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Publication numberUS2052029 A
Publication typeGrant
Publication dateAug 25, 1936
Filing dateDec 31, 1935
Priority dateDec 31, 1935
Publication numberUS 2052029 A, US 2052029A, US-A-2052029, US2052029 A, US2052029A
InventorsBenjamin R Harris
Original AssigneeBenjamin R Harris
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Phosphoric acid esters
US 2052029 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

They are in seneral 8 11 i wherein "n."

Patented Aug. :5, 193s PATENT OFFICE 2.05am mosrnoarc acm Esme B-HarrlaChicagmm.

No mam. Application December :1, ms,

' Serial No. 51.010

Claim (CL 260-9930) My invention relates to a new classof chemical substances. -It relates more in particular to a class of chemical substances having the properties of interface modifiers when employed in a treating bath containing textile, leather or ores. The object of, the invention is the provision of a new class of chemical substances.

- Anotherobiect is the provision of a class of chemical substances adapted for use as interface modifiers.

Still another object is the provision of a treating bath employing the new interface modifiers of my invention.

'The substances of my invention have many useful applications in the arts where frothing. wetting, penetrating, detergent. emulsifying, and other interface modifying functions are required. h. of at least two one having .a the other having a lipophile fimction in the molecule. The hydrophile function is performed primarily by a phosphate group; that is, a group containing phosphorus in the form of a phosphorus oxide acid radical. giving the molecule as a whole an affinity for aqueous materials. The lipophile group is any radical such as acyl or alkyl derived from 'a fatty acid or its corresponding alcohol and has a definite, afflnity for oils and fats. The hydrophile phosphate group is linked to the lipophile group by means of a polyhydroxy substance of a class consisting of sugars,

sugar alcohols, glycols, glycerols, polyglycerols, polyhydroxycarboxylic acids, and p lyslycols. In general. an ester linkage joins the polyhydroxy substance and the phosphate group. The link.

age between the polyhydrox'y substance and th llpcphile group may be either an ester or ether linkage.

hydrophile function and Preferably, for use in foods, the compounds are devoid of groupings wherein nitrogen is linked directly to carbon belonging to radicalsinesterifled form, as, for example, in choline groups, but by this expression I do not mean to exclude oompounds with inorganic ammonium nitrogen and compounds of nitrogen linked to carbon belonging to cationic, i. e.. salt-forming radicals which are not in esterifled form. Whenever the term non-nitrogenous" is hereinafter employed, it will be understood to have this significance.

The lipoplnle group may include any fatty acid group'havlng at least four carbon atoms such as the fatty acid radicals of the following acids: caproic acid, capric, capryllic, valeric, butyric, abietic, hydroxystearic, benzoic, benzoylbenzoic, naphthoic, tolulc, palmitic acid, stearic, lauric, melissic, oleic. myristlc, ricinoleic, linoleic acid or mixed fatty acids derived from animal or vegetable fats and flsh oils such as lard, 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, oetyl alcohol, lauryl alcohol. etc.

Specific examples of polyhydroxy substances, the residues of which may serve as linkages between the iipophile groups and the hydrophile phosphate groups are as follows: music acid, tartaric acid, saccharic acid, gluconic acid, glucuronic acid, gulonic acid. mannonic acid, trihydroxyglutaric acid, glyceric acid, and the like, as well as carboxylic oxidation products of polyglycerols which may be represented by the formulae:

on on o no-cm-cn-cm-o-cnr-cn-g-on More specifically, the compounds of my invention may be defined as phosphoric acid esters of polyhydroxy substances wherein at least one hymay group of the p lyhydroxy substance has its hydrogen substituted by a lipophile group.

0 HO-CHr-CH-CHr-OH HO-OHr-CH-lL-OH 0 on on o no-ti-tn-cnro-om-tn -on n 0 on o on o nocn-cra-o-om-dn-cnr-o-onr-on- -on c on on o HO-E-(EH-CHa-O-CHr-K-CHrO-CEra-OH and sugars such as:

mlose, galactose, fructose, oo

maltose. sorbitol, glucose. dulcitol, arabitol glycerols and their oxidation be represented as follows:

and other sugar alcohols such as hexahydric aloohols derived from sugars, and other substances having free hydroxy groups. The above polyproducts 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 poiyglycerols, the size .of the molecules depending upon the time of polymerization. The mixtures of polyglycerols are then oxidized with mild oxidizing agents to convert at least one oi the primary hydroxy groups to a carboxylic group.

Examples ofsubstances of my invention may (1) H- OH Monolaurinphosphato (Disodlumsslt) m PONa om O HaC-O--Cufisa H -OCHQ- H-OHa-O-P-ONIEQ 0NH (3) Cetyl sorbitol phosphate mm-o-om-om-o o Gui1--0-CHs-GHi0 OK 0 O I (5) CisHuaO-OH:CHr-OCHQCHQOPONB 0Na 0 (6) HaO-O-A-Cfliu Dica roin phos hate n- -0I'- 0Na (1580mm 5 v ONs H9 g-O-O-CLHII r (7) C4Hr-O-CHz-CHr-O-CHr-CHr-O-P -O & Diolein phosphate spasms Bteario acid ester oi dicthyleno glycol dlsodium orthopboophato r r (m CmHsa-O-CHs-CErU-GHr-GHr-O-PiONa Okla (15) Borbitol uteamto moarophospllate (ammonium mit) (16) Borbitol melimate monophosphate (sodium wit):

(l8) CHa-O-CuHu H-O-C10Hu HOB HOE O Hr-O-P--ONs ONE Dieatl other oi oorbitol hos hate y (disodium salt) p p 0 1e) omr-o-l-cnn n-o n om 303 Disleorio add ester oisorbitoldi-phoel HOE j photo (dlsodium salt) i-0-lPitGNs cm.

0 Hr- D\Zri8u [21) Dioleicacidestorofsuuoln H (lodiuinsalt) o-cnr-"ono-cn.-o-cnr-cnon-cnr-o Dims acid oi at: l i imgnonovmhais (di-am o= -C|1Hu o n, ,0

. Disteaflolsidostct oi triglycuol dipbosphats (dlsodium OKs mo om There are several methods by means of which the materials of my invention may be made. The method employed should be determined primarily by considering the type of substance to be produced. In introducing the phosphate radical. for example. a material containing an esteriiiable hydroxy group is reacted with phosphorus pentoxide, phosphoric acids, phosphorus halides; ethyl metaphosphate, phosphorus oxychloride or some other reagent capable of furnishing the elements of phosphoric acid. Either one or more phosphate radicals may be introduced, depending upon the substance desired. A condensing asent and/or a solvent may be added where required.

As a specific example, '1 parts of monostearyl glycerol (monostearlne) are dissolved in parts of dry pyridine. To this solution are added, with simultaneous cooling, 12 parts of phosphorus oxychloride dissolved in parts of dry acetone, the mixture being stirred meanwhile. This mixture is allowed to stand over night and it is then throwninto 300 parts of water with stirring. A precipitate forms at first. but after a" few moments this becomes completely dispersed. ,On warming to about C.. the solution becomes highly colored. 15% of salt is now added to throw the product out in the form of a precipitate. This precipitate contains approximately 73% of moisture after the greater proportion of salt solution has been separated therefrom. The product may be; used in this form or it may be further washed or otherwise purified. It may be dried or not. as desired. The product so formed is primarily a double glycerine ester in which one hydroxy group is esteriled with a stearic acid radical and another hydroxy group is esteriied with phosphoric acid. .The monolauric ester glycerine phosphate may be prepared in a lar manner, but using substantially pure lauc acid, or the fatty acids of coconut oil 00H.

taining about 40% lauric acid in preparing the monoglycerides which are to'be subsequently reacted with phosphorus oxychlorlde. The resultant product is neutralized with sodium bicar- 5 monobutyl ether of diethylene bonate to ure for the preparation of phosphoric esters is a convenient method for making certain materials of my invention which are represented by Nos. 3, 4, 6, 7, 11 and 13 in the list of examples shown herelnabove, as well as others. bearing in mind that particularly where secondary phosphates are concerned (such asNos. 4, 11, 13 in the list of produce the sodium salt. This proced-.

with 58 parts of phosphorus pentoxide. This is accomplished best by adding the phosphorus pentomde gradually and in small portions to the monobutyl ether of diethylene glycol with stirring, cooling somewhat if necessary to avoid excessive heating. This mixture is allowed to remain at room temperature for about half an hour. The mixture is then taken up with about 800 parts of cold water and 20 parts of barium chloride stirred in, the latter being in the form bin 10% aqueous solution. 125 parts of salt are now dissolved in this mixture. The entire mixture is allowed to remain at rest until the product floats to the surface. whereupon the brine is withdrawn and discarded. The product may be used in this form or it may be filtered or concentrated further or otherwise treated, as desired. The finished product, the principal portion of which may be represented by No. '1 in the list of examples shown hereinabove, is easily dispersible in water and exhibits many useful colloidal. properties and particularly as an interface modifier.

W hile all of the substances of my invention fall lnto'the category of interface modifiers. they modify the 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 interiaciai function of. the molecule as awhole.

For example: the barium salt of the butyl ether of diethyleneglycol phosphate (No. 'l of the 111% trative examples given above) and dlolein phow phate (No. 9 of the list of illustrative examples given above) serve well to show how the properties of my interface modifiers may vary. No. 'I is predominantly hydrophillic, practically freely soluble in water: whereas, No. 9 is predominantly lipophillic, imbibes cold water but cannot be said to disperse therein. The latter does, however, dis-.

perse in hot water, particularly readily in the presence of a very low concentration of electrolyte such as sodium chloride. It is well to note-that the hydrophile group in both cases is essentially the same, but the lipophile group in the cascof No. 9 contains approximately five times as many carbons, if not more, than the lipophile group in No. I. No. 9 is predominantly lipophillic: No. I is predominantly hydrophillic, though each possesses both hydrophile and lipophile properties.

No. 9 when touched with moist flnsers appears greasy; whereas No. '1, as stated above, is practically water soluble. No. 9 promotes water in oil emulsions; No. '1 promotes oil in water emulsions. Between such two relatively extreme examples may be inserted a series of-other examples in the order of diminishing hydrophile characteristics starting with No. 7 upward and, per contra, with increasing lipophile characteristics working up to No. 9 and beyond. Between two vicinai members of such a series, the difierences may be only very slight, becoming more appreciable the further removed any two selected members of the series are from each other. I

While the illustrative examples listed hereinabove represent principally 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 mixtureoi the substances of my invention and to use such a mixture. For example, I may prepare a mixture of dlglycerides by any convenient method, such as described hereinbelow and then introduce into each member of this mixture of diglycerides a phosphate radical by a convenient method.

E:eumple.--Preparai;ion of mixture of diglyceride phosphates from corn oil.

Heat a mixture of 880 parts of corn oil and 50 parts oi glycerol in an inert atmosphere with stirring to 220 C. Add 0.88 part of flake caustic soda. Raise the temperature to 250 0., continue stirring and heat at 250 C. or thereabout for two hours. Cool to room temperature in an inert at mosphere. This product is essentially a mixture of diglycerldes.

To 200 parts of the above product dissolved in 600 parts oi isopropyl ether (free of alcohol and water) add 50 parts of phosphorus pentoxide and heat under reflux with stirring for three hours to 60 Q, taking care to keep the reaction mixture out of contact with atmospheric moisture.

Now free this reaction production of ether, preferably by distillation.

The residue is a somewhat sirupy. oily material which may be used as such, or it y be neutrald with gaseous. ammonia or aqueous ammonia or other alkaline agents. Also, the product may m washed by salting it out with brine several times, purified, or otherwise treated if desired. it consists in the main of a mixture of diglyceride phosphates, the significant, predominant constituent oi whichis represented by No. 9 in the list of examples hereinabove.

In place oi corn oil in the above, I can use cottond oil, peanut oil, sesame oil, sunflower oil, nts ioot oil, coc )nut oils, hydrogenated oils, lard, tallow, etc., cod oil and other common triglycerides.

Ii, on the other hand, it is desired to prepare a single substantially pure substance analogous the above, it is only necessary .to treat dioleln with phosphorus pentoxide as described above.

procedure, Ior introducing phosphate radicais, described directly above, I have also successfully used in the preparation oi materials represented by Nos. 1, 2, 5, 6, 8, 10,12, 14, 15 and 16 in the list of examples shown hereinabove, as well others. It is, of course, obviously within the sl of any qualified chemist. to compute molal or multiples .of moial proportions of the reactants.

with respect to each other.

it is evident that I may prepare the others or ers of the polyhydroxy substances in any ed or known ways and subsequently'esteriiy one or more of the remaining hydroxy groups of the poiyhydroxy substance to introducet phosphoric acid radical or, alternatively, I ay esteriiy the polyhydroxy substance with a phosphorus containing derivative to form a pphoric acid esterand I may then ester-try or etherify one or more of the remaining hydro groups of the polyhydroxy substance by esteriiying or ether-trying procedures well mom: in the be conveniently considered as falling into two groups. The first of these groups includes compounds containing less than four esteriiiable hy-. dro n groups and is exemplified by glycerlne, fglycol and polyglycols. The second group contains those substances which have more than three esteriilable 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 phosphate radicals attached to the polyhydroxy substance. Thus for example, I may have the mono-phosphate oi the di-oleic acid ester of sucrose, or the (ii-phosphate of the dioleic acid ester of sucrose. Similarly, I may have the di-stearic or other fatty acid ester of dior tri-glyceroi monoor di-phosphate. In a similar way. as described above, instead of the acyl derivatives oi 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 octylate CHa-CHr-CHr-ONh.)

is treated with a 25% mol'al excess of glycerine alpha bromhydrin. The mixture is heated under reflux with exclusion of moisture and with stirring until the anticipated amount of sodium bromide has formed. The sodium bromide is filtered out of the hot reaction mixture and the product,

(@(CHz) hreacted with excess ethylene glycol chlorhydrin by the procedure described in the above'example to form the glycol mono octyl ether. This is then treated with Pro: to form a phosphoric acid ester of cetyl glycol ether. This may be neutralized with onia or some other alkaline or potentially alkaline material to give salts of the cetyl glycol ether phosphate.

In the neutralization of the phosphate. group or groups, considerable latitude and modification may be employed. While the phosphate group may be left unneutraliaed, I find that, in general, 1 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. Mamples of inorganic and organic anti-acid agents which may beused satisfactorily are bi-' g potassium,

or groups is replaced by a cation such as sodium, ammonium, calcium, magnesium, aluminum, zinc, amines, alklylolamines, 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 hearing a positive charge.

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, more dantingsalts, fabrics and other reagents or substances used in treating baths, and the treating bath so formed can be employed-with satisfaction in all of the arts in which interface modification is desired. For example, dyeing, bleaching, scouring, leather stufling, and otherwise treating tabrics, fibers and other materials in a treating bath of this character is productive of good results. Also in the stufling of leather, dyeing, and otherwise treating furs, and in many other arts, 9.

treating bath employing the materials of my invention may be used. In flotation of ores it may be used in connection with other reagents to modify the interface between the finely divided ore and the aqueous medium.

While I have described several methods 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 oi 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 originally understood chemical significance. For example, where one of the hydroxyl groups of glycerine is esterified with a fatty acid or etherified with an alcohol and another of the hydroxyl so oups of the glycerine is esterified with a phosphoric acid, that which remains of the glycerine molecule, for example is the residue" or the polyhydroxy substance, in this case glycerine.

This application is a continuation-in-part of my application, Serial No. 705,825, filed January 8, 1934.

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

1. A phosphoric acid ester of a polyhydroxy substance having not less than four esterifiable hydroxy groups but not including hexahydric alcohols, the hydrogen of at least one of said hydroxy groups being replaced by a lipophile radi cal having at least four carbon atoms.

2. The product of claim 1 wherein said ester is at least partially neutralized.

3. 'The product of claim 1 wherein the lipophile radical is an acyl radical.

4. A- polyphosphoric acid ester of a polyhydroxy substance having not less than four esterifiable hydroxy groups, the hydrogen of at least one of said hydroxy groups being replaced by a lipophile radical having at least four carbon atoms.

5. The product of claim 4 wherein said ester is at least partially neutralized.

6. The product of claim 4 wherein the lipophile radical is an acyl radical.

7. The product of claim 4 wherein the polyhydroxy substance is a sugar.

8. A phosphoric acid ester of a polyglycerol, the hydrogen of at least one hydroxy group of the polyglycerol being replaced by a lipophile radical having at least four carbon atoms.

9. The product of claim 8 wherein the lipophile radical is an acyl radical.

10. An ester of phosphoric acid with lipophile and hydrophile groups, said ester being represented by the formula wherein R, the lipophile portion of the molecule, has at least tour carbon atoms, X is the residue of a polyhydroxy substance having not less than four esterifiable hydroxy groups but not including hexahydric alcohols, Y and Z represent cations, and w is an integer.


Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2430569 *Dec 8, 1943Nov 11, 1947Eastman Kodak CoMethod of the production of neutral esters of phosphoric acid
US2603632 *Apr 6, 1949Jul 15, 1952American Cyanamid CoMethod of preparation of phosphoric acid esters of riboflavin
US2604470 *Jul 15, 1950Jul 22, 1952Hoffmannla Roche IncPhosphorylation of dihydroriboflavin
US2815342 *Mar 4, 1955Dec 3, 1957Canadian Patents DevSynthesis of pyrimidine nucleoside phosphates
US2948717 *Jan 14, 1959Aug 9, 1960Drew & Co Inc E FSugar ester preparation and purification
US2954372 *Nov 16, 1956Sep 27, 1960Novak Leo JHigher fatty acid esters of dextran
US2961378 *Feb 3, 1959Nov 22, 1960Robert G BenedictMethod of producing phosphomannan by saccharide fermentation
US3002966 *Dec 18, 1959Oct 3, 1961Slodki Morey EMethod of producing mannose-6-phosphate
US3002967 *Dec 18, 1959Oct 3, 1961Morey E SlodkiProcess for preparing phosphoric acid monoesters of mannose polymers
US3084105 *May 24, 1961Apr 2, 1963Morey E SlodkiDispersants comprising phosphoric acid monoesters of mannose polymers
US3103507 *Feb 23, 1960Sep 10, 1963 Chjoh
US3309352 *Mar 31, 1964Mar 14, 1967Swift & CoAlkylolamine phosphated alkylolamides prepared by heating a mixture of fat, protein, an alkylolamine and phosphoric acid
US3350389 *Dec 30, 1964Oct 31, 1967Wyandotte Chemicals CorpProcess for the preparation of phosphorus-containing sucrose polyols
US4624919 *Apr 10, 1984Nov 25, 1986Meito Sangyo Kabushiki KaishaEnzymatic production of phospholipid-saccharide derivatives
US5164232 *Feb 11, 1991Nov 17, 1992Xerox CorporationInk compositions
US5679459 *Jun 6, 1995Oct 21, 1997Alliance Pharmaceutical Corp.Perfluorinated amphiphilic phosphorous compounds: liposomal compositions
US5846516 *Jun 3, 1992Dec 8, 1998Alliance Pharmaceutial Corp.Perfluoroalkylated amphiphilic phosphorus compounds: preparation and biomedical applications
EP0288255A2 *Apr 20, 1988Oct 26, 1988Kabushiki Kaisha Yakult HonshaMethod of producing phospholipid derivatives
U.S. Classification536/117, 558/160, 558/180, 516/DIG.600, 516/DIG.100, 558/179, 516/57, 558/186, 554/78, 510/469, 987/233, 554/79
International ClassificationC07F9/10
Cooperative ClassificationY10S516/01, C07F9/10, Y10S516/06
European ClassificationC07F9/10