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Publication numberUS2576285 A
Publication typeGrant
Publication dateNov 27, 1951
Filing dateMay 29, 1948
Priority dateMay 29, 1948
Publication numberUS 2576285 A, US 2576285A, US-A-2576285, US2576285 A, US2576285A
InventorsBernhard Keiser, De Groote Melvin
Original AssigneePetrolite Corp
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Oxyethylated hydrophile derivatives of certain fractional esters of triricinolein
US 2576285 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

Patented Nov. 27, 1951 OXYETHYLATED HYDROPHILE DERIVA- TIVES or CERTAIN FRACTIONAL ES- TERS or 'riimrcmousm Melvin De Groote, University City, and Bernhard Keiser, Webster Groves.- Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware No Drawing. Application May 29, 1948, Serial No. 30,186

6 Claims. 1

This invention relates to a new chemical product or compound and to the manufacture of same, our present application being a continuation-in-part of our co-pending application Serial No. 758,487, filed July 1, 1947, now abandoned, which was in turn, a division of our co-pending application Serial No. 666,819, filed May 2, 1946, now abandoned.

Complementary to the above aspect of our invention is our companion invention concerned with the new chemical products or compounds used as demulsifying agents in the resolution of water-in-oil emulsions, particularly petroleum emulsions, as described in our co-pending application Serial No. 30,188 filed May 29, 1948, now Patent 2,498,658, granted February 28, 1950.

The new products herein described are also useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid washing of fruit; in the acid washing of building stone and brick; as wetting agents and spreaders in the application of asphalt in road building and the like, as a constituent of soldering flux preparations; as a flotation reagent in the flotation separation of various aqueoussuspensions containing negatively charged particles such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides. emulsifying agents, as, for example, for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc.

Briefly stated, the new compounds herein contemplated, and which, in addition to being particularly desirable as demulsifying agents for petroleum emulsions of the water-in-oil type, but are also useful for other purposes, are derived by the oxyethylation of certain acidic fractional esters of triricinolein. Such acidic esters are obtained by reacting triricinolein with one to three moles of polycarboxy acid, and particularly a dicarboxy acid such as phthalic acid, adipic acid, diglycollic acid, etc. The hereto appended claims are limited to derivatives of dicarboxy acids oranhydrides.

Acidic esters of triricinolein can be manufac-'- tured in two difierent ways, although using the same general procedure. One method is to use The second procedure radical may be attached to the glyceryl radical and not limited to attachment to the ricinoleyl radical. This latter type of structure will be clarified by subsequent description. It is to be noted, however, that the compounds contemplated herein are those obtained from intermediates in which the dicarboxy acid radical is attached to the ricinoleyl radical, and thus excludes acidic esters obtained by rearrangement at higher temperatures, or in presence of catalysts.

The manufacture of fractional esters of triricinolein is well known and described in numerous patents. The literature including various patents, also describes the esteriflcation of such fractional esters with polyhydric alcohols including polyglycols under various conditions involving, for example, either the presence or absence of catalysts, or a variety of catalysts, including both acid and basic catalysts.

It has been suggested that the reaction of a fractional ester with a polyethylene glycol under various conditions would, in essence, result in a product substantially the same as that obtained by reacting with ethylene oxide, so as to obtain the same stoichiometric relationship. We have found that this is not the case and that the resultant products are significantly different in composition, and those products obtained by oxyethylation are much more effective, for a number of purposes, such as, for example, demulsification of petroleum emulsions, break inducers, in the doctor treatment of sour hydrocarbons, etc.

Since this difference in composition involves the inherent nature of the reactants and resultants, it is deemed desirable to point out clearly the nature of the product obtained when triricinolein is reacted with polycarboxy acids, and particularly those having 4 to 10 carbon atoms, and particularly dicarboxy acids having 4 to 8 carbon atoms, such as succinic acid, adipic acid, diglycolic acid and phthalic acid. The anhydrides, of course, are the abvious equivalent of the acid and include among others phthalic anhydride, maleic anhydride, citraconic anhydride, etc. Other suitable acids include maleic, fumaric, oxalic, tricarballylic, tartaric, azelaic, sebacic, etc. Other acids include cisA -tetrahydrophthalic anhydride obtained by the action of butadiene on maleic anhydride, and 3,6-endomethyleneM-tetrahydrophthalic anhydride obtained by the action of cyclopentadiene on maleic anhydride. It is to be noted that none of these acids have more than 10 carbon atoms. As stated, it is understood that the acids and anhydrides are considered as equivalents.

A preferred ester product may be obtained by esterification reaction between triricinolein and a dibasic carboxylic acid such as phthalic acid.

Ricinoleic acid may be indicated by the following formula:

on CH3(CH2)5.41H.CH2.CHCH(CH2)7.COOH

which may be conveniently abbreviated for many purposes to HORCOOH Employin HORCOO as the acyloxy group of ricinoleic acid, triricinolein may be represented by the formula HO RC 0 CH2 HORCOOCH HORCOO Hz and contains the residue of the polyhydric alcohol glycerol, which may be represented as HOCHE H0 H HO(.I7H2' Trirlcinolein readily esterifies with phthallc acid, and if three moles of phthalic anhydride or acid are caused'toreact with one mole of triricinolein, a fractional acidic ester will be obtained according to the following reaction:

CO noacooom 3 0 noaooocn coon COORCOO H COOH COORCOO Hi It is not necessary to use three moles of phthalic anhydride per mole of triricinolein, and if desired, onemay use one or two moles, although the preference is to use approximately 2 to 2%; or 3 moles.

Likewise, in carrying on the esterification reactions broadly, without limitation to the particular type herein employed as intermediates, it is not essential that a carboxylic group'of the .dibasic carboxylic acid react with the alcoholiform hydroxyl in the ricinoleyl radical While the ricinoleyl radical remains directly connected with the polyhydric alcohol radical. One might react ricinoleic acid monophthalate, obtained by reaction between ricinoleic acid andphthalic anhydride, mole for mole, with glycerol, in-the ratio of three'moles of the fractional ester .for one mole otglycerol. This would yield a mixture of compounds suchas the following:



HOOCROO 00011: HO-OCROO (BOO H H0O; OORCOO Hz HOOCROO} OOCH: H003 OORCOO Hr H006 OORCOO Ha Not only may compounds of the above type be obtained by the procedure previously described, but such compounds may-occur to a greater or lesser degree, as the result of molecular rearrangement in the production of acidic fractional esters from triricinolein and various polycarboxy acids, as previously mentioned, provided one employs temperatures in excess of 210 C. or employs catalysts, or both.

In carrying on the esterification reaction, there may develop cross-linkages either through the polyhydric alcohol, or through the polybasic carboxylic acid, due to the polyfunctionality of these materials; For example, in an esterification reaction between triricinolein and phthalic acid, the resulting product may comprise more complex molecules, such as the following, which illustrates cross-linkage through the polyhydric alcohol residue. I




It is apparent that other cross-linkages may occur. Such ester products containing more complex molecules are also suitable. It is also apparent that there may be great variations-in the molecular weight of the product. The molecular weight of the ester product, as determined by cryoscopic methods, or from obvious composition of the ester, usually runs between about 300 and about 4,000 and is seldom over 6,000. Ester products having a molecular weight over about 10,000 preferably are not employed. During the esterification reaction there may be some polymerization and polymerized products, as well as simple monomers, may be used. Attention is directed to what has been said previously for the sake of clarification, and that is that the intermediates herein contemplated, i. e., the acidic esters derived by reaction between triricinolein and various dicarboxy acids or anhydrides, are limited to those obtained by manufacture under conditions which preclude drastic rearrangements, and thus, are characterized by the fact that the dicarboxy acid radical is attached directly to the ricinoleyl radical and not to the glyceryl radical.

Tricarboxy acids may be employed as reactants in the same manner as dicarboxy acids.

However, it is obvious, in light of what is said subsequently, that if a tricarboxy acid is used, subsequent oxyethylation results in a branched chain or two chains of polyglycol radicals instead of one. In other Words, if a dicarboxy acid,,su ch as phthalic acid, is employed, there is a single carboxyl radical available for oxyethylation. If, on the other hand, tricarballylic acid is employed, then there may be, and in most instances, there happens to be, two carboxyls available for oxyethylation, thus resulting in either a branched chain or two separate polyglycol radicals. Actually, the configuration so produced from a structural standpoint, closely approximates that ob-- tained by treating a sole carboxyl radical remaining from phthalic acid with glycide or glycerol and then oxyethylating such ester so as to obtain a branched chain polyglycol or two separate polyglycol radicals. Since this type of compound is contemplated in our co-pending application Serial No. 30,187, filed May 29, 1948, now Patent 2,498,657, granted February 28, 1950, it will be noted that the specific examples herein included and the claims themselves are directed to derivatives of dicarboxy acids.

TRIRICILNOLEIN ACIDIC 'FRACTIONAL ESTERS Example 1 One pound mole of triricinolein (in the form of castor oil which ordinarily contains approximately to triricinolein) is reacted-with.

2 pound moles of phthalic anhydride to produce a mixture of acid phthalates consisting essentially of triricinolein dibasic phthalate and triricinolein tribasic phthalate. The reaction may be caused to occur by heating the mixed materials at a temperature of approximately to C. for approximately 6 to 12 hours. The reaction can be followed roughly by withdrawing a small sampleof the partially reacted mass and permitting it to cool on a watch crystal. When the reaction has become completed no crystals of phthalic anhydride appear. When the sample no longer shows the presence of such crystals on cooling, it can be titrated with a standard volumetric alkaline solution, since the acid which remains is due entirely to carboxylic hydrogen in the fractional ester and not to any unreacted phthalic anhydride. If care is taken not to use too high temperatures which would cause formation of heterocyclic bodies of the character above referred to, one can depend upon the standard alkaline solution to indicate the disappearance ofthe phthalic anhydride. It is not to be inferred, however, that any cyclic bodies, if formed, would be unsuitable.

The product thus obtained, however, seems to consist largely of triricinolein dibasic phthalate and triricinolein tribasic phthalate. Apparently, there is no evidence of rearrangement there.

This fact is indicated by a molecular weight de termination and also based on the acid value which usually runs from a little over 100 to slightly less than 110.

TRIRICINOLEIN ACIDIC FRACTIONAL ESTERS Example 2 Maleic acid or anhydride is substituted for phthalic anhydride in preceding Example 1 to give the corresponding maleic acid derivative, i. e., triricinolein dibasic maleate and triricinolein tribasic maleate.

TRIRICINOLEIN ACIDIC FRACTIONAL ESTERS Example 3 Adipic acid or anhydride is substituted for phthalic anhydride in preceding Example 1 to give the corresponding adipic acid derivative, i. e., triricinolein dibasic adipate and triricinolein tribasic adipate.

TRIRICINOLEIN ACIDIC FRACTIONAL ESTERS Example 4 succinic acid or anhydride is substituted for phthalic anhydride, in preceding Example 1, to give the corresponding succinic acid derivative, i. e., triricinolein dibasic succinate and triricinolein tribasic succinate.

TRIRICINOLEIN ACIDIC FRACTIONAL ESTERS Example 5 7 resembling somewhat blown'castor' oil in consistency, and water-insoluble.

It is to be noted that the triricinolein acidic fractional esters herein contemplated as the preferred reactants are characterized by the fact that they are obtained by esterification reactions involving the use of at least one mole of the dicarboxy acid per mole of triricinolein. For instance, previous formulae indicate combinations wherein 1 moles to 3 moles of phthalic anhydride are used per mole of triricinolein. In all instances, regardless of the ratio of dicarboxy reactant to triricinolein, there must be at least one free carboxyl per mole of triricinolein inthe finished product. Such requirement is met, of course, by triricinolein monobasic phthalate derived from one mole of triricinolein and one mole of phthalate anhydride. Attention is also directed to the fact that all the fractional esters are prepared in. such a manner that the final product is anhydrous. The next step is the obvious one of subjecting such anhydrous ester to the action of ethylene oxide.

If one examines the formula for ricinoleic acid,

'it becomes obvious that the dicarboxy acid, such as phthalic acid, becomes attached approximately half-way in the carbon atom chain, and thus oxyethylation attacking any residual carboxyl group which is part of the dicarboxy acid radical, must, of necessity, cause the hydrophile polyglycol group to enter or make its effectiveness felt halfway in the carbon atom chain, as differentiated with the introduction of a hydrophile group at the end of a carbon atom chain. For instance, when a high molal alcohol or a high molal acid is subjected to oxyethylation, obviously such hydrophile effect is produced terminally and not at a mid-point. In this connection it is interesting to note that oxyethylation does not, as was one time believed, attack the secondary alcohol of triricinolein when castor oil is subjected to oxyethylation. For this reason, oxyethylation of the fractional esters give a product having a hydrophobe-hydrophile balance, which is entirely different from that obtained from a number of apparently kindred products. Generically speaking, oxyethylation is conducted in substantially the same manner as applied to a number of other products, in which the ethylene oxide group is introduced between an oxygen atom and a hydrogen atom, as, for example, in oxyethylation of high molal acids or high molal alcohols, substituted phenols, etc. Usually a small amount of alkaline catalyst is added, such as one-tenth of 1% to 1% of caustic soda, sodium stearate, sodium methylate, or the like. Oxyethylation is conducted with constant stirring and a gauge pressure of 100 to 200 pounds per square-inch is generally satisfactory. The temperature of reaction may be varied from 100C. to less than 200 C. If desired, an inert solvent may be present such as xylene, tetralin, cymene, decalin or the like. The ethylene oxide may be used continuously, provided the addition is regulated so that it is used up more or less uniformly as it enters the reaction vessel or autoclave. Our preference, however, is to add the material batch-wise, as indicated, and continue oxyethylation not only until the product is distinctly hydrophile but until it gives a substantially clear solution in water. As to other oxyethylating procedure, attention is directed to the following United States patents and to the following British patent: U. S. Patent Nos. 2,142,007, dated December 27, 1938, P. Schlack; 1,845,198, dated February '16, 1932, O. Schmidt et al.; and 1,922,459, dated August 12, 1933, O. Schmidtet al.; and British Patent No; 302,041, dated August 7, 1928, James Y. Johnson.

WATER-SOLUBLE OXYETHYLATED TRIRI- CINOLEIN ACIDIC FRACTIONAL ESTER Example 1 650 pounds of triricinolein acidic fractional ester manufactured as described under the heading Example 1, preceding, is mixed with one-half pound of sodium methylate and then reacted with approximately 161 pounds of ethyleneoxide in three batches of 53.7 pounds each. The maximum pressure during the reaction was pounds per square inch gauge pressure. The time of reaction required for each batch was three to five hours. The temperature employed was approximately C. The material was tested for water-solubility after the addition of 161 pounds of ethylene oxide and found to be water-insoluble. If the theoretical molecular weight of triricinolein tribasic phthalate is considered as 1.450, then the average molecular weight of the raw material employed was taken as 1300. On this basis, the amount of ethylene oxide added at this point represented a molal ratio of 1 to 7.3, approximately.

Oxyethylation was then continued by the addition of three more portions of approximately 68 pounds each so that at the end of the sixth batch the molecular ratio had more than doubled and was approximately 1 to 18.0. The product at this point began to show some distinctly hydrophile character and solubility, but was reacted further with five additional portions of approximately 65 pounds each. Thus, the total amount of ethylene oxide added represented 161 pounds, plus pounds, plus 325 poundsbeing a total of 666 pounds of ethylene oxide added to 650 pounds of the original resin. On a weight basis this represented slightly in excess of '1 to 1, and on a molal basis it represented approximately 30 to 32 moles of ethylene oxide per mole of monomeric fractional ester. The resultant product was a thin, deep amber-colored oil, watersoluble, having a clear appearance in solution and some foaming properties. a

The product so obtained consists principally of oxyethylated triricinolein dibasic phthalate and oxyethylated triricinolein tribasic phthalate. The composition of these two compounds may be shown in the following manner:


HORCOO H COORCOOL /H @CPC? WATER-SOLUBLE OXYETIV-IYLATED .TRIRI- CINOLEIN ACIDIC FRACTIONAL ESTER Example 2 The same procedure is followed as in Example 1, immediately preceding, except that trl ricinolein acidic fractional esters, Examples 2 to 5, inclusive, are substituted for triricinolein acidic fractional ester, Example 1. In each instance ethylene oxide is added in the same molecular proportion, i. .e.,.approximately 30 to 32 moles of ethylene oxide per mole per mixture averaging about 2 molesof dicarboxy acid per mole of triricinolein. In all instances the molecular weight is figured-based on the theoretical combination of the dicarboxy reactant and triricinolein without the loss of any water in the case of the anhydride andwith the lossof only one molecule of water per molecule of dicarboxy acid, in-the event an acid reactant such as diglycollic acid or adipic acid is used insteadof an anhydride. However, the proportions by weight mayube employed just as satisfactorily, i. e., adding'enough ethyleneoxide so that itis approximately equalin weight of the acidic ester.

WATERASOLUBLE OXYETHYLATED TRIRI- CINOLEIN ACIDIC FRACTIONAL ESTER Example 3 WATER-SOLUBLE OXYETHYLATED TRIRI CINOLEIN ACIDIC FRACTIONAL ESTER Example 4 The same procedure is followed as in Examples 1 and 2, preceding, except that the amount of ethylene oxide added was increased per batch, so that the total amount is equal to approximately 40 moles, instead of 24 or 32 moles, and is equal in weight to approximately 125% of the original atom, whether the hydroxyl; be. a carboxylic hydroxyl or an alcoholichydroxyl, as shown by the previous examples where a carboxyl radical is converted first into a glycol esterandlthen subsequently into a polyglycol ester. This means,

of course, that if the triricinolein acidic fractional esters had been reacted with ethylene oxide or propylene oxide or butylene oxide, mole for mole, so as to give a hydroxylated ester in;

stead of an acidic ester, such hydroxylated 'ester woul'd be just-a s'lsusceptible ;to oxyethyla aortas" the acidic ester? In -"other words; an iii- 1G termediate step in'the previously described'reace tions represent compounds exemplified byrthe following:

0 O OCZHlOH --COORCOOCH2 COORCOO H2 Compounds of the above type could also be obtained by esterifying the free carboxyls with a glycol such as ethylene glycol, propylene glycol, etc. It is understood, however, that this particular specification does not include those types wherein such glycols would be replaced by polyhydric alcohols having a larger number of hydroxyl groups per molecule, 1. e., does not include glycerol, diglycerol, triglycerol, etc. Furthermore, the compounds herein'contemplated are derived solely from triricinolein and do not include compounds derived from monoricinolein, diricinolein, or any other type of fractional ester where the number of ricinoleic acid radicals is less than the valency of the polyhydric alcohol (the glyceryl radical) to which they are attached. Valency of the radical in such circumstances is measured by the number of availablehydroxyl groups, i. e., the valency of a glyceryl radical be ing considered as 3. The reason for this difference is perfectly obvious, in that an available glyeeryl hydroxyl radical, as in the case of, a derivative of monoricinolein or diricinolein, provides an additional point of reaction for a polybasic acid, such as phthalic anhydride, or if not so reacted upon, provides a point of reaction for ethylene oxide. Similarly, if the acidic esters are esterified with glycide or methylglycide instead of ethylene oxide or the like, or glycerol for that matter, then such esters are capable of attack by ethylene oxide so as to provide a branched chain, rather than a single chain' involving polyglycol radicals. What has been said herein immediately preceding is intended to define the herein contemplated compounds with greater clarity and also to point out the line of demarcation between these particular compounds and those contemplated in our abandoned copending application Serial No. 666,820, filed May 2, 1946. f Products of value as demulsifying agents have been prepared by reacting triricinolein phthalates of the kind described under the heading Triricinolein Acidic Fractional Esters with polyhydric alcohols, although not necessarily with polyethylene glycols having a large number of repetitious ether linkages in such proportion and manner as to render such fractional esters Water-soluble or water-miscible. At first casual examination, it would appear that if one were to react the acid phthalates, as exemplified by Triricin'olein Acidic Fractional Esters, Example 1 with polyethyleneglycol representing approximately 10 or 12 ethylene oxide units, there should be obtained a product approximately identical with the product, described under the heading Water-Soluble Oxyethylated Triricinolein acidic Fractional Ester, Example 1. For instance,'the






COORCOO Ha ooonoooom nwnlonnooc teem-e a 31120 "o ooR-oo-olm' *ooownnoynn The above reaction emphasizes this very important feature, that if an attempt is made to obtain similar products by reaction with a poly 'e'thyleneglycol, then water results rromthe reac= um and cognizance must be taken of the fact. Thus, if the reaction is conducted in th e presence of water, whereas, oxyethylation is conducted under anhydrous conditions, then one must bear in mind that the water formed may become a reactant before elimination. Hence, it isobvious that the course of reaction may be changed.

Another courseof difference in the reaction in vowing etliy1ene'oxide on the one hand and a polyethylene glycol on the other, is this articular situation; the esters employed are poly functional having, for example, preferably two or more carboxyls per original molecule of tri=- ricin'olein. The polyethyleneglycols are difunctional. Thus, when reacted together,-there is a tendency to form a sub-resinous polyester by reactions involving simultaneously one moleo'f a polyethylene glycol and two carboxyls, which are part of tlie same molecules or much more probable parts of two difierent molecules.

0 con oboncooom o 0 one o 0" H2 electorate 06H H OOCROO OH it connect (500 -1100031 wherein HOCzH r- -X CaI-IaOI-I represents the original polyethyleneglycol.

In connection with what is said herein, in re gard to the 'd-ifierence between ,oxyethylation, on the one hand, and'esteri'fication on the other hand, it mustbe-rememb'ered that oxyethylation takes'pl'ace readily and rapidly; at temperatures considerably under 200 C. and that this particu lar temperature may be considered the upper limit. Esterification, such as is shown subsequently, invariably involves much higher temperatures, such as 230 to'340 C.

An examination of such esterification reactions are best conducted on a laboratory scale. In other words, if one were to start withap roximately 650 g-rams of the mixturedescribed under'the heading Triricinolein Fractional Ester, Example 1 having an acid value of approximately and add thereto the equivalent of 2 /2 moles of a .po-lyethyleneglycol having approximately 10 to 1-1 structural units on completion of reaction, one would anticipate that there would be a drop in acid value to approximately zero, corresponding to the acid value of the product described under the heading Water-Soluble Oxyethylated Triricinolein Fractional Ester, along with the elimination of a stoich'iometric'al amount of water which would be equivalent to 2 moles or 17 grains.

Such reaction can be conducted in any one of three ways: (a) Absence of a catalyst; (b) lp're'senee of an acid catalyst, or (0') presence of a basic teata1yst. Actually, there is little or no justification for using a basic catalyst, for the' reason that under such circumstances, one would not expect to obtain a product comparable to that described under the heading Water- Soluble Oxyethylatd 'Triricinolein Fractional Ester, Example 1, but would expect to get a product in which a large degree of glycerol had been replaced by the 'nonaethyleneglycol with subsequent corresponding freaction. In. other words, one would expect tran's-esterification, which is sometimes referred to as ester-interchange or alcoholy'sis. "(See Organic Chemistry, .Fieser and Fieser, 1'94 4, page 1182 and Organic Chemistry, Fuson and Snyder, 1942 page 92.)

conducting these exploratory experiments it becomes obvious that the 'two end points not coincide, -i. e., the elimination oithe theoreti cal amountof water of reaction {and reductionpf the acidity to the value of 1 or 2. In each instance an attempt was made to carry the reaction to the end point indicated in both ways. In the case of the acid catalyst one-half percent of para-toluene sulfonic acid was added. In connectionwith the polyethyleneglycol reactant attention is directed to the article entitled Technology of the Polyethyleneglycols and Carbowax Compounds, Chemical and Engineering News, 1 volume 23, No. 3, page 247 (1945). Such article points out, among other things, why the value of n as herein contemplated represents an average L value, rather than'an absolutely definite value ,of one-single compound. The result of these exwithin the range which produces rearrangement in the manufacture of acidic esters, as previously noted. In other words, at such temperature range, even though no catalysts were added, one would expect rearrangements whereby at least to a substantial extent, there would be present compounds in which the dicarboxy acid radical would be directly attached to the glyceryl radical. It is to be noted that this type of material is specifically excluded in the hereto appended claims.

In light of what has been said as to the nature of the reactions taking place and as to the results obtainedin, the above experiments, it is perfectly obvious that there is a very marked difference periments are 1ndicated in the following table: in the nature of the products obtained, depend- Experiment A Experiment B Experiment 0 L-24l42 L-24143 Ill-24144 Triricinolein Fractional Ester Example 1 650 grams, Acid 650 grams, Acid 650 grams, Acid I v.=l05. v.=l05. v.=l05. HO(C2H40) "H, 7t=10 or 11.- rams 700 7 700. Cataly Nmw %%Toluene Sul- 36% Sodium Methfonic Acid. ylate. Acid Value of Mixture 50.5 52.0 0.2. Conditions to bring acid value to about 2 Could not get be- Could not get be- 4 hrs. at 325 0.,

low 14. low 15.6. 4 7.85 acid v. Time hnurs 3" 4 4.

Maximum temperature At this point H1O eliminated Rem ark 66.8 cc. H20 and 53.4 cc. oil.

Conditions to bring about elimination of 17% gr. water (theo.).

In comparison with Experiments A, B and C, it has been pointed out previously in Oxyethylated Water-Soluble Triricinolein Acidic Fractional Ester, Example 1 that such reactants as was used in Experiments A, B and C can be 4 treated with ethylene oxide under a comparative- 1y low temperature, approximately 120 C. in absence of water to give a product which is clearly water-soluble and which has an average molecular weight approximately equivalent to that of the products obtained in Experiments A, B and C, provided there was complete chemical combination. The acid value of oxyethylated derivative was approximately 2. I

In Examining Experiments A, B andC, it is to be noted that it was impossible to reduce the acid, value in any one of the three cases to that obtainable by oxyethylation, to wit, a value of 2. Actually, the values range from approximately 8 to 14. Furthermore, the theoretical amount of water which would be expected to be eliminated in Experiments A, B and C so as to give a product identical withthat previously referred to as Example 1, would be 17 /2 grams of water. Actually, when 17 /2 grams of water had been eliminated in all three cases, the acid value varied from ap proximately 20 to approximately 33. On the other hand, when the minimum acid value was obtained, even though it did not approach the amount of 2, there was a great deal more water 55 eliminated than theory; varying from 54, in one instance, to 346 in the other. Furthermore, in order to obtain the result indicated, instead of using a temperature of approximately 130 C. or somewhat higher, but in any event, under 200 C., the temperature actually varied from 230 C. to 340 C. Attention is directed to a very significant fact, and that is, that these temperatures employed in Experiments A, B and C, as previous- 13; noted, vary from 230 C. to 340 C. and are 54 cc. H20 and 15 cc. oil.

Acid v. rose on cid v. rose on further heating.

further heating.


Time 25 min Maximum Temperature" 0.. 230 285.

Acid value at this point 36.6 20.4.

.Remar s 11; cldy. Clear oil; Cldy. Clear oil; cldy. sol.

, sol. w/water. Sol. w/water. w/water.

ing on whether an acidic fractional ester is subjected to oxyethylation, or whether it is subjected to an esterification with a polyglycol,.in an efiort to obtain substantially the same product; although, for the sake of brevity, reference is made only to products obtained by phthalation, actually other experiments conducted with other polycarboxy acids, particularly succinic acid, adipic acid, diglycollic acid, etc., indicate that results are substantially the same.

The difference in the nature of the products obtained by the two different procedures is illustrated further by their effect upon emulsions. The following table shows results obtained by adding an equal amount of the same four materials to certain emulsions. One demulsifying agent consists of the product described under the heading Water-Soluble oxyethylated Triricinolein Acidic Fractional Ester, Example 1, the other three consisting of the clear oils obtained as resultants from Experiments A, B and C, described previously, in tabular form. Here again, it is to be noted that, although the results indicated are concerned with merely one particular derivative, 1. e., phthalic acid derivatives, the results are'thes'aine as far as demulsification when other polycarboxy acid derivatives are examined the same way. This is particularly true of adipic acid; succinic acid, diglycollic acid, etc.

It may be desirable to point out that distillable polyglycols of the kind previously referred to and exemplified by nonaethylenegylcol or the like, and particularly those having 8 to 12 oxyalkylated groups, are sometimes referred to as upper distillable' ethyleneglycols. (See U. S. Patent No. 2,324,489, dated July 20, 1943, to De Groote and Keiser.)

Althoughit hasbeen old to subject emulsions to emulsi yin a ents, obta ned by .r a t n' tween certain resinous products and polyhydrfc alcohols free from repetitious ether linkages.-yet,

as far aswe are aware, products of the kind exemplified by Experiments A, B and C have not been hereto prepared or employed as demulsifying agents.

Demu'lsifying test I Date of test Oct. 30, 1945 State of California Oil fiel Oak Qanyon Oil company V. B. Wickham Lease. No.4 Well No 4 Per cent emulsion in fluid from well 510 Per cent free water in fluid from well Trace Per cent water obtained by complete dcmulsiflcatiou- 46 Per cent demulsifier in test solution 6 Temperature of tests 140 F Period of agitation after adding .demulslfie min Nature of agitation; machine with shaker-arm, ute. 130 Ratio of demulsifier to well fluid 126700 11-24142 11-24143 11-24144 L-l28fi6 Blank Time test started 2:45. cc. Water out at 26 41' Trace 33 42 Do. 37 43 Do. 38 44 Do. 40 44 Do. 41 44 Do.

Dec. 13, 1945 California Wilmington Oil company. Royalty Service Lease Santa Fe B-2 Per cent emulsion in fluid from welL. 21.0 Per cent free water in fluid from well Trace Per cent water obtained by complete demulsification 18.0 Per cent demulsifier in test solution 2% Temperature of tests; l. l. 160 0. Period of agitation after adding d'emulsifier 5 min.

Nature of agitatiommachine with shaker arm ;"shakes per minute 130 Ratio of demul sifier to well fluid.. lzaOOO 11-24142 L-24143 L-24144 L-12866 Blank Time test started :50. cc. Water out at- 1:25 (12-13) a Trace 2: D

Per cent free Water in fluid from well Per cent water obtained by complete demulsification Per cent demulsifier in test solution 2 Temperature of tests 160 F. Period of agitation after adding demulsifier l. 5 min.

Nature of agitation; machine with shaker arm; shakes per'minute 130 Ratio of demulsifier to well fluid 1:5000

L-24l42 11-24143 L-24144 b12866 Blank Time test started 10:50. cc. water out at Trace Trace Trace 8 Trace 2 'Trace Trace 13 Do. 3 1 Trace 14 Do. 6 2 3 1 15 'Do. 7 3 4 l7 Do. 7 2 5 17 Do. 11 3 8 19 Do.

It is of considerable interest to compare compounds of the kind 'hereindescribed with somewhat analogous compounds described elsewhere in the literature or prepared from data appearing elsewhere. The reagents employed, for example, ricinoleic acid, glycerol, ethylene oxide, phthalic anhydride, etc.. can be considered as building blocks or structural units which can be fitted together to give various compounds. Castor oil (triricinolein) may be considered as ricinoleic acid and glycerol in combination.

Some such other structures may be exemplified by examples which appear in the series of U. S. Patents Nos.v 2,295,163 through 2,295,170, inclusive, all datedpseptember 8, 1942, to De 'Groote and Keiser. Briefly stated, a'pol'yglycol acid ester such as nonaethyleneglycol dihydro'gen dimaleate, or dihydrogen diphthalate, obtained by reaction between one mole of nonaethyleneglycol andrtwo moles of an appropriate dicarboxyv acid or anhydride, is reacted with various hydroxylated compounds, including triricinolein, diricin olein, monoricin'olein, etc.

The following table briefly describes four such compounds, the first being an ethylene oxide compound of the kind herein specified. In the next three compounds, or products, an ethylene polygycol is used instead of ethylene oxide. The compounds were prepared in an effort to have the ultimate composition of the last three compounds approximate with, or identical to, that of the first compound, in terms of structural units;

Needless to'say, as has been pointed out already, such resemblance is only superficial for the reason that, depending on the temperature of reaction, order in which reactants are added, and the very nature of the possible reactions themselves, one does obtain products which are inherently and intrinsically difierent in molecular structure, size of molecule, etc.

It is well to recall that the use of compounds of the kind herein described for the purposes involving surface activity, particularly demulsification, does not involve chemical reactivity in the ordinary sense. Surface activity, and particularly surface aotivityphenomena as exemplified by'demulsifica-tion, is concerned with the actual shapes and sizes of molecules. Such concept, even though obscure and difficult to define, acquires a large degree of reality and value in an invention of the kind herein specified even though it is difficult to set forth such qualities in measures which are more concise and specific than those which have been included.

Only a few examples need be repeated at this point to emphasize these difi'erences which, in our opinion, are related to the sizes, shapes, and

associated of molecules, and especially at interfaces. If phthalated castor oil is reacted with ethylene oxide, one builds up -a derivative of the type in which there is always a residual hydroxyl for the reason that ethylene oxide acts like a monofunctional reactant. If one substitutes a glycol for ethylene oxide, then one is employing a difunctional reactant, and one mole of a glycol can act as a coupling reagent to unite two moles of phthalated .castor oil. Likewise, with the glycol and a glyceride, or any ester including a phthalated acid ester,.alcoholysis can and usually does take place, particularly at elevated temperatures. This is not true in the case of ethylene oxide. 7

' ulif i i d P 1: Identifying Per cent of g y at can Per cent ical m final glycerol resx 5 Reactants and how made igfzg gfig product idue in final ggg' g 3%,

pound final product f 3 835 3 I product L--24633. Castor oil plus 2% moles phth. anhyd. (135 C.) 33.2 12.0 1. 75 51.5

to give acid ester plus Ethylene Oxide (140 0.).

L24645 Castor oil plus 2% moles phth. anhyd. plus poly- 32. 4 11.7 1. 70 53. 7

glycol, M. W. 1540 (235 0.).

L-24646 Polyglycol, M. W. 1540, .8 mole plus phthalic 31. 2 13. 1 1.64 52.8

anhyd. 1.6 mole plus castor oil .8. The polyglycol plus anhyd. heated until acid v. drops to of orig. The castor oil is added and heated again for 2 hrs. at 250 C. L24650. Castor oil plus 2% moles phth. anhyd. (135 C.) 31.4 11.3 1.05 i 53.1

plus polyglycol 770.

In examining the above table it will be noted all radicals shown do not add to quite 100%. The reason is that some connective oxygen atoms are not included, particularly those attached to glycerol and that, in some instances, there may have been elimination of Water Which affected the final percentage.

Attention is directed to the. fact again that L-24633 typifies one of the compounds described herein. In L-24645 the same intermediate (phthalated castor oil) was reacted with a polyethyleneglycol having a molecular weight of 1540, so as to give a compound which is analogous as far as its structural parts are concerned, as in the case of 11-24633. In 1 -24646 the polyglycol was first combined with a phthalic anhydride and reacted with a castor oil in a manner decribed in the series of patents previously referred to, to wit, U. S. Patents Nos. 2,295,163 through 2,295,170. was substantially the same as in L-24645, to wit, the intermediate was the same as in 11-24633 (phthalated castor oil), but instead of using a mole of a polyethyleneglycol having a molecular weight of 1540, there was used instead two moles In compound L-24640 the procedure This .is illustrated by noting the comparative wetting efl'l'ciencies (which properly in turn are related to surface activity) in the case of some of the simpler polyglycol fatty acids and a selected alkoxy derivatives.

of polyethyleneglycol having a molecular weight y l In addition to the four compounds above described, i. e., one derived by the use of ethylene oxide and the others by the use of a polyethyleneglycol, it is obvious that other compounds could be made, including the use of an alkoxy polyethyleneglycol. For instance, one could introduce a residue from a monohydric alcohol, such as methyl alcohol, ethyl alcohol, or propyl alcohol, etc., into a glycol. Such alkyl radical is introduced rather easily by simply substituting the monohydric alkyl ether of a glycol for the dihydric glycol. A suitable compound could be obtained by treating methyl or ethyl alcohol with ethylene oxide so as to give an ether glycol having a single hydroxyl and a molecular Weight com parable to the molecular Weight of the glycol previously described, that is, 770 and 1540.

Concentration (g. per cc.) for 25 sec. wet- Wetting Agent ting at 25 0.

Demulsifymg test 4 1 Date of test April 2 1948 State ol' California 011 field-l Montebello Oil company Century Lease 4. Repetto Well No. 15

Per cent emulsion in fluid from Well.-. Per cent free water in fluid from well Per cent water obtained by complete demulsification 44 Per .cent demulsifier, in test solution Temperature of tests.'.- Period of agitation after adding dexnulsifie Nature of agitation; machinewith shaker arm hakes per inute. Ratio of demulsifier to well fluid 1113,000; 1:26,000 (see below See values in table 00 F.

April 2, 1948 Signal Hill L. Brown #1- Per cent free water in fluid fr'oih' well. L Per cent water obtained by completeidemulsificatzom 46 Per cent demulsifier in test solutlon See values in table Temperatureof tests; 90 F.

Period of agitation after adding demulsifier Nature of agitation; machine with shaker at min. er minute 130 Ratio of demulsifier to well'fluid 1,13,000 l:26,000 (see below) L-24633 L-24645 L-24646 L-24656 Per Cent Demflslfier 1/2e,ooo 1/13,000 1/13,000 1/13,000 Blank Time test started 1:20. cc. water out at 8 9 7 7 Trace 22 24 22 22 D0. 26 27 26 26 D0. 31 2s 1 2s 30 Do. 31 28 28" 30 Do. 32 31 31 31 D0.

Demulszfymg test 6' Date'oftest April 2, 19i8 State of California Oil field Seal Beach Oil compan Hellman Estates Lease; 3A WelL 3A Per cent emulsion in fluidlr'oni well.

Per cent free water in fluid from wellu 6 Per cent water obtained by complete demulsification 16 Per cent demulsifier in test solution See values in table Temperature of tests 0 Period of agitation after adding demulsifier Nature of agitation; machine with shaker arm; u

Ratio of demulsifier to well fluid 1:l0,000 1:20,000 (see below) L-24633 L-24645 L 24c46 L-24650 Per Gent Demflsfler 1120,0o0 1 1o,000 1 10,00o 1 10,0oo- Blank Time test started :20. cc. water out at-' I 1:20 (4/2) 10 10 8 8 Trace n45 (4 2)-. 12 11 10 11 Do. 12135 13 11 11 12, Do. 10:40 (4 13 12 11 12 Do. 10:55 (4/4)-; 13 13 13 Do.

7 In addition to the foregoing demulsifying tests, the same fourcompounds identified as ill-24633, 11-24645, L-24646 and L-24650, have been tested on other emulsions with comparable differences. For sake of brevity these other tests are omitted but they include, among others, a test on an oil from Well No. 16, Cueller Lease oi Coxand Hammond, in the I-Io'finian Pool, Alice, Texas; the Stanolind Oil & Gas Company composite sample from the battery from. a lease located in the Wink Field near Kermit, Texas, etc.

These series of tests reveal that the compound obtained by the use of ethylene. oxide was 35% to 65 better in numerous instances, and not infre'-' quently was 100% better.

What has been said previously in regard to the structure of compounds which appear to be analogous at first superficial examination, should be reconsidered in light ofthe previous descrip tion of 11-24633, L24645, L-24646, and 11-24650, together with the foregoing tests. The same sorts of differences would be shown in other comparable tests where surface activity is-concerned with the industrial application; as for instance, break induction in doctor'treat'ment of sour hy- "drocarbons.'- The fact that there is a'similarity,

in fact, almost an identity of structure when I California;

measured in terms of acid radicals, ethylene oxide radicals, etc., does not mean that the size of molecules is the same for the obviousreason that the same materials of construction yield architecturally different products.

In the" hereto appended claims the word water-miscible is employed to designate a sol or solution which is permanent for either an indefinite period of time;- or for such extended period of time as would unquestionably permit its utilization for the herein designated purposes without undue difiiculties.

The products herein described, andparticularly for use as demulsiiying. agents, may be considered as intermediates for further reaction. For example, they may be reacted, with chloroacetic acid or similar low molal alpha-halogenated carboxy acid to produce an ester. Such ester will serve many of the purposes herein described, i. e.-, as a demulsifier, break inducer, etc. Such alpha-halogenated carboxy acid ester may be reacted further, for example, with a tertiary amine, such as dimethyldodecylamine, esterified triethanolamines in which the acyl radical is derived from a detergent-forming monocarboxy acid, and from hydroxylated amines obtained, for example, by reaction with high molal amines, such as octadecylamine with two moles of ethylene oxide. Such compounds or derivatives again can be employed for all of the various purposes herein indicated, and. particularly for demulsification.

The word miscible is. frequently used to mean soluble in all proportions. In a technical sense it is sometimes employed to mean soluble without necessarily meaning in all proportions, and such solubility may include a colloidal dispersion orv sol as well as molecular solution. The Word water-miscible is employed in the hereto appended claims in this more restricted meaning.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is: 7

1. A Water-miscible oxyethylated triricinolein acidic ester; said triricinolein acidic ester being that of a saturated di'carbox'y acid having not over 10' carbon atoms and characterized by the fact that prior to oxyethylation there is present at least one dicarboxy' acid carboxyl radical for each triricinolein radical, and all dicarboxy acid radicals are directly attached to the ricinoleyl radical.

2. A water-miscible oxyethylated triricinolein acidic ester; said t'riri'cinolein acidic ester being that of a saturated dicarboxy acid having not over 10 carbon atoms and characterized by the fact that prior to oxyethylation there is present a plurality of dicarboxy acid carboxyl radicals for each triricinolein radical, and all dicarboxy radi cals are directly attached to the ricinoleyl radical.

3. A water=miscible oxyethylated triricinolein acidic ester; said triricinolein acidic ester being that of a saturated dicarboxy acid having not over 10 carbon atoms and characterized by the fact that prior to oxyethylation there is present a plurality of dic'arboxy acid carboxylradicals for each 'tririci'nolein radical, and all dicarboxy radicals are directly attached to the ricinoleyl radical; with the further-proviso that the weight of ethylene oxide added by reaction based on the weight of the triricinolein acidic ester prior to oxyeth'ylation is within the range of to 1 25%.

4. A water-miscible triricinolein acidic ester; said triricinolein acidic ester being that of plithal-ic acid and characterized by the fact that prior to oxyethylation there is present a pluralityof phthalic acid radicals for each triricinolein radical, and all phthalic acid radicals are directly attached to the ricinoleyl radical; with the fur- 21 ther proviso that the weight of ethylene oxide added by reaction based on the weight of the triricinolein acidic ester prior to oxyethylation is within the range of 75% to 125%.

5. A water-miscible triricinolein acidic ester; said triricinolein acidic ester being that of adipic acid and characterized by the fact that prior to oxyethylation there is present a plurality of adipic acid radicals for each triricinolein radical, and all adipic acid radicals are directly attached to the ricinoleyl radical; with the further proviso that the weight of ethylene oxide added by reaction based on the weight of the triricinolein acidic ester prior to oxyethylation is within the range of 75% to 125%.

6. A water-miscible triricinolein acidic ester; said triricinolein acidic ester being that of diglycollic acid and characterized by the fact that prior to oxyethylation there is present a plurality of diglycollic acid radicals for each triricinolein 22 radical, and all diglycollic acid radicals are directly attached to the ricinoleyl radical; with the further proviso that the weight of ethylene oxide added by reaction based on the weight of the triricinolein acidic ester prior to oxyethylation is within the range of to MELVIN DE GROOTE.


REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,081,266 Bruson May 25, 1937 2,295,168 De Groote Sept. 8, 1942 2,343,434 De Groote Mar. '7, 1944 2,353,695 De Groote July 18, 1944

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2081266 *May 10, 1932May 25, 1937Resinous Prod & Chemical CoCondensation product of castor oil with half ester of maleic acid
US2295168 *Mar 21, 1941Sep 8, 1942Petrolite CorpProcess for breaking petroleum emulsions
US2343434 *Feb 28, 1941Mar 7, 1944Purolator Products IncFilter
US2353695 *Jun 15, 1942Jul 18, 1944Petrolite CorpProcess for breaking petroleum emulsions
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2695909 *Apr 10, 1952Nov 30, 1954Petrolite CorpReaction product of a polycarboxylic acid and oxypropylated triricinolein
US2925429 *Jul 12, 1954Feb 16, 1960Visco Products CoChemical compositions
US2971923 *Mar 7, 1955Feb 14, 1961Visco Products CoProcesses for breaking petroleum emulsions, especially in desalting operations
US6342527 *May 11, 2001Jan 29, 2002Zenitech LlcPolymeric castor polyesters
US6626070May 4, 2001Sep 30, 2003Irwin Industrial Tool CompanyCompound toggle link retention mechanism
U.S. Classification554/116
International ClassificationC10G33/00, C11D1/74, C10G33/04
Cooperative ClassificationC11D1/74, C10G33/04
European ClassificationC10G33/04, C11D1/74