US2476972A

US2476972A - Mineral oil composition

Info

Publication number: US2476972A
Application number: US709930A
Authority: US
Inventors: Everett W Fuller; Ellwood M Johnson
Original assignee: Socony Vacuum Oil Co Inc
Current assignee: ExxonMobil Oil Corp
Priority date: 1946-11-15
Filing date: 1946-11-15
Publication date: 1949-07-26
Anticipated expiration: 1966-07-26
Also published as: FR955566A; DE898066C; NL71357C; GB645267A

Description

Juy 26 l949 E. w. FULLER x-:rAL 2,476,972

MINERAL OIL COMPSTION Filed Nov. l5, 1946 2 Sheets-Sheet l OJO 0.07 Pff? CEA/7' BY W15/@HT UFA/5ML /A/ 0/1.

July 26, 1949- E. w. FULLER r-:TAL 2,475,972

MINERAL oIL COMPOSITION Filed Nov. 15, 1946 2 Sheets-Sheet 2 EVE'FET MFUALE/P oom ow- OQ O om. O9 O Ow QQ Dm Q o# INVENTO RS Patented July 26, 1949 MINERAL OIL COMPOSITION Everett W. Fuller and Ellwood M. J ohnlon, Woodbury. N. J., assignors to Socony-Vacnnm Oil Company, Incorporated, a corporation of New York Application November 15, 1946, Serial No. ,709,930

10 Claims. (Cl. 252-33A) This invention relates to a novel mineral oil composition and, more particularly, is concerned with a mineral oil composition containing minor proportions of an oil-soluble detergent and of an oil-soluble, phosphorusand sulfur-containing reaction product.

As is well known to those familiar with the art, mineral oils generally possess one or more undesirable characteristics which limit their use. One such characteristic ls their instability under operating conditions normally encountered in present day engines, such that within a relatively short time, metal engine parts become contaminated with sludge. lacquer and resinous materials. In most instances, these contaminants are deposited on and about piston rings causing them to stick, the phenomenon being referred to in the art as ring-sticking." As a. consequence of this instability of the mineral oils, engine operating efliciency is seriously reduced. Another undesirable characteristic of mineral oils is their tendency to oxidize producing acidic materials. These acidic materials corrode metal engine parts, particularly alloy bearings such as those of the cadmium-silver, copper-lead, etc., type. As is also well known to those familiar with the art, numerous materials have been proposed for use in mineral oils to counteract or retard the aforementioned undesirable characteristics. For example, the use of oil-soluble metal sulfonates as addition agents for mineral oils has been suggested, and they have been, found to be satisfactory from the standpoint of imparting detergent properties to mineral oils. Unfortunately, however, such oil-soluble sulfonates fail to improve, and in some cases even impair, other characteristics of mineral oils. In some instances, for example, oil-soluble metal sulfonates have increased the formation of acidic materials in mineral oils during use, thus inducing corrosion of metal parts with which the mineral oils come in Contact.

As set forth in copending application Serial Number 539,597, led June 9, 1944, now U. S. Patent No. 2,416,281, issued February 25, 1947, it has been found that the corrosion and oxidation characteristics of'a mineral oil containing a small amount of an oil-soluble metal sulfonate can be greatly improved by incorporating therein a small amount of an oil-soluble, phosphorusand sulfur-containing reaction product of a dicyclic terpene and a phosphorus sulde. More specically, it has been found that an extremely stable mineral oil having outstanding detergent, oxidation and corrosion characteristics can be obtained by incorporatingln a mineral oil containing a metal sulfonate, a small amount of a reaction product of the aforesaid type. The oilsoluble metal salts of wax-substituted aromatic sulfonic acids are mentioned specifically in the copending application referred to and of these. the sodium, calcium, barium, zinc and aluminum salts are stated to be preferred.

We have discovered that the oil-soluble magnesium sulfonates, when used in combination with an oil-soluble phosphorusand sulfur-containing reaction product of a dicyclic terpene and a phosphorus sulfide, are particularly effective in improving the corrosion and oxidation characteristics of mineral oils.

We have now found that mineral oils containing an oil-soluble magnesium sulfonate and an oil-soluble phosphorusand sulfur-containing reaction product of a dicyclic terpene and a phosphorus sulde are extremely stable and possess outstanding detergent, oxidation and corrosion characteristics, and that oil-soluble magnesium sulfonates are appreciably more eifective in this connection, than other oil-soluble metal sulfonates both from the standpoint of weight per v cent of metal, and from the standpoint of mole per cent of metal which must be present in the mineral oil in order to effect the desired improvements in the characteristics thereof. Indeed, due to their relatively low molecular weight. the use of magnesium salts has the inherent added advantage of introducing relatively small amounts of metal in mineral oils which means low ash contents when the oil is burned.

Accordingly, it is an object of the present invention to provide an improved mineral oil composition. Another object is to provide a mineral oil composition possessing improved detergent, oxidation and corrosion characteristics. An important object is to afford a mineral oil concentrate containing a mineral4 oil in combination with an oil-soluble magnesium sulfonate and an oil-soluble phosphorusand sulfur-containing reaction product of a phosphorus sulde with a dicyclic terpene. A more specific object is to provide a mineral oil composition having improved vcharacteristics which comprises in combination,

' minor proportions of an Oil-soluble magnesium conjunction with the following drawings, in which:

Figure 1 shows a series of curves representing graphically the relationship between they E. C. (engine cleanliness) rating of various oil blends containing anoil, 0.75% by weight of a pinenephosphorus pentasulde reaction product, and varying amounts of yvarious metal diwax phenyl sulfonates, and the weight per cent of metal in the oil blends; and

Figure 2 shows a series of curves representing graphically the relationship between the E. C. rating of various oil blends containing an oil, 0.75% by weight of 'a pinene-phosphorus pentasulde reaction product and varying amounts of various metal diwax phenyl sulfonates, and the mole per cent of metal in the oil blends.

Broadly stated. the present invention provides a mineral oil composition comprising a. viscous mineral oil fraction having in admixture therewith: an'oil-soluble magnesium sulfonate, and an oil-soluble, phosphorusand sulfur-containing reaction product obtained by reaction between I a phosphorus sulfide and a dicyclic terpene.

All oil-soluble magnesium sulfonates are contemplated herein. Typical of oil-soluble magnesium sulfonates are those obtained from aromatic hydrocarbons or substituted aromatic hydrocarbons, and a sulfonating agent such as strong sulfuric' acid, oleum, chlorsulfonic acid and the like. Other typical sulfonates are those obtained by treatment of parains, naphthenes and various petroleum fractions-paranic, naphthenic or aromatic-with the same reagents. Preferred, however. are the magnesium salts of sulfonic acids of wax-substituted benzene and y naphthalene, wherein the wax substitutent is a long-chain aliphatic hydrocarbon group containing at least about eighteen carbon atoms and is obtained from paraflin wax. Especially preferred are the basic magnesium salts of diwax-benzene sulfonate.

The following examples illustrate these oilsoluble magnesium sulfonates and the preparation thereof:

EXAMPLE 1 Preparation of the basic magnesium salt of diwax-phenyl sulfonic acid A paraiiin wax having an average of 24 carbon atoms per molecule and a. melting point of 126 F. was chlorinated ata temperature of about 100 C. with chlorine gas until the Weight of the wax had increased about 12%. The chlorowax thus obtained was then blown with nitrogen to remove any occluded chlorine and hydrogen chloride.

1000 grams of the chlorowax were then mixed with 500 grams of benzene in a 3-necked flask equipped with a stirrer, a reflux condenser and a thermometer. The mixture was heated to a temperature of 60 C. Aluminum chloride'was then added slowly over a period of two hours. The addition of aluminum chloride was accompanied by a vigorous evolution of hydrogen chloride. The temperature was then raised to a tem- Derature of 80 C. and held there for one hour. The excess benzene was then removed by inverting the reflux condenser and heating to a temperature of 116 C. 200 milliliters of benzene were thus recovered. The mixture was cooled to a temperature of 60 C. and then another 1000- grams of chlorowax were added slowly. [After completing the addition of this chlorowax, the

4 temperature was raised to 100 C. and held ther for one hour. The product was allowed to stand overnight at a temperature of about C., and then was separated from the sludge by decantation and iiltration by suction through clay.

1738 gramsof lthe diwax-benzene thus obtained were placed in a 3-necked ask equipped with a stirrer and a thermometer and heated to a temperature of 40 C. 869 grams of oleum (15% S03) were added slowly to the diwax-benzene from a dropping funnel at a rate regulated to maintain thetemperature below 50 C. The addition of oleum consumed about 3 hours. The mixture was then stirred for an additional hour to ensure complete reaction. The mixture was then poured into 1000 milliliters of water and subsequently, 1810 grams ofl mineral oil were added to the mixture. The mixture thus obtained was stirred thoroughly and then allowed to stand until the water separated into a layer. The water layer was then drained off. The product thus obtained was approximately a 50% blend of diWax-benzene sulfonic acid in mineral oil and had a neutralization number of 40.7.

. 500 grams of the diwax-phenyl sulfonic acidthus obtained were mixed with 23.3 grams of magnesium hydroxide in a 3-necked flask equipped with a stirrer, a thermometer and water takeoff, and heated to a temperature of 150 C, until all the water was distilled off. 'I'he mixture (oil blend) was then ltered through clay to yield a product weighing 359 grams. This product contained 1,29% magnesium and 2.09% sulfur, indicating it to be principally the basic magnesium salt.

EXAMPLE 2 Preparation of the neutral magnesium salt of diwax-phenyl sulfonic acid 2500 grams of the diwax-phenyl sulfonic acid produced in accordance with the procedure set forth in Example 1 were mixed with a methanol solution of sodium hydroxide consisting of 75.7

- grams of sodium hydroxide in 550 milliliters of methanol, and the mixture was heated to a temperature of' 150 C. to remove Water and the methanol. f

500 grams of this product were mixed with 37.4 grams of magnesium chloride (MgClzHaO) and the mixture thus obtained was heated to a temperature of about 175 C. to remove residual methanol and water. The resulting product was so viscous that it was found necessary to dilute it with 500 milliliters of mineral oil. The mixture was then filtered through clay. This product was found to contain 0.39% magnesium and 0.81% sulfur indicating it to be mainly the neutral magnesium salt.

The oil-soluble, phosphorusand sulfur-containing reaction products contemplated herein are those obtained by reacting a dicyclic terpene and a phosphorus sulde at a temperature above about C. Although any one of the several phosphorus sulfides such as PaSe (or PS2), P4Sn (0r P2S3) P483, P2Ss (0r P4810), P4S'l, etc., may be used in the preparation of the said reaction products, particularly preferred are those reaction products obtained using PaSs.

Dicyclic terpenes are defined herein as those terpenes which are characterized by the presence of one double bond in the molecule and which are comprised of two ring systems. Typical of such terpenes are pinene, camphene and fenchene.

contemplated as coming within this particular designation are those materials which are predominantly comprised of one or more dicyclic terpenes; representative of such materials are the essential or volatile oils which are predominantly comprised of such a terpene, or terpenes, and are typified by turpentine oil, the predominant constituent of which is pinene. Preferred of the dicyclic terpene reactants are pinene and turpentine oil. Accordingly, the preferred reaction products are those obtained from Piss and pinene, and P255 and turpentine oil.

Although a, .complete understanding of the chemical composition of the reaction products contemplated here is not known at this time, a partial understanding of their composition may be realized by noting the characteristics involved in the reaction. The reaction between phosphorus pentasulde and pinene, for example, commences at about 100 C. and is exothermic in nature. During the reaction, the reaction mixture increases appreciably in viscosity and little, if any, hydrogen sulde is evolved therefrom. The reaction product obtained in this reaction contains phosphorus and sulfur in substantially the same amounts as are added through the particular phosphorus suliide used. It would appear, then, that the reaction is one of addition, that is, addition of the prosphorus suliide to the oneV unsaturated bond present in pinene.

While the reaction temperature for the reaction described above should be one of at least about 100 C., the preferred temperatures fall within the range of about 100 C. to about 160 C.

The proportions of reactants used herein may be varied in order to prepare reaction products having different degrees of oil solubility and different degrees of oil-improving power. It is preferred, however, to use about 1 mol of a phosphorus sulfide With 4 mols of a dicyclic terpene for the preparation of a reaction product readily soluble in petroleum oils. For example, when more than 1 mol of PzSs is used with 4 mols of pinene, a viscous gel-like reaction product is obtained Which is difliculty soluble in petroleum oils. Also, when less than 1 mol of Pass is used with 4 mols of pinene, a viscous oil somewhat insoluble in mineral oils is obtained after the unreacted pinene has been recovered by distillation.

Accordingly, it is to -be understood that while effective mineral oil improving. agents of the type contemplated herein can be obtained by using different ratios of reactants, particularly preferred improving agents are those obtained by using approximately 1 mol of a phosphorus sulde for every 4 mols of a dicyclic terpene.

There is, however, still another desirable procedure for preparing the reaction products contemplated here. In order to obtain a relatively non-viscous reaction product, a blend of a dicyclic terpene, such as pinene, and a comparatively inert solvent such as a petroleum oil, may

be treated as described above to provide an oil blend of the reaction product. The preferred procedure of this type involves the use of a 1:1

blend of dicyclic terpene and petroleum oil with a phosphorus sulfide, the molar ratio of said terpene to said sulde being 4:1.

Further details regarding the character of the aforesaid dicyclio terpene-phosphorus sulfide reaction products may be obtained by referring to copending application Serial Number 482,482, filed April 9, 1943, of Everett W. Fuller et al.

The following example illustrates these oilsoluble, phosphorusand sulfur-containing reaction products and the preparation thereof:

Examen: 3

After partial cooling of the mixture and the subsequent addition of 32 grams of clay thereto, the mixture was iiltered. The filtrate which weighed 1842 grams was subjected to distillation at a temperature of 150 C. at 5 millimeters pressure. 149

grams of a low-boiling liquid were thus removed. The remaining product was a clear, viscous oil containing 12.5% sulfur and 5.11% phosphorus, by weight.

The oil compositions contemplated herein may also contain, in addition to an oil detergent and a dicyclic terpene-phosphorus sulfide reaction product, a small amount of one or more other oil-soluble, phosphorusand sulfur-containing reaction products. One such reaction product is that which is obtained by reaction of approximately one mol of phosphorus pentasulde with four mols of oleyl alcohol, or ocenol, at a temperature falling Within the range varying between about 125 C. and about 150 C., for a relatively short time. These reaction lproducts are described in further detail in copending application Serial Number 524,490, iled February 29, 1944, now U. S. Patent No. 2,411,153, issued November 19, 1946, of Everett W. Fuller et al. Another such reaction product is that which'is obtained by reacting a cycle stock with about 5-15% by weight of phosphorus pentasuliide.v

This type of product is fully described in copending application Serial Number 515,418, led December 23, 1943, now U. S. Patent No. 2,450,405, issued October 5, 1948 of Berger et al.

The following test results are provided to demonstrate the properties of mineral oils containing small amounts of metal sulfonates, other .than magnesium sulfonates, oil detergents and of the aforementioned dicyclic terpene-phosphorus sulde reaction products, and "the outstandingly superior properties of mineral oils containing small amounts of the magnesium sulfonate oil detergents and of the aforementioned dicyclic terpene-phosphorus suliide reactionV products. The metal sulfonates, other than magnesium sulfonates, were prepared by reacting the diwaxphenyl sulfonic acid obtained in accordance with the procedure set forth in Example 1, with the proper metal hydroxide or chloride in accordance with the procedures outlined in Examples 1 and 2.

The following metal sulfonates were thus prepared:

The oil-soluble, phosphorusand sulfur-containing reaction product utilized in preparing the mineral oil blends used in obtaining the test re- 7 suits set forth hereinafter was prepared in accordance with the procedure set forth in Ex-` ample 3.

In each run, a. single-cylinder, 4-cycle, gasoline Lauson engine was operated for 30 hours with an 5 .oil temperature of 225? F., a jacket temperature of 350 F., at a speed of about 1830 R. P. M., at

one-half throttle, and using a 13:1 fuel (100% the type referred to hereinbefore were tested in the engine separately. At the end of each run,

vthe piston of the engine was examined and rated for lacquer and sludge deposits, an engine cleanliness (E. C.) of 100 indicating a perfectly clean 8 from about 0.10% to about 3.0%; in general, however, about 1.0% will be satisfactory.

As indicated herinbefore, .the mineral oil compositions of this invention may also contain one or more other oil-soluble, phosphorusand sulfur-containing reaction products, such as those obtained from cycle stocks and Pass, and' oleyl alcohol and Pass, all as dened above. Oils of excellent quality are obtained with from labout l 0.10% to about 3.0% of such s. reaction product,

incorporated with the aforesaid quantities of a magnesium-containing oil detergent Aand of a dicyclic terpene reaction product of the type defined hereinbefore.

Mineral oil concentrates are also contemplated herein, such concentrates containing substantially larger concentrations of amagnesium sulfonate oil detergent and of a dicyclic lterpenephosphorus sulfide reaction product, than those piston and lower ratings indicating increasing enumerated abQVe- That iS, TelatiVely large amounts of deposits. The pertinent data of each run are tabulated in Table II.

amounts of the said materials may be incorporated in an oil fraction in which they are readily Table II Per Cent oi Metal Example Metal Diwax phenyl Pefty in o cllismm No. Sulfonate (Detergent) Detergent E` C Rating Weight Mole 3. 0 0. 0387 0. 00160 89 l. 0 0. 0129 0. 00054 87 0. 5 0. 0065 0. 00027 86 4. 0 0. 20 0. 00146 74 2.0 0. 10 0. 00073 76 1.0 0. 05 0. 00037 75 0. 5 0. 025 0. 00018 69 2. 5 0. 0115 0. 00047 63 f 4. 0 0. 0156 0. 00065 87 do 2. 0 0.0078 0.00032 78 Neutral Ba... 5. 0 0. 108 0. 00079 7l do 1.0 0.022 0.00016 68 Neutral Ca... 3.0 0.039 0.00098 82 .do 1.5 0.0195 0.00049 76 Neutral Zn.-. 3.0 0. 0504 0. 00078 83 .do 1.5 0.0252 0.00039 73 The relationships between the data set forth in Table 1I are presented graphically in Figures soluble, and the oil concentrate so obtained may thereafter be diluted with a suitable quantity of 1 and 2, 45 the said oil fraction prior to use. It is to be It will be apparent from inspection of the data tabulated in Table II, that the reference oil is comparatively unsatisfactory in view of its relatively low E. C. rating. It will be apparent also understood that these mineral oil concentrates may also contain one or more of the aforesaid other oil-soluble, phosphorusand sulfur-containing reaction products, such as those obtained that on a per cent by weight basis of comparison, from oleyl alcohol or a cycle stock, in .amounts the magnesium-containing detergents are superior to the other metal suli'onates. This superiority is particularly marked in the case of the basic magnesium sulfonates. When the comparisubstantially in excess of those described above.

In preparing the mineral oil compositions and concentrates contemplated herein, an oil-soluble magnesium sulfonate and a dicyclic terpeneson is made on the basis 0f per cent of metal in 55 phosphorus sulde reaction product, as defined hereinbefore, may be incorporated in a mineral oil in any one of several ways. For example, the

dicyclic terpene reaction product; may be added to an oil fraction containing .an oil-soluble magnesium sulfonate; also .an oil-soluble magnesium sulfonate may be added to the reactants (dicyclic terpene and phosphorus sulde) used in the preparation of the said reaction product and, in such case, will be present during the reaction.

high degree of resistance to oxidation and partic- It 1S possible that the oil-soluble magnesium sulularly desirable detergent properties.

As contemplated by the present invention, concentrations of from about 0.5 per cent to about 10 per cent of a magnesium-containing oil defonate may react with the dicyclic terpene and phosphorus sulde to form a complex reaction product under the reaction conditions enumerated herein; the product obtained in this manner tergent are used in an oil fraction, but coi'icen-` 70 may then be added to an oil fraction. Accordtrations of the order of about 2% have been found to,be satisfactory for most purposes. The concentration of the oil soluble, phosphorusand sulfur-containing reaction product of a dlcyclic ingly; it will be apparent that the mineral oil compositions and concentrates of this invention 1 are complex in nature, for it is posisble that an oil-soluble magnesium sulfonate and a dicyclic terpene and a phosphorus sulde may be varied 75 terpene-phosphorus sulfide reaction product may l 9 be present individually in an oil fraction, or may also be present therein as a physical combination or, further, may be present therein in the form of a single chemical composition. In the same connection, it will also be apparent that an oil-soluble magnesium sulfonate and a reaction product of the aforesaid type may enter into chemical reaction when the oil composition is used as a lubricant under certain conditions, such forexample, as a lubricant in an engine operating at relatively high temperatures.

In view of the foregoing,l the term "mineral oil composition, as used herein, and as recited in all of the appended claims, isinclusive of all mineral oil fractions containing an oil-soluble magnesium sulfonate and' a dicycllc terpenephosphorus sulfide reaction product of the type deilned hereinbefore, in the concentrations previously enumerated, and is inclusive of oil compositions obtained or prepared by any of the aforesaid several procedures. Correspondingly, the term "mineral oil concentrate is inclusive o! all mineral oil fractions containing relatively large amounts of the said oil-soluble magnesium sulfonates and said reaction product.

It is to be understood that the examples, procedures and oil compositionsk describedrhereinbefore are illustrative only and are not to be construed as limiting the scope of this invention thereto. For example, all dicycllc terpenes as broadly recited herein may be used in place of pinene shown in the examples; however, pinene is preferred. Similarly, any phosphorus sulde may be used in place of phosphorus pente-sulfide shown in the examples, but the latter phosphorus sulilde is preferred. Also, while the magnesium diwax phenyl sulfonates are preferred, al1 other oil-soluble magnesium sulfonates coming within the deiinition herein of a magnesium-containing oil-detergent may be used. Furthermore, the mineral oil fraction disclosed herein is but typical of the mineral oil fractions which may be used.

-We claim:

1. An improved mineral oil composition comprising a viscous mineral oil fraction having in admixture therewith a minor proportion, from about 0.5 per cent to about 5.0 per cent, of an oil-soluble magnesium sulfonate; and a minor proportion, from about 0.10 per cent 'to about 3.0 per cent, of an oil-soluble. phosphorusand sulfur-containing reaction product obtained by reaction of substantially one mol of a phosphorus sulfide with four mols of a material selected from the group consisting of a dicyclic terpene and an essential oil predominantly consisting of a dicycllc terpene, at a temperature varying between about 100" C. and about 160 C.

2. An improved mineral oil composition comprising a. viscous mineral oil fraction having in admixture therewith a minor proportion, from about 0.5 per cent to about 5.0 per cent, of an oilsoluble magnesium sulfonate;` and a minor proportion, from about 0.10 per cent to about 3.0 per cent, of an oil-soluble, phosphorusand sulfurcontaining reaction product obtained by reaction of substantially one mol of phosphorus pentasulde and four mols of a material selected from the group consisting of a dicyclic terpene and an essential oil predominantly consisting of a dicycllc terpene, at a temperature varying between about 100 C. and about 160 C.

3. An improved mineral oil composition comprising a viscous mineral oil fraction having in admixture therewith a minor proportion, from about 0.5 per cent toabout 5.0 per cent, of an oilsoluble magnesium salt of a wax-substituted aromatic sulfonic acid; and a minor proportion, from about 0.10 per cent to about 3.0 per cent, of an oil-soluble, phosphorusand sulfur-containing reaction product obtained` by reaction of substantially one mol of a phosphorus sulfide with four mols of a material V`selected from the group consisting of a dicycllc terpene and an essential oil predominantly consisting of a dicycllc terpene, at a temperature varying between about 100 C. and about 160 C.

4. An improved mineral oil composition comprising a viscous mineral oil fraction having in admixture therewith a minor proportion, from about 0.5 per cent to about 5.0 per cent, of an oilsoluble magnesium salt of a wax-substituted aromatic sulfonic acid; and a minor proportion, from about 0.10 per cent to about 3.0 per cent, of an oil-soluble, phosphorusand sulfur-containing reaction product obtained by reaction of substan- 1 tially one mol of phosphorus pentasulde and Cil four mols of a material selected from the group consisting of a dicycllc terpene and an essential oil predominantly consisting of a dicyclic ter-4 soluble magnesium salt of a wax-substituted benzene sulfonic acid; and a minor proportion, from about 0.10 per cent to about 3.0 per cent, of an oilsoluble, phosphorusand sulfur-containing reaction product obtained by reaction o1' substantially one mol of a phosphorus sulilde with four mols of a material selected from the group consisting of a dicyclic terpene and an essential oil predominantly consisting or a dicylic terpene, at a ternpgature varying between about C. and about l C.

6. An improved mineral oil composition comprising a viscous mineral ,oil fraction having in admixture` therewith a minor proportion, from about 0.5 per cent to about 5.0 per cent, of an oilsoluble magnesium salt of a. wax-substituted benzene sulfonic acid; and a minor proportion, from about 0.10 per cent to about 3.0 per cent, of an oilsoluble, phosphorusand sulfur-containing reaction product obtained by reaction of substantially one mol of phosphorus pentasulfide and four mols of a material selected from the group consisting of a dicycllc terpene and an essential oil predominantly consisting of a dicycllc terpene. at a temperature varying between about 100 C. and about C.

7. An improved mineral oil composition comprising a viscous mineral oil fraction having in admixture therewith a minor proportion, from about ,0.5 per v'cient-.15b about 5.0 per cent, of an oil-soluble magnesium salt of a diwax-substituted benzene sulforiic acid; and a minor proportion, from about 0.10 per cent to about 3.0 percent, of an oil-soluble, phosphorusand sulfur-containing reaction product obtained by reaction of substantially one mol of a phosphorus sulfide with four mols of a material selected from the group consisting of a dicyclic terpene and an essential oil predominantly consisting of a dicycllc terpene, at a temperature varying between about 100 C. and about 160 C.

8. An improved mineral oil composition comprising a viscous mineral oil fraction having in admixture therewith a minor proportion, from about 0.5 per cent to about 5.0 per cent, of an oil- 11 soluble magnesium salt of a diwax-substituted benzene sulfonic acid; and a minor proportion, from about 0.10 per cent to about 3.0 per cent, of an oil-soluble, phosphorusand sulfur-containing reaction product obtained by reaction of substantially one mol of phosphorus pentasulde and four mols of a material selected from the group consisting of a dicyclic terpene and an essential oil predominantly consisting of a dfcylic terpene.:

at a temperature varying between about 100 C. and about 160 C. V A

9. An improved.- mineral oil composition comprising a. viscous mineral oll fraction having in admixture therewith a minor proportion, from` 10. An improved mineral oil composition comprising a viscous mineral oil traction having in admixture therewith va minor proportion, from about 0.5 per cent to about 5.0 per cent, of an oil-soluble basic magnesium salt of a diwaxsubstituted benzene sulfonlc acid; and a minor proportion, from about 0.10 per cent to about 3.0 per cent, of an oil-soluble, phosphorusand sulfur-containing reaction product obtained lby reaction of substantially one mol of phosphorus pentasultlde and four mols of a material selected from the group consisting of a dicylic terpene and an essential oil predominantly consisting of a dicyclic terpene, at a temperature varying between about 100 C. and about 160 C.

EVERETT. W. FULLER. ELLWOOD M. JOHNSON.

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

UNITED STATES PATENTS Number Name Date 2,379,453 Noland July 3, 1945 2,402,325 Grlesinger June 18, 1946 2,416,281 Berger Feb. 25, 1947