US2421004A - Mineral oil composition - Google Patents

Description

properties to mineral oil.

MINERAL on. coosrrrou Henry G. Berger, Glen Rock, and Everett W.

Fuller, Woodbury, N. I... assignore to Socony- Vacuum (Ml Company Incorporated, a corporation of New York No Drawing. Application August 3, 1944, Serial No. 547,981

11 Claims.

This invention hasto do with a new and novel mineral oil composition and, more particularly, has to do with a mineral oil composition containing minor proportions of an oil-soluble detergent and of an oil-soluble, phosphorusand sulfurcontaining reaction product.

It is well known to those familiar with the art that mineral oils are generally characterized by one or more undesirable characteristics which limit their use. One such characteristic is their instability under operating conditions normally encountered in present-day engines, such that after a relatively short time, metal engine parts become contaminated with sludge, lacquer and resinous materials. In many instances, the said materials form in and about piston rings causing them to stick, the phenomenon being referred to as ring-sticking. As a consequence of the instability of the oil, engine operating efficiency is seriously reduced. Another undesirable characteristic of mineral oils is their tendency to oxidize whereupon acidic materials are formed. These acidic materials corrode metal engine parts, particularly alloy bearings such as those of the copper-silver, copper-lead, etc., type.

It is also well known in the art that numerous materials have been proposed as improving or fortifylng agents for use in mineral oils to counteract or retard the aforesaid undesirable characteristics. Of the improving agents previously proposed, oil-soluble metal sulfonates have been found to be satisfactory in imparting detergent Unfortunately, however, such sulfonates fail to improve, and in some cases even impair, other characteristics of mineral oils. In some instances, for example, metal sulfonates have increased the formation of acidic materials in mineral oils during use, thus inducing corrosion of metal parts with which the oils come in contact.

It has now been found that the corrosion and oxidation characteristics of an oil containing a small amount of an oil-soluble metal sulfonate can be greatly improved by incorporating therewith .a small amount of an oil-soluble phosphorusand sulfur-containing reaction product of phosphorus pentasulfide and a cycle stock characterized by an olefin and an aromatic content of from about 3 per cent to about '7 per cent and from about 40 per cent to about 60 per cent, respectively. More specifically, it has been found that an extremely stable oil having outstanding detergent, oxidation and corrosion characteristics is obtained by incorporating in an oil containing a metal sulfonate, a small amount 5 2 of a reaction product of the aforesaid type. It has also been found that oils similarly characterized are obtained by incorporating a small amount of the said reaction product into oils containing small amounts of oil-soluble salts of organic acids, which possess detergent properties.

All oil-soluble metal sulfonates are contemplated herein, typical of which 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 paraffins, naphthenes and various petroleum fractions-paraflinic, naphthenic or aromatic-with the same reagents. Preferred, however, are the metal salts of sulfonic acids of wax-substituted benzene and wax-substituted naphthalene wherein the wax substituent is a long-chain aliphatic hydrocarbon group containing at least about 18 carbon atoms and is obtained from paraflin wax.

All metals are contemplated herein as constituents of the said metal sulfonates. Especially suitable, however, are sodium, barium and zinc. It is to be understood that when the metal substituent is polyvalent, basic as well as neutral metal sulfonates are obtained and serve the purposes of this invention. Typical and preferred sulfonates are the sodium, basic calcium, basic barium, neutral barium, zinc and dibasic aluminum salts of diwax-benzene sulfonate. Several such materials are described in further detail hereinafter in the examples.

As indicated hereinabove, oils containing other detergents-oil-soluble salts of organic acids possessing cleansing or detergent action in oilare also substantially improved in character when a. small amount of the aforesaid oil-soluble, phosphorusand sulfur-containing reaction product of phosphorus pentasulfide and a cycle stock is incorporated therein. Typical oil detergents contemplated herein are metal salts of carboxylic acids, as a calcium salt of an alkylated salicylic acid; metal salts of hydroxyaromatic carboxylic acids, as a barium phenate-carboxylate of an alkyl-substituted phenol carboxylic acid; sulfides of metal salts of hydroxyaromatic carboxylic acids, as a barium phenate-carboxylate of an alkyl-substituted phenol carboxylic acid disulflde; metal salts of acid esters, as vanadyl oleyl phthalate; etc. Oil-soluble salts of organic acids such as the foregoing typical salts are well known in the art and may be prepared by any suitable method.

The oil-soluble, phosphorusand sulfur-constock, as defined abov taming reaction products contemplated herein are those obtained by reacting Pass and a cycle under the following interrelated reaction conditions:

1. Between about 1 per cent and cent by weight of Past of said cycle stock,

2. A temperature between about 125 C. and

about 200 C., and i 3. A relatively sh'ort reaction time.

The hydrocarbon reactants are, as indicated above, cycle stocks containing from about 3 per cent to about 7 per cent of olefins and from about 40 per cent to about 60 per cent of aromatics, as determined by the following test method:

Twenty-five milliliters of a solution containing 70 per cent by weight of sulfuric acid (sp. gr. 1.84) and 30 per cent of P305 are placed in a glass stoppered sulfonation bottle (a modified Babcock bottle-A. S. troleum Products and Lubricants, September 1943, p e 381). The bottle is immersed in ice water for five minutes; then milliliters of the hydrocarbon are added. The bottle is shaken for ten minutes while cooling with ice water. Sulfuric acid (sp. gr. 1.84) is added until the top meniscus of the hydrocarbon layer is brought up to the 100 per cent mark of the graduated portion of the neck. The bottle is then stoppered and is centrifuged for ten minutes. The milliliters of hydrocarbon oil layer remaining are read and this valu is subtracted from the original 10 milliliters to obtain the combined amounts of aromatic and olefin contents of the sample. By repeating the same procedure, except for using 85 per cent sulfuric acid instead of the H=SO4P=O5 mixture, the olefinic content of the sample is obtained. Thus, olefinic content subtracted from the combined olefin and aromatic content gives the amount of aromatic material present.

Preferably, the hydrocarbon reactants are also characterized by the following: boiling range from about 90 C. to about 400 C. and specific gravity from about 0.88 to about 0.93. In general, such cycle stocks are obtained from thermal cracking operations of crude oils; but other stocks characterized as above may also be used. Typical of such other stocks are light gas oils, such as a light gas oil containing 4 per cent oleabout 8 per based upon the weight T. M. Standards on Pefins and 46 per cent aromatics, a specific gravity of 0.8833 and a boiling range from 150 C. to 380 C. For this reason, the hydrocarbon reactants may be broadly considered as hydrocarbon stocks characterized by the aforesaid percentages of olefins and aromatics.

The amount of P185 reacted with the cycle stocks contemplated herein is an important consideration. Stable oil-soluble reaction products containing appreciable quantities of phosphorus and sulfur are obtained when the amount of PzSs so reacted is from about 1 per cent to about 8 per cent by weight of the hydrocarbon reactant. Particularly preferred reaction products, however. are obtained with about 5 per cent by weight of Past. When amounts of the order of 10 per cent and 15 per cent of P185 are used. it has been found that the phosphorusand sulfur-containing reaction products obtained therewith are unstable when heated and are oil-insoluble. As used herein the term oil so1uble"-is descriptive of those reaction products which are soluble in oil in amounts of at least 1 per cent by weight.

Another important consideration in the prepthereto and aration of the aforesaid reaction products is re.- action time. In nets, in quantities such as shown in the following examples, ar obtained when the reaction time is relatively short, such as from about 2 hours to about 8 hours. While reaction times as long as about 12 hours have been used and satisfactory reaction products obtained therewith, reaction times in the neighborhood of 4 hours are preferred. It is to be understood, however, that the reaction time may be varied considerably depending upon the quantities of reactants and the reaction temperatures used in the preparation of said reaction products.

The interrelation of the foregoing reaction factors will be apparent from the following typical examples recited below, and also those set forth in Table I.

. EXAMPLE 1 A reaction stock-recycle stock A-from a thermal liquid phase cracking operation and having the following characteristics, was used:

One thousand parts by weight of recycle stock A was reacted with stirring, with 70 parts of P285 at 180 C. for 8 hours. The reaction mixture thus obtained was diluted with naphtha (boiling range 88-135 0.), washed with 20% NazS solution, water washed, filtered and the filtrate heated to 150 to remove the naphtha. The reaction product contained 1.19% phosphorus and 3.06% sulfur, and is identified hereinafter as Product One.

Exams: 2

One thousand parts by weight of recycle stock A was reacted, with stirring, with 50 parts of P285 at 150 so obtained was then cooled to C., 52.5 parts (5% by weight) of Attapulgus clay were added the clay was subsequently removed therefrom by filtering. The reaction product-- Product Two-contained 1.26% phosphorus and 3.6% sulfur.

EXAMPLE 3 Five hundred parts by weight of Product Two obtained in Example 2 were vacuum distilled to a maximum temperature of 172 C. at 3 mm. in order to remove unreacted recycle stock therefrom. The residue-Product Three-contained 3.34% phosphorus and 7.9% sulfur.

Reaction products obtained from recycle stock A and prepared as in Example 2 above are shown in Table I below in order to demonstrate the infiuence of each of the several reaction variablestime, temperature and concentration of Past. The copper strip tests referred to in the table were made by immersing a polished copper strip in a. 1% blend of areaction product in oil and heating the blend at 100 C. for 24 hours. The copper strip test indicates the presence or absence of free or active sulfur which corrodes copper. An asterisk has, been used in the table wherever general, superior reaction prod i C. at 10 mm. pressure C. for 8 hours. The reaction mixtureaeaaoca the copper strip used in the copper strip test was not corroded in each test; that the reaction product was stable; and that the reaction product was 6 atoms to the molecule and a melting point oi." 126 F. was chlorinated at about 05 C. with chlorine gas until the weight or the'wax had increased It will be apparent from the data tabulated in Table I above that where a reaction temperature in excess of 200 C. was used the product is unsatisfactory. The desired reaction products as indicated in Table I are those prepared under the reaction conditions defined herelnabove.

Another cycle stock which was also found to be particularly desirable was a cycle stock, obtained from a Cross still, and characterized by the following:

Olefin content -per cent-.. 5 Aromatic content do 57 Specific gravity 0.9236 Aniline number 80 Boiling range 0-- 140-370 Further details regarding the character of the aforesaid reaction products may be obtained by referring to copending application Serial No. 515,418, filed December 23, 1943, of Henry G. Berger, Thomas T. Noland and Everett W. Fuller.

The oil compositions contemplated herein may also contain. in addition to an oil detergent and a cycle stock-Pass reaction product. a small amount of one or more other oil-soluble, phosphorusand sulfur-containing reaction products. One such reaction product is that obtained by reacting a dicyclic terpene, as pinene, and a phosphorus sulfide, as P285, at a temperature above about 100 C. Further details regarding the character'of the said dicyclic terpene-phosphorus sulude reaction products may be obtained by refer-- ring to copending application Serial No. 482.482, filed April 9, 1943, of Everett W. Fuller et a1.

Other oil-soluble, phosphorusand sulfur-containing reaction products which may be incorporated in the oil compositions defined above are those obtained by reaction of substantially one mol of phosphorus pentasulfide and four mols of oleyl alcohol. or ocenol, at a temperature between about 125 C. and about 150 C. forarelatively short time. These' reaction products are de-' scribed in further detail in a copending application, Serial No. 524,490, filed February 29, 1944, of Everett W. Fulle Henry G. Berger and Robe H.Wllliams.

In the following examples, typical and preierred metal sulionates and other oil-soluble metal detergents are described in order to lure .ther explain the oil addition agentscontemplated 70 herein.

Examrn 4 Basic barium diwax benzenesulfonate 55 sulfuric acid occluded therein.

soluoleinoil. about The chlorowax (10% Cl) thus ob- Tablel P 8 Composition 0 I Tom Time w Solu- Product per cent g s m bywt. I Percent Percent Tea? y a 2 ....a z is a z ve... Tamp Six 6 220 4 1 a Four.... 5 160 4 1.41 3.4 Time 8n-.- 6 150 8 1, 26 3, a w o u i. it 0on0 Pas. 5 150 4 n o o Unstabla. Insoluble.

weight. of benzene in the presence of 62 parts of MCI: at about 60 C. for about 2 hours. The excess benzene was then distilled off by warming to 115 C. with a stream of nitrogen gas bubbling through the mixture. The monowax benzene 30 thus formed was treated with an additional 1020 parts of chlorowax and the mixture heated to 85 C. until reaction stopped. It was allowed to stand overnight at about 60 C. and then decanted from the settled AlCh sludge and flitered. The product consisted essentially of diwax benzene.

Five thousand two hundred parts of the diwax benzene, prepared as described above, were treated with successive 250 parts of oleum, con- 40 taining 15% S03, while maintaining the temperature at 35-50 C. After 2600 parts of oleum had been added and the reaction had ceased, 3000 part of water were added while the mixture was thoroughly stirred. An S. A. E. 30 grade motor oil (5400 parts) was then added and the mixture was allowed to settle overnight at about 75* C. The lower layer. consisting mostly of .dilute sulfuric acid, was withdrawn leaving diwax benzene sulfonic acid .in the upper layer. This upper layer was treated with 3170 parts by weight of barium hydroxide octahydrate (Ba(OH)a.8H-:O), which represents an excess of barium hydroxide over that required to neutralize the diwax benzene sulfonic acid and any free The reaction mixture thus formed was heated to about 140 C. for about 6 hours with nitrogen gas bubbling through it to.remove water, and it was then filtered through a layer of clay. The product Product A--consisted of an approximately 50% oil blend of basic barium diwax benzene sulfonate (analysis: 5.17% barium and 1.5% sulfur).

Examm: 5

Basic barium diwax naphthalene sulfonate Five hundred parts of chlorowax, containing 12% chlorine, were added to 500 parts of Stoddard solventand 108 parts of naphthalene. The mixture was warmed to 50-60 C. and 30 grams of A101: were added gradually. When the reaction stopped the mixture was heated to 90 C. andv blown with nitrogen gas to remove HCl. It was then allowed to stand overnight at room tempera- A paraflin wax having an average oi 24 carbon ture. The lower sludge layer was removed and the oil layer was filtered through clay. This consisted essentially of diwax naphthalene.

The diwax'naphthalene was treated with 250 parts of oleum (15% $03) by adding the latter slowly so as to keep the temperature at 40-50 C. One thousand parts of water were then added with stirring and this was followed by 500 parts of an S. A. E. 30 grade motor oil. The mixture was allowed to stand at 60-70" C. overnight and the oil layer was then withdrawn. This consisted essentially of 50% diwax naphthalene sulfonic acid in motor oil. This acid was treated with an excess of barium hydroxide and the mixture was heated to a maximum temperature of 150 C. in the presence of a stream of nitrogen to remove the water. After filtering, the Stoddard solvent was removed by heating .to 170 C. at a vacuum of 5 mm. This left an approximately 50% solu-- tion of the basic barium diwax benzene suli'onate in the petroleum motor oil, which i identified as Product B. It contained barium and 2.0% sulfur.

Exmrrn: 6

Barium salt of petroleum oil suljonate A Mid-Continent distillate of 95 seconds Saybolt viscosity at 100 F. was treated with oleum, the sludge was settled and removed, and the oil layer was neutralized with caustic soda solution. The sodium sulfonates thus formed were recovered by adding ethyl alcohol, separating the alcohol layer, and then evaporating off the alcohol.

This left a mixture of oil and sodium sulfonates.

This was contacted with a water solution of barium chloride and, after separation of the oil layer and drying, the latter-Product Cwas found to contain 6.9% barium and 2.5% sulfur.

Exmu: 7 Barium triwax phenol carbozylate A barium salt of a triwax phenol carboxylate- Product D-was prepared by the method described in U. S. Patent 2,197,835. It was formed in an oil blend and contained 4.0% barium.

EXAMPLE 8 Sulfurieed barium triwax phenol carbon late A sulfurized barium triwax phenol carboxylate Product E-wa prepared by the method described in U. S. Patent 2,256,441. It was prepared in'an oil blend and analyzed to give 4% barium and 0.9% sulfur.

EXAMPLE 9 Cobalt .salt of triwax phenol carbomylate A cobalt salt-Product F-was prepared corresponding to the barium salt above (Product D). This salt contained 1.83% cobalt.

The following test results are provided to demonstrate the properties of mineral oils containing small amounts of oil detergents and the outstandingly superior properties of mineral oils containing small amounts of the said detergents and of the aforesaid oil-soluble, phosphorusand sulfur-containing cycle stock-Pass reaction products.

EXAMPLE 10 grade motor oil with a specific gravity of 0.872, a flash point of 435 E, and a Saybolt Universal viscosity of 318 seconds at 100 F. The oil was tested by adding a section of a bearing contain-- ing a cadmium-silver alloy surface, weighing about 6 grams, and heating it to 175 C. for 22 hours while a stream of air was bubbled against the surface of the bearing. The loss in weight of the bearing during this treatment measures the amount of corrosion that has taken place. The resultsobtained in this test are set forth in Table 11 below.

Table II t? e t? can:

Blank Oil. 21 Product A---" 2 21 Do 2 l-Product Two. 1 0 Product 13..... 2 21 Do 3; +Product Two 1 3% g +Produot Two. 1 g 2 +Product Two. 1 0 2 83 2 +Product Two. 1 i 2 26 2 l-Product Two. 1 0

It will be apparent from inspection of the resuits presented in Table II that the blank oil is unsatisfactory in view of its corrosivity, as shown by the high milligram loss in weight of the bearing. When a detergent alone is added to the oil there is little or no improvement and in some instances the oil is impaired. The results with Products 0, E and F, for example, demonstrate that some detergents accelerate corrosion. However, when a small amount of a cycle stock- P285 reaction product, such as Product Two, is

added to the oil containing any one of the detergents, the resulting oil blends are substantially non-corrosive to hearing metals.

EXAMPLE 11 Tests of an oil, of oil blends containing only an oil detergent, and of oil blends containing an oil detergent and an oil-soluble, phosphorusand sulfur-containing reaction product as defined above, were carried out to determine further the comparative behavior of the unblended oil, the 011 containing only the detergent and the oil containing a detergent and said reaction product, under actual operating conditions.

In this test a single cylinder Lauson engine was operated for 36 hours with an oil temperature of 290 F. and a jacket temperature of 212 F. The oil used was a solvent-refined oil having a Baybolt Universal viscosity of 45 seconds at 210 F. (Kinematic viscosity 5.75 at 210 F.). After 36 hours the acidity, as measured by the neutralization number (N. N.), and the Kinematic viscosity of the oil were determined. The neutralization number (N. N.) rating is obtained by dividing the specific neutralization number oi. the oil alone which is run in the engine preceding the oil blend, by the neutralization number of the oil blend. Ratings of greater than 1 indicate that the oil blend is less acidic than the oil alone and, therefore, superior thereto: and ratings of less than 1 indicate that the oil blend is more acidic than the oil alone and, therefore, inferior thereto. Average results for the oil alone (unblended oil) are presented inasmuch as the neutralization number and kinematic viscosity of the oil alone vary slightly when samples of the same are run in the same engine; this Oil alone Q 9 v variation is attributed to the condition of the engine parts and other factors involved in the test. The results of these tests are set forth in Table III below.

The results in' Table III indicate that a detergent oil blend, without a stabilizer, is only of the same order of efiectlveness as the oil alone; whereas, an oil blend containinga detergent and a stabilizer is appreciably-more effective than the oil alone or the said detergent oil blend.

Exlmrtr: 12

The eil'ectiveness of the oil composition of this invention in actual engine tests is further demoncarbons. This preference is influenced by their outstanding pour depressing properties as illustrated below in Table VI, wherein a related oil detergent, derived from a. petroleum fraction (barium salt 0t a petroleum oil sulfonate, Product C) is also shown for comparative purposes. The latter detergent is ineifective as a pour point depressant. The oil used in these tests was a solvent refined oil having an S. U. V. of 65 secstrated by the following results which were obtained in a Chevrolet engine. This test consisted of operating a Chevrolet engine for 36 hours at brake horse wer with an oil temperature of 280 F. and jacket temperature of 200 F. A solvent-refined oil having an S. U. V.-

of 65 seconds at 210 F.,was used. At the end of the test, the neutralization number (N. N.) of the oil and the average weight loss of a half bearing were determined. Copper-lead bearings were used. The results, presented below in Table IV, demonstrate that the oil alone is rather unsatisfactory, and that the corrosivity thereof is substantially reduced when small amounts of a detergent and a stabilizer are incorporated therein. These test results also indicate that the corrosivity of the oil is materially counteracted by using suitable concentrations of a stabilizer with a given concentration of a detergent.

A three cylinder General Motors 3-71 Diesel engine was run at 2000 R. P. M. with an oil temperature of 230 F. and a jacket temperature of 180 F. When the air box pressure increased more than 3 inches of mercury over the original pressure, the ports were considered sufiiciently closed to stop the test. In Table V below the time in hours to reach this condition is noted. A solvent refined S. A. 1'1. 30 grade Mid-Continent oil was used in these tests.

Table V Hours to Port Closure 122 Oil+2.5% Product+0.'l5% Product Two 322 As indicated. hereinabove, preference is given hereinto those oil detergents defined as metal sulionates of wax-substituted aromatic hydroonds at 210 F., and A. S. T. M. pour tests are reported in F.

Table VI Conc., A B.T.M Detergent perwtent pourFtest,

. v 20 Product A 1. 0 n) Product B 1. 0 15 Product 0 1.0 +20 The results set forth in Tables'lI through V demonstrate the outstanding qualities of the mineral oil compositions contemplated herein. As shown in these tables, they possess a high degree of resistance to oxidation and particularly desirable detergent properties. The results presented in Table VI above further demonstrate the superior quality of the preferred oil detergents, metal salts of wax-substituted aromatic hydrocarbon sulionic acids, as evidenced by their pour depressant properties.

As contemplated by the present invention, concentrations of from about 0.5 per cent to about 10 per cent of an oil detergent are used in an oil fraction, but concentrations of the order of about 2 per cent have been found to be satisfactory forvmost purposes.

. per cent; in general, however, about 1.0 per cent will besatisfactory.

As indicated hereinabove, the mineral oil compositions of this invention may also contain one or, more other oil-soluble, phosphorusand sulfurcontaining reaction products, such as those obtained from oleyl alcohol and P285, and a dicyclic terpene and a phosphorus sulfide, all as defined above. Oils ofexcellent quality are obtained with from about 0.10 per cent to about 1.0 per cent of such a reaction product, incorporated with the aforesaid quantities of an oil detergent and of a cycle stock reaction product of the type defined above.

Mineral oil concentrates are also contemplated herein, such concentrates containing substantially larger concentrations of an'oil detergent and of a cycle stock-P285 reaction product, than those enumerated above. That is, relatively large amounts of the said materials may be incorporated in an oil fraction in which they are readily soluble, and the oil concentrate so obtained may thereafter be diluted with a suitable quantity of the said oil fraction prior to use. It is to be understood that these mineral oil concentrates may also contain oneor more of the aforesaid other oil-soluble, phosphorusand sulfur-containing reaction products, such as those obtained from oleylalcohol or a dicyclic terpene, in amounts substantially in excess of those described above;. v

In preparing the mineral oil compositions and concentrates contemplated herein, an oil detergent and a cycle stock-Pass reaction product, as

defined hereinabove, may be incorporated in a mineral oil in any one of several ways. For example, the cycle stock reaction product may ;be added to an oil fraction containing an oil detergent; an oil detergent may be added to the reactants (cycle stock and P285) used in the preparation oi the said reaction product and, in such case, will be' present during the reaction. It is possible that the oil detergent may react with the cycle stock and P285 to form a complex reaction product under the reaction conditions enumerated above the product obtained in this manner may then be added to an oil fraction. According y. it will be apparent that the mineral oil compositions and concentrates of this invention are complex in nature, for it is possible that an oil detergent and a cycle stock reaction product may be present individually in an oil .iraction, 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 detergent 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 for example, as a lubricant in an engine operating at relatively high temperatures.

In view of the foregoing, the term mineral oil prising a viscous mineral on traction having in' admixture therewith: a minor proportion, irom about 0.5 per cent to about -per cent, of anper cent, of an oil-soluble, phosphorusand suifur-containing reaction product obtained by reaction of phosphorus pentasulilde and a hydrocarbon stock at a temperaturebetween about 125 C. and about .200 C. for a relatively short time, said hydrocarbon stock being characterized by an olefin content of irom about 3 per cent composition,.as used herein and as recited inno all of the appended claims, is inclusive oi all mineral oil fractions containing an oil detergent and a cycle stock reaction product as defined above, in'the concentrations recited above, and is inclusive of oil compositions obtained or prepared by any one or the aforesaid several typical procedures. correspondingly, the term mineral oil concentrate" is inclusive of all mineral oil fractions containing relatively large amounts of the said oil detergent and said reaction product.

It is to be understood that the examples, procedures and oil compositions described hereinabove are illustrative only and are not to be construed as limiting the scope of this invention thereto. For example, all cycle stocks as defined above may be used in place oi those shown in the examples, although those shown are preferred. Also, while the sulionates and other illustrative oil detergents are preferred of their class, all compounds coming within the aforesaid definition of an oil detergent may be used. Furthermore, the mineral oil fractions disclosed above are but typical of the fractions which may.

about 0.5 per cent to about 10 per cent, of an oil-soluble salt characterized by detergent action in oil; and a minor proportion, from about 0.05

to about '7 per cent and an aromatic content of from about 40 per cent to about 6.01m cent, and the said phosphorus pentasulfide representing from about 1 per cent to about 8 per cent by weight oi'the said hydrocarbon stock.

3. An improved mineral oil composition comprising a viscous mineral oil traction having in admixture therewith: a minor proportion, from about 0.5 per cent to about 10 per cent, oi an oil-soluble metal salt of an organic acid characterized by detergent action in oil; and a minor proportion, from about 0.05 per cent to about 5.0 per cent, or an oil-soluble, phosphorusand sulfur-containin reaction product obtained by reaction or phosphorus pentasulfide and a cycle stock at a temperature between about 125 C. and about 200 C. for a relatively short time, said cycle stock being characterized by an olefin con-' tent or from about 3 per cent to about 7 percent and an aromatic content of from about 40 per cent to about 60 per cent, and the said phosphorus pentasuifide representing from about 1 per cent to about 8 per cent by weight oi the said cycle s o 4. An improved mineral oil composition com- 7 iur-containing reaction product obtained by reaction of phosphorus pentasulfide and a cycle stock at about 150 C. for about four hours, said cycle stock being characterized by an olefin content or from about 8 per cent to about I per cent and an aromatic content of from about 40 per cent to about, 60 per cent, and the-said phos- -phorus pentasuliide representing about 5 per cent per cent to about 5.0 per cent, of 'an oil-soluble,

phosphorusand sulfur-containing reaction product obtained by reaction of phosphorus pentasuliide and a hydrocarbon stock at a temperature between about 125 C. and about 200 C. for a relatively short time, said hydrocarbon stock being characterized by an olei in content of from about 3 per cent to about 7 per cent and an aromatic content of from about 40 per cent to about 60 per cent, and the said phosphorus pentasulfide representing from about 1 per cent to about 8' per cent by weight of the said hydrocarbon stock.

2. An improved mineral oil composition comof the cycle stock.

5. An improved mineral oil composition com prising a viscous mineral oil traction having in admixture therewith: a minor proportion, from about 0.5 per cent to about 10 per cent, of an oilsoluble metal salt of an organic acid characterized by detergent action in oil; and a minor proportion, i'rom about 0.05 per cent to about 5.0 per cent of an oil-soluble, phosphorusand sulfur-containing reaction product obtained by reaction of phosphorus pentasulfide and a thermal recycle stock at about C. for about four hours, said thermal recycle stock being characterized by an olefin content of about 6 per cent and an aromatic content of about 47 per cent, and the said phosphorus pentasulfide representing about 5 per cent by weight or the said thermal recycle stock.

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 10 per cent, oi an 011-.

soluble metal salt oi an organic acid character-;

ized by detergent action in oil; and a minor proportion, from about 0.05 per cent to about 5.0

' being characterized by an olefin content or per cent, of an oil-soluble, phosphorusand sulfur-containing reaction product obtained by reaction of phosphorus pentasulflde and a thermal about 3 per cent to about? per cent and an aromatic content oi from about 40 percent'to about 60 per cent, and the said phosphorus pentasulflde representing from about 1 per cent to about 8 per cent by weight of the said cycle stock. f

recycle stock at about 150? C. for about four hours.

said thermal recycle stock being characterized by an olefin content of about 5'per cent and an arcmatic content of about 57 per cent, and the said phosphorus pentasulflde representing about 5 per cent of the said thermal recycle stock.

7. An improved mineral oil composition comof phosphorus pentasulflde and a cycle stock at I a temperature between about 125 C. and about 200 C. for. a relatively short time, said cycle stock being characterized by an olefin content of from about 3 per cent to about 7 per cent and an aromatic content of from about 40 per cent to about 60 per cent, and the said phosphorus pentasulv prising a viscous mineral oil fraction having in" iide representing from about 1 per cent to about 8 per cent by weight 01' the said cycle stock,

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 10 per cent, of an oil soluble metal salt of a. wax-substituted benzene sulfonic acid; and a minor proportion, from about 0.05 per cent to about 5.0 per cent, 01' an oilsoluble, phosphorusand sulfur-containing reaction product obtained by reaction of phosphorus pentasulfide and a cycle stock at a temperature between about 125 C. and about 200 C. for a relatively short time, said cycle stock being characterized by an olefin content of from about 3 per cent to about 7 per cent and an aromatic content of from about per cent to about 60 per cent, and the said phosphorus pentasulflde representing from about 1 per cent to about 8 per cent by weight of the said cycle stock.

9. An improved mineral oil composition comprising a viscous mineral oil traction having in admixture therewith: a mino proportion, from about 0.5 per cent to about 10 per cent, 01' an oil-soluble barium salt of a diwax-substituted benzene sulfonic acid: and a minor proportion, from about 0.05 per cent to about 5.0 per cent, of an oil-soluble, phosphorusand sulfur-containing reaction product obtained by reaction 01' phosphorus pentasulflde and a cycle stock at a temperature'between about 125 C. and about 200 C. for a relatively short time, said cycle stock I I to about 8 stock.

, 10. An improved mineral oil composition'comprising a viscous mineral oil-fraction having in I admixture therewith: a minor proportion, from about 0.5 per centto about 10 per cent, of an onsoluble basic barium salt 01' a diwax-substituted benzene sulfonic acid; and a minor proportion, from about 0.05 per cent to about 5.0 per cent,

' of an oil-soluble, phosphorusand suli'ur-containing reaction product obtained by reaction oi phosphorus penta'sulflde and a .cycle stock'ata temperature between about 125 C. and about 200 C. for arelatively short time, said cycle stock being characterized by an olefin content or from about 3,per cent to about 7 per cent and an aromatic content oitrom about 40 per cent to about per cent, and the said phosphorus pentasulfide representing from about 1- per cent.

per cent by weight of the-said cycle j stock. 1 1 I 11. Animproved mineral oil composition comadmixture therewith; a minor proportion, from v 1 about 0.5 per cent to about 10 per cent, or an oil-soluble basic bariumsalt of a diwax-substituted naphthalene suli'onic acid; and a minor proportion, from about 0.05 per cent to about 5.0 per cent, of an oil-soluble, phosphorusand sul-. fur-containingreaction product obtained by reaction of phosphorus pentasulflde anda cycle stock at a temperature betweenabout C. and about 200 C. for a relatively-short time, said cycle stock being characterized by an olefin content of from about 3 per cent to about! per cent and an aromatic content oi from about 40 per cent to about 60 per cent, and the said phosphorus pentasulfide representing from about 1 per cent to about 8 per cent by weight of the said cycle "mm? a. Banana. mm w. m.

anrmmncas cn'an The following references are of record in the iile of this patent:

. tmn'no s'raTEs PATENTS Number Name Date 2,316,082 Loane et al. Apr. 6, 1948 2,316,083 Loane et a1. Apr. 6, 1943 2,279,086 Bergstrom Apr. '7, 1942 2,197,835 Beifl Apr. 28, 1940 2373.094

Berger et a1. Apr, 10, 1945