US3170879A

US3170879A - Lubricant

Info

Publication number: US3170879A
Application number: US112511A
Authority: US
Inventors: Richard A Butcosk
Original assignee: Socony Mobil Oil Co Inc
Current assignee: ExxonMobil Oil Corp
Priority date: 1961-05-25
Filing date: 1961-05-25
Publication date: 1965-02-23
Anticipated expiration: 1982-02-23
Also published as: GB1011485A

Description

United States Patent 3,170,379 LUBRECANT Richard A. Butcosir, Westrnont, N.J., assignor to Socony Mobil Oil Company, Inc, a corporation of New York No Drawing. Filed May 25, 1961, Ser. No. 112,511 33 Qlaims. (Cl. 252-48) This invention relates to the production of lubricating compositions containing salts and soaps of aliphatic monocarboxylic acids of varying molecular weight. More particularly, this invention is primarily directed to the provision of an improved procedure for preparing grease compositions of this type.

As used herein, the term grease denotes a composition comprising a major proportion of an oil of lubricating viscosity thickened to a grease consistency with a soap or soaps, the composition having an unworked penetration, when tested by ASTM Method D217-52T, of at most 475, using the modified cone recommended by ASTM Technical Committee G of ASTM Committee D-2.

The manufacture and use of greases and similar lubricating compositions in which the thickening effect is obtained through the utilization of any of various combinations of salts and soaps of aliphatic monocarboxylic acids of different molecular weights are now customary in the.

lubricating art. Such grease compositions, as is well known, possess a number of desirable characteristics, especially important among which is stability at relatively high temperatures. Depending on the oily material that is employed as the oil vehicle or base and depending on the particular formulation selected, grease compositions of this type retain their body or structure over more or less wide temperature ranges including operating temperatures as high as of the order of 500 F.

In order to produce such a grease composition of entirely satisfactory nature, it is often desirable and generally necessary to resort to the use of processing temperatures in excess of 350 F. and frequently up to as high as 550 F. Although such relatively high processing temperatures may not be undesirable in and of themselves, it is readily apparent that the necessity to employ the same imposes corresponding limitations on the nature of the equipment utilized to produce these grease compositions. More specifically, the manufacture of such grease compositions at high temperatures makes necessary efficient heat transfer and adequate mixing; local overheating is to be avoided. In short, it is essential to maintain a thin film with reasonably good circulation velocity, as opposed to operating with a static thick film.

Again, where preformed salts and soaps are admixed with the oil vehicle or base, the compounding operation can be carried out in the presence of a slight acidity so that, as higher processing temperatures are necessarily employed, the possibility of and the resulting danger due to corrosion are perforce increased.

It is apparent, therefore, that it would be most desirable, if possible, to carry out such grease-compounding operation at relatively lower temperatures, with the concomitant avoidance or elimination otherwise of the indicated difficulties.

I have now found that this objective can be effectively attained by including or incorporating a nitrogen-containing compound of the type hereinafter specified with the oily vehicle or base and the thickening agent or ingredient to be formulated into the desired grease or other lubricating composition. In some manner that can not be satisfactorily explained, the use of even a relatively small proportion of such compound results such that bodying or gelling of the grease composition occurs at a considerably lower temperature than would be required in the absence of such compound. This lower-temperature effect has been found to be especially significant where the oil ve- 3,170,8i9, Patented Feb. 23, 1965 hicle or base comprises a synthetic oily material such as a silicone oil or a relatively high molecular weight ester or polyester of lubricating viscosity.

I have also found that in some instances the resulting grease is produced in a greater yield; that is, less of the thickening agent or ingredient is required to produce a grease of the same character from the oil base. This is an advantage in providing long term lubrication at high temperatures.

I have further found that in some instances the stability of the resulting grease during storage is materially enhanced. Finally, particularly where preformed salts and soaps are utilized to produce the desired thickening, the use of such a nitrogen-containing compound tends to inhibit corrosion of manufacturing equipment that would otherwise occur.

Basically, the present invention provides a method of preparing a lubricating or grease composition, which comprises providing a charge mixture of an oil of lubricating viscosity, a thickening agent or ingredient as hereinafter specified, and a nitrogen-containing compound as also hereinafter set forth, and then mixing and heating the resulting charge mixture to a temperature and for a time sufficient to thicken the oil vehicle or base to the extent desired.

The oil component or vehicle employed in carrying out the present invention may vary considerably in nature and can comprise a mineral oil, a synthetic oil, or a combination of the same. Generally, such oil component is characterized by a Saybolt Universal viscosity of greater than about 40 seconds at F. and preferably from about 60.

seconds to about 6000 seconds at 100 F. Any suitable mineral oil can be utilized; but it is to be noted that the character of the mineral oil-that is, whether such oil is parafiinic or naphthenic, for exampleusually influences the characteristics of the resulting grease. Various synthetic oils of lubricating viscosity can also be utilized and include polymerized olefins, fluorocarbons, perfluoroalkyl ethers, esters of phosphorus-containing acids, amines, numerous silicone oils (e.g., polysiloxanes), polybasic acids esterilied with monohydroxy alcohols, and polyhydroxy alcohols esterified with monocarboxylic acids. Typical examples of synthetic esters comprise di-(Z-ethyl-hexyl) sebacate, di-(Z-ethybhexyl) adipate, polyethylene glycol di-(Z-ethyl-hexoate), and the tricaprylate of trimethylolpropane.

The thickening agent or ingredient can comprise an admixture of a basically reacting alkaline earth metal compound and a mix of an aliphatic monocarboxylic acid having 7 to 12 carbon atoms and an aliphatic monocarboxylic acid having 1 to 6 carbon atoms and with or without an aliphatic monocarboxylic acid having at least 13 carbon atoms. In such event, as will be understood, the basically reacting alkaline earth metal compound and the aliphatic monocarboxylic acid mix react in situ to form a complex salt-soap which serves as the actual thickening medium. Alternatively, a preformed salt-soap complex of this type can be directly incorporated in the oil vehicle or base for the purpose of thickening the same.

It is to be understood that the expression basically reacting alkaline earth metal compound as used herein means an oxide, a hydroxide, a carbonate, a hydride, or an alcoholate of an alkaline earth metal. At the same time it is to be understood that the term alkaline earth metal as used herein means magnesium, calcium, strontiurn, or barium. Of these metals calcium and barium are customarily employed, with calcium generally being preferred and used in the form of its hydroxide (lime). It

is to be noted that calcium is generally associated with av small amount of magnesium, since the hydroxides are generally associated with each other.

The aliphatic monocarboxylic acid mix contains an acid having 7 to 12 carbon atoms. Such acid is employed with an aliphatic monocarboxylic acid having 1 to 6 carbon atoms or with the latter and an aliphatic monocarboxylic acid having at least 13 carbon atoms, usually 13 to 36 carbon atoms. Grease formulations containing various combinations of such acids as salt-soap complexes have been previously proposed as is well known: for example, greases containing an admixture of a salt of an aliphatic monocarboxylic acid having 1 to 6 carbon atoms and a soap of an aliphatic monocarboxylic acid having 7 to 12 carbon atoms are described in application Serial No. 78,842, now Patent No. 2,999,066, filexi December 28, 1960 by Clarence Liddy; and greases containing an admixture of a salt of an aliphatic monocarboxylic acid having 1 to 6 carbon atoms, a soap of an aliphatic monocarboxylic acid having 7 to 12 carbon atoms, and a soap of an aliphatic monocarboxylic acid having at least 13 carbon atoms, are described in application Serial No. 67,499, now Patent No. 2,999,065, filed November 7, 1960, by Clarence Liddy. It has been found particularly desirable to employ acetic acid, caprylic acid, and stearic acid as the three specified types of acids, and combinations of calcium acetate, calcium caprylate, and calcium stearate are considered especially preferable for use as the thickening agent or ingredient whether formed in situ or preformed.

As will be appreciated, the thickening ingredient is utilized in an amount to produce the desired bodying or gelling efiect. Such amount of the thickening ingredient, determined as salt-soap complex, is generally from about 1 to about 50% by weight and preferably from about to about 20% by weight, based upon the total charge mixture. Where the thickening ingredient comprises a twoacid system composed of a 1 to 6 carbon atom aliphatic monocarboxylic acid component and a 7 to 12 carbon atom aliphatic monocarboxylic acid component, the mole ratio of the former to the latter desirably ranges from about 1:1 to about :1. Where the thickening ingredient comprises a three-acid system composed of a 1 to 6 carbon atom aliphatic monocarboxylic acid component, a 7 to 12 carbon atom aliphatic monocarboxylic acid component, and a 13 to 36 carbon atom aliphatic monocarboxylic acid component, the mole ratio of the 1 to 6 carbon atom component to the other two components combined is desirably from about 1:1 to about 10:1, with the mole ratio of the 13 to 36 carbon atom component to the 7 to 12 carbon atom component being desirably from about 0.01:1 to about 10:1.

As indicated above, the essence of the present inven tion resides in the incorporation of a specific nitrogencontaining compound in the grease formulation as it is being processed with the result that the gelling or bodying temperature of such formulation is materially reduced, an equivalent or frequently superior grease thereby being obtained. In addition, as indicated hereinafter, new and novel greases are formed when particular nitrogen-containing compounds are so employed.

Improvement is achieved, I have found, only with certain nitrogen-containing compounds; and, on the basis of the extensive experimental investigation carried out in this regard, I find that a compound to be useful for the present purpose is an ammonium salt of an aliphatic monocarboxylic acid, an ammonium salt of an aryl aliphatic monocarboxylic acid, an ammonium sulfate, an ammonium phosphate, an ammonium salt of a sulfated castor oil, an ammonium salt of a sulfonic acid which is a phenyl sulfonic acid, a naphthyl sulfonic acid, or an alkyl-substituted phenyl or naphthyl sulfonic acid, or ammonium salt of a mineral oil sulfonic acid, an addition product of an amine and an aliphatic monocarboxylic acid.

A common characteristic of the specified nitrogen-containing compounds is that they decompose with liberation of the nitrogen-containing constituent when the grease formulation is heated to elfect bodying or gelling. Where the compound is an ammonium salt as specified,

the nitrogen-containing constituent, namely, ammonia is liberated as a result of such heating and is driven off; the anionic acidic residue generally remains in the grease formulation. However, when a low molecular weight compound such as ammonium acetate is used, ammonia is driven oif and acetic acid released can be driven off too, in part at least, at the operating temperature. In the case where the anionic acidic residue is an aliphatic monocarboxylic residue, it appears to function as part of the thickening agent or ingredient and to form a salt or soap by reaction with any basically reacting alkaline earth metal compound that may be present.

I find that ammonium acetate is particularly useful for the present purpose. It may be added as such, or ammonium acetate may be formed in situ by reaction of ammonium hydroxide and acetic acid added individually. A typical ammonium sulfate is (NI-10 50 and a typical ammonium phosphate is NH H PO As previously indicated, where the nitrogen-containing compound comprises an addition product of an amine and an aliphatic monocarboxylic acid (e.g. morpholine acetate), decomposition also occurs during processing of the grease formulation. In such case, however, the nitrogen-containing constituents, namely, the amine remains in the grease composition as such unless, of course, the processing temperature becomes sufficiently high so as to effect its volatilization or distillation. If desired, the amine portion of such addition product may be so selected as to impart various properties such as resistance to oxidation to the ultimate grease product. Various such addition products have been found especially suitable; and these include n-propylarnine acetate, aniline acetate, and morpholine acetate. (Whether a true acetate is formed or whether an acetic acid addition salt is actually formed does not appear to be material; and the term addition product of an amine and an aliphatic monocarboxylic acid is meant to cover either possibility.) Naphtbylamine acetate has also been employed with satisfactory results.

Particularly unusual results have been obtained with ammonium salts of alltyl-substituted naphthyl sulfonic acids; and I have found the ammonium sulfonates of dinonyl naphthalenes to be outstandingly effective for the present purpose. Not only is the bodying or gelling temperature markedly lowered by the use of such a nitrogencontaining compound, with concomitant improvement in yield (as discussed above); but the resulting grease exhibits unusual storage stability in contrast with that possessed by a grease made in the absence of such compound.

More importantly, a grease prepared with such a naphthalene sulfonate is new and novel as revealed by electron microscope data. Such a grease has an unusual structure as evidenced by the fact that an approximately 4000-diametcr magnification reveals a product containing two types of materials: one type comprises needles having a len th-to-diameter ratio of about 6: 1, and the other type, present in approximately an equal amount, comprises bundles of fibers having a length-to-diameter ratio of about 8:1. Furthermore, the ratio of the length of such fibers to the length of such needles is about 10:1. A grease prepared from the same formulation, except for the omission of the indicated naphthalene sulfonate, comprises needles or rods having a length-to-diameter ratio of about 6-8: 1-and no fibers.

The alkyl-substituted naphthalene sulfonic acid residue or other sulfonic acid residue that results from the decomposition of the corresponding ammonium salt appears to form a salt with any basically reacting alkaline earth metal compound that may be present. At any rate, such sulfonic acid residue appears in the resulting lubricating or grease composition as the corresponding salt of such alkaline earth metal.

Just what function the nitrogen containing constituent of the nitrogen containing compound plays in the present invention is not clear or certain. It has been definite -v 1y established, however, that it is not merely the liberation of the nitrogen-containing constituent such as ammonia that is critical; for other nitrogen-containing compounds that decompose upon heating or otherwise to liberate ammonia do not produce the same results when used in accordance with this invention. For example, ammonium carbonate and urea both decompose and liberate ammonia upon being heated; but I find that neither of these compounds has any measurable eifect in lowering the gelling temperature of the present type of grease formulations.

The nitrogen-containing compound is included in or incorporated into the grease formulation in an amount sufiicient to significantly lower the bodying or gelling temperature of such formulation. Generally, such amount is of the order of from about 1 to about by weight of the total charge mixture, with the preferred range being from about 2 to about 5% by weight. Such compound may be incorporated into the grease formulation either initially or during the course of its processing-for example, after a mixture of the oil and the thickening ingredient has been preliminarily heatedso long as it is present at the time when thickening occurs.

In practicing the present invention, customary greasemaking procedure is basically followed except, of course, that it is not necessary to utilize as high a processing temperature to elfect the desired bodying or gelling. Once the charge mixture of the oil vehicle, the thickening agent or ingredient, and the nitrogen-containing compound has been provided, it is subjected to the requisite degree of mixing and heating to thicken the oil vehicle as desired. Where the thickening ingredient comprises an admixture of a basically reacting alkaline earth metal compound and a mix of the indicated aliphatic monocarboxylic acids, such heating also serves to eifect a reaction therebetween. Toward the end of the heating step an alkaline material such as lime can be added to the grease formulation in order to neutralize any free acidity that may exist or to render the resulting mass alkaline.

Other advantageous processes useful herein are the spray or jetting techniques described in US. Patent Numbers 2,950,248 and 2,950,249, issued August 23, 1960, and in in application Serial Number 51,139, now Patent No. 3,108,965, filed August 22, 1960.

Especially desirable results are obtained when grease compositions are prepared in accordance with the present invention from charge mixtures of the tricaprylate of trimethylolpropane or a silicone oil of lubricating viscosity, from about 10 to about 20% by weight based upon the total charge mixture of a salt-soap admixture of calcium acetate, calcium caprylate, and calcium stearate, the mole ratio of the acetate to the caprylate and the stearate combined being from about 1:1 to about 5 :1 and the mole ratio of the stearate to the caprylate being from about 0.05:1 to about 5:1, and from about 2 to about 5% by weight based upon the total charge mixture of an ammonium sulfonate of a dinonyl naphthalene. Where the tricaprylate of trimethylolpropane comprises the oil vehicle, sufficient lime is desirably added near the end of the heating step to render the resulting grease substantially neutral; similarly, where a silicone oil comprises the oil vehicle, sufllcient lime is added near the end of the heating step to render the resulting grease alkaline.

As indicated above, the sulfonic acid residue of the ammonium dinonyl naphthalene sulfonate is present in the resulting grease as a calcium salt. The amount of such calcium salt in such grease composition, based on the total grease composition, is essentially the same as the amount of the corresponding ammonium sulfonate included in the charge mixture, based on the total charge mixture, since, as will be appreciated, the molecular weights of the two sulfonates are relatively high and the difference between such molecular weights is quite small.

6 Similar remarks apply to the amounts of the salt-soap admixture respectively included in the charge mixture and contained in the resulting grease. Consequently, the same percentage ranges are employed in setting forth the amounts of the indicated ingredients except that in one instance the basis is the total charge mixture and in the other instance the basis is the total grease composition itself.

The following examples will serve to illustrate the nature and the scope of the present invention. Unless otherwise indicated, all proportions represent percentages by weight based on the charge mixture.

EXAMPLE I Set forth in Table I below are data which establish that a lower gelling temperature is obtained with an ammonium acetate:

Table I Grease A. Grease B Grease C Acetic acid 10.00 10.00 8. 42 Gapryhc acid 1.20 1.20 1.01 Stearic acid 2. 40 2. 40 2. 02 Mineral oil (solvent refined naphthenic,

S.U.S. viscosity of 500 seconds at F. Balance Balance Balance Calcium hydroxide--- 7. 75 8. s5 7. 47 Ammonium acetate 2.00 3. 37 Thickening temperature, "F 500 350 330 Penetration, unworked/worked..- 255/302 239/279 263/390 Roll stability, initial/after 2 hours 92/82 86/83 99/86 Mean Hertz Load 51. 50. 2 60.2

In each formulation the mole ratio of the acetic acid component to the caprylic acid and the stearic acid components combined is about 10:1, with the mole ratio of the stearic acid component to the caprylic acid component being about 1: 1.

Grease A was prepared by initially mixing the mineral oil and the calcium hydroxide in a grease kettle and then admixing the acids therewith at room temperature. The resulting charge was thereafter gradually heated with continual stirring over a period of about 2 hours to 510 F. The charge remained very fluid until the temperature reached 500 F., at which temperature the grease formulations began to thicken. Following cooling to 200 F., the grease was passed through a Tri- Homo colloid mill (0.002-inci1 setting in this and the succeeding examples unless otherwise mentioned).

Grease B was prepared in the same manner as Grease A except that the ammonium acetate was added to the resulting charge prior to heating the same. Ammonia was detected as the temperature was increased from 300 F. to 350 F., at which point the grease formulations began to thicken substantially. Heating was continued to 500 F. and the reaction mixture was cooled and milled, as before.

In the preparation of Grease C there was initially treated in the same manner as Grease B a charge containing 92.45% of mineral oil. Ammonia was detected at about 330 F., at which point a heavy product had already been formed. Since the resulting product from such initial treatment was too heavy, additional mineral oil was incorporated therein to provide the composition of Grease C. Again, heating was continued to 500 F., followed by cooling and milling.

The penetration values in this example (and in the succeeding examples) were obtained in accordance with ASTM Method D21748, Cone Penetration of Lubricating Grease. Roll stability tests were carried out in accordance with the procedure described at page 4 of the March, 1943 issue of The Institute Spokesman, volume 6, No. 12. Mean Hertz Load data represented extreme pressure values as measured by Federal Test Method Standard No. 791, Method 6503.

7 EXAMPLE II The data contained in Table II below indicate the applicability of the present invention to the production of a barium-base grease:

In each formulation the mole ratio of the acetic acid component to the caprylic acid and the stearic acid components combined, is about 2.3:1.

To prepare Grease D an initial formulation containing less mineral oil was utilized. A major portion of the mineral oil and the remaining ingredients of such initial formulation were mixed in a grease kettle, and the resulting mixture was slowly heated to 510 F. with constant stirring. The balance of the mineral oil was added at about 480 F. As the temperature reached 510 F., the charge began to thicken to the consistency of a heavy, viscous mineral oil. Following cooling to room temperature, the mass was passed through a Tri- Homo colloid mill. Additional mineral oil was thereafter incorporated in the resulting product to provide the composition of Grease D.

Grease E was prepared in a similar manner as Grease D, except that the ammonium acetate was added to the charge at about 170 F. and a small portion of the barium hydroxide was added with the balance of the mineral oil at about 350 F. Ammonia was detected as the temperature was increased past 215 F. Considerable thickening occurred at about 420 F. As with Grease D, additional mineral oil was incorporated in the resulting product to provide the composition of Grease E.

It is especially noteworthy that a better yield was obtained with Grease E than with Grease D.

EXAMPLE III That acetic acid and ammonium hydroxide can be effectively utilized to provide the essential ammonium acetate in accordance with the invention is shown by the following data:

Table IH Grease G Stearic acid. Calcium hydroxide Ammonium hydroxide Silicone oil (Dow Corning Fluid 710) Acetic acid Thickening temperature, F. Penetration, unworlred monium hydroxide was added. Heating was continued slowly with stirring to about 350 F., at which point 'the charge thickened substantially. The calcium hydroxide was then added, and the temperature was maintained at about 350 F. for a short time. Following cooling to about 200 F., the mass was passed through a threero ll ink mill.

Grease G was firm and smooth. Moreover, as will be apparent, its yield was superior to that of Grease F.

EXAMPLE IV The data set forth in Table IV below (all proportions in parts by weight) further illustrate the effectiveness of the present invention:

Table IV Grease I Calcium acetate-H2O Calcium caprylate. Calcium stearatc Ammonium acetate Calcium hydroxide Tricaprylate of trimethylol propane Thickening temperature F Bala EXAMPLE V This example involves the use of a different type of synthetic ester as the oil base or vehicle:

Grease J Calcium acetate.H O 11.6 Calcium caprylate 8.0 Calcium stearate 3.7

Ammonium acetate 2.0

Di-(2-ethyl-hexyl) sebacate Balance Calcium hydroxide 0.2

The mole ratio of the acetate component to the caprylate and the stearate components combined is about 2.3:1.

To prepare this grease, all the ingredients except the calcium hydroxide were heated together .to about 350 F. At this point the calcium hydroxide was added, and heating was continued for a few minutes. After cooling to about 200 F., the mass was passed through a three-roll ink mil-l.

Thickening of this grease formulation occurred at a much lower temperature than that required in the absence of the ammonium acetate.

EXAMPLE VI The following data further illustrate the present invention in connection with the production of a two-acid system grease:

Table V Grease Grease K L Acetic acid 22. 50 22. 50 Caprylic acid. 2.16 2. 10 Calcium l1ydroxide 21. 50 21. 50 Mineral oil (as in Table 1)-. Balance Balance Ammonium acetate .00 Calcium hydroxide 2.00 Thickening temperature, F 510 250 Penetration, uuworked/worked 420+/420+ 403/413 In these two formulations the mole ratio of the acetic acid component to the caprylic acid component is about 25:1.

Grease K was prepared by first admixing the mineral oil and the calcium hydroxide in a grease kettle and then adding the acids thereto with continued stirring. The resulting charge was heated slowly with stirring to about 510 F. without, however, thickening substantially. Following cooling to about 200 F., the mass was passed through a Tri-Homo colloid mill.

Grease L was prepared in a similar manner except that the ammonium acetate was incorporated into the charge before the charge was heated, and except that a small portion of the calcium hydroxide was withheld from the initial admixture and was added to the charge as the temperature reached about 350 F. Ammonia began to be detected at about 250 F., at which point the charge began to thicken as the temperature was increased.

EXAMPLE VII The particular effectiveness of the use of an ammonium sulfonate of an alkyl-substituted naphthelene with preformed salts and soaps is illustrated by the following data:

In both instances the mole ratio of the acetate component to the caprylate and the stearate components combined is about 2.3:1.

To prepare Grease M, the remaining materials were initially mixed with about half of the tricaprylate oil base in a grease kettle. The balance of the tricaprylate oil was then added to the resulting admixture; and such charge was heated to about 385 F. without, however, thickening. Following cooling to about 280 F., the mass was passed through a charlotte mill (0.025-inch setting).

Grease N was prepared from an initial formulation containing somewhat less of the tricaprylate oil vehicle. The charge for such initial formulation consisted of the indicated ingredients except for the calcium hydroxide. Such charge was heated slowly to about 400 F. At a temperature of about 300 F. the charge thickened substantially and ammonia was given oil. The calcium hydroxide was added when the temperature reached about 400 F., and the mass was then cooled to about 300 F. and passed through a three-roll ink mill. The resulting product being very heavy, additional tricaprylate oil was added to give Grease N.

These two greases were stored following their preparation to determine their respective storage stabilities, a factor of considerable commercial significance. It was found that Grease M, a semi-fluid grease, changed in storage after days to approximately a No. 1 consistency grease. In contrast, Grease N remained a No. l consistency, essentially unchanged after 30 days.

It was further found that Grease N exhibited rust-preventive properties in contrast to the slight corrosion that was obtained with Grease M. The test method used was CRCL41.

EXAMPLE VIII The use of (NI-1.9 80 as the nitrogen-containing compound is illustrated by this example:

Table VII Grease Grease 0 P Acetic acid 7.9 7. Caprylic acid 6. 7 3. 4O Stearie acid 3. 4 3. 40 Calcium hydroxide.-- .4 9. 15 (NILi)2SO4 I 2. 00 Mineral oil (as in Example I)- Balance Balance Thickening temperature, F 240 Penetration, unworked/worked 325/330 208/240 Roll stability, initial/after 2 h0urs 122/137 71/68 Mean Hertz Load 38. 8 50 In these two formulations the mole ratio of the acetic acid improvement to the capryliic acid and the stearic acid components combined is about 2.311.

In preparing Grease O, the calcium hydroxide and the mineral oil were first admixed in a grease kettle. The acetic acid and the caprylic acid were then slowly added to such mixture, followed by the stearic acid. This charge was slowly heated to about 510 F., at which point it had thickened. Following coolingto room temperature, the mass was passed through a Tri-Homo mill.

Grease P Was prepared by initially mixing the mineral oil, the three acids, and the major proportion (87 percent) of the calcium hydroxide in a grease kettle. The ammonium sulfate was then added, and the charge was slowly heated to about 510 'F. At about 240 F. ammonia was detected, and the charge already had thickened. The balance of the calcium hydroxide was added at about 240 F. Following cooling to about F., the mass was passed through a Tri-Homo colloid mill.

EXAMPLE IX This example involves the use of NH H PO as the nitrogen-containing compound; the proportions are given in parts by Weight:

All the ingredients except the calcium hydroxide were initially admixed, and the resulting mixture was slowly heated to about 400 F. At about 300 F. ammonia was detected, and the calcium hydroxide was added at about 350 F. Adequate thickening developed before the temperature had reached 400 F. Following cooling, the mass was passed through a three-roll ink mill.

Thickening occurred at a considerably lower temperature than what would have been required in the absence Of NH4H2PO4.

EXAMPLE X The following data illustrate the use of various aminealiphatic monocariboxylic acid addition products as the nitrogen-containing compound:

Table VIII Grease Grease Grease Calcium acetate. H2O 9. 60 7. 55 10. 54 Calcium caprylate. H3O 6. 62 5. 20 7. 27 Calcium stearate 3. 06 2. 40 3. 36 n-Propylamine acetate 1.65

N apholine aeetate 3. 18 Aniline-acetic acid addition product 5.45 Tricaprylate of trimethylolpropane Balance Balance Balance Calcium hydroxide 0. 83 0.65 0. 90 Thickening temperature, F 22 250 280 Penetration, unworkcd/worked 183/213 227/246 324/362 Roll stability, initial, after 2 hours 47/64 59/81 90/132 In each instance the mole ratio of the acetate compound to the caprylate and the stearate components combined is about 2.3 1.

In preparing Grease R, all the ingredients except the calcium hydroxide and a minor proportion of the tricaprylate oil base were mixed in a grease kettle. The resulting charge was slowly heated to about 400 F. and began to thicken at a temperature in the range of 200 to 220 F. When the charge temperature rose to about 400 F., the balance of the oil vehicle was added with continued heating. Following addition of the calcium hydroxide and cooling to 200 F., the mass was passed through a Tri-Homo colloid mill.

To prepare Grease S, an initial formulation containing all the ingredients except the calcium hydroxide and a minor proportion of the ester base was provided. This charge was slowly heated to about 400 F.; it began to thicken at about 250 F. and became very heavy at about 350 F. When the charge temperature reached about 400 F., a further portion of the oil base was added with continued heating. The mass was then cooled to about 200 F. with addition of the calcium hydroxide during cooling, and the cooled mass was passed through a Tri- Homo colloid mill. The balance of the oil base was then incorporated in the milled mass to provide Grease S.

Grease T was prepared by mixing all the ingredients except the calcium hydroxide and a minor proportion of the ester base in a grease kettle. Such charge was slowly heated with stirring to about 400 F., with thickening beginning at about 280 F. When the temperature reached about 400 F., the balance of the oil vehicle was added with continued heating. Following cooling to about 200 F. with addition of the calcium hydroxide during cooling, the mass was passed through a Tri-Homo colloid mill.

In each of these formulations thickening developed at an appreciably lower temperature than would have been the case in the absence of the respective nitrogen-containing compound.

EXAMPLE XI This example demonstrates the effectiveness of an ammonium salt of a sulfonated castor oil in reducing the thickening temperature Grease U Calcium acetate.H O 7.44 Calcium caprylate.5H;.O 5.41 Calcium stearate 2.38 Ammonium salt of sulfonated castor oil 4.17

Tricaprylate of trimethylolpropane Balance Calcium hydroxide 0.25 Thickening temperature, F. 350 Penetration, unworked/ worked 184/ 190 Charged to a grease kettle were all of the salts and soaps and approximately one-half of the ester vehicle. The resulting mixture was well mixed and was heated slowly to 400410 F. Thickening occurred at 350 F. The temperature was reduced to about 35 F., whereupon about one-quarter of the ester vehicle was added. When the temperature again reached 400 F., the remainder of the ester was added. Calcium hydroxide was added when the kettle contents were at 410420 F. The product was cooled and passed through the Tri Homo mill. The product was smooth and a No. 4 consistency.

EXAMPLE XII As indicated above, greases which have been prepared with an ammonium salt of an alkyl-substituted naphthyl sulfonic acid in accordance with the present inventions are novel in and of themselves. The thickener in such greases, as previously pointed out, comprises a mixture of the alkaline earth metal salt-soap complex and an alkaline earth metal salt of such alkyl-substituted naphthyl sulfonic acid. Such mixture, which can be either isolated from a grease containing the same or prepared by physical admixture of the individual ingredients, itself represents a novel composition that forms part of the present invention.

Where such mixture is to be isolated or separated from the oil base in a grease containing the same, a grease such as that of Example VII is uniformly suspended in petroleurn ether. The resulting suspension is thus centrifuged to separate most of the liquid. Additional petroleum ether is added to the residue to resuspend the same, and such further suspension is also centrifuged to again separate most of the liquid. The resulting residue is then permitted to air-dry, with the production of the desired thickener mixture. Obviously, further resuspension and centrifugation operations can be employed if desired or necessary.

It will be appreciated that the thickener mixture can be prepared in situ in a vehicle other than the oil base of the type utilized in formulating greases in accordance with the present invention. Such a suitable alternative vehicle comprises cetane, which can be separated from the resulting grease-like mass in the manner described above to provide the desired thickener mixture.

As will be apparent, this thickener mixture can be incorporated in any appropriate oil vehicle or base to provide a lubricant of desired or specified characteristics. For example, the mixture can be incorporated in an oil to provide an extreme pressure lubricant which is useful, for example, in gears operating under low speed, high load conditions. Moreover, such thickener mixture can be transported as such, an arrangement which has obvious economic and commercial advantages.

Illustrations of extreme pressure lubricants are shown below in Table IX. The illustrations are two-acid. system products.

In each formulation the mole ratio of the acetic acid component to the caprylic acid component is about 49:1.

Lubricant V was prepared by slowly heating to about 510 F. while stirring all th ingredients in admixture. Thickening did not occur until about 500 F. After cooling to about 200 F., the mass was passed through a Tri- Homo colloid mill.

Lubricant X was prepared in a similar manner except that ammonium acetate was included in the charge and a small portion of the calcium hydroxide was omitted from the initial charge. In this instance the mass thickened at about 400 F., at which point the above-mentioned small portion of calcium hydroxide was added.

As indicated earlier, some ammonium compounds and others closely related thereto are inelfective or are substantially so in regard to effecting a reduction in thickening temperature. This is demonstrated below in Example XIII.

EXAMPLE XIII (A) AMMONIUM CARBONATE Calcium acetate.H O 11.6 Calcium caprylate 8.0 Calcium stearate 3.7 Ammonium carbonate 2.0

Tricaprylate of trimethylolpropane Balance Thickening temperature, F. 450

The materials were charged to a grease kettle in which they were mixed and heated slowly to about 450 F. Ammonia was evolved as the mixture was heated. Thickening did not occur until the temperature was about 450 F. The product was very grainy; however, when cooled to about 300 F. and passed through a 3-roll ink mill, the product was smooth.

It is to be noted that the thickening temperature was about 450 F. when ammonium carbonate was used. In contrast, comparable Grease H (Example IV) prepared without any ammonium compound, thickened at about 520 F. and comparable Grease I (Example IV) prepared with ammonium acetate, thickened at 350 F. That is, ammonium carbonate is only slightly etfective, reducing the thickening temperature only 70 F., from 520 F. to about 450 F.; whereas, ammonium acetate is far superior, reducing the said temperature 170 F from 520 F. to 350 F.

(B) AMMONIUM BIBORATE Acetic acid 10.00 Caprylic acid 1.20 Stearic acid 2.40 Calcium hydroxide-7=0.4% CaO 8.85 Ammonium biborate-(NH B O-;.4H O 2.90 Mineral oil (as in Table I) Balance Thickening temperature, F.. 500 Penetration, unworked/worked 235/235 Roll stability, initial/ after 2 hrs. 72/62 The mineral oil and about 90 percent of the total calcium hydroxide were added to a grease kettle, wherein they were mixed for about 5 minutes. All of the acids were added slowly and the resulting mixture was mixed thoroughly for about 5 minutes. The latter mixture was heated to about 180 F. Ammonium biborate was added. Heating was continued to about 400 F., when the remaining calcium hydroxide was added. It was not until about 500 F. that thickening occurred. Heating was discontinued when the temperature reached 510 F. The product was cooled to 180 F. and was passed through the Tri-Homo mill.

By way of comparison with Greases A through C (Example I, above), no reduction in thickening temperature was realized with ammonium biborate, while a reduction of 150 F. was gained with the use of ammonium acetate.

(C) AMMONIUM BIBORATE Calcium acetate.H O 11.6 Calcium caprylatel-l O 8.0 Calcium stearate 3.7 Ammonium biborate-(NH B O .4H O 2.9 Calcium hydroxide-70.4% CaO 1.1 Tricaprylate of trimethylolpropane Balance Thickening temperature, F. 500 Penetration, unworked/worked 192/203 Roll stability, initial/after 2 hrs. 46/48 All of the materials were charged to a grease kettle, with the exception of the calcium hydroxide. The materials so added were mixed and heated. When the temperature reached 400 F., the calcium hydroxide was added. Thickening did not occur until the temperature reached 500 F. Heating was continued until the maximum temperature was 510 F. The product was cooled to 180 F. and was passed through the Tri Homo mill.

Ammonium biborate was ineffective in reducing the thickening temperature, since a comparable product produced without any ammonium compound thickened at the same temperature, 500 F.

Thickening temperature, F. Penetration, unworked/worked 194/213 Charged to a grease kettle were approximately 60 percent of the ester vehicle, all of the salts and soap and urea. The charge was mixed well at room temperature (about 70 F.). The charge was then heated, with mixing continued. At 390 F., calcium hydroxide was added, followed by the balance of the ester vehicle. Thickening occurred at about 450 F. The maximum temperature reached was 520 F. The product was cooled to about 200 F. and was then passed through the Tri Homo mill.

In contrast with the use of urea, characterized by a thickening temperature of about 450 F., a comparable preparation made with 2 percent of ammonium acetate resulted in thickening at 250 F. When the ammonium compound or urea is omitted, the thickening temperature is about 500 F.

It is to be understood that the greases of this invention can also contain other characterizing materials and fillers. For example, the greases can contain anti-oxidants such as amines (e.g., phenyl alpha-naphthylamine), phenols (e.g., 2-6-ditertiarybutyl-4-methyl phenol), and the like; lubricity improving agents such as free fat, free fatty acids, esters of alkyl and/ or aryl acids, sulfurized fats, lead soaps, etc. However, as a cautionary note, it is advisable to use small quantities of such characterizing materials to obtain the customary beneficial effects there of.

The greases of this invention are suitable for a wide range of industrial applications. Some, for example, are suitable for multi-purpose automotive greases, serving as chassis, wheel-bearing, water-pump grease, lubricants; typical of such a grease is that shown about and identified as Grease 1. Others are multi-purpose industrial greases serving as plain-bearing and anti-friction greases for normally loaded and heavily loaded equipment. In general, then, greases contemplated herein range from semi-fluid types suitable as textile machinery lubricants, to solid block type greases used in lubrication of machinery in steel mills, paper mills, cement mills, etc.

I claim:

1. A method of preparing a lubricating composition, which comprises: (I) providing a charge mixture of (1) an oil of lubricating viscosity, (2) a thickening ingredient selected from (A) an admixture of a basically reacting alkaline earth metal compound and a mix of aliphatic monocarboxylic acids comprising a mix selected from (i) an aliphatic monocarboxylic acid having from 1 to 6 carbon atoms and an aliphatic monocarboxylic acid having from 7 to 12 carbon atoms, and (ii) the acids specified in (i) and an aliphatic monocarboxylic acid having at least 1-3 carbon atoms, and

(B) an admixture of an alkaline earth metal compound selected from (iii) a salt of an aliphatic monocarboxylic acid having from 1 to 6 carbon atoms and a soap of an aliphatic monocarboxylic acid having from 7 to 12 carbon atoms, and (iiii) the salt and soap specified in (iii) and a soap of an aliphatic monocarboxylic acid having at least 13 carbon atoms, and (3) a compound selected from the group consisting of an ammonium salt of an aliphatic monocarboxylic acid, an ammonium salt of an aryl aliphatic monocarboxylic acid, an ammonium sulfate, an ammonium phosphate, an ammonium salt of a sulfated castor oil, an ammonium salt of a sulfonic acid-the sulfonic acid being selected from the group consisting of a phenyl sulfonic acid, a naphthyl sulfonic acid, an alkyl-sub stituted phenyl sulfonic acid, an alkyl-substituted naph-' thyl sulfonic acid and a mineral oil sulfonic acid-and an addition product of an amine and an aliphatic monocarboxylic acid, the amount of said thickening ingredient determined as salt-soap complex being from about 1 to about 50 percent by weight, the amount of said compound specified in (3) being from about 1 to about 10 percent by weight, and said lubricating oil being present in an amount of at least about 40 percent by weight, the amounts based upon the total charge mixture; and (II) mixing and heating the resulting charge mixture to a temperature and for a time sufficient to effect reaction of any of said basically reacting alkaline earth metal compound present and said mix of acids, and to thicken said oil 'to the extent desired.

12. 'A method according to claim 1, in which the amount of the compound specified in (3) is about 2 to about by weight based upon the total charge mixture.

3. A method according to claim 1, in which the compound-specified in (3) is ammonium acetate.

4. A method according to claim 3, in which ammonium hydroxide is reacted with acetic acid in said charge mixture to form the ammonium acetate.

5. A method according to claim 1, in which the compound specified in (3) is an ammoniumsalt of an alkylsubstituted naphthyl sulfonic acid.

6. A method according to claim 1, in which the compound specified in (3) is an ammonium sulfonate of a dinonyl naphthalene.

7. A method according to claim 1, in which the compound specified in (3) is (NH SO 8. A method according to claim 1, in which the compound specified in (3) is NH H PO 9. A method according to claim 1, in which the amount of the thickening ingredient determined as saltsoap complex is from about 5 to about 20% by weight based upon the total charge mixture.

10. A method according to claim 1, in which the thickening ingredient contains (i) a 1 to 6 carbon atom aliphatic monocarboxylic acid component and (ii) a 7 to 12 carbon atom aliphatic monocarboxylic acid com ponent in a mole ratio of from about 1:1 to about 10: 1.

11. A method according to claim 10, in which component (i) is acetic acid and component (ii) is caprylic acid.

12. A method according to claim 1, in which the thickening ingredient contains (i) a 1 to 6 carbon atom aliphatic monocarboxylic acid component, (ii) a 7 to 12 carbon atom aliphatic monocarboxylic acid component, and (iii) a 13 to 36 carbon atom aliphatic monocarboxylic acid component, the mole ratio of component (i) to component (ii) and component (iii) combined being from about 1:1 to about 10:1, and the mole ratio of component (iii) to component (ii) being from about 0.01:1 to about 10:1.

13. A method according to claim 12, in which component (i) is acetic acid, component (ii) is caprylic acid, and component (iii) is stearic acid.

14. A method according to claim 1, in which the thickening ingredient comprises a basically reacting calcium compound and a mix of (i) an aliphatic monocarboxylic acid having 1 to 6 carbon atoms, (ii) an aliphatic monocarboxylic acid having 7 to 12 carbon atoms, and (iii) an aliphatic monocarboxylic acid having 13 to 36 carbon atoms, the mole ratio of acid (i) to acid (ii) and acid (iii) combined being from about 1:1 to 10:1, and the mole ratio of acid (iii) to acid (ii) being from about 0.01:1 to about 10:1.

15. A method according to claim 14, in which the basically reacting calcium compound is lime.

16. A method according to claim 1, in which the thickening ingredient comprises an admixture of the calcium salt of an aliphatic monocarboxylic acid having 1 to 6 carbon atoms, the calcium soap of an aliphatic monocarboxylic acid having 7 to 12 carbon atoms, and the calcium soap of an aliphatic monocarboxylic acid having 13 to 36 carbon atoms, the mole ratio of said salt to said soaps being from about 1:1 to about 10:1, and the mole ratio of' said latter calcium soap to said former calcium soap being from about 0.01:1 to about 10: 1.

17. A method according to claim 1, in which the oil is a synthetic ester.

18. A method according to claim 17, in which the synthetic ester is the tricaprylate of trimethylolpropane.

19. A method according to claim 1, in which the oil is a mineral oil.

20. A method according to claim 1, in which the compound specified in (3) is added to the oil and the thickening ingredient after a mixture of the latter has been preliminarily heated.

21. A method of preparing a grease composition, which comprises (I) providing a charge mixture of (l) at least about 40% by weight based upon the total charge of the tricaprylate of trimethylolpropane, (2) from about 10 to about 20% by weight based upon the total charge mixture of a salt-soap admixture of calcium acetate, calcium caprylate, and calcium stearate, the mole ratio of the acetate to the caprylate and the stearate combined being from about 1:1 to about 5:1, and the mole ratio of the stearate to the caprylate being from about 0.05:1 to about 5:1, and (3) from about 2 to about 5% by Weight based upon the total charge mixture of an ammonium sulfonate of a dinonyl naphthalene; and (II) mixing and heating the resulting charge mixture to thicken said tricaprylate ester t0 the extent desired.

22. A method according to claim 21, in which sufiicient limeis added near the end of the heating step to render the resulting grease substantially neutral.

23. A method of preparing a grease composition, which comprises (I) providing a charge mixture of (1) at least about 40% by weight based upon the total charge of a silicone oil of lubricating viscosity, (2) from about 10 to about 20% by weight based upon the total charge mixture of a salt-soap admixture of calcium acetate, calcium caprylate, and calcium stearate, the mole ratio of the acetate to the caprylate and the stearate combined being from about 1:1 to about 5:1, and the mol ratio of the stearate to the caprylate being from about 0.05 to about 5:1 and (3) from about 2 to about 5% by weight based upon the total charge mixture of an ammonium sulfonate of a dinonyl naphthalene; and (II) mixing and heating the resulting charge mixture to thicken said silicone oil to the extent desired.

24. A method according to claim 23, in which sufiicient lime is added near the end of the heating step to render the resulting grease slightly alkaline.

25. A grease composition comprising (1) at least about 40% by weight based upon the total composition of an oil of lubricating viscosity; (2) from about 5 to about 20% by weight based upon the total composition of an admixture of an alkaline metal soap of an aliphatic monocarboxylic acid having 7 to 12 carbon atoms and at least one member selected from the group consisting of an alkaline earth metal salt of an aliphatic monocarboxylic acid having 1 to 6 carbon atoms and an alkaline earth metal soap of an aliphatic monocarboxylic acid having at least 1.3 carbon atoms, and (3) from about 1 to about 5% by weight based upon the total composition of an ammonium salt of an alkyl-substituted naphthyl sulfonic acid.

26. A grease composition comprising (1) at least about 40% by weight based upon the total composition of an oil of lubricating viscosity; (2) from about 5 to about 20% by Weight based upon the total composition of an admixture of a calcium salt of an aliphatic monocarboxylic acid having 1 to 6 carbon atoms, a calcium soap of an aliphatic monocarboxylic acid having 7 to 12 carbon atoms, and a calcium soap of an aliphatic monocarboxylic acid having 13 to 36 carbon atoms; and (3) from about 1 to about 5% by weight based upon the total composition of an ammonium salt of an alkyl-substituted naphthyl sulfonic acid.

27. A grease composition according to claim 26, in which the alkyl-substituted naphthyl sulfonic acid is a dinonyl naphthyl sulfonic acid.

28. A grease composition comprising (1) at least about 40% by weight based upon the total composition of the tricaprylate of trimethylolpropane, (2) from about 10 to about 20% by weight based upon the total composition of an admixture of calcium acetate, calcium caprylate, and calcium stearate, the mole ratio of the acetate to the caprylate and the stearate combined being from about 1:1 to about 1, and the mole ratio of the stearate to the caprylate being from about 0.05:1 to about 5:1, and (3) from about 2 to about 5% by weight based on the total composition of an ammonium sulfonate of a dinonyl naphthalene.

29. A composition of matter consisting essentially of a mixture of (1) from about 5 to about 20 parts by weight of an admixture of an alkaline earth metal compound selected from (iii) a salt of an aliphatic monocarboxylic acid having from 1 to 6 carbon atoms and a soap of an aliphatic monocarboxylic acid having from 7 to 12 carbon atoms, and (iiii) the salt and soap specified in (iii) and a soap of an aliphatic monocarboxylic acid having at least 13 carbon atoms and (2) from about 1 to about 5 parts by weight of an ammonium salt of an alkyl-substituted naphthyl sulfonic acid.

30. A composition of matter consisting essentially of a mixture of (1) from about 5 to about 20 parts by weight of a calcium salt of an aliphatic 'monocarboxylic acid having 1 to 6 carbon atoms, a calcium soap of an aliphatic monocarboxylic acid having 7 to 12 carbon atoms, and a calcium soap of an aliphatic monocarboxylic acid having 13 to 36 carbon atoms and (2) from about 1 to about 5 parts by weight of an ammonium salt of an alkyl-substituted naphthyl sulfonic acid.

31. A composition of matter according to claim 30, in which the alkyl-substituted naphthyl sulfonic acid is a di nonyl naphthyl sulfonic acid.

32. A composition of matter consisting essentially of a mixture of (1) from about 10 to about 20 parts by weight of an admixture of calcium acetate, calcium caprylate and calcium stearate, the molar ratio of the acetate to the caprylate and the stearate combined being from about 1:1 to about 5:1, and the molar ratio of the stearate to the caprylate being from about 0.05:1 to about 5:1, and (2) from about 2 to about 5 parts by weight of an ammonium sulfonate of a dinonyl naphthalene.

33. A lubricant comprising (1) at least about by weight based upon the total composition of an oil of lubricating viscosity; 2) from about 1 to about by weight based upon the total composition of an admixture of an alkaline metal soap of an aliphatic monocarboxylic acid having 7 to 12 carbon atoms and at least one member selected from the group consisting of an alkaline earth metal salt of an aliphatic monocarboxylic acid having 1 to 6 carbon atoms and an alkaline earth metal soap of an aliphatic monocarboxylic acid having at least 13 carbon atoms, and (3) from about 1 to about 5% by weight based upon the total composition of an ammonium salt of an alkyl-substituted naphthyl sulfonic acid.

References Cited in the file of this patent UNITED STATES PATENTS 2,846,392 Morway et ah Aug. 5, 1958 2,999,065 Liddy Sept. 5, 1961 2,999,066 Liddy Sept. 5, 1961 FOREIGN PATENTS 879,991 Great Britain Oct. 1, 1961 UNITE-D STATES-PATENT OFFICE 4 CERTIFICATE OF CORRECTION Patent No. 3,170,879

February 23, 1965 g Richard A. Butcosk It is hereby certified that error appears in'-the.above numbered pa pent reqiiring correction and that the said Letters Patent should read as I corrected below Column 6, Table I, under the heading "Grease C", 1ine8 thereof, for "263/390" read 263/290 columnlO, Table VII,&

underthe heading "Grease P"' opposite "Caprylic acid", for 5 "3.40" read 6.70 column 14, line 31,. for

, "about"-r'ead above I Signed and sealed this 24th day of August I965,

(SEAL) Attest:

' ERNEST w. SWIDER EDWARD J. BRENNER -All.csting Officer Commissioner of Patentsv

Claims

1. A METHOD OF PREPARING A LUBRICATING COMPOSITION, WHICH COMPRISES: (I) PROVIDING A CHARGE MIXTURE OF (1) AN OIL OF LUBRICATING VISCOSITY, (2) A THICKENING INGREDIENT SELECTED FROM (A) AN ADMIXTURE OF A BASICALLY REACTING ALKALINE EARTH METAL COMPOUND AND A MIX OF ALIPHATIC MONOCARBOXYLIC ACIDS COMPRISING A MIX SELECTED FROM (I) AN ALIPHATIC MONOCARBOXYLIC ACID HAVING FROM 1 TO 6 CARBON ATOMS AND AN ALIPHATIC MONOCARBOXYLIC ACID HAVING FROM 7 TO 12 CARBON ATOMS, AND (II) THE ACIDS SPECIFIED IN (I) AND AN ALIPHATIC MONOCARBOXYLIC ACID HAVING AT LEAST 13 CARBON ATOMS, AND (B) AN ADMIXTURE OF AN ALKALINE EARTH METAL COMPOUND SELECTED FROM (III) A SALT OF AN ALIPHATIC MONOCARBOXYLIC ACID HAVING FROM 1 TO 6 CARBON ATOMS AND A SOAP OF AN ALIPHATIC MONOCARBOXYLIC ACID HAVING FROM 7 TO 12 CARBON ATOMS, AND (IIII) THE SALT AND SOAP SPECIFIED IN (III) AND A SOAP OF AN ALIPHATIC MONOCARBOXYLIC ACID HAVING AT LEAST 13 CARBON ATOMS, AND (3) A COMPOUND SELECTED FROM THE GROUP CONSISTING OF AN AMMONIUM SALT OF AN ALIPHATIC MONOCARBOXYLIC ACID, AN AMMONIUM SALT OF AN ARYL ALIPHATIC MONOCARBOXYLIC ACID, AN AMMONIUM SULFATE, AN AMMONIUM PHOSPHATE, AN AMMONIUM SALT OF A SULFATED CASTOR OIL, AN AMMONIUM SALT OF A SULFONIC ACID-THE SULFONIC ACID BEING SELECTED FROM THE GROUP CONSISTING OF A PHENYL SULFONIC ACID, A NAPHTHYL SULFONIC ACID, AN ALKYL-SUBSTITUTED PHENYL SULFONIC ACID, AN ALKYL-SUBSTITUTED NAPHTHYL SULFONIC ACID AND A MINERAL OIL SULFONIC ACID-AND AN ADDITION PRODUCT OF AN AMINE AND AN ALIPHATIC MONOCARBOXYLIC ACID, THE AMOUNT OF SAID THICKENING INGREDIENT DETERMINED AS SALT-SOAP COMPLEX BEING FROM ABOUT 1 TO ABOUT 50 PERCENT BY WEIGHT, THE AMOUNT OF SAID COMPOUND SPECIFIED IN (3) BEING FROM ABOUT 1 TO ABOUT 10 PERCENT BY WEIGHT, AND SAID LUBRICATING OIL BEING PRESENT IN AN AMOUNT OF AT LEAST ABOUT 40 PERCENT BY WEIGHT, THE AMOUNTS BASED UPON THE TOTAL CHARGE MIXTURE; AND (II) MIXING AND HEATING THE RESULTING CHARGE MIXTURE TO A TEMPERATURE AND FOR A TIME SUFFICIENT TO EFFECT REACTION OF ANY OF SAID BASICALLY REACTING ALKALINE EARTH METAL COMPOUND PRESENT AND SAID MIX OF ACIDS, AND TO THICKEN SAID OIL TO THE EXTENT DESIRED.