2,411,957 Patented Dec. 3, 17946 UNITED ‘STATE, S OFFICE Q‘ esst??jiiies I I it i I’ Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to , Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Original application June 23, 1943, Serial No. 492,180. Divided and this applica tion April 7, 1944,'Serial No. 530,042 10 claims? (01. 260-404) 1 * see U, s. Patent No.2,242,837, dated May 20,- 1941, This invention relates to a new‘ chemical prod uct or compound, and to a novel method for manufacturing the same, our present applica'» tion being a division of our pending application to Shields. Serial No. 492,180, ?led June 23,1943, now Patent No. 2,372,254fissued March '27, 1945; I ., Although any of the high molal monocarboxy acids canv be converted into esteramides of the kind described, by conventional procedure, it- is our preference to ‘employ hydroxylated ester , amides derived from higherv fatty‘acids, rather "fO'ne. object of our invention is’ to provide a than petroleum. acids, rosin acids, and'vthe like. We have found that by far the most effective new-chemical product ‘ or compound ‘ that is capablefof various uses, but which is particularly adapted for use as a'demulsi?er in the resolution 10 demulsifying agents are obtained from un saturated fatty acids having ‘18 carbon atoms.’ or crude‘ oil emulsions or the wateri-in-oil type,. I Such unsaturated fatty acids include the higher ,Another object is to provide-a "practicable method for manufacturing said chemical product , fatty acids, such as, oleic acid, ricinoleic acid, 'linoleic acid, linolenic acid, etc, One may. em or compound. ~ I - ’ » . I a 125 ' Brie?y described, our new chemical product ploy mixed fatty acids, as,_for example, the fatty acids obtained by hydrolysis ‘of cottonseed oil, consists of a sub-resinous or semi-resinous prodr not. obtained by reaction between a polybasic carboxy acid or its equivalent, such as the Van hydride, and a hydroxylated esteramide-ofthe soyabean oil, corn oil, etc. When our new product or compound is intended to be used as a demulsi her ‘for resolving petroleum emulsions of the water-in-oil type, it is preferably obtained from 20 kind hereinafter described.’ Said hydroxylated unsaturated fatty acids, and morespeci?cally, esteramide is of the kind in. which the" amido ' unsaturated fatty acids containing a hydroxyl acyl radical is derived fromia hydroxylated'mono carboxy acid having not over 5lecarbonatoms, and the acyloxy radical is characterized bybeiiig radical or unsaturated fatty'acidswhich have been subjected to oxidation or'oxyalkylation, such acid having at least 8 and not more. than 32 ' ‘ derived‘from a monocarboxyjdetergentrforming 25 carbon ' atoms. ‘ . " ’ ,~ . as oxyethylation. _, ' , " I‘ 5 p U ‘ The esteramidesiof the‘ kind herein described may be obtained in ‘any conventional manner. They are usually derived from the hydroxylated _ It .is Well 1 known that certain .monocarboXy low molal acids themselves; .but if desirable, ,the organic acids containing eight carbon atoms or more, and not more than 32v carbon atoms, are characterized by. the fact that they combine with alkalies to produce soap or soap-like‘ materials. functional equivalents'such as the anhydrides, These detergent-forming acids include ,fatty _acyl chlorides, or other. derivatives, maybe ‘em-H ployed.i suitable acids ‘include, hydroxyacetic- acid (glycollicv acid), ,hydr'0Xypr0pionic acid, “(lactic acids, resin acids, petroleum acids, etc.» 'For'. the polyb'asic ‘ hydroxy} acids. acid), and others. It 'is' not intended to include Not only‘ may alpha sake of‘ convenience, these acids will be indicated by the formula R'COOH. Certain derivatives of hydroxy acids be employed, but one may also detergent-forming acids react with'alkali to pro_-' hydroxy butyric acid, betahydroxy propionic acid, employ'the betahydroxy acids, for'insta'ncqbeta- . duce soap or soap-like materials, and are the . . etc. The objection’ to the use, of such betah'ydroxy, obvious equivalent. of Y the unchanged or . un acids which contain, a hydrogen atomon the 40 modi?ed detergent-forming acids;‘;for instance alpha, carbon atom, is that they are rather ,un- ‘ instead ‘of fatty‘ acids, one rmightlem/ploy" the stable. Thus, on heating, they, lose the elements chlorinated» fatty vacids. ' Insteadgofthe ‘resin of water, forming unsaturated acids. This is acids, one might employ the hydrogenated resin ‘ acids. Instead of’ naphthenic acids,‘ one-might 45 employ brominated naphtheniciacids, etc.‘ ' ' ' The fatty‘ acidsnlare of the rtypebcommonlyQ referred ‘to as highe'rfatty acidsyl and of'cour'se, this is-also trueinr'egard to derivatives ‘of’ the illustrated by the formation of acrylic acid from betahydroxy .propionic acid; For all practical purposes, the'two hydroxy acids'most' suitable are lactic acid, and hydroxyacetic acid. ‘7 In some 'instances;thereare available derivativesiof acids ‘ such as ethanolacetic‘a'cid, propanolacetic acid, kind indicated, insofar ‘that such derivatives are 50 and v,the like. See U. S. Patent No. 2,238,928, I ‘obtained from higher fiatt’yiacids. ‘The'petroleum’ acids include I not: 5 only: naturally-“occurring naphthenic acids,.'b:ut1 also acidsobtained by the oxidation offwax, paraiiin; etc. Such, acids ‘may have as many-as 32 carbon atoms. 1 For. instance,» dated April 22, ‘1941, to Cahn and Harris, and Y particularly Example ,51, on page 3. Note par ticularly Examples 64-66 on pagej‘i. .' If vsuch acids ‘ bevgconsidered as derivatives of‘ hydroxyac'etic ' acid, and ,obtai'ried hypothetically.v by an oxy-~ 2,411,957 3 4 alkylation reaction involving alcoholic hydroxyl radical of hydroxyacetic acid, and ethylene oxide, then it is apparent that analogous compounds previously mentioned. As illustrating such hy droxylated esters, reference is made to the fol lowing formulas: would be derivable by the use of glycid. In this connection note Examples 69 and 70 of the afore mentioned Cahn and Harris patent. In actual’ manufacture, these particular types of acid are obtainable by other means. The amide of such low molal hydroxy acid may be treated with an oxyalkylating agent, such as ethylene oxide, propylene oxide, butylene oxide, or the like, so as to produce a compound of the’ following type: - O alkylene. OH 15 alkylene. 0 H Actually, the alkylene radical might represent an equivalent divalent radical, in which the car bon atom chain is interrupted at least once by 20 oxygen, as Having obtained a bis(hydroxyalkyl>amide of the kind described, such compound can then be reacted in aconventional manner with a high molal acid or its equivalent, to give an esteramide, In the above formulas, RCO represents the acyl radical derived from a hydroxylated acid having in other words,»a compound of the following type: hydroxypropionic, hydroxybutyric, etc. OHR’CO 5 carbon atoms or less, such as hydroxyacetic, represents the acyl radical of a hydroxylated (I? /alkylene. O O C R’ acid, such as ricinoleic acid, hy'droxystearic acid, R CN orsimilar acids obtained by oxidation, such as alkylene . O H A procedure that is frequently more readily adaptable is simply the reaction between a low molal acid, such as acetic acid, and a material 3 of the kind exempli?ed by diethanolamine, di propanolaminaor the like. For the sake of brev ity, reference hereafter will be, made largely ,to diethanolamine and acetic acid, although other ', . suitable reactants have already been described. The method of manufacturing esteramides is so well known that no further description is re quired; but for convenience, the following exam ple is given in substantially verbatim form, as it blown oleic acid or'acids obtained by the hydroly sis of blown olein. ‘Such acyl radicals all contain at least 8 and not more than 32 carbon atoms and are apt to contain 18 carbon atoms. R”CO is the-acyl radical derived from a non-hydroxy late'd monocarboxy detergent-forming acid, par ticularly an unsaturated acid, such as oleic acid, linolenic acid, etc. It is understood, of course, that a mixture of fatty acids might be employed instead'of a single fatty acid; R'” is a hydro carbon radical having 4 to 12 carbon atoms. , In examining the above formulas, it is to be notedthat comparable products might be obtain appears in U. S. Patent No. 2,238,923, dated April ' able from ,monobutanolamine, dibutano-lamine, 22, 1941, to Cahn .hHarris: monopropanolamine, dipropanolamine, mono glycerylamine, diglycerylamine, or the like, in stead'of being derived from mono-ethanolamine or diethanolamine. Similarly, the products Example 0 (1) 156 grams of methyl lactate and 157.5 grams of diethanolamine were re?uxed for 3 hours at 94 degrees (1., the alkalinity calculated as diethanolamine dropping from 50 shown in the last two formulas are derived from 50.5% to 5.4%. To the reaction mass 78 grams of methyl trisdiydroxymethyl)aminomethane. Similar de lactate were added and re?uxlng was continued for 3% hours at 95 degrees C. The alkalinity dropped to 0.9% rivatives may be derived from 2-amino-2-ethy1 expressed as diethanolamine. The excess methyl lactate and the methyl alcohol which formed during the reaction were removed by distillation at a pressure of 10 mm. and at a temperature up to about 120 degrees C. The reac tion product was a reddish brown, water-soluble, somewhat viscous material and comprised largely or essentially the lactic acid amide of diethanolamine. _ (2) 37.3 grams of the lactic acid amide of diethanola mine, produced in part (1)‘ hereof, and 9.8 grams of lauric acid were heated together to 60 degrees C., _whereupon a homogeneous solution resulted, and the heating was then continued for 20 minutes at 140 degrees C., for 20 minutes 60 at 150 degrees C., for 20 minutes at 170 degrees C., and for 15 minutes at 180 degrees C. Previous reference has been‘made, however, to the fact that our preference isv'to use hydroxy acetic acid, due to its low cost and ready avail ability. ~ 1,3-prop'anediol and 2-amino-2-rnethyl-1,3-pro panediol. " ' . ' The hydroxylated esteramides may, of course, be derived in any other suitable way, such as reaction with ammonia, followed by oxyethyla tion, or some other suitable process. Thus, the low molal acids themselves, or, if desirable, the functional equivalents, such as the anhydrides, acyl chlorides, or other derivatives, may be re acted with ammonia, or a primary amine, such as‘any suitable alkylamine, or an alicyclic amine, or an aralkylamine, to give the amide or substi- , tuted amide; in any event, a, compound contain ing at least one amino hydrogen atom. Suit vIllustrating somewhat'similar types of reac tions, see U. S. Patent No. 2,238,902, dated April 22, 1941, to Katzman and Harris; and also U. S. Patent No. 2,257,180, dated April 30, 1941, to Munz 70 when an amine is used instead of ammonia for and Tra'skan. reaction with the low molal hydroxyl acid, one . V In View of what has been said, it will be obvious that hydroxylated esterarnides of the kind herein able amines include butylamine, amylamine, octylamine, decylamine, cyclohexylamine, benzyl amine, phenylamine, etc. Generally speaking, may employ a hydroxylated detergent-forming acid such as ,ricinoleic acid, in order to insure a employedas reactants, may be obtained in various pluralityof available alcoholic hydroxyl groups manners, including those described in the patents 75 for subsequent reaction with the polybasic car 2,411,957 26 non-hydroxylated detergent-forming acid, such be treated with four moles or six moles of ethyl as oleic acid, is employed, there still'is available ene oxide, or even more. under any circumstances at least one alcoholic Previous reference has been made to the fact hydroxyl radical, to wit, the hydroxyl radical or ‘radicals of the low molal acyl radical. » . i. e., the low molal amide, instead of being treated with two moles of ethylene oxide or the like, might ‘boxy-acid or its equivalent. However, even ifa that the preferred compounds are derived from - ' hydroxyacetic acid, unsaturated fatty acids, par 1 g In this connection it may be wellto point out ticularly ricinoleic acid, etc. The type of amide which we prefer to employ for reaction with stituted amide so obtained can be reacted with'a '10 phthalic anhydride or the like, may be illustrated polybasic carboxy-acid or its equivalent without ' by the following: further modi?cation. However,» the most desir Esteramide, Example 1 able type of compound is derived from such low One pound mole of hydroxyacetic acid is re ‘molal amides as are characterized by aplurality acted with one pound mole of monoethanolamine; of alcoholic hydroxyl radicals.- Thus, if the sub 15 and after the amide has been formed in substan stituted amide obtained by reaction between butyl tial yield, the mass is then reacted with one pound amine and hydroxyacetic acid is treated with the following: By considering the reaction involv inghydroxyacetic acid and butylamine, the sub mole of ricinoleic acid so as to form the ester. ethylene oxide, glycid, or the like, and then re The reaction is illustrated by the following equa acted with oleic acid, or some equivalent non-hy droxylated high molal acid, one still has available 20 tions: a plurality of alcoholic hydroxyl radicals. How 1. HOCH2COOH+HOC2H4NH2+ . HOCH2CONHC2H4OH ever, on treatment of such-7 amide with ethylene oxide, glycid, or the like, at least under certain 2. HOCH2CONHCZH4OH+HORCOOH+ HOCHzCONHCzHrOOCROH Esteramide, Example 2 One pound mole of diethanolamine is substi conditions, there is formed to a very minor de gree amides of certain low molal acids of the kind previously described; 1. e., it is exempli?ed by ethanolacetic acid. lAS a matterof fact, how ever, it is our preference that even under such tuted for monoethanolamine in Example 1, pre circumstances, i. e., even where there is a plu rality ‘of alcoholic hydroxyl radicals present, the 30 high molal acid also contains a hydroxyl group. This, ricinoleic acid is the preferred reactant employed to supply the high molal acyloxy radi cal; and in such instance, the hydroxyl radical, which is part of the ricinoleyl radical, would . serve as a reactive function forcombination with ticularly as demulsi?ers, must present a rather acids are used, in light of the fact thateither one, a Esteramz'de, Example 3 Monopropanolamine, dipropanolamine, mono butanolamine, dibutanolamine, tris(hydroxy methyl) aminomethane, bis (hydroxymethyl) ami 14, preceding, are treated by a conventional oxyalkylation process with 1-2 moles of ethylene phthalic acid radical ‘or its equivalent is attached directly to the low molal acyl radical, as differ entiated from being attached in an altogether oxide, propylene oxide, butylene oxide, glycid, or ' the like; different position to a ricinoleylradical or ‘an ' ethanol (b) There radical; would or be present . a terminal . . . hydroxy-i . H . Esteramz‘de, Example 5 Esteramides of the kind obtained in Examples . 'A molecular arrangement whereby - Examples 1-3, preceding. ‘or'possibly. both, .‘of the following structural ar (a) ' Oleic acid is substituted for ricinoleic acid in peculiar structure when hydroxylated low molal ‘ . nomethane, and the like, are substituted in place of monoethanolamine and diethanolamine in Examples 1 and 2, preceding. Esteramicle, Example 4 phthalic anhydride or the like by esteri?cation. In this connection, it may be pointed out ‘that .such‘compounds herein contemplated, and par rangements may occur, to wit: ceding. to methyl group, or its equivalent, as, for example, when derived from hydroxyacetic acid; .and thus Esteramide, Example 6 Methyl lactate is employed in the manner previously indicated to produce lactic acid de rivatives instead of hydroxyacetic acid deriva such a terminal radical would be distinctlyihydro tives. In any event, the reaction of the hydroxylated phile in character, as compared with the ordinary, ., methyl radical appearing in. acetic acid or the . , ester amide of the kind described with a poly basic carboxy acid or its functional equivalent, such as the anhydride, is a well-known reaction Other. procedures suggest themselves for prepa like. '~ I . . . .. ., ration ofcompounds having a plurality of-alcoe and is nothing more or less than an esteri?cation holic hydroxyl radicals. _ For instance, in. the case ? 60 reaction of the kind employed to produce ,of compounds derived fromt‘butylamine, cyclo hexylamine, benzylamine, or the like, one might phthalated castor oil, phthalated ricinoleoamide, etc. For instance,.common comparable reactions use glycid or the like as an oxyalkylating agent. " are described in U. S. Patent No. 1,976,602, to Another procedure involves preparing the amide . from ammonia and treating such amide with an; De-Groote, Keiser and Adams, dated October 9, 1934, and U. S. Patent No. 2,078,652, to De Groote oxyalkylating agent, such as‘ethylene oxide, p-ro and Keiser, dated April 27, 1937. pylene oxide, butyleneoxide, glycid, or the like, Brie?y stated, the molar combination of the re actions selected depend upon the available num ber of hydroxyl groups and may be illustrated by to produce acompound of the following type: ' 0 alkyleneOH " V the following examples: _ . . BXIIIJN alky1ene.OH ‘ 7‘ _ Actually,’t_he alkylene radical might represent an i'equivalentédivalent ‘radical _in1 which the carbon, I 'latoiii'chairi is interrupted atTle'ast'i onoe'by oxygen;- ~ a ' » - Final product, Example‘ 1 One pound mole of a polyhydroxylated ester ' - amide of the kind exemplified by ,Ev‘steramide, Ex amples T145} preceding, is reacted:v with ‘one pound 2,411,957 7 .8 mole of phthalic anhydride at approximately being condensed by the trap. This is a conven tional-procedure, commonly employed in this type led-165° C. until esteri?cation is complete, as in dicated by the substantial elimination of one al ;or similar types of reaction. , Although we prefer toruse phthalic anhydride coh-olic hydroxyl radical. The product so ob tained has one free carboxyl radical. as the most desirable source of the polybasic car boxy acid, one may use other polybasic carboxy acids or their anhydridessuch as succinic, malic, Final product, Example 2 fumaric, citric,.maleic, adipic, tartaric, glutaric, The same procedure is followed as in the pre ceding Final product, Example 1, except that the 10 .diphenic, naphthalic, oxalic, ,pimelic, .suberic, azelaic, sebacic, etc. Naturally, a simple deriva esteramide employed is the kind exempli?ed by tive of a polybasic acid, such as chlorophthalic Esteramide, Example 6, instead of E'steramide, acid, can be used as advantageously as phthalic Examples 1-5, inclusive. acid itself, although there isno added advantage Final product, Example 3 in the use of the more costly chemical compounds. 15 The same procedure is followed as in Final product, Examples 1 and 2, except that two, moles of phthalic anhydride are employed instead of In View of the large number of .reactants and types of, materials described, it maybe well to note those which we particularly prefer. It has been. pointed out that we prefer to use unsatu one mole; and the ?nal product is characterized rated fatty acids as the source of the high molal by the presence of two free carboxyl radicals. 20 acyloxy radical, and particularly the hydroxylated fatty acids commonly available, to Wit, ricinoleic Final product, Example 4 acid. We prefer to use phthalic acid, maleic acid, or their anhydrides,or oxalic acid as the source of the poly-basiccarboxy acid. We prefer to use hydroxyaceticacid or its equivalent as the source Insofar that some of the esteramides described in Esteramide, Examples l~6, inclusive, may have more than two alcoholic hydroxyl groups per molecule, one may employ-the same type or” re action as described in theexamples immediately preceding, except that the maximum amount of phthalic anhydride which can be employed from a sto-ichiometrical standpoint is employed, and thus, the ?nal product of reaction has a. plurality of carboxyl groups and a substantial absence of of the low molal acyl radical. We prefer to use monoethanolamine or diethanolamine as the re actant for formation of the substituted amide em ployed for subsequent reaction to produce the 30 hydroxyl groups. esteramide. ' > > In view of what has been said, it is apparent that the hydroxylated esteramides of the kind described ,previouslylmay be considered, for the sake of simplicity, as being in- the classof an alcohol, i. e.,'a monohydric or polyhydric, alco incl product, Erample 5 In the preceding examples, where phthalic anhydride is used, maleic anhydride or oxalic acid is employed. In such instances where ox~ alic acid is employed, it is desirable to use a lower ‘ temperature, in view of the fact that oxalic acid, or most of its functional equivalents, de compose at a temperature as high as 105°, or :hol. If an alcohol is indicated by theformula Y'(OH)n, where nlindicates the number 1 or more-and if a polybasic acid body beindicated by the formula X’»(COOH)n, where n indicates the number 2 or more, then the reaction between a‘monohydric alcohol and a polybasic acid will result in a compound which may be indicated by the following formula: X’Y'(COOH) n’, where n’ indicates the number 1 or more, and which is in thereabcuts, and instead, a temperature‘ of 105— 12° C. should be employed. Such lower We fix reality a contraction of a more elaborate struc tural formula, in which X’ and .Y' are joined by temperature requires longer time for esteri?ca a‘ carboxyl radical or residue. Assuming, how tion to take place. ~ ever, as would-be‘ true in the majority of cases, In certain instances, desirable productsare that the alcohol actually would. be a polyhydric obtained from mcnohydroxylated esteramides. alcohol, and that the acid body would be poly For instance, hydroxyacetic acid, or methyl lac- . basic in nature, for instanca'if one employed a tate, can be reacted with ethyl ethanolamine, propyl ethanolamine, ethyl propan-olamine, pro pyl butano-lamine, or the like, and the esteramide diphthalate ofa polyhydroxylated esteramide of the kind previously described, then examination reveals that the formula might result in a com so obtained then reacted with a non-hydroxylat ed high molal acid, such as oleic acid. Such a OI OI bination, in which there were neither residual product containing only one hydroxyl radical, to wit, the hydroxyl radical of the low molal acyl radical, can be reacted with phthalic anhydride or the like. ‘ - ' ' 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 E-steri?cation can beconducted in the usual 60 might be residual carboxyl radicals and no resid ual hydroxyl radicals; or there might‘ be both. ‘manner, simply ‘employing heat to drive off the This is indicated by the following: water formed._'In some instances, where an 'an~ hydride is employed, water'may not be ‘formed. If desired, one may pass a dried, inert gas, such - as dried nitrogen gas, through the mass to hasten esteri?cation. E‘steri?cation is also hastened at times by the presence of a mere'trace of a suit in which q indicates a small whole number (one able acid, ‘such as benzene sulfonic acid. In in the case of a monomer, and probably not over other instances, the reaction is most suitably 20 and usually less than 10), and m’ and n’ in conducted in the presence of an inert high boil dicate the number 1 or more, and m" and n” ing solvent, such as xylene. The xylene is con indicate zero or a small or moderately-sized whole tinuously distilled under a re?ux condenser, con~ number, such as 'zero,’ one or more, but in any densed by such condenser, and returned to the re event, probably a, number not in ‘excess of 10-15. action chamber through a trap. The xylene va ,Naturally, each residual hydroxyl. could combine , pors carry off the water, which is removed after 75 witna. phthalic acid__ bodyor; its equivalent, or 10' ~11 1'."A sub-resinous‘esteri?cation product, of the‘ with a similarcompound ‘derived from a tribasic acid, such ascitric acid; and in such event, there following formula: ' would be a large number-of free or uncombined ' carboxyl radicals present, possibly 20 or more. Actually, the preferable type of reagent would be 01 more apt .to include less than 20, and in fact, less than 10 free hydroxyl radicals. It is not neces sary to remark that the residual carboxyl radicals I (c 0 on»... (OH) "(Ya/Xx’) _ . (o o 0 .2) ml in which :c’ and y’ are small whole numbers not greater than 10 and m, n, and m’ are small whole can be permitted to remain as ‘such, or can be numbers not over 10, and including zero; Z is an neutralized in any suitable manner, such as con 10 acidic hydrogen atom equivalent; and X is a versioninto salts, esters, amides, amino esters, or’any othersuitable form.. Usually,such~con version into salt form would be by means of so- - residue derived from a polybasic carboxy acid; and Y is a residue derived from a hydroxylated esteramide containing (a) one amido-linked acyl radical derived from a hydroxylated carboxy acid having not over 5 carbon atoms; and (b) dium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium 15; at least one acyloxy radical derived from a mono hydroxide, amylamine, butanolamine, ethanol amine, ' diethanolamine, triethanolamine, cyclo carboxy detergent-forming acid having at least hexanolamine, benzylamine, aniline, toluidine, 8 and not more than 32 carbon atoms, and linked by a divalent‘ aliphatic radical to the amido nitro etc. Conversion into the ester would be by means ofa monohydric alcohol, such as methyl alcohol, , ethyl alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, _octyl alcohol, decyl alcohol, ethylene glycol, diethylene glycol, glycerol, diglycerol, tri ' gen atom. 2. A polar sub-resinous esteri?cation product of the following‘formula: ' ethylene glycol, or the like. One could employ found that such products are soluble to a fairly de?nite extent; for instance, at least 5% in some (coon); (OH)n(Yv'Xz/) an amino alcohol so as to produce an‘ester. We have found, however, as suggested, that the most suitable products are sub-resinous, semi resinous, or balsam-like products, and are prefer ably derived from polyhydroxylated reactants, i.‘ e.,.polyhydroxylated esteramides. We have 30 ‘ (000.2)...’ in which a." and y’ are small whole numbers not greater than 10, and m, n, and m’ are small Whole numbers not over 10, andv including zero; Z is an acidic hydrogen atom equivalent; and X is a residue derived from a polybasic carboxy ,acid; and Y is a residue derived from a hy solvent such‘ as water, alcohol, benzene, dichlor ethyl ether, acetone, cresylic :acid, or the like. droxylated esteramide containing (a) one amido linked acyl radical derived from a hydroxylated This is simply another way of stating that it is 35 carboxy acid having‘ not over 5 carbon atoms; and preferable, ifthe product be one of the sub-resins, (b) at least one acyloxy radical derived from whichvare commonly referred to as an A resin, or a monocarboxy"detergent-forming acid having B‘ resin, .as distinguished from a C resin, which at least 8 and not more than 32 carbon atoms, is'a highly infusible, insoluble resin (see Ellis, and linked by a divalent aliphatic radical to the Chemistry ofSynthetic Resins, 1935, page 862, et amido nitrogen atom. 3. A polar sub-resinous esteri?cation product In recapitulating what has been said previous- -v of the following formula: ly, the sub-resinous, semi-resinous, or balsam (00 on)... like product herein contemplated may be indi 45 cated by the following formula: (0H)»(YwX=') seq‘) ' , .7 - . . > (c 0 0.2),.’ in which :1:’ and y’ are small whole numbers not greater than 10 and m, n, ‘and m’ are small whole numbers not over 10, and including zero; 50 Z is an acidic hydrogen atom equivalent; and in which’ the characters have their previous X is a residue derived from a polybasic carboxy signi?cance, and y’ represents a small whole acid; and Y is a residue derived from a hy-' number not greater than 5, and 0:’ represents a droxylated esteramide containing (a) one amido small whole number not greater than 5; Z repre-' acyl radical derived from a hydroxylated sents a hydrogen ion equivalent, such as metallic 55 linked carboxy acid ‘having not over 5 carbon atoms; atom, organic radical, etc. ' v' > and free from an alcoholic hydroxyl radical; and It will be noted that compounds of the type (b) at‘least one acyloxy radical derived from just described having at least one hydrophobe a higher fatty acid having at least 8 and not nucleus aredesignated as being “polar” when than 32 carbon atoms, and linked by a di there is present either an unesteri?ed hydroxyl 60 more valent aliphatic radical to the amido nitrogen radical, or an unesteri?ed carboxyl radical, or both. We have. found that the polar type of 4; A polar sub-resinous esteri?cation product material is by far the most effective for demulsi of the following formula: ?cation, and it is our preference to use such type. Indeed, this particular type is so much 65 atom. ' » I more effective for demulsi?cation than the non polar type, that it may be considered in essence an invention with an invention. The chemical products or compounds above ' in which :c' and y’ are small whole numbers not described are adapted to be used as demulsi?ers 70 greater than 10 and m, n, and m’ are small whole numbers not over 10, and including zero; Z is an and also as plasticizers or softening agents in acidic hydrogen atom equivalent; and X is a the manufacture of resin-like materials. residue derived from a poly-basic carboxy acid; Having thus described our invention, what we and Y is a residue derived from a hydroxylated ‘ claim as new and desire to secure by Letters 75 esteramide containing (a) one amido-linked acyl Patent is: 2,411,957 11 12 radical derived from a hydroxylated carboxy acid having not over 5 carbon atoms and free'from an alcoholic hydroxyl radical; and (b) at least an alcoholic hydroxyl radical; and (b) at least one ricinoleyl oXy radical, and linked by a di valent aliphatic radical to the amido nitrogen one acyloxy radical derived from a higher un atom.‘ saturated fatty acid having at'least 8 and not more than 32 carbon atoms, and linked by a divalent aliphatic radical to the amido nitrogen atom. 5. A polar sub-resinous esteri?cation product of the following formula: ‘ 8. A polar sub-resinous esteri?cation product of the following formula: in which a," and y’ are small whole numbers not greater than 10 and m, n, and m’ are small whole numbers not over 10, and including zero; Z is an, acidic hydrogen atom‘ equivalent; ‘and X is a residue derived from phthalic acid; and Y is a residue derived from a hydroxylated esteramide containing (a) one amido-linked acyl radical de rived from a hydroxylated carboxy acid having in which as’ and 2/’ are small whole numbers not greater than 10 and m, n, and m’ are small whole numbers not greater than 10, and including zero; Z is an acidic hydrogen atom equivalent; and X is a residue derived from a polybasic carboxyv acid; and Y is a residue derived from a hydroxyl ated esteramide containing (a) one amido-linked not over 5 carbon atoms and free from an alco ‘holic hydroxyl radical; and (b) at least one ricinoleyl oxy radical; and linked by a divalent I acyl radical derived from a hydroxylated carboxy acid having not over 5 carbon atoms and free from an alcoholic hydroxyl radical; and (b) at aliphatic radical to the'amido nitrogen atom. 9.- A polar sub-resinous esteri?cation product of the following formula: » least one acyloxy radical derived from a higher ' eunsaturated fatty acid having 18 carbon atoms, (OHQAYv’Xz’) and. linked by a divalent aliphatic radical to the amido'nitrogen atom. (000mm _ (0001),», I '6." A polar sub-resinous esteri?cation product of the following formula: ' ~ . . i in which in’ and y’ are small wholenumbers not greater than 10 and ‘m, n, andm' are small whole numbers not over 10, and including zero; Z is an acidic hydrogen atom equivalent; and X .is a residue derived from maleicacid; and Y is, a residue derived from a hydroxylated esteramide containingla) one amido-linked acylradical de rived from a hydroxylated carboxy acid having not over 5 carbon atoms and freefromvan valco-. ' (000mm (OH)..(Y,,IXZ') ' (0001),.’ in which a" and y’ are small Whole numbers not greater than 10, and ‘m, nrand m’ are small whole numbers not over 10, and including zero; Z is an acidic hydrogen atom equivalent; and X is a holic hydroxyl radical; and lb) at‘ least one de residue derived-from a. polybasic carboxy acid; > and Y is a residue derived from a hydroxylated 40 rived from a ricinoleyl oxy radical, and linked, by a divalent aliphatic radical to the amido nitrogen esteramide containing (a) one amido-linked acyl radical derived from a hydroxylated carboxy acid having not over 5 carbon atoms and free from an alcoholic hydroxyl radical; and (b) at least one ricinoleyl oxy radical; and linked by a di valent aliphatic radical to the amido nitrogen atom. atom. ' ' Y is a residue derived from a hydroxylated ester v . ~ (oooH)m~ (000.2)“, in which :0’ and y,’ are small whole numbers not 50 greater than 10 and m, n, and m’ are small whole in which a," and y’ are small whole numbers not , greater than 10 and m, n, and m’ ‘are small whole ' numbers not over 10, and including zero; Z is an acidic hydrogenatom equivalent; and X is a residue derived from a dibasic carboxy acid; and . (OH)1|(Y1/'X=’) p ' , ofthe following formula: _7. A polar‘sub-resinous esteri?cation product of the following formula: V 10. A polar sub-resinous esteri?cation product numbers not over 10, andv including zero; Z is an acidic hydrogen atom equivalent; and X is a residue derived‘ from oxalic acid; and Y is-a residue derived from a hydroxylate'd- esteramide ' containing (a) one amido-linked acyl radical de-' ~ rived from a hydroxylated carboxy acid having not over 5 carbon atoms; and free from an alco 2holic hydroxyl radical; and (b) at least one ricinoleyl oxy radical, and linked by a divalent amide containing (a) one amido-linked acyl rad (ill; aliphatic radical‘to the amido nitrogen'atom. ical derived from a hydroxylated carboxy acid ~' MELVIN DE GROOTE. having not over 5 carbon atoms and free from BERNHABD KEISER.