. While the tetraphosphate group may be left unneutralized, I find that, in general, the products are more suited to the purpose for which they are intended if they are treated with a suitable inorganic or organic anti-acid agent to form the neutral'or acid salt. Examples of inorganic and organic anti-acid agents which may be used satisfactorily are bicarbonates of the alkali metals, potassium hydroxide, potassium carbonate, metallic sodium, sodium hydroxide, sodium oxide, sodium carbonate, ammonium hydroxide, ammonia gas, and other anti-acid materials of the alkaline earth group, sodium stearate, calcium stearate, aliphatic and aromatic amines including tertiary amines, pyridine, quinaldine, alkylolamines, such as mono-, diand triethanolamine and mixtures thereof, quaternary ammonium bases such as tetramethyl and tetra-ethyl ammonium hydroxide, and also other anti-acid materials in which case hydrogen of the tetraphosphate group or groups is replaced by a cation such as sodium, potassium, ammonium, calcium, magnesium, aluminum, zinc, amines, alkylolamines, etc. It will be understood that by the term cation, as used throughout the specification and claims, is meant such elements as are mentioned herein and, in general, atoms or radicals which are regarded as bearing a positive charge. The tetraphosphoric ester may be neutralized to methyl orange, litmus, or phenolphthalein.

The products above described may be added in suitable proportions to a treating bath containing an aqueous medium, with or without an additional substance, such as for example alkalis, mordants, dyes, color discharging reagents, H202, color reducing agents, oils, sulphonated oils, mordanting salts, and other reagents or substances used in treating baths, and the treating bath so formed can be employed with satisfaction in the arts in which interface modification is desired. For example, dyeing, bleaching, scouring,

leather stufilng, and otherwise treating fabrics, fibers and other materials in a treating bath of this character is productive of good results. Also in the stuffing of leather, dyeing, and otherwise treating furs, and in many other arts, a treating bath employing the materials of my invention may be used. In flotation of ores it may be used by itself or in connection with other reagents such as oleaginous agents of vegetable or mineral origin, collecing agents such as fatty acids, depressants, etc.', to modify the interface between the finely divided ore and the aqueous medium. Various of the compounds of my invention also serve to increase the stability and modify the character of egg white foam made by beating egg whites or egg albumin.

While I have described various examples for the preparation of the materials of my invention, it must be understood that the scope of the invented class of substances is by no means limited by these methods. Other convenient methods may be used. This also applies, and particularly so, to supplementary procedures of purification or isolation which lie strictly within the province of skill of any qualified chemist whose procedures in each instance must be governed by the properties of the materials concerned, and by the degree or the character of the purity desired.

Wherever the prefix "poly is employed, it will be understood to mean more than one.

The term residue., as used throughout the specification and claims, is employed in its ordinarily understood chemical significance. For

example, where one of the hydroxy] groups of glycerine is esterified with a fatty acid or etheriiied with an alcohol and another of the hydroxyl groups of the glycerine is esterified with tetraphosphoric acid, that which remains of the glycerine molecule, for example CHr- HOH

is the "residue of the polyhydroxy substance, in this case glycerine.

' The term higher, as used hereinabove and in the appended claims, will be understood to cover at least six carbon atoms unless otherwise specifically indicated.

What I claim as new and desire to protect by Letters Patent of the United States is:

1. A tetraphosphate of an aliphatic polyhydroxy substance wherein the hydrogen of at least one hydroxy group of the aliphatic polyhydroxy substance is replaced by a radical selected from the group consisting of alkyl and acyl radicals.

2. A tetraphosphate of an aliphatic polyhydroxy substance wherein the hydrogen of at least one hydroxy group of the aliphatic polyhydroxy substance is replaced by a radical selected from the group consisting of alkyl and acyl radicals containing at least four carbon atoms.

3. A tetraphosphate of an aliphatic polyhydroxy substance wherein the hydrogen of at least one hydroxy group of the aliphatic polyhydroxy substance is replaced by a radical selected from the group consisting of alkyl and acyl radicals, said polyhydroxy substance being a member of the group consisting of glycerol, glycols, polyglycerols, polyglycols, sugars, sugar alcohols, and hydroxycarboxylic acids.

4. A tetraphosphate of an aliphatic polyhydroxy substance wherein the hydrogen of atcleast one hydroxy group of the aliphatic polyhydroxy substance is replaced by a radical selected from the group consisting of alkyl and acyl radicals containing at least four carbon atoms, said polyhydroxy substance being a member of the group consisting of glycerol, glycols, polyglycerols, polyglycols, sugars, sugar alcohols, and hydroxycarboxylic acids.

5. A tetraphosphate of a polyhydroxy substance wherein the polyhydroxy substance has only one hydroxy group in which the hydrogen has been replaced by an acyl group containing at least four carbon atoms.

6. A tetraphosphate of an aliphatic polyhydric alcohol wherein at least one hydroxy group of the alcohol has its hydrogen replaced by an acyl group containing at least four carbon atoms. '7. A tetraphosphate of an aliphatic polyhydric alcohol wherein at least one hydroxy group of the alcohol is esterified by a fatty acid contain- Cfl the fatty acid radical of which contains-at least six carbon atoms.

11. A tetraphosphate of an aliphatic dihydroxy substance, where the hydrogen 0! one hydroxy group is replaced by an acyl radical containing at least four carbon atoms.

12. A tetraphosphate of an aliphatic polyhydroxy substance with at least four carbon atoms and with at least two esterlfiable hydroxy groups, wherein the hydrogen of one hydroxy group is replaced by an acyl radical which contains at least four carbon atoms.

13. A tetraphosphate of a polyhydroxy substance having not less than four esteriflable hydroxy groups, the hydrogen of at least one hydroxy group being replaced by a radical selected from the group consisting of alkyl and acyl radicals.

14. A poly-tetraphosphate of a polyhydroxy substance, the hydrogen of at least one of said hydroxy groups being replaced by a radical selected from the group consisting of alkyl and acyl radicals.

15. A tetraphosphate of a polyglycerol, the hydrogen of at least one hydroxy group of the polyglycerol being replaced by a radical selected from the group consisting of alkyl and acyl radicals.

16. A tetraphosphate of an alcohol containing at least six carbon atoms.

17. A tetraphosphate of a straight chain aliamaeie phatio alcohol containing at least six carbon atoms.

18. A tetraphosphate of an aliphatic alcohol derived from natural fats and oils and containing at least six carbon atoms.

19. A chemical compound represented by the general formula wherein R represents a radical containing a hydrocarbon chain'of at least eight carbon atoms, M is a tetraphosphoric acid group, Y is a cation, and w is a small whole number.

20. A chemical compound represented by the general formula wherein R. represents the radical of an aliphatic polyhydroxy substance wherein the hydrogen of at least one hydroxy group is replaced by an aliphatic radical containing at least eight carbon atoms, M is a tetraphosphoric acid group, Y is a cation, and w is a small whole number.

21. A reaction product of a tetraphosphate with an alkyl or acyl derivative of a polyhydroxy substance, said derivative having at least one hydroxy group in its molecule.

22. Tetraphosphates of mixed cocoanut oil mono-fatty acid esters of a glycol.

23. The product of claim 22 wherein the glycol is diethylene glycol.

MORRIS B. KATZMAN.