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Publication numberUS2026785 A
Publication typeGrant
Publication dateJan 7, 1936
Filing dateJan 8, 1934
Priority dateJan 8, 1934
Publication numberUS 2026785 A, US 2026785A, US-A-2026785, US2026785 A, US2026785A
InventorsBenjamin R Harris
Original AssigneeBenjamin R Harris
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Phosphoric acid esters of fatty acid monoglycerides
US 2026785 A
Abstract  available in
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Description  (OCR text may contain errors)

Patented Jan. 7, 1936 rnosrnoitio ACID as'rniis or mm' v AomMoNoGLrcEnmEs v I Benjamin}. Harris, Chicago, Ill. I

" No Drawing. Application January 8, 1934,

' Serial N0.V'705,825 t as (c1. ate-99.20)

ing bath containing textile, leather or ores. benzoylbenzoic.'nap th ic, to ui rpa mi ic. ci

The object of the invention is'the provision of stearic, lauric, melissic, oleic, myristic, ricinoleic, V a new class of chemicalsubstances, linoleic acid or mixed fatty acids derived from Another object is the provision of a class of animal or vegetable fats and'fish oilssuch'as lard, a chemical substances adapted foriuse as interface coconut oil, corn oil, cottonseed on,- partially or flu modifiers.- I r x "completely hydrogenated vegetable oils such as 1o Still another object is the provision ofi'a treatcottonseed oil, corn oil, sesame oil andfattyacids A ing bath employing thelnew'interface modifiers 'of various "waxes suchas beeswax and'carnauba of my invention. i wax; or the lipophfle group maybeanalkyl radi The substances of my invention have many cal'derived'from analcohol'corresponding to any 13 useful applications in the arts where frothing, of the preceding acids such as cetyl alcohol, -15 wetting, penetrating, detergent, emulsifying, and lauryl alcohol, etc. 1' V v i p other interface modifying functions are required. specific examples of poyhydrcxy substances. They are in general possessed of at least two the residues of which may serve as linkages begroups, one having a hydrophile function and the tween the lipophile groups and the hydrophile other havingalipophile function in the molecule. phosphate groups are as follows: :niucic acid, The hy rop e function" is performed primar ly tartaric acid; saccharic acid; gluconic acid, by a phosphate group; 'that'is,'a group'contaim glucuronic' acid, gulonic acid, mannonic acid, ing phosphorus in the form of a phosphorus oxide trihydroxyglutaric acid, glyceric ,acid, and the V a i N acid radical, giving the molecule as a whole an like,as well as carboxylic oxidation products of 1" afiinity for aqueous materials. The lipophile Ypolyglycerols which by he represented by the group is any radical such as acyl oralkyl-derived formulae: I I from a fatty acid or itscorresponding alcohol and 0H has a definite aflinity for oils and fats. hy- I r (\J v a i drophile phosphate group is linked-to the lipo- 304m" 3- f I phile group by means of a polyhydroxy substance I OH H i 1 of a class consisting of sugars, sugar alcohols, p g gc bg g glycols, glycerols, polyglycerols, polyilitydroxycar 1 1 o 7 bcxylic acids, and polyglycols. Inge eral, anfesi X I i ter linkage joins the polyhydroxy substance and "T V flr l g fi the phosphate group.' The linkage" between the I polyhydroxysubsta'nce and the lipophile group E in, may be either an ester or'etherlinkage.= f j a Many of thecompoun'ds of my invention may V v be represented-by the formula I -QH Hi 4o 0 v "'0 011%." 0110' Y H t t -("3OH RO-.XOP OY.\ z no-cn-crn-o H V OH O 0 on H" i p- 7. gl 5 5i; HO- -CH-CHs-O-CH:- H-CHr-G-Cflr- H OH H wherein R is a lipophilegroup, X is the resi- 0 OH 1 (If due of a polyhydroxy substance, FY, and Z are It l I cations, and w is a small whole number. Ho'cflHCHPO CHhCHfCHfiOTGHP50E' More specifically, the compounds of myinvenand sugars such as: xylose, galactose, fr os tion may be defined as non-nitrogenous esters ofmaltose, sorbitol, glucose,-dulcitol, farabitol and, i

My invention relates to a new class of chemiof interface modifiers when employed in a treata phosphoric acid and a polyhydroxy'substance wherein atleast one hydroxy group of the polyhydroxy substance has its hydrogen substituted by a lipophile group I employthe term non nitrogenous to indicate that my substances are devoid of nitrogen linked directly to carbon,

; '1'helip phile groupmay'include any fatty acid group such as the fatty acid radicals of theifoilowingacidsi caproic acid, capric, capryllic,va-

leric, butyric, abietic, hydroxystearic, jbenzoic;

other sugar alcohols such as hexahydric alcoihols derived from sugars, and other substances having free hydroxy groups. Theabove polyglycerolsand their, oxidation products are produced by polymerizing glycerine, preferably by, heating with about 1% of alkali at temperatures from 250 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 uponthe time of polymerization. glycerols are then oxidized with mild oxidizing agents to convert at least one of the primary hydroxyg'roups to a carboxylic group.

Examples of substances of) my inventionj fli be represented as follows:

The mixtures of poly- Monolaurin ester of )glycel'inel phos- 1; N8 (15)- Sorbitol stearate monophosphate (ammonium salt) I There are several methods by means of which the materials of my inventiongmay be made. The .method employed should be determined primarily 'by consideringthe type of substance to be produced. ,In introducing the phosphate radical, for example, a material containing-anesteriiiable hydroxygroup .isjreacted with phosphorus pentoxide; phosphoric acids; phosphorus halides,

- ethyl metaphosphate. phosphorus oxychloride or 7 some other reagent capable of furnishing the elements of phosphoric acid. Either one 01"}1'101'8 phosphateradicals may be introduced, depending upon thesubstancedesired. A condensing agent and/ora solvent may .beadded where required.

As a specific example 7 parts of monostearyl glycerol (monostearine) are dissolved in parts of dry pyridine. To this solution are added, with simultaneous cooling, 12parts' of phosphorus oxychloride dissolved in partsof dry acetone, the" mixture being stirred meanwhile. This mixture is allowed to stand over night and it is then thrown into 300 parts of water with. stirring. A precipitate iorms at -first,- but after a few moments this b ecomes completelydispersed. .On warming toflabout 0.. the solution .becomes highly colored. 15% of salt is now added to throw the product outjin the form of a precipitate. This precipitate contains approximately 73% of :moistu'reafter 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 esterified with a stearic acid radical and another hydroxy group is esterified .with phosphoric acid. The monolauric ester glycerine phosphate may be preparedin a similar manner, but using substantially pure lauric acid, or'the fatty acids of coconut oil containing about 40% lauric. acid in preparing the monoglycerides which are to be subsequently reacted with phosphorus oxy'chloride. The resultant product is'neutralized with sodium bicarbonate to producethe sodium salt. This procedure for the preparation of phosphoric esters is a convenchloride stirred in, the latter being in the form ient method for making certain materialsof my invention which are represented by Nos. 3, 4, 6, 7, 11 and 13 in the list of examples shown hereinabove, as well as others, bearing in mind that particularly where secondary phosphates are concerned (such as Nos. 4, 11, 13 in the list of examples shown hereinabove) the phosphorus oxychloride must be added gradually to the reactant with the hydroxy group, so that the latter'is always present in excess throughoutthe courseof the reaction.

According to another 7 example, 66 .parts of monobutylether of diethylene glycol are mixed with 58 parts of phosphorus pentoxide. 'I'hisis accomplished best by adding the phosphorus pentoxide gradually and in'small portions to the monobutyl ether of diethylene glycol with stirring, cooling somewhat if necessary to avoid ex cessive 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 of a 10% aqueous solution. 125 parts of salt are now dissolved in this mixture. The entire mix-' ture is allowed to remain at rest until the product floats to the surface, whereupon the brine is with drawn 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. 7 in the list of examples shown hereinabove, is easily dispersible in water and exhibits many useful colloidal properties and particularly as an interface modifier.

While all of the substances of my invention fall into the category pf 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 interfacial function of the molecule as a whole. I

For example: the barium salt of the butyl ether of diethyleneglycol phosphate (No. 7 of .the il- I ily 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 case of No. 9 contains approximately five times as many carbons, if not more, than the lipophile group in No. 7. No. 9 is predominantly lipo philic; No. 7 is predominantly hydrophilic, though each possesses both hydrophile and lipophile properties, No. 9 when touched with moist fingers appears greasy; whereas No. '7, as stated above, is practically water soluble. No. 9 promotes water in oil emulsions; No. 7 promotes oil in water emulsions. Between such two rela-' tively extreme examples may be inserted a series of other examples in the order of diminish-'- ing hydrophilecharacteristics starting'with No. 7 upward and, per contra, with increasing lipophile characteristics working up to No. 9 and.

beyond. Between two vicinal members of such a series, the differences may be only very slight. becoming more appreciable the further removed any two selected members of the series arev from each other.

While the illustrative examples listed herein above represent principally single substances, it

mustbe'understood'that the invention is by no means limited to single substances. Indeed, in.

practice, it is frequentlyv more convenient to pre- .pare a mixture of the substances of my invention and use such a mixture; For example, Imay prepare a mixture of diglycerides by any convenient method, such as 'describedhereinbelow and then introduce into each'me'mber of thismixture of diglycerides a phosphate ient method. I v Example:-Preparationlof mixture of diglyc-' radical by a conveneride P osphates from corn on;

Heat a mixture of 880 partsof corn oil and 50 parts of glycerol in an inertatmosphere' with stirring to 22 C. Add 0.88 part of flake caustic soda. Raisethe temperature to 250 C., continue stirring and heat at 250 C. or thereabout for two hours. Cool to room 'temperaturefinan inert atmosphere. This product is essentially a mixt'ureof diglyceridesf l v To 200" parts of the aboveproduct dissolved in 600 parts of'isop'ropyl ether (free of alcohol and water) add .50 parts of phosphorus pentoxide and. heat 'under reflux with stirring for three diglyceride' phosphates, the significant, predominant constituent of which is represented byNo.

9 in the list of examples hereinabove. v

In place of corn oil in the above, I can use cotton seed oil, peanut oil, sesame oil, sunflower oil, neats-foot oil, coconut oils, hydrogenated} oils, lard, tallow, etc., cod oiland other common triglycerides. I

If, on the other hand, it is' desired to prepare a single-substantially pure substance analogous to the above, it is only-necessary tov treat diolein withv phosphorus pentoxide as described above.

This procedure, for introducing phosphate rad-v icals, described directly above, I have also suc-. cessfully used in thepreparation of materials represented by Nos. 1, 2, 5, 6, 8, 10, 12, 14, 15,

and 16 in the list of examples shown hereinabove, aswell as others. It is, of course, obviously within'the'skill of any qualified chemist to compute molal or multiples of molal proportions of the reactants with respect to each other.

The products abovexdescribed may be added in suitable proportions tofa treating bath-containing an aqueous medium, with or without an additional substance, such as for example al-" kalis, mordants, dyes, color discharging reagents, H202, color reducing agents; oils, sulphonated oils, mordanting salts, 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 smiling, and

otherwisetreating fabrics, fibers and other materials in a treating bath of this character is productive of. good results. Alsoin the stufling of leather, dyeing, and otherwise treating furs.

and in many other arts, a.,treating bath em' ployi ng the-materials, my inventionmay be used. In. flotation oi ores it may be used in connection with other reagents to modifythe interfacelbetwe'en the finely divided ore andthe aqueousrmediumr V 7 While I have described several methods forthe preparation of the materials of my invention,

it must ,.beunderstood that the scopevof the invented class of substances is by no means lim-v ited by these methods. Other convenient methods maybe used. This also applies, and par? .ticularly so, to supplementary procedures of purification or isolation which lie strictly within the province of. skill ofa'nyqualifledchemist-whose sired.

procedures ineach instance must be governed by 't heproper'ties of the materials concerned, and

by the degree or the character of the purity de- The .term fresid'ue",

dinarily understood chemical significance. For example, where one of the, hydroxyl groupsof glycerine is esterified with a fatty acidor etherified with an alcohol and another of the 'hydroxyl groups of the glycerine is esterified with a phosphoric acid, that which'remains .of the glycerine molecule, for example,

(EH2- onon is the fresidue of the=polyhydroxy substance, in

this case glycerine. j 7 e What I claim as new and desire to protect by LettersPatent of the United States is:

13A non-nitrogenous hydrophillic ester of phosphoricacid with lipophile, and hydrophile' groups, saidiest'er, ,beingzrepresented by the, forwherein R, the lipophile portionfot'thejmolecule, is an acyl radical and has at least'four carbon atoms, X isa glycol residue, Y and Z represent cations, and 10" is an integer.

2.-A hydrophillic ester of phosphoric acid with lipophile and hydrophile-groups, said ester being represented by the formula 2T0 i a-o-x-o-r o- Z 7 Q H wherein *R" is a higherlfatty acid radical, '5.x'" is a glycerol ,f'adical, fY and Z represent cations, and "w is an integer, and the remain:

ing OHoI the glycerine is free and ,unesterified. .3. Anon-nitrogenousphosphoric acid ester of a polyhydroxy substance wherein the polyhydroxy substance has only one hydroxy group in which the hydrogen has been replaced by an acyl' group with at least four but less than eighteen carbon atoms. r.

4 A non-nitrogenous phosphoric acid ester of a polyhydric alcohol wherein only onehydroxy group of the alcohol has its hydrogen replaced by an acyl group with at least four but lessthan eighteen carbon atoms.

5. A non-nitrogenous phosphoric acid ester of a polyhydric alcohol wherein only one hydroxy aslusecl throughout the: specification and claims, is employed inuits orgroup of the alcohol is esterified by a fatty acid, with at least fourbut less than eighteen carbon atoms.

6; A non-nitrogenousphosphoric acid. ester of a'hexahydric alcohol derivedfrom sugar wherein the hexahydric alcohol derived from sugar has at least one hydroiiy group in which the hydrogen is replaced by a lipophile group. I

- A non-nitrogenous phosphoric acid ester of sorbitol'wherein thesorbitol has at least one hyby a lipophile group.

g 8, A phosphoric-acid ester oi'fa fatty acid .monoglyceride, the fattyfacid radicalihavingiat least fourc'arbon atoms.

9. A non-nitrogenous hydrophillic ester of phosphoric a'cid with lipophile and hydrophile groups, said ester being represented by the formula V wherein It, the lipophile portion of themole cule, is an acyl radical'and has at least four carbon atoms, X is the residue of an aliphatic polyhydroxy substance with at least two esterifiable hydroxy groups, Y-and Z represent cations, and-"112 is an integer.

-10. A non-nitrogenous hydrophillic ester of phosphoric acid with lipophile and hydrophile groups, said ester being represented by the formula f V R-ox o-P o- Z OY w wherein "R", the lipophile portion of the molecule, isan acyl radical and has at least four droxy group in which the hydrogen is replaced carbonatoms, X is theresidue of apolyhydricalcohol, fY? and Z representcations, and w" is an integer. Y i r 5 i 11. A non-nitrogenous hydrophillic ester' of phosphoric acid with lipophile and hydrophile wherein R", the lipophile portion of the molecule,rhas at least four carbon atoms, X is a glycerol residue, Y and Z represent cations,

wherein R, the lipophileportion of the molecule, has at-least'four carbon atoms but not more than'eighteen, X is a glycerol residue, Y and Z represent cations, and w is an integer.

v 13. Anon-nitrogenous phosphoric acid ester of ja glycerol wherein the glycerol has one hydroxy group in .which the hydrogen is replaced by a lipophile radical, another hydroxy group where in the hydrogen is replaced by a hydrophile phosphate radical, and wherein the remaining hygroups, said ester being represented bythe i hydrogen of by a lipophile acyl group with at least four carbon atoms, said ester having hydrophile properties.

16. A non-nitrogenous phosphoric acid ester of a fatty acid monoglyceride wherein at least one fatty acid radical fatty acid.

17. A non-nitrogenous ester of phosphoric acid and an aliphatic polyhydroxy substance with at least two esterifiable hydroxy groups, wherein the hydrogen of at least one hydroxy group is replaced by a hydrophile phosphate radical, wherein the hydrogen of only one other hydroxy group is replaced by a lipophile radical, and wherein the lipophile portion of the molecule contains an is that of a normally liquid acyl radical which contains at least four but less than 36 carbon atoms, said ester having hydrophillic properties.

18. A non-nitrogenous ester of phosphoric acid and an aliphatic polyhydroxy substance with at least two esterifiable hydroxy groups, wherein the placed by a hydrophile phosphate radical, wherein the hydrogen of only one other hydroxy group is replaced by a lipophile radical, wherein the lipophile portion of the molecule contains at least four but less than 36 carbon atoms, said ester having hydrophillic replaced by a cation.

' I9. A non-nitrogenous phosphoric acid ester of glycerol having a hydrophile phosphate group esterified at one hydroxygroup, and a. lipophile hydrogen of only one the] group replacing one remaining hydroxy groups. the lipophile'portion at least onehydroxy group is re'-- roperties, and wherein at least one hydrogen of the phosphate radical is.

of the molecule having less. than 36 carbon atoms.

20. An ester of phosphoric acid and an aliphatic dihydroxy substance, wherein the hydrogen of one hydroxy group is replaced by a hydrophile phosphate radical and wherein the hydro-, 5

gen of the other hydroxy group is replaced by an 1 acyl radical with at least four carbon atoms, but not more than 18 carbon atoms;

21. A non-nitrogenous ester of phosphoric acid and an aliphatic polyhydroxy substance with at least four carbon atoms and with at least two esterifiable hydroxy groups, wherein the hydrogen of at least one hydroxy group is replaced by a hydrophile phosphate radical, wherein the hydrogen of at least one other hydroxy group is replaced by a lipophile radical and wherein the lipophile portion of the molecule comprises an acyl radical which contains at least four carbon atoms, said ester having hydrophile properties.

22. A non-nitrogenous ester of phosphoric acidgoand an aliphatic dihydroxy substance, wherein the hydrogen-of one hydroxy group is replaced by a hydrophile phosphate radical-and wherein,

the hydrogen of the other hydroxy group is replaced by an acyl radical with at least-four carbon 35 atomstsaid ester having hydrophile properties.

23. A non-nitrogenous phosphoric acid ester of a polyhydroxy substance with at least two esterifiable hydroxy groups, wherein two molecules of the polyhydroxy substance are esterified with and linked through one and the same hydrophile phosphoricacid radical, wherein the hydrogen of at least one hydroxy group of the polyhydroxy substance is replaced by a lipophile radical with at least four carbon atoms, said ester having hydrophile properties. 7

24. A non-nitrogenous phosphoric acid ester or a fatty acid mono-glyceride.

. 25. A non-nitrogenous phosphoric acid ester of .a fattyacid mono glyc'eride, the fatty acid containing at least four carbon atoms.

. 26. A non-nitrogenous chemical compound of the class consisting of mono olein phosphate and alkali salts thereof.

.BENJAmFHARRlS.

Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2441295 *Mar 19, 1945May 11, 1948Gulf Oil CorpManufacture of oil soluble dialkyl phosphoric acids
US2651829 *Jul 25, 1950Sep 15, 1953Metallgesellschaft AgSurface active media
US2839545 *Nov 24, 1953Jun 17, 1958American Lecithin Company IncProcesses of phosphorylating phosphatides and products thereof
US3153080 *Jan 31, 1961Oct 13, 1964Eastman Kodak CoAcyloxyneopentyl and acyloxycyclobutane phosphate partial esters
US3275667 *Jan 21, 1963Sep 27, 1966Hoechst AgProcess for the manufacture of phosphate ester derivatives of polyalkylene glycols
US5130463 *Aug 6, 1990Jul 14, 1992Byk-Chemie, GmbhPhosphoric acid esters, method of producing them, and use thereof as dispersants
US5155244 *Feb 28, 1990Oct 13, 1992Karlshamns AbPreparation of antioxidant glyceride derivatives utilizing esterification
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
US8404779Mar 26, 2010Mar 26, 2013Actamax Surgical Materials LlcTissue adhesive and sealant comprising polyglycerol aldehyde
US8680200Mar 26, 2010Mar 25, 2014Actamax Surgical Materials LlcPolyglycerol aldehydes
USRE46234Mar 26, 2010Dec 13, 2016Actamax Surgical Materials, LlcTissue adhesive and sealant comprising polyglycerol aldehyde
CN102361911A *Mar 26, 2010Feb 22, 2012阿克塔马克斯手术器材有限责任公司Polyglycerol aldehydes
DE942466C *Jul 6, 1951May 3, 1956Hoechst AgVerfahren zur Reinigung von Kleidung und anderen Textilien
DE975547C *Jan 21, 1950Jan 4, 1962Hoechst AgVerfahren zur Herstellung polykondensierter Phosphorsaeureester
EP0417490B1 *Aug 14, 1990May 15, 1996Byk-Chemie GmbHPhosphoric acid esters, process for their preparation and use as dispersing agent
WO2010111570A1 *Mar 26, 2010Sep 30, 2010E. I. Du Pont De Nemours And CompanyPolyglycerol aldehydes
Classifications
U.S. Classification554/79, 516/DIG.100, 554/78, 558/180, 558/179, 558/186, 209/166, 987/233, 516/57
International ClassificationC07F9/10
Cooperative ClassificationC07F9/10, Y10S516/01
European ClassificationC07F9/10