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Home , Hydroxy group

Patented Jan. 7, 1936 2,026,785 UNITED STATES PATENT office 2,026,85

PHOSPHORIC oF , MONOGLYCERIDEs Benjamin R. Harris, Chicago, III. Application January 8, 1934, No Drawing.

Serial No. 705,825.

26 claims. (CL 260-99.20)The lipophile group may include any fatty acid My invention relates to a new class of chemi group such as the fatty acid radicals of the foll cal Substances. It relates more in particular. to a

class of chemical substances having the properties ... lowing : caproic acid, capric, capryllic, va- -

leric, butyric, abietic, hydroxystearic, benzoic, . of interface modifiers when employed in a treat benzoylbenzoic, naphthoic, toluic, palmitic acid, 5 5 ing bath containing textile, leather or ores. The object of the invention is the provision of stearic, lauric, melissic, oleic, myristic, ricinoleic,

a new class of chemical substances; or mixed fatty acids derived from Another object is the provision of a class of animal or vegetable fats and fish oils such as lard, chemical substances adapted for use as interface coconut oil, corn oil, cottonseed oil, partially or - completely hydrogenated vegetable oils such as 10 it) modifiers...... cottonseed oil, corn oil, sesame oil and fatty. acids - Still another object is the provision of a treat of various waxes such as beeswax and carnauba ing bath employing the new interface modifiers wax; or the lipophile group may be an radir of my invention...... The substances of my invention have many cal derived from an corresponding to any - ls useful applications in the arts where frothing, of the preceding acids, such as cetyl alcohol, 15 Wetting, penetrating, detergent, emulsifying, and lauryl alcohol, etc...... - ...... other interface modifying functions are required, Specific examples of poyhydroxy substances,

the residues of which may serve as linkages be They are in general possessed of at least two tween the lipophile groups and the hydrophile 20. groupS, One having a hydrophile function and the other having a lipophile function in the molecule. groups are as follows: mucic acid, The hydrophile function is performed primarily tartaric acid, saccharic acid, gluconic acid, by a phosphate group; that is, a group contain glucuronic acid, gulonic acid, mannonic acid, ing phosphorus in the form of a phosphorus trihydroxyglutaric acid, glyceric acid, and the ...... acid , giving the molecule as a whole an like, as well as carboxylic oxidation products of s 5 affinity for aqueous materials. The lipophile polyglycerols which may be represented by the

group is any radical such as acyl or alkyl derived formulae: from a fatty acid or its corresponding alcohol and oH OB O

has a definite affinity for oils and fats. The hy ...) drophile phosphate group is linked to the lipo Ho-oh-oh-oh-o-CH-CH-i-oh '' phile group by means of a polyhydroxy substance OB. OB ; pH 9 30 of a class consisting of , , - Ho-oh-i-o-o-c-e-chi-o-oh-e--on glycols, , polyglycerols, polyhydroxycar O. : -

boxylic acids, and polyglycols. In general, al‘eS ter linkage joins the polyhydroxy substance and Ho-CH-CH-CH-OH Ho-oh-GE--on 5 the phosphate group. The linkage between the polyhydroxy substance and the lipophile group &H, may be either an or linkage. . . . . Many of the compounds of my invention may H-C-OH be represented by the formula . . . . ; o--on 40 ... O or OH OB O R-O-X-O-P-O- Ho-5-be-ch-0-CH-it--oh Yoy O OB . Ho--on-ob-o-oh-oh-oh-o-on-bit-i-or... O 45

Wherein 'R' is a lipophile group, 'X' is the resi O OH, OBI due of a polyhydroxy substance, 'Y' and “Z” are Ho--on-oh-o-oh-in-chi-O-OH,--OH. cations, and 'u' is a small whole number. . . and sugars such as: xylose, galactose, fructose, . . . More specifically, the compounds of my inven tion may be defined as non-nitrogenous esters of maltose, , , dulcitol, arabitol and a phosphoric acid and a polyhydroxy substance other sugar alcohols such as hexahydric alco- 50

hols derived from sugars, and other Substances ... wherein at least one hydroxy group of the poly having free hydroxy groups. The above poly- . hydroxy substance has its substituted glycerols and their oxidation products are pro by a lipophile group. I employ the term “non duced by polymerizing glycerine, preferably by - nitrogenous' to indicate that my substances are devoid of nitrogen linked directly to carbon, heating with about 1% of alkali attemperatures 55

2 - 2,026,785 from 250° to 260° C. for about three hours in (12) H.-O-C Has the presence of an inert gas. This reaction mix O ture will give a mixture of various polyglycerols, 2 the size of the molecules depending upon the 5 time of polymerization. H--O-PONsONa The mixtures of poly 5 glycerols are then oxidized with mild oxidizing O. agents to convert at least one of the primary r 2 hydroxy groups to a carboxylic group. Ea -O-PON Examples of substances of my invention may oNa 10 be represented as follows: - - - 10 O (13) CitHas-C-O-CH-CH-O-CH-CH-o or (1) HC-O-C-CHaso ...O...-- . A s: N2P H-C-OH : Monolaurin ester of glycerine phos ...... / N 5 O phate (disodium salt) Critiss-C-O-CH-CH-O-CH-CH-O ONa) C-O- roN :O O 5 ONa (14) CH-CH-C-O-CH-CH-O-CH-CH-O-P-ON (Na 20 (2) HC-O-C-CitBal (15) - Sorbitol stearate monophosphate (ammo nium salt) 20 - (16) Sorbitol melissate monophosphate (sodium H-C-O-C-CitHis salt): pH pH pH 25 . . . --- -b - a HC-O-CH-CH-CH-O-P-ONH3. Hig-bti-CH-CH-CH-CH, 25

...... oNH, () (bH ()2 or (3) cetyl sorbitol phosphate ... . . O=C-C3oEst sons (4) E-o-CH-CH-0. 2o . ONa 30 : : - . ... P . . . . . There are several methods by means of which ... ." CHir-o-CH-CH-0 . OK. - . . . . the materials of my invention may be made. The to ...... o. method employed should be determined primarily CHC-O-CH-CH-O-CH-CH-O-P-ONa by considering the type of substance to be pro - ...... YoNa - - i. duced. In introducing the phosphate radical, for example, a material containing: an esterifiable - O hydroxy group is reacted with phosphorus pen H.0-0--C.H. toxide, phosphoric acids, phosphorus halides, ethyl metaphosphate, phosphorus oxychloride or ; : ...... some other reagent capable of furnishing the ele Dicaprin phosphate (disodium salt) ments of phosphoric acid. Either one or more . . ONa

phosphate radicals may be introduced, depending upon the Substance desired. A condensing agent H.0-0--Chi, and/or a solvent may be added where required. As a specific example, 7 parts of monostearyl (monostearine) are dissolved in 35 parts of dry . To this solution are added, with CH-O-CH-CH-O-CH-CH-0-ro-Bao . simultaneous cooling, 12 parts of phosphorus oxy Butyl diethyleneglycol phosphate (barium salt). chloride dissolved in 50 parts of dry acetone, the mixture being stirred meanwhile. This mixture 50 (8) HC-O-CHit . is allowed to stand over night and it is then H-b-o-CHr ...... thrown into 300 parts of water with stirring. A . OH O precipitate forms at first, but after a few mo 2 ments this becomes completely dispersed." On Hac-O-CH-CH-CH-O- roNa - warming to about 60. C., the solution becomes 55 ONa 5 5 O 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 (9) H.C-O-C-CitHas moisture. after the greater proportion of salt so 60 1---O a. . . . . lution has been separated therefrom. The prod B- -o-roNE, Diolein phosphate- (anmonium salt) luct may be used in this form or it may be fur 60 ONE ther washed or otherwise purified. It may be dried or not, as desired. The product so formed -o-,-cutta is primarily a double glycerine ester in which one hydroxy group is esterified with a stearic acid 65 s radical and another hydroxy group is esterified with phosphoric acid. The monolauric ester (10) chi-3-O-CH-CH-O-CH-CH-O-P-ONs glycerine phosphate may be prepared in a simi-. . . ONa lar manner, but using substantially pure lauric 70 Steary diethylene glycol disodium orthophosphate acid, or the fatty acids of coconut oil containing about 40% lauric acid in preparing the mono which are to be subsequently reacted (11) Chi-C-O-CH-CH-O-Chi-Chr-o 9. - . with phosphorus oxychloride. The resultant O P2. product is neutralized with sodium bicarbonate -- /N to produce the Sodium Salt. This procedure for CHss-C-O-CH-CH-O-CH-CH-O OK the preparation of phosphoric esters is a conven- 75.

2,026,785 3 ient method for making certain materials of my any two selected members of the series are from invention which are represented by Nos. 3, 4,6,7, each other. 11 and 13 in the list of examples shown herein While the illustrative examples listed herein above, as well as others, bearing in mind that par above represent principally single substances, it ticularly where secondary are con must be understood that the invention is by no cerned (such as Nos. 4, 11, 13 in the list of ex means limited to single substances. Indeed, in amples shown hereinabove) the phosphorus oxy practice, it is frequently more convenient to pre chloride must be added gradually to the reactant pare a mixture of the substances of my inven with the hydroxy group, so that the latter is al tion and use such a mixture. For example, I may 10 ways present in excess throughout the course of prepare a mixture of diglycerides by any conven 10 the reaction. ient method, such as described hereinbelow and According to another example, 66, parts of then introduce into each member of this mixture monobutyl ether of diethylene glycol are mixed of diglycerides a phosphate radical by a conven with 58 parts of phosphoruspentoxide. This is ient method. .. .' - - - - 5 accomplished best by adding the phosphorus Ecample: Preparation of mixture of diglyc 15 pentoxide gradually and in small portions to the eride phosphates from corn oil. monobutyl ether of diethylene glycol with stir Heat a mixture of 880 parts of corn oil and 50 ring, cooling somewhat if necessary to avoid ex parts of glycerol in an inert atmosphere with cessive heating. This mixture is allowed to re stirring to 220°C. Add 0.88 part of flake caus 20 main at room temperature for about half an tic soda, Raise the temperature to 250° C., con 20 hour. The mixture is then taken up with about tinue stirring and heat at 250° C. or thereabout 800 parts of cold water and 20 parts of barium for two hours. Cool to room temperature in an ... chloride stirred in, the latter being in the form inert atmosphere. This product is essentially of a 10% aqueous solution. 125 parts of salt are a mixture of diglycerides...... 2 5 now dissolved in this mixture. The entire mix To 200 parts of the above product dissolved in 25 ture is allowed to remain at rest until the product 600 parts of isopropyl ether (free of alochol and floats to the Surface, whereupon the brine is with water) add 50 parts of phosphorus pentoxide drawn and discarded. The product may be used and heat under reflux with stirring for three in this form or it may be filtered or concentrated hours to 60° C., taking care to keep the reaction 30 further or otherwise treated, as desired. The fin mixture out of contact with atmospheric mois 30 ished product, the principal portion of which may ture. be represented by No. 7 in the list of examples Now free this reaction product of ether, pref shown hereinabove, is easily dispersible in wa erably by distillation. ter and exhibits many useful colloidal properties The residue is a somewhat sirupy, oily material 5 and particularly as an interface modifier. which may be used as such, or it may beneu 35 While all of the substances of my invention fall tralized with gaseous ammonia... or aqueous am into the category of interface modifiers, they monia or other alkaline agents. Also, the prod modify the interface in various ways and to vari uct may be washed by salting it out with brine ous extents, depending upon the relative poten several times, purified, or otherwise treated if 40 cies of the hydrophile and lipophile groups, the desired. It consists in the main of a mixture of 40 resultant of the two representing the interfacial diglyceride phosphates, the significant, predom function of the molecule as a whole. ". . . . inant constituent of which is represented by No. For example: the barium salt of the butyl ether 9 in the list of examples hereinabove, of diethyleneglycol phosphate (No. 7 of the ill In place of corn oil in the above, I can use lustrative examples given above) and diolein cotton seed oil, peanut oil, sesame oil, sunflower 45 phosphate (No. 9 of the list of illustrative ex oil, neat's-foot oil, coconut oils, hydrogenated. amples given above) serve well to show how the oils, lard, tallow, etc., cod oil and other common properties of my interface modifiers may vary. . ... . No. 7 is predominantly hydrophilic, practically If, on the other hand, it is desired to prepare 5) freely soluble in water; whereas, No. 9 is predom a single. Substantially pure Substance analogous 50 inantly lipophilic, imbibes cold Water but can to the above, it is only necessary to treat diolein not be Said to disperse therein. The latter does, with phosphorus pentoxide as described above. however, disperse in hot water, particularly read This procedure, for introducing phosphate rad ily in the presence of a very low concentration icals, described directly above, I have also SIC of electrolyte Such as sodium chloride. It is well cessfully used in the preparation of materials to note that the hydrophile group in both cases represented by Nos. 1, 2, 5, 6, 8, 10, 12, 14, 15, is essentially the same, but the lipophile group. and 16 in the list of examples shown hereinabove, in the case of No. 9 contains approximately five as well as others. It is, of course, obviously with times as many carbons, if not more, than the lipo in the skill of any qualified chemist to compute 6) phile group in No. 7. No. 9 is predominantly lipo molal or multiples of molal proportions of the 60 philic; No. 7 is predominantly hydrophilic, reactants with respect to each other. . . . . though each possesses both hydrophile and lipo The products above described may be added phile properties. No. 9 when touched with moist in suitable proportions to a treating bath-con fingers appears greasy; whereas No. 7, as stated taining an aqueous medium, with or without 5 above, is practically water soluble. No. 9 pro an additional substance, such as for example al 65 motes water in oil emulsions; No. 7 promotes kalis, mordants, dyes, color discharging reagents, oil in water emulsions. Between such two rela HaO, color reducing agents, oils, sulphonated tively extreme examples may be inserted a se oils, mordanting salts, fabrics and other re ries of other examples in the order of diminish agents or substances used in treating baths, and ing hydrophile characteristics starting with No. the treating bath so formed can be employed 70 7 upward and, per contra, with increasing lipo with satisfaction in all of the arts in which in phile characteristics working up to No. 9 and terface modification is desired. For example, beyond. Between two vicinal members of such dyeing, bleaching, scouring, leather stuffing, and a series, the differences may be only very slight, otherwise treating fabrics, fibers and otherma becoming more appreciable the further removed terials in a treating bath of this character is pro 75

4. 2,026,785 ductive of good results. Also in the stuffing of group of the alcohol is, esterified by a fatty acid. leather, dyeing, and otherwise treating furs, with at least four but less than eighteen carbon and in many other arts, a treating bath en atons. ploying the materials of my invention may be 6. A non-nitrogenous phosphoric acid ester of 5 used. In flotation of ores it may be used in a hexahydric alcohol derived from sugar where 5 connection with other reagents to modify the in the hexahydric alcohol derived from sugar has interface between the finely divided ore and the at least one hydroxy group in which the hydrogen aqueous medium...... - is replaced by a lipophile group. while I have described several methods for the 7. A non-nitrogenous phosphoric acid ester of O. preparation of the materials of my invention, sorbitol wherein the sorbitol has at least one hy it must be understood that the scope of the in droxy group in which the hydrogen is replaced vented class of substances is by no means lin-. by a lipophile group. . . . ; : . . . . . ited by these methods. Other convenient meth 8. A phosphoric acid ester of a fatty acid ods may be used. This also applies, and part monoglyceride, the fatty acid radical having at ticularly so, to supplementary procedures of pur least four carbon atoms. ification or isolation which lie strictly within the 9. A non-nitrogenous hydrophillic ester of province of skill of any qualified chemist whose phosphoric acid with lipophile and hydrophile procedures in each instance must be governed groups, said ester being represented by the by the properties of the materials concerned, and formula by the degree or the character of the purity de 2O Sired. - ...... The term “residue', as used throughout the R-0-X-O-Péo-2 - specification and claims, is employed in, its or Yoy w dinarily understood chemical significance. For : wherein "R", the lipophile portion of the mole. , 2 5 example, where one of the hydroxyl groups of cule, is an acyl radical and has at least four glycerine is esterified with a fatty acid or ether carbon atoms, 'X' is the residue of an aliphatic ified with an alcohol and another of the hydroxyl polyhydroxy substance with at least two esteri groups of the glycerine is esterified with a phos fiable hydroxy groups, “Y” and “Z” represent phoric acid, that which remains of the glycerine cations, and "w" is an integer. 30 molecule, for example, . . . - 10. A non-nitrogenous hydrophillic ester of 3) gh phosphoric acid with lipophile and hydrophile CHOH groups, said ester being represented by the formula . . . . -

is the “residue” of the polyhydroxy substance, in . . . . e'. this case glycerine...... R-O-X-O-P-O-Z "What I claim as new and desire to protect by Yoyle Letters. Patent of the United States is: . . . . . 1. A non-nitrogenous hydrophillic ester 0 wherein "R", the lipophile portion of the mole 40 phosphoric acid with lipophile and hydrophile Cule, is an acyl radical and has at least four () ... groups, said ester being represented by the for carbon atoms, “X” is the residue of a polyhydric: mula ...... ; . alcohol, “Y” and “Z” represent cations, and "up" is an integer. . . . m v to 11. A non-nitrogenous hydrophillic ester ... of R-0-x-o-réo- z phosphoric acid with lipophile and hydrophile ... ' oY to groups, said ester being represented by the wherein “R”, the lipophile portion of the mole forniula cule, is an acyl radical and has at least four O carbon atoms, 'X' is a glycol residue, “Y and 2 50 'Z' represent cations, and 'up' is an integer. - R-0-x-o-réo- 2. 50 2...A hydrophillic ester of phosphoric acid with oy to lipophile and hydrophile groups, said ester being represented by the formula . . . . wherein "R", the lipophile portion of the mole cule, has at least four carbon atoms, “X” is a 5 5 ...... to . glycerol residue, 'Y', and 'Z' representications, 5 and 'u' is an integer. . . . - R-0-x-o-réo- 2. 12. A non-nitrogenous hydrophillic ester of roy to phosphoric acid with lipophile and hydrophile wherein "R" is a higher fatty acid radical, "X" groups, said ester being represented by the 60 is a glycerol adical, 'Y', and 'Z' represent CO cations, and 'up' is an integer, and the remain formula - . . . - ing OH of the glycerine is free and unesterified. - O 3. A non-nitrogenous phosphoric acid ester of R-0-x-O-Péo- 2 a polyhydroxy substance wherein the polyhydroxy Yoyo 5 substance has only one hydroxy group in which the hydrogen has been replaced by an wherein "R", the lipophile portion of the mole with at least four but less than eighteen carbon cule, has at least four carbon atoms but not atoms...... more than eighteen, “X” is a glycerol residue, “Y” 4. A non-nitrogenous phosphoric acid ester of and “Z” represent cations, and 'u' is an integer. a polyhydric, alcohol wherein only one hydroxy 13. Anon-nitrogenous phosphoric acid ester of : group of the alcohol has its hydrogen replaced a glycerol wherein the glycerol has one hydroxy by an acyl group with at least four but less than group in , which the hydrogen is replaced by a eighteen carbon atoms. lipophile radical, another hydroxy group where 5. A non-nitrogenous phosphoric acid ester of in the hydrogen is replaced by a hydrophile phos par a a polyhydric alcohol wherein only one hydroxy phate radical, and wherein the remaining. hy

2,026,786 5 of the molecule having less than 36 carbon atoms. droxy group is free and unesterified, said ester 20. An ester of phosphoric acid and an ali having hydrophillic properties. phatic dihydroxy substance, wherein the hydro 14. A non-nitrogenous phosphoric acid ester of gen of one hydroxy group is replaced by a hydro a polyhydric alcohol, wherein the hydrogen of phile phosphate radical and wherein the hydro- 5 5 Only one hydroxy group of the alcohol is re gen of the other hydroxy, group is replaced by an placed by a lipophile acyl group with at least acyl radical with at least four carbon atoms, but four carbon atoms, said ester having hydrophile not more than 18 carbon atoms." properties. 21. A non-nitrogenous ester of phosphoric acid 15. A non-nitrogenous phosphoric acid ester of and an aliphatic polyhydroxy substance with at 10 10 a glycerol, wherein the glycerol has only hy least four carbon atoms and with at least two droxy group in which the hydrogen is replaced esterifiable hydroxy groups, wherein the hydro by a lipophile acyl group with at least four car-. gen of at least One hydroxy group is replaced by bon atoms, said ester having hydrophile prop a hydrophile phosphate radical, wherein the hy erties. drogen of at least one other hydroxy group is 15 16. A non-nitrogenous phosphoric acid ester of replaced by a lipophile radical and wherein the a fatty acid monoglyceride wherein at least One lipophile portion of the molecule comprises an fatty acid radical is that of a normally liquid acyl radical which contains at least four carbon fatty acid. atoms, said ester having hydrophile properties. 17. A non-nitrogenous ester of phosphoric acid 22. A non-nitrogenous ester of phosphoric acid 20 and an aliphatic polyhydroxy substance with at and an aliphatic dihydroxy Substance, wherein least two esterifiable hydroxy groups, wherein the the hydrogen of one hydroxy group is replaced hydrogen of at least one hydroxy group is re by a hydrophile phosphate radical and wherein placed by a hydrophile phosphate radical, where the hydrogen of the other hydroxy group is re in the hydrogen of only one other hydroxy group placed by an acyl radical with at least four carbon 25 25 is replaced by a lipophile radical, and wherein atoms, said ester having hydrophile properties. the lipophile portion of the molecule contains an 23. A non-nitrogenous phosphoric acid ester of acyl radical which contains at least four but less a polyhydroxy substance with at least two esteri than 36 carbon atoms, said ester having hydro fiable hydroxy groups, wherein two molecules of phillic properties. the polyhydroxy substance are esterified with and 30 18. A non-nitrogenous ester of phosphoric acid linked through one and the same hydrophile and an aliphatic polyhydroxy substance with at phosphoric acid radical, wherein the hydrogen least two esterifiable hydroxy groups, wherein the of at least one hydroxy group of the polyhydroxy hydrogen of at least one hydroxy group is re substance is replaced by a lipophile radical with placed by a hydrophile phosphate radical, where at least four carbon atoms, said ester having 35 35 in the hydrogen of only one other hydroxy group . is replaced by a lipophile radical, wherein the hydrophile24. A non-nitrogenous properties. phosphoric. . . . . acid ester of lipophile portion of the molecule contains at least a fatty acid mono-. four but less than 36 carbon atoms, said ester 25. A non-nitrogenous phosphoric acid ester of having hydrophillic properties, and wherein at a fatty. acid mono-glyceride, the fatty acid con- 40 40 least one hydrogen of the phosphate radical is taining at least four carbon atoms. replaced19. A non-nitrogenousby a cation. phosphoric acid ester of 26. A non-nitrogenous chemical compound of glycerol having a hydrophile phosphate group the class consisting of mono olein phosphate and esterified at one hydroxy group, and a lipophile alkali salts thereof. BENJAMIN. . . . P.. HARRIS...... 45 group replacing one hydrogen of only one the w 45 remaining hydroxy groups, the lipophile portion