US3773804A - Lipophilic detergent compositions - Google Patents

Abstract

A SERIES OF NEW COMPOSITIONS COMPRISING SALTS OF PARTIAL FATTY ACID-PHOSPHORIC ACID ESTERS OF POLYALKOXYLATED POLYOLS HAVING 4 TO 6 CARBON ATOMS HAVE BEEN FOUND ESPECIALLY USEFUL AS LIPOPHILIC DETERGENTS. AMINE SALTS OF COMPOSITION HAVING FROM 1 TO 8 POLYOXYALKYLENE GROUPS, 1 TO 4 FATTY ACID ESTER GROUPS, AND 1 TO 2 PHOSPHORIC ACID GROUPS PER MOL OF POLYOL ARE PARTICULARLY USEFUL AS ASHLESS FUEL OIL SLUDGE DISPERSANTS.

Description

United States Patent 3,773,804 LIPOPHILIC DETERGENT COMPOSITIONS Ernest C. Ford, Jr., Newark, and John D. Zech, Wilmington, Del., assignors to Atlas Chemical Industries, Inc., Wilmington, Del. N0 Drawing. Filed June 10, 1971, Ser. No. 151,963 Int. Cl. A23j 7/00; C071. 9/02 US Cl. 260403 6 Claims ABSTRACT OF THE DISCLOSURE A series of new compositions comprising salts of partial fatty acid-phosphoric acid esters of polyalkoxylated polyols having 4 to 6 carbon atoms have been found especially useful as lipophilic detergents. Amine salts of compositions having from 1 to 8 polyoxyalkylene groups, 1 to 4 fatty acid ester groups, and 1 to 2 phosphoric acid groups per mol of polyol are particularly useful as ashless fuel oil sludge dispersants.

This invention relates to detergent compositions which are especially useful in organic liquids such as dry cleaning solutions, gasoline, fuel oils, kerosene, chlorinated hydrocarbons, etc. Such detergents are further characterized as being hydrophobic and having little tendency to form water-in-oil emulsions. More particularly, the invention relates to additive compositions for fuel oils or mixtures containing straight-run fuel oils which is untreated gradually oxidize and otherwise decompose during storage to form insoluble sludge and sediment which are often responsible for the subsequent clogging of fuel lines, filters, and passageways in engines and burner systems through which such fuels pass. When such plugging occurs, the system ceases to operate or reduces operating efiiciency to the point where the engine or burner must be shut down for cleaning. The invention also relates to dry cleaning detergent compositions which are useful in halogenated hydrocarbon dry cleaning solutions and kerosene. The detergent compositions are further utilized as motor oil antiwear agents.

It is a primary object of the invention to provide lipophilic detergent compositions useful as fuel oil and dry cleaning detergents.

It is also an object of the invention to provide a process for synthesizing improved fatty acid-phosphate esters of polyalkoxylated polyols having 4 to 6 carbon atoms and at least one hydroxyl group per primary, secondary, or tertiary carbon atom and salts thereof.

The compositions are especially useful in the treatment of fuel oils which upon standing accumulate moisture from the air which enters the tank and condenses to form an aqueous layer which if emulsified with the oil may cause rusting and corrosion of fuel lines, engines, nozzles, and other associated equipment. Furthermore, the deterioration of distillate fuel oils on storage and the subsequent formation of both soluble and insoluble residue has been recognized for sometime, but the mechanism by which these sludges are formed is not clearly understood. It is believed, however, to be associated with oxidation and polymerization of free radicals that are thereby formed. Incorporation of antioxidants is not successful in stabilizing the fuel oil fraction petroleum distillate as it is in others such as gasolines, greases, lubricating oils, etc.

Additives such as esterified ethanol ammonium phosphate salts described in US. 2,574,954 and US. 3,574,955; tetraalkyl ammonium salts of an alkyl polyalkyleneoxy ester of phosphoric acid such as described in US. 2,904,416 or aliphatic ammonium salts of dialkyl ortho phosphoric acid such as described in US. 2,905,541 have F ice not proven to be completely satisfactory for economic reasons. 1

The dispersant and stabilizing compositions of this invention comprise a series of condensation products formed by reacting a partial fatty acid ester of a polyalkoxy ether of a polyol having 4 to 6 carbon atoms having one hydroxyl group per primary, secondary, or tertiary carbon atom with a phosphoric acid or a phosphoric acid anhydride (phosphorous pentoxide P 0 having from 69-100% by weight of phosphorous pentoxide equivalent, wherein said ether contains up to about 15 polyoxypropylene or polyoxyethylene groups per mol, said partial ester contains from 1 to 4 acylate radicals per mol of polyol, and said condensation product contains from 1-2 mols of phosphoric acid equivalent/mol of polyol ester. These condensation products can be neutralized by adding strong organic or inorganic bases such as alkali or alkaline earth metal hydroxides, ammonium hydroxides, or organic bases such as primary, secondary, or tertiary amines and diamines.

The compositions of this invention are formulated in a sequence of reaction steps, the first of which comprises condensing a polyol having 4 to 6 carbon atoms and in most cases at least 1 hydroxyl group per primary, secondary, or tertiary carbon atom with an oxyalkylene compound such as ethylene or propylene oxide. Such compounds as erythritol, pentaerythritol, adonitol, and the several hexitols are useful polyols. Sorbitol and mannitol are preferred hexitols.

These polyols can be condensed with up to 15 mols and preferably from 1 to 8 mols of ethylene oxide or propylene oxide by any of many well-known techniques. Usually, however, condensations are performed in an autoclave under pressure. The condensation of alkylene oxide with a hydroxy group produces at a hydroxyl site a ,B-hydroxyethyl ether linkage. As is well recognized, the condensation of several mols of an alkylene oxide with a polyol produces etherified polyols containing the same number of hydroxyl groups as the polyol with oxyalkylene groups more or less randomly distributed in the molecule. It is customary in the art to designate such mixture as the number of oxyalkylene groups condensed per mol of polyol and such terminology will be adopted hereafter. Thus, for example, the condensation of 4 mols of propylene oxide with 1 mol of sorbitol will be called Polyoxypropylene (4)Sorbitol or POP(4)Sorbitol. Likewise, a condensation product formed by condensing 15 mols of ethylene oxide with adonitol will be called POE- (15 Adonitol.

In the next synthesis step, a polyol-polyether composition of the type described previously including readily available intermediates such as those listed in Table I is further condensed with from 1 to 4 mols of a saturated or unsaturated fatty acid having from 10 to 20 carbon atoms such that at least one hydroxyl remains unreacted. Such acids as capric, lauric, myristic, palmitic, stearic, and arachidic are preferred saturated acids; while palmitoleic, oleic, ricinoleic, linoleic, and other acids Within the range which are easily obtained from natural products are most useful. Readily available odd-numbered acids such as undecyclic, tridecylic, for example, are to be included. Portions of each of the two compounds are mixed together and reacted at temperatures in excess of 200 C.

In this reaction, the acyl group attacks a hydroxyl group either on the polyol molecule or at the end of a hydroxy ether side chain to form an ester of the fatty acid. A condensation product wherein 2 mols of oleic acid is condensed with Polyoxypropylene(4)Sorbitol is designated as POP(4)Sorbitol Trioleate.

In the next synthesis step, the alkoxylated polyol ester obtained either as described above including readily available intermediates such as those listed in Table II are further reacted with phosphoric acid, polyphosphoric acid, or their anhyride (phosphorous pentoxide--P O to form a condensate containing on the average 1 to 2 mols of phosphoric acid equivalent per mol of alkoxylated polyol ester. If one mol of the polyethoxylated polyol ester is reacted with one mol of phosphoric-oxygen compound equivalent to one mol of phosphoric acid, the term monophosphate is applied; however, if 2 mols of the polyol ester is condensed with 3 mols of the orthophosphoric acid equivalent, the term sesqui or 1.5 phosphate is employed. The acid links with the alkoxylated polyol ester through available hydroxyl groups either on the polyol molecule or on the hydroxy ether side chain. When phosphoric acid, per se, is used, water is split out in the condensation. However, if the anhydride such as phosphorus pentoxide is used, no water is eliminated. A most expeditious route for forming these phosphate derivatives is to add phosphorus pentoxide either as a dry powder or slurried in an inert organic liquid to a heated fatty acid ester. Any residue which is insoluble in the mix can be filtered from the reaction product prior to the removal of the organic liquid. A condensation product formed by condensing one mol of palrnitic acid with one mol of POE(1)Erythrito1 followed by condensation of 1 mol of phosphoric acid equivalent is termed POE (1)Erythritol Monopalmitate-l- 'Phosphate.

The above phosphates can then be neutralized by reaction with strong inorganic or organic bases. Such salts are formed by mixing with the phosphates low molecularweight organic primary, secondary, or tertiary amines such as propylamine, isopropylamine, butylamine, ethylamine, methylamine, dimethylamine, diethylamine, diisopropylamine, hydroxyethylamine, monoethanolamine, diethanolamine, trimethylamine triethylamine, and others to form neutral products. Higher molecular-weight amines are also suitable, but those with up to 5 carbon atoms per organic group are preferred. Alkali metal salts such as sodium, potassium and alkaline earth metals such as calcium, magnesium, etc. are similarly formed by adding respective base compositions containing the metals. The amount of base to be added varies from composition to composition and depends upon the structural complexity of the phosphate. A suitable method for determining the acid content of the composition is to determine the neutralization equivalent with such bases as sodium hydroxide prior to the addition of amine. A composition resulting from neutralization with isopropylamine (IPA) and the sesqui phosphate of mannitol condensed with 5 mols of ethylene oxide and 3 mols of stearic acid would be designated IPA-POE(5) Mannitol Tristearate-l.5 Phosphate.

The following examples are given to illustrate the types of compositions and their application:

EXAMPLE 1 IPA-POP(4)Sorbitol Diolate-1.5 Phosphate 1273 parts by weight of Po1yoxypropylene(4)Sorbitol made in an autoclave by the condensation of propylene oxide with sorbitol at a mol ratio of 4 to 1 is mixed with 1988 parts by weight of a commercial grade of oleic acid (Acintol-FA No. 2) produced by the Arizona Chemical Company and heated under a blanket of nitrogen with stirring over a period of 4 hours at a temperature of 250 C. 1440 parts by weight of this composition is heated to 105-110 C. under a nitrogen blanket and mixed with 115 parts by Weight P slurried in toluene. Since a small portion of P 0 does not react initially, the liquid product requires additional quantities of P 0 to be added to bring the phosphorus content up to 4.16% The amine salt of this composition is formed by mixing 342.8 parts of the phosphate with 31.2 parts of isopropylamine and heated to 87- 99 C. over a period of 1.25 hours to yield a product containing 1.96% nitrogen.

4 EXAMPLE 2 IPA-POE(4)Sorbitol Trioleate-1.5 Phosphate 1184 parts by weight of Polyoxypropylene(4)Sorbitol and 2272 parts by weight oleic acid were heated together under a nitrogen blanket to 250 C. for a period of 11 hours to produce 3114 parts of 'PO-P(4)Sorbitol Trioleate. 1452 parts of this composition was mixed with 110 parts by weight of P 0 slurried with 100 parts toluene over a period of 1 hour, then heated to 100i5 C. with stirring for a total of 2.5 hours. The mix was filtered to remove residue and vacuum stripped at 0.1 mm. Hg at 100-105 C. to remove volatiles from the residual product. 311 parts by weight of this composition is mixed with 23 parts by weight of isopropylamine and heated to C. with stirring until homogenous. The product obtained contains 3.02% phosphorus and 1.43% nitrogen.

EXAMPLE 3 P01 (4)Sorbito1 Trioleate mono-acid Phosphate 621 grams (1.5 mols) POP(4) sorbitol were reacted with 1,269 grams (4.5 mols) oleic acid for 12 hours at 195-200 C. using a xylol azeotrope for by-product water removal. Solvent and unreacted oleic acid are then stripped ofi under a final temperature of 210 C. at 4 mm. Hg pressure. The product is a clear amber liquid which analyzes: AN=6, SAP: 142, and OH No.=ll0.

1,768 grams of this material are then reacted with 106 grams (.7 mols) phosphorous pentoxide (slurried in 300 ml. of toluene), which is added over a period of 1 hour at a temperature of -405 C. The resulting product, an amber liquid, is filtered and then stripped of solvent at final temperature conditions of C. at 8 mm. Hg of pressure. The analysis of such material is: AN =85, SAP=222, and OH No.'=58.

EXAMPLE 4 Na-POP (4) Sorbitol Trioleate Mono-Phosphate 400 grams of the acid phosphate of Example 3 are reacted with 22 grams of sodium hydroxide to form the neutralized product. The analysis is 3.8% Na and 2.7% P.

EXAMPLE 5 NH -POP (4) Sorbitol Trioleate Mono-Phosphate 400 grams of the acid phosphate of Example 3 were reacted with 35 mls. of concentrated ammonium hydroxide to form a material having an analysis of 1.4% N and 2.7% P.

EXAMPLE 6 IPA-POP (4) Sorbitol Trioleate Mono-Phosphate 400 grams of the acid phosphate of Example 3 were neutralized with 29.7 grams of isopropylamine to give a product having analysis of 1.6% N, and 2.6% P.

EXAMPLE 7 Ca-POP (4) Sorbitol Trioleate Mono-phosphate 400 grams of the acid phosphate of Example 3 are neutralized with 20.3 grams of calcium hydroxide to form a material having an analysis equal to 1.8% Ca and 2.4% P.

In Tables III and IV are listed many other compositions which were made according to precedures similar to that of the above examples. While the examples and procedures are directed specifically to sorbitol and oleic acid derivatives, they apply as well to the previously cited polyols and fatty acids of the invention.

Because many of the additive detergents described above are thick and viscous at room temperatures, concentrated fluids are made by incorporating them with minimum quantities of organic solvents such as hydrocarbons, halogenated hydrocarbons, petroleum distillate products, fuel oil, kerosene, and the like to form fluids which can be easily pumped and metered.

PUMPING TEST The effectiveness of the additives as fuel oil sludge dispersants is demonstrated in a test apparatus comprising a reservoir with agitator from which an oil is recycled in series through a water trap, a filter, a pump, and a standard nozzle return outlet. The equipment is also provided with a pressure gauge and means for controlling the pressure in the line. In this apparatus two-gallon portions of untreated No. 2 fuel oil or kerosene are treated with sufiicient quantities of the dispersant listed in Column I of Table III to yield the concentrations indicated in Column 2 of Table III. To the treated oil are then added synthetic sludge designated K-801 provided by the Baltimore Paint and Color Company to adjust the concentration of the oil mix to 0.06 mls. per 99.14 mls. and 66 mls. of a synthetic rust slurry prepared by separately dissolving 20.32 gms. of ferric chloride-6 hydrate and 16.04 gms. of ferrous chloride-4 hydrate in 600 ml. portions of tap water, mixing these together and adding to this solution 200 mls. of a water solution containing 15.5 gms. of sodium hydroxide, diluting to 2,000 mls. with water and aging for 1 week. The contents of the reservoir are agitated for 2 minutes during the addition of the sludge and rust slurry.

A felt filter having a permeability for No. 2 fuel oil of 530 1:30 mls. per minute under a hydrostatic head of 18 inches is placed in the filter holder. The test is run for a total period of 3 hours with the circulating pump pulling the oil from the reservoir through the filter back to the reservoir. At the end of 1 hour of circulation and also after 2 hours, the flow through the filter is measured at a hydrostatic head pressure of 18 inches and is compared with the initial flow of clean No. 2 fuel oil. Each time, an additional charge of additive, sludge, and rust slurry equivalent to that used originally is placed in the reservoir as described. After one additional hour of circulation, the flow is again measured at an 18-inch hydrostatic head pressure. The results are expressed in Table III for the several concentrations tested, as percentages of the flow rate of clean No. 2 fuel oil. The results in the table are compared with fuel oil having no additive and equal concentrations of additives available commercially.

TEST FOR EMULSIIFICATION PROPERTIES It is critical in some instances that a sludge dispersant be ineffective in the formation of oil-in-water or waterin-oil emulsions. To demonstrate the desirable water separation properties, the distillate fuel oils containing the above-described additives are tested for water tolerance according to US. Federal Test Method Standard No. 791a, Method 3201.5 entitled Emulsion" and Method 3251.7 entitled Interaction of Water and Aircraft Fuels as described in Lubricants, Liquid Fuels and Related Methods of Testing. The following test is a modification and combination of these tests and involves vigorous agitation of 150 mls. of the oil containing the additive with 50 mls. of water at 1,500 r.p.m. for 5 minutes at room temperature and thereafter allowing the emulsion to remain undisturbed for a period of 24 hours. After periods of 1, 2, 5, and 24 hours, the waterfuel interface was observed and rated. The clarity of the oil layer was determined by removing the top-20 ml. portion and measuring its light transmission with a Beckman Model B spectrophotometer, using fuel oil as the standard (100% T) and a wave length of 420 mu. These results are recorded in Table III and indicate that the additives of this invention do not appreciably emulsify water and at the same time give improved sludge dispersancy.

6 DRY CLEANING DETERGENCY TEST To demonstrate the effectiveness of the compositions of the invention as dry cleaning detergents, 400 mls. of solution containing 1% of the additive shown in the first column of Table IV in the dry cleaning solvent shown in columns 2 and 3. Reflectance measurements are then made on two soiled swatches and two unsoiled swatches of standard materials. These swatches are then conditioned at 60 to 70% relative humidity overnight and then placed in a Terg-O-Tometer beaker which contains 400 mls. of detergent solution to be tested. The Terg-O-Tometer is then run for 30 minutes at 60 r.p.m. with the temperature of the test solution within a range of 70-75 F. The swatches are then removed, placed on paper towels, and dried at room temperature until solvent odor is no longer evident. Reflectance of each swatch is remeasured and compared with the originals. Under each solvent used in Table IV, there are two columns labeled D (denotes soil redeposition on unsoiled swatch) and R (denotes soil removal from dirty swatch). The performance of each detergent is measured from excellent to inoperable on a scale 7 of 1 to 5, respectively.

MOTOR OIL WEAR TEST A Precision-Shell Four Ball Wear Tester consisting of four /2-inch chrome alloy steel balls arranged in the form of an equilateral tetrahedron is used to measure the effectiveness of 0.5% motor oil solutions containing the detergents of Table IV. The three lower balls are held immovable while the fourth rotates in a vertical axis in contact with them. The points of contact are lubricated by immersion in oil held in a cup surrounding the four ball assembly. During the test, circular scars are worn on the surface of the three stationary balls. The average diameter of the scar indicates the degree of wear and which is affected by the load, speed of rotation, time of test, temperature, and character of the lubricant. The set of conditions used to evaluate candidates in Table IV for their anti-wear characteristics were as follows: A temperature of 54 C., a speed of 600 r.p.m., and a loading of 40 kg.

TABLE 1.AVAILABLE INTERMEDIATES Sor bitol derivatives:

(A) POE(2)Sorbitol (B) POE(3)Sorbitol (C) POE(4)Sorbitol (D) POE(6)Sorbitol (E) POE(8)Sorbitol (F) POP(l)Sorbitol (G) POP(3)Sorbitol (H) POP(6)Sorbitol (I) POP(8)Sorbitol Mannitol derivatives:

(J) POP(6) Mannitol TABLE II.--AVAILABLE INTERMEDIATES Esters of POE and PCP Mannitol and Sorbitol:

(A) POE(6)Mannitol Dioleate (B) P=OE(3)Sorbitol Monolaurate (C) POE(6)Sorbitol Monolaurate (D) POE(6)Sorbitol Dilaurate (E) POE( 6)Sorbitol Trilaurate (F) POE(6)Sorbitol Tetralaurate (G) POE(6)Sorbitol Trioleate (H) P OE(6)Sorbitol Tetraoleate (I) POE(3)Sorbitol Monopalmitate (J) POE(6)Sorbitol Monopalmitate (K) POE(6)Sorbitol Dipalmitate (L) POE(6)Sorbitol Tripalmitate (M) POE(6)Sorbitol Tetrapalmitate (N) POP(6)Sorbitol Trioleate (O) POP(6)Mannitol Dioleate TABLE III Emulsification test, hours Coneen- Pump Light transmission,

tram/(11316 tes; Interface rating 2 Separation, ml. H O percent T a. percen Additive ml. flow 1 1 2 5 24 1 2 5 24 1 2 5 24 Untreated fuel oil #2 14 Ashless acrylic polymer having M. Wt. of 50,000 00. 013 76 3 3 3 3 48 48 48 48 99 99 0065 6 Barium petroleum sulfonate 0.013 9% 2 2 2 IPA-POP (4) sorbitol dioleate, 1.5-phosphate 00. 013 5 5 5 28 32 32 35 92 89 95 99 IPA-POP (4) sorbitol trloleate, 1.5-phosphate 0.013 93 0.00325 68 IPA-POP (6) sorbitol dioleate, 1.5-phosphate 0%813 86 5 5 5 5 6 14 16 2O 84 81 97 100 IPA-POP (4) sorbitol trioleate, l-phosphate 0060:}? $5 5 5 5 5 43 43 44 91 83 95 97 IPA-POE (4) sorbitol dicleate, l-phosphate 0.013 89 0. 0065 71 1 Percent Flow=Final fioWXlOO/initial flow.

2 Rating-1=Clean or clear; lb=A few small bubbles covering of interface and no shreds, lace, or film at interface; 2=Shread of lace and/or film;

3=Loose lace and/o1 light scum; 4=Tight lace and/or heavy scum;

TABLE IV 5=Tight lace and/or heavy scum and ml. tight emulsion.

Detergent additive Perchlorethylene Dry cleaning Stoddard solvent Antiwear agent motor oil POE(4) sorbitol dioleate, l-aeid phosphate POE(4)sorbitol dioleate, 1.5-aeid phosphate POE(6)sorbitol dioleate, l-aeid phosphate POE(6)sorbitol dioleate, 1.5-aoicl phosphate POE(4) sorbitol tnoleate, l-acid phosphate POE (6)sorbitol trioleate, l-acid phosphate POP (4) sorbltol trioleate, 1.5-acid phosphate POP(6)sorloitol trloleate, l-acid phosphate POP (6)sorbitol trioleate, LES-acid phosphate POP(4)sorbltol dioleate, l-aoid phosphate P OP (4) sorbitol dioleate, 1.5-aoid phosphate POP(6) sorbitol dioleate, Lacid phosphate POP(6)sorbito1 dioleate, 1.5-acid phosphate. POP(4)sorbitol trioleate, l-acicl phosphate. Na-POE (4) sorhitol dioleate, l-phosphate Na-POE(4)sorbit dioleato, 1.5- hosphate.

IPA-POE(6)sorbitol di 11? A-P OE (4) sorbitol tn IP A-P O E (6) sorbitol trioleate, 1 IPA-P OP (4)sorbitol tn'oleate, 1.5-phosphate IPA-POP (6) sorbitol trioleate, lphosphate IPA-P OP (6)sorbito1 trioleate, 1.5-phosphate. IPA-POP(4) sorbitol dioleate, l.5-phosphate IPA-POP (6) sorbltol dioleate, l-phosphate IPA-POP (6) sorbitol dioleate, l.5-phosphate IP A-P OP (4)sorbit0l trioleate, l-phosphate (la-POE (4) sorbitol dioleate, l-phosphate Ca-P OE (6) sorbitol dioleate, 1- hosphate Ca-P OE (4) sorbitol trioleate, l-phosphate Ca-P OE (6) sorbitol trioleate, l-phosphate Ca-P O P (4) sorbitol tn'oleate, 1-phosphate Ca-P OP (4) sorbitol tu'oleate, 1.5-phosphate Ca-POP(6)sorbitol trioleate, l-phosphate Ca-P OP (6) sorbitol trioleate, 1.5-phosphato Ca-I O P (4) sorbitol dioleate, 1.5-phosphate Ca-POP(6)sorbitol dioleate, l-phosphate Oa-POP(6) sorbitol dioleate, 1.5-phosphate NH P OP (4) sorbitol trioleate, l-phosphate o:cnare:o1came-vwwoawcnmoauwawwwwwwmmwwwoewoawwwwmu N99 NOTE.1=Exeellent; 2=Good; 3=Fair; 4=Poor; 5=InefiectuaL What is claimed is:

1. A dispersant composition soluble in organic liquids which comprises a condensation product formed by reacting at temperatures up to 110 C. a partial fatty acid ester of a polyalkoxy ether of a polyol having 4-6 carbon atoms and 1 hydroxyl group per primary, secondary, or tertiary carbon atom with phosphoric acid, polyphosphoric acid or their anhydride to form a condensate containing on the average of 1-2 mols of phosphoric acid equivalent per mol of alkoxylated polyol ester, said fatty acid ester being a condensation product of a mol of polyalkoxy ether having from 1-15 polyoxyethylene or polyoxypropylene units with from 1-4 mols of fatty acid having 10 to 20 carbon atoms such that at least one hydroxyl group remains unreacted, and salts thereof formed by reacting said phosphate-ester condensation product with strong inorganic or organic bases selected from the group consisting of alkali and alkaline earth metal hydroxides, ammonium hydroxide, primary, secondary, or tertiary organic amines, and organic diamines.

2. A composition of claim 1 wherein said polyol is selected from the group consisting of mannitol and sorbitol and said fatty acid is selected from the group consisting of oleic, lauric, and palmitic acid.

3. A composition of claim 2 wherein said polyol is sorbitol having 4-6 polyoxyethylene or polyoxypropylene groups per mol, from 2-3 oleic acyl groups per mol, and said organic base is selected from the group consisting of organic amines with up to 5 carbon atoms per organic group, and said inorganic base is selected from the group consisting of sodium hydroxide, calcium hydroxide, and ammonium hydroxide.

4. A composition of claim 2 wherein said polyol is sorbitol having 4-6 polyoxyethylene or polyoxypropylene groups per mol, from 2-3 oleic acid groups per mol, and from 1-1.5 phosphoric acid equivalents per mol.

5. A process for making a dispersant composition soluble in organic solvents which comprises the steps of forming an alkoxylated polyol having 4 to 6 carbon atoms and 1 hydroxyl group per primary, secondary, or tertiary carbon atom by reacting said polyol with from 1-15 mols of ethylene oxide or propylene oxide per mol of said polyol, condensing said alkoxylated polyol with from 1 to 4 mols of fatty acid having 10-20 carbon atoms at temperatures up to 250 C. such that at least one hydroxyl group remains unreacted to form a fatty acid polyol ether ester, further condensing said fatty acid polyol ether ester with from 1-2 mols of phosphoric acid equivalent in the form of an anhydride (phosphorous pentoxide) at temperatures up to C.

6. A process of claim 5 which includes the additional step of neutralizing said phosphate ester compositions withstrong bases selected from the group consisting of organic amines having up to 5 carbon atoms per organic group, alkali and alkaline earth metal bases, and ammonium hydroxide.

References Cited UNITED STATES PATENTS 3,275,667 9/1966 Bohunek 260-403 ELBERT L. ROBERTS, Primary Examiner UNITED STATES PATENT OFFICE CERTEFECATE {)F (IQRRECTIQN DATED November 20, 1973 Nu/magi, 1 Ernest C. Ford, Jr. Newark, DE and John D. Zech,

Wilmington, DE H is certif 2d that error appears in the above-identified patent and that said Letters Patent are hereby corrected shown beiow:

Column 1 line 29 "is should read if Column 1, line 64, after "tion" and before "Petroleum" insert the word of Column 2, line 35, "hydroxy" should read hydroxyl Column 2, line 42, "mixture" should read mixtures Column 2, line 66, "2" should read 3 Column 5, line 34, after "filter" and before "back" insert the word and Column 5, line 42, "an should read the Column 5, lines 59-60, "Lubricants, Liquid Fuels and Related Methods of Testing" should read Lubricants,

Liquid Fuels and Related Methods of Testing Table III, "Concentration, a./l00 ml." should read Concentration, grams/100 ml.

. Table III, "Do. should read IPA-POE(4)Sorbitol Dioleatel.5-Phosphate Table III, "Do. should read IPA-POE ('4)Sorbitol Trioleate l-Phosphate:

Signed and Scaled this fourth Day Of November I 975 [SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer (ummisximrer oj'Palems and Trademarks