US2375533A - Esters of hydroxylated acylated ureas - Google Patents

Description

' Patented May 8, 1945' Esrms' OFIHYDRO XYLATED ACYLATED UREA Melvin De Groote, University City, and Bernhard Kaiser, Webster Groves, ,M0.,

assl'gnors to Petrolite Corporation, Ltd, Wilmington, m1, 'a corporationof Delaware No Drawings Original applicationfMarcli 9, 1943,

SerialNo. 478,596. Divided. and this applicatlon September Z, 1943, Serial No, 501,030

Claims (01. 260-4045) This invention relates to a new composition of matter, our present application being a division of our H 478,596, filed March 9, 1943.

The main object of our invention is to provide a new material or composition of matter, that is particularly adapted-for use as a demulsifier in the resolution of crude oil emulsions, but which is adapted for use in other arts, as'hereinafter indicated. 'For instance, the said material may be used as abreak inducer in doctor treatment of the kind intended to sweeten gasoline. Certain of the compositions of matter herein described are of value as surface tension depressants in the acidification of calcareous oil bearing strata by meansof} strong mineral acid, such as hydrochloric acid. Similarly," some members are efiective as surface tension depressants, or wetting agents in the flooding of exhausted oil-bearing strata.

Anotherobject ofv our invention is to provide a novel method for producing sai'd' new" material or composition of matter. a f

The new compound or composition of matter herein described, particularly when it is employed as a demulsifier for petroleum emulsions of the water-in-oil type, consists of the resultant products obtained by reactioninvolving polybasic car-- boxy acids, preferably-and conveniently intl'ie form of an ester, such as diethyl 'phthalate,and acylated ureas, and particularly acylat'edsubstituted ureas having in the most preferred form, at least one, and more preferably, at least two hydroxyl radicals.

Such acylated ureas, or substituted ureas,. are of the kind in which the vacyll radical which is introduced is derived from detergentforming.

pending p'plication Serial No.

tain'derivatives of detergent-forming acids'react with alkali to, produce soap or soap-like monocarboxy acids containing eight carbon atoms ,or more,. and not;more than 32'carbon atoms, and arecharacterized by the i aetthat they combine with alkalies to produce soap or: soap like materials. These detergent-forming. acids include .fatty acids, .r'esin acid's, petroleum acids, etc. "Fer the sake officonvenience, .these acids will 'be indicatedabythe fomnulaRlCOOl-L "Ge!" materials, and are the obvious equivalent oijthe unchanged .01" unmodified detergent-forming.

acids; forinstance, instead of fatty acids, one

might employ the chlorinatediatty acids. 1 Instead ofthe'resin acids, one might employ the hydrogenated resin acids. Instead of naphthenic acids, one might employ brominated. naphthenic acids, etc. Acids obtained by the oxidationoi petroleum fractions or waxes may be employed.

Thistype of acid may also be subjected to various, modifications, provided such' modifications still retain detergent-forming properties.

Reference is made to our .co-p'endi'n'g. applica .tions Serial Nos.478',5914 and 478,595; filedlMarch 9, 1-943.- Said' co-pending applications describe new compositions of matter, for instance, the acylatedi derivatives ofreac'tionproducts obtained by combination with'dietha'no'lamine and' diethyl carbonate. This is illustrated in a" very simple aspect by the Ithree following reactions:

. Thesame reaction aspabove illustrated will take placein connection with other materials, such asvdipropano'lamine, dibutanolamine, and also in connection with secondary amines of the type ethyl .ethanolamine, ethyl p'rop'anolamine, ethyl butanolamine, propyl ,ethanolamine, propyl propanolamine, Q ,cyclohexyl. jethanolainine, Ibenzyl ethanolaminegphenyl. ethanolamine, .etc. I This is a alsotnue ,inaregard\.-to primary amines; such as n onoetl ano lamine, -monopropan.olamine, monoanolamine, etc.

butanolamine, monopentanolamine, mo'nohex-I Reconsidering the three reactions immediately: preceding, it is obvious that they may be considered as substituted ureas, substituted urethanes, and carbonic acid esters. The urethanes are, of course, esters of carbamic acid. It is also obviousthat the products of reaction above described, the esters, urethanes, the substituted ureas, etc, can be treated with ethylene oxide suitable. reactants, such as ethyl oleate, ethyl introduced a high molal detergent forming monocarboxy radical or acylated radical.

'It is also of interest to note that, as previously pointed out, the acylation reactions herein contemplated, whether involving the introduction of an acyl radical from a high molal detergentforming monocarboxy acid, or the acyl radical of a polybasic carboxy acid, need not be limited to the esterification type of acylation, i. e., reaction I of the subsequently described examples, it is high molal detergent naphthenate, ethyl resinate, etc., all of which is v 750T pounds of the kind herein contemplated,

' described in detail in said aforementioned 00- pending applications.

, I201. Attention is directed to U. S. patents to, De Groote Nos. 2,083,221, datedLJunef 8,1937, and" 2,059,273, dated June 3, 1936, to Pigg'ott.. It is to be noted that said aforementioned De Groote patent gives a more'elaborate description of the monocarboxy detergent-forming acids herein contemplated as reactants. It is" also believed, j-

in the light ,of subsequent investigationathat' in many instances reaction with a compound having a reactive ethylene oxide ring, such as ethylene oxide, propylene oxide, butylene oxide, glycid,y orthe like, may'res'ult in the'complete elimination of: any amino hydrogen atom, as

obvious that if oxyethylation'were omitted, the product would still be susceptible to reactions of the kind described, i. e., 'acylation reactions.

, 3 .It would appear that perhaps the simplest and most attractive reaction for the formation or 'rather, for the. formation of certain desirable intermediates, would be a reaction involving the ','amide of a highimolal detergent-forming acid,

such oleoamide, ricinoleoamide, etc., with 1 diethyl carbonate or the like, in the ratio of two moles of the amide for each mole of diethyl carbonate; particularly in the presence of a small amount of catalyst, such as sodium bicarbonate.

Our experience with this reaction has been that "the yields have been insignificantly low or nil, al-

through possibly, under difierent conditions, im-

our preference 'is' to follow the procedure illustrated by the following examples:

shown in both of said aforementioned patents,

i. e., the De Groote and Piggott patents.

"It is'also'obvious that substituted ureas in considerable variety and suitable for use' as a reactant-in preparing compounds of the kind herein contemplated, both for use as demulsifiers and ior'other uses, are readily obtainablefrom a variety of amines." j

It'may be Well to point, out that our preferred de'tergent forming acid, as a source of the required acyl radical, iseXempIified by the higher fatty acids, for instance, oleic, ricinoleic, linoleic, linolenic, stearic, lauric, etc. One need not employ' a single higher fatty acid, but may employ the fatty acids,"particula rly in ester form, as derivedf rom'various natural sources. In other words, one mayemploy the fatty acids or esters of fatty-acids as they occur inmixed form in cottonseed oil, corn 'oil, castor oil, soyabeanoil, olive oil, cocoanut oil, teaseed oil, linseed oil, etc.

In many instances, one. need not separate the acylated ureas, or substituted ureas, otthe kind herein "described from other members of a cogeneric mixture,such as esters of carbonic acids, or urethanes. Previous reference in'regard to this aspect has already'been made in connection with our two co-pending applications Serial Nos.

478,594 and 478,595, filed March 9, 1943. jThe,

use of such cogeneric mixtures as reactants will serve to yield afinallproduct which contains a significant amount of the compositions or -new orthe likep Itiis to: be noted that in some in'- stances it is more advantageous to reverse the procedure andreactflwith'a-compound such as diethyl phthalate fir'stfand then follow with an acylation reaction of the kind in-which there is SUBSTITUTED UREA Eazample 1 Diamylurea is prepared from amylamine, and

a cyanate. (See Berichte, 12, 1331, Custer.) 1

SUBSTITUTED UREA xample, 2

ceding example, except that 'cyclohexylamine is substituted for amylamine.

' SUBSTITUTED UREA-- Example 3 g g The same procedure is followed as inExample 1,

preceding, except that benzylamine is substitut'ed for amylamine.

' 'Synunetrical diamyl'urea is'reacted with a low molal ester of a hydroxylated highmolaldetergent-forming acid, such as the ethyl ester of ric inoleic acid, the ethyl ester of hydroxystearic acid, theethyl ester of dihydroxystearic acid, the

ethyl ester of hydroxylated acids obtained'by the oxidation of petroleum wax, etc. Equal molal ratios are employed.. One amino hydrogen atom remains without entering "into reaction. Such compound may-be illustrated in the following formula in' which: OCR.OH" represents 'the'acyl rade;

that aniline is substituted for vi I-HYd txfl W sh m detergent m ia m; y:

ISUaSTITU ED Unitas Example? The same procedure is followed as in the preceding example, except that instead of employing the amylated urea, one employs instead, varaevmea' ious substituted ureas described under the head-M" ing Substituted ureas, Examples 2-4.

OxYAtKYLATnn SUBSTITUTED U'REAS Example 1 .1 pound mole or we is treated with at 'iea t four pound moles of,.ethy1e'ne oxide (seeaforementioned U.. S. patent 'toD'e GrooteNoi 2,083,221}? and U, S. patent to Piggott No. 2,059,273). Suchtype of compound maybe illustrated by" the fol lowing. formula: 7

1100211406511 0 ezniooirnori t c n .v I i a H0IC2H4OC2H4- I 62114002134011 QXYALKYLATED SUBSTITU ED UREA Example 2- 1 pound mole of amylated'ureaof the kind described under the heading Substituted ureas; Ex-

ample 1, pre'cedingpis-treated with 2 pound moles of ethylene oxide so as to yield the corresponding oxyethylated deriyative. v

OxYALKYLATaD SUBsTTTU'rEb Una/i KExample '3 actant, one employs insteadvari'ous otherj'substituted ureas of the kind-described under the previous headings fSubstituted ureas, Examples 2-4, inclusive.

OxYliLxYLATEn SUBSTITUTED UREA Example 4' The same procedure is followed as in the three preceding examples, except that some other reactant containingiaireactive ethylene oxide ring, for instance, propylene oxide, butylene oxide, glycid, or thelike, are employed instead of ethylene oxide. t

ESTER-TYPE ACYLATED SUBSTITUTED URE'AS Example 1 -Hydroxylated substituted ureas; preferably havq ing at leasttwo' alcoholic junctions, are reacted with low molal esters of high molal detergentfo'rmin-g acids which may ormaynot behydroxylated; rforexample, one pound mole of an oxyalkylated urea exemplified byp- 0xya1kylated Example 1, preceding, is reacted with. 1 pound moleofLethyloleate. The reaction may beindicated in the. following manner:

I i I I "J 'HOC2HAOC2H4 O A *C'aH40C2H40iH-l-C1H50}OC.R I N- C'N\ 1""" 110 0111.0 cm. ogn o ozmon in "the above "reaction 02115000113 1 represents Instead of employing amylated urea asja re Esme-Tyre :AoYL-Am' suasrirmmftixms Example 2 1 ESTER-TYPE AoYL'ATEn SUBSTITUTED Una/is I Example 4 Ethyl naphthenate ate in Example]; or 2, preceding;

a a Es'raR-TYPE ACxL TEn SUBSTITUTED UREASH Examplefi.

Ethyl resinate, prepared by the esterificationfiof' rosin. with ethyl alcohol, is substitutedjfor ethyl;

oleate in Examples '1 and 2, preceding. FINAL Comrosrrron or- M TTER V Example .1 pound mole of an amide acylated substituted urea, as exemplified by the type of material} described under Example 1, preceding is reacted. with 1 pound ;mole of diethyl phthalate. The

substituted urea is preferably, reacted with 2 to 4 moles ofzan oxyalkylating agent,priorto re-' action, with diethylphthalate. Ethylene oxideis Such reactions, 5 at: least; as

especially suitable. far as formationof a comparatively simple monomer, may be exemplified 'in-1the'fol1o'v'ring manner:

ocitorr c Frmr. comeosrTron or MATTEE' I Example 2 ".Ihe same procedure is followed as in Ester-type acylatedsubstituted ureas, Example 1-, preceding, but there is employed as a reactant'the type of material under the heading Amido-type acylated substituted ureas, Example 2 a exemplified by- Example. 3 or low molal essubstituted. for ethylole v t FINAL comrosrrronjor ,MArrEa V Eicample #3 The same procedure followedas in Examples 1 "and 2, 'prec'eding, q but instead ofthe previ'.

ous reactants employed in c'onjun'ctionwwith cli ethyl phthalate, there is employed instead a majterialof the kind. described under the} headin Ester-type Acylated substituted ureas, Example 1. The reaction maybe indicated, thus:

Y niaterial 'fof 'thekind typified by Ester-typeac y la'ted substituted ureas, Examples '2 to 5, inclusive.

FINAL Co PosrrIoN or MATTER Examp e v The same procedure isfollowed as in the preceding'examples, except that where the reactant employed in-conjunction with diethyl phthalate is 'p'olyfunctionaLthe molar proportion ofdiethyl phthalate to the 'a'cylated "intermediate (-,acyl" having reference to the high molal "deter-- gent-forming monocarboxy acid radical) is inacylation, which .generally;means,thegelimination,

of water, or an alcohol, or possibly, ammonia. In

view of the employment of a reactant's'uch as ethyl oleate, or ethyl ricinoleate, it is obvious that acylation will take place, withthe elimination of ethyl alcohol. Naturally, methyl oleate, methyl ricinoleate, propyl 'oleate, propyl ricinoleate, butyl oleate, butyl ricinoleate, or the like, might be employed. Such reactions i'ar'e generally conducted at a point somewhat in' excess, of the boiling point of the alcohol involved?Forginstance, wherethe reaction involves v the evolution of ethyl alcohol, a

suitable! working temperature is approximately 1 150 C. 'On the other hand,.if butyloleate, or

butyl ricir'ioleate-i'sj employed, a suitable temper-' ature would be approximately 200 CQ 'Such re-, actions are conducted with constant stirring, and generally take place in; a comparatively short Comperiod of time, for instance, 2-12 hours. pleteness of reaction is generally indicated by the fact that substantially the theoretical amount of 1 alcohol, after making allowance for impurities and mechanical loss, is evolved and may be concreajsed' to" a polymolecular proportion, for ine e a w 1 a j Sm oo'nrosirron OFMA'T'TERT .5 1 Eaiample'li The same procedure is followedas in the pre ceding Examples 1 to 5, inclusive, except that" the diethyl ester of someiother suitable'polybasic carboxy acid, such as diethyl maleate, diethyl fumarate, diethyl adipate, diethylsuccinate, di'-' ethyl azaleate, diethyl citrate, di-ethyl citracow.

nate, diethyl' se'bacate, diethyl tartrate, or the like, isemployed. 1 FINAL Comrosrrrorf 0F MATTER Example 7 The same procedure is followed in Examples 1 to 6, preceding, exceptthat some other low molal alkyl ester, particularly a dialkyl ester, is

employed instead of the diethyl i ester. For in stance, one might employ 'dimethyl phthalate,

ethyl methyl phthalate, dipropyl phthalate, methyl propyl phthalate, ethyl-propyl phthalate,

dibutyl phthalate, propyl butyl phthalate, ethyl butyl phthalate, etc. In various of the above in-j stances, the acid itself or anhydride, such as phthalic anhydride, maleic anhydride, citraconic I anhydride, or the acid, such as adipic acid,

' azaleic acid, or the like, may be used.

Reference is again made to the fact that it has'been previously noted'that in some instances it is more convenient and desirable to react a selected raw material or intermediate with a, re-

densed and measuredn fI'he same applies when the acylation reaction, involves areactant such as diethyl phthalate, or the like. This is also true in regard to reactions involvingdiethyl carbon! ate. The diethyl carbonatemeactlons areisometimes c'atalyzedeby. thejadditi'on of a. small amount, for instance, approximately /4% to /g%' of sodium bicarbonate' Conventional acylation reactions of the kind involved in the formation of oleoamide, or ricinble, -.insoluble'resin'... (See Ellis, Chemistry ,Of.

Synthetic Resins, 1935, "page 862, .et. seq.)

It is. our preferencethat the products be ob-; tainedfrom --polyhydroxylated acylatedproducts.

actant suchasdiethyl phthalate, or the like,.and

, subsequently react with ethyl ,oleate, ethyl ri'cinoleate, orfthe lik'e.=,

v In the precedingexamples, it ism be noted 1 that the reactions, in part, involve conventional oleoamide, are so well k'nownjthat 'descriptioniis not required.

We have found that the most suitable products for various purposesi'and particularly, fornde mulsification, are sub-resinous, semi res'in'ous, or

balsam-like productsand are. preferably. derived from polyfunctionalia'cylated reactants, in which the acyl group is derived from a high 'molal de- I We have foundthat-such products are soluble to a fairly, definite state, for example, 5% :in somesolvent, such 'as water, alc0hol,-benzene, dichloroethyl" tergent-formingmonocarboxy acid.

ether, acetone, cresylic. acid, dilute acidic acid, dioxane, or the like. -'I'his is simply another way of stating that it is preferable, that the product be one of the sub-resins, which are commonly referred to as an A resin, or a B resin, as distinguished-from a" C resin, which isa highlyinfusiby reaction with diethyl phthalate, or the like;

*Indeed;- 'it"isour *preference to employ polyhy-- droxylated acylated products of'the kind in which there is no amino hydrogen atom present, i. e., the kind in which acylation is limited entirely to the esterification type of reaction.

In view of what has been said as to the numerous and varied aspects of the present inven-' i 1 tion, it is apparent that'a monohydroxylated acmat d. product fr e m an a i o :,.h o en.

atom, can form only'a monomer such asa --plete ester or fractional, ester. Thus, if the hydroxylated acylated products employed as reactants for combination with diethyl phthalate,

or the like, they may be 'consideredfas an alcohol,

polybasic acid will result in a compound which may be indicated by the following formula: Yx(COOH)n' in which YX represents the ester radical, exclusive of the carboxyl groupor groups,

where n indicates the number 1 or more, and which is in reality'a contraction 'of a more elaborate structural formula, in which X and Y are joined by a carboxyl radicalior residue. Assuming, however, as would be true in the majority of cases, that the alcohol actually'would be a polyhydric alcohol, and that the acid body wouldbe polybasic in nature, for instance, if one employed a diphthalate of a polyhydroxylated ester diamide oxygen atom. Compare reactionsinvolved when a glyceride such as a castor oil or olive ,oil is' treated with ethylene oxide. v, r

In addition to the various uses previously enumerated, the new compounds herein described are capable of use for theremoval of the residual mud sheath of a well drilled by the rotary meth-" od. Said new compounds are also adapted for various uses where wetting agents of the conventional type .are used. As to some of such uses, which are well known, see The expanding application of wetting agents) Chemical Industries, volume 48, page 324 (1941). v

.The words acidy and acy and the words acidylation and acylation are usually, used synonymously. Compounds of the type herein contemplated, and particularly for use. as demulsifiers, are characterized by having two different types of carboxylic acid radicals, or carboxylic acyl radicals present. One type is derived from high molal detergent-forming monocarboxy acids, such as higherfatty acids, and the of the kind previously described, then examination reveals that the formula might result in a combination, in which there were neither residual carboxyl radicals, nor residual hydroxyl radicals, or might result in compounds in which there were residual hydroxyl radicals, and no residual carboxyl radicals, or compounds where there might be residual carboxyl radicals and no residual hydroxyl radicals; or there might be both, This is indicated by the following:.

in which YX, as previously, represents an ester radical, and more particularly, a fractional ester radical, exclusive of the hydroxyl group or groups, and exclusive of the carboxyl groupor groups and in which q indicates a small wholenumber (one in the case of a monomer, and probably not over 10, and usually less than 5, and m and n indicate the number 1 or more, and m" and n" indicate zero or a small or moderately sized whole number, such as zero, one or more, but in any event, probably a number not in excess of 4-8.

Actually, in view of what has been said as to the most desirable procedure of manufacture, in

order to avoid decomposition, it is obvious that the free carboxyl atom above will not appear, but the ester (radical, i. e., one where the carboxylic hydrogen atom has been replaced by a methyl, ethyl, propyl, or butyl group, will appear.

It is also obvious that the solubility of the reagents herein described may be enhanced by oxyalkylation, i. e., the final composition of matter-exemplified by Examples 1 to 9, preceding, may, in various instances, be subjected to treatment with a reagent containing a reactive ethylene oxide ring, for example, ethylene oxide, propylene oxide, butylene oxide, glycid, etc. In such instances, the ethylene oxide or equivalent reactant reacts with any amino hydrogen atom present or any hydroxyl radical present, or may cause a rearrangement or re-esterification by replacing a low mole alkyl radical, such as an ethyl radical, by a hydroxy ethyl radical, or an equivalent radical, in which thecarbon atom chain is interruptedone or more times by an other type is derived from polybasic acids, particularly phthalic acid, and the like, or other suitable derivatives thereof, such as diethyl phthalate. For purpose of clarity, in the hereto attached claims, the use. of the words acy acylatedfand acylation is limited to high molal monocarboxy detergent-forming acids, whereas, the expressions acidyl, acidylated" and acidylation are used in connection with polybasic carboxy acids.

Attention has been previouslydirected to the fact that the expression alkanol includes the type of hydroxy aliphaticradicals, in which the carbon atom chain is interrupted at leastonce by an oxygen atom, i. e., contains an ether link- I age. We have foundthe type in which the ether linkage recurs a fairly large number of times, for instance, 4to 18 times, represents the most desirable type of demulsifier, and also the most desirable type of compound forother purposes enumerated. Unquestionably, the recurring ether linkage, particularly that derived from low molal oxyalkylated agents, "such as ethylene oxide, propylene oxide, butylene oxide and glycid, has a distinctlyfunctional significance. .The esters which are obtained by reaction between polyin which R is selected from members of the class consisting of hydrocarbon radicals having not over 6 carbon atoms; R1CO(OR2)12; R and H(OR2)11. in which R100 is the acyl radical of a monocarboxy detergent-forming acid having at least 8 and not more than 32 carbon atoms; R: is an alkylene radical having not over 5 carbon atoms, and n is a small whole number not over 5, with the proviso that there must be present at least 1 hydroxyl radical, at least one occurrence of the radical R100 and at least one occurrence of the radical 0R2.

Previously included formulas show the acyl radical in a form equivalent to an R.CO or to OH.R"CO. The former presentation represents any acyl radical, and the latter is limited to-the hydroxylated types, such as the .ricinoleyl radical. For convenience, the word acyl has been limited to use in connection withmonocarboxy :18 carbon acids) as defined. 1 the' other :handfthe synonymous word acidyl" has-beenemployed in 'connectionwith pclycarboxy acids, suchas the radical bta'ined' from phthalic acid, to wit:

Mdre'compmemthe ala radical might be indicated by the following formula: 06.3".00', with the proviso, that in' the case of a tribasic acid, there is a carbonyl group or carboxy group present as an integral "part, of Bi";

' Having thus described our invention, what we claim as new and P e t is? 1; 'lifhe pclycarboxy acid estersof hydroxylated acylated ureas of the following formula;

desire 1:0 [secure by Letters in which'B, selected 'from members.of the class consisting of; hydrocarbon radicals having not Krona in yvhich R1CQ i the, acylradical of a monocarboxy detergent-forming acid. having at least 8 and not morethan 32 carbon atoms; R2

1 is analkylene radical having not over 5 carbon atoms, and n is a smalljwhole number not over 5,

'with'the proviso that theremusthe present at 7. The esters define'd' in claim 1, wherein R'CO is the acyl radicalofa higher fatty acid having 18 carbon atoms and at least one ethylene linkage, the polycarboxy'acid is-maleic acid, Riis the ethylene radical, and n .is one. a w 8. 'The esters 'definedin claim 1, wherein RCO is the acyl' radical of'a higher fattyacid' having 'l8carb'on atoms and at least one ethylene linkage, the polycarboxyacid is iphthalic 'acid, Risis the .ethylenevradical, and n is one. 9. The esters defined in claim 1, wherein R'CO is the acyl radical of a higher fatty acid having I l8 carbon atoms and at leastone ethylene linkage, the ;polycarboxy acid iszadipicacid, Ra is the ethylene radical;- and nis one.

least lhydroxyl radical, at'least oneoccurrence of the radical-R100 and at least one occurrence *oftheradicalORa g I 1 h g e esters definedin claim 1, wherein R700 is thecacyl radical of a higher fatty acid having laca'rbon atoms.

3. The esters defined in claim l tvherein R 'CO is the acyl radical ofa higher fatty, acid having atoms and atleast one ethylene, linkage "4. The esters defined: in claim L wherein R'CO is't he acyl radical of ahi'gher fatty acid having 18*carbon atoms and at least; one ethylene linkage, and the polycarboxy acid isdicarboxy.

, 5. The esters defined Lin claim Lwherein R'CO is the acyl radical ofa higher fatty acid having 7 v 10. In the manufacture of esters, as defined in claim 1, the step of esterifying hydroxylated acylated areas of the following formula:

in which Rlis selected, from members or the class consisting of hydrocarbon radicalshavin'g. not over 6 carbon atoms; R1CO(OR2).n; R and H(OR 2)n, in which R1CO is the acyl radicaliofsa monocarboxy detergent-forming acid having at least'8 and not more than 32 carbon atoms;' R2 is an alkylene v radical having not over 5 carbon atoms, and n is a smallwhole'numbernot over 5,

'with the'proviso that there must-be presentat least 1 hydroxyl radical, :at least. one occurrence of the radical R100 and at least one occurrence of the radical 0R with the dialkyl esters. of polycarboxy acids in which the alkyl radical contains less than 6 carbon atoms. MELVIN DE GRQOTEQ BERNHARD KEISER.