US2383498A - Mineral oil composition - Google Patents

Description

Q Patented Aug. 28, 1945 MINERAL OIL COMPOSITION Ferdinand P. Otto and Ronald E. Meyer, Woodbury, and Robert C. Moran, Wenonah, N. J assignors to Socony-Vacuum Oil Company, Incorporated, a corporation of New York No Drawing. Application July 10, 1943, Serial No. 494,262

17' Claims.

This invention has to do with the stabilization of petroleum products against the deleterious effects of oxidation and deterioration with use.

More specifically, it has to do with the improvement or stabilization of mineral oil fractions,

particularly viscous mineral oils, by the use of novel reaction products, or a novel class of reaction products, which when admixed with. a mineral oil fraction in minor proportions will prevent oil delay undesirable changes taking place in the o l It is well known to those familiar with the art phorusand sulfur-containing reaction products obtained by reacting substantially 1 moi of P285 with 4 mols of a sulfurized ketone (unsaturated), or of a related reaction product obtained by suliurizing an acidic reaction product of the type initially described with elementary sulfur. Sulfurized ketones (unsaturated) and sulfurized acidic, phosphorusand sulfur-containing reacthat substantially all of the various i'ractions obtained from mineral oils and refined for their numerous uses are susceptible to oxidation. 'This susceptibility of an oil fraction to oxidation and the manner in which oxidation manifests itself within the oil varies with the type and degree ofrefinement to which the oil has been subjected and the conditions under which the oil is used or tested. In other words, the deleterious products formed in an oil fraction as a result of oxidation and the degree to which they are formed depends upon the extent to which the various unstable constituents, which may act as oxidation cataysts, have been removed by refining operations, and also upon the conditions of use. i

A large number of compounds and composi-- tions havebeen proposed for use as improving or stabilizing agents for petroleum products. For example, various compounds or reaction products containing metalloids or metals, or combinations or one or more of such elements, have been credited with improving petroleum products in certain respects.

This invention relates to metal salts of phosphorusand sulfur-containing reaction products possessed of the capacity ofeffectl ng a high degree of improvement in mineral oil fractions. More particularly, the present invention is predicated upon the discovery of a new and novel class of oil soluble ammonium and metal salts of acidic, phosphorusand. sulfur-containing reaction products obtained by reacting substantially 1 mol of phosphorus pentasulfide (P285) with 4 mols of an unsaturated ketone at a temperature between about 135 C. and about 200 C. Particularly preferred of such salts are those in which the aforesaid acidic reaction products were prepared at a reaction temperature from about 135 to about Also contemplated by the present invention are the ammonium and metal salts of acidic, phostion products of P285 and unsaturated ketones are described in detail in a copending application Serial No. 491,946, filed June 23, 1943, of the present applicants with E. A. Oberright.

* While all unsaturated ketones are contemplated for use herein, particularly preferred is dioleyl ketone, which is also referred to as dl-heptadecenyl ketone; and contemplated for use also is the technical grade of dioleyi ketone commonly referred to as oleone.

While the exact chemical structure of the reaction products obtained in the aforesaid reaction oi! an unsaturated ketone and PzSs, and of a sul-' Iurized ketone (unsaturated) and P255, is not known at this time, it has been found that such reaction products are acidic in character as evidenced by their neutralization number (N. N.) and by their ability to form metal salts, and contain appreciable amounts of both phosphorus and sulfur. These reaction products are believed to be new inasmuch as previous disclosures have shown that compounds containing sulfur, not phosphorus an sulfur, are formed in the reaction of P285 with certain ketones. More specifically, Spring, in the Bull. Soc. Chim. (France) 2, 40, 6'7, has disclosed that a dimer thioketone,

CaHmSa, is obtained when acetone is warmed with,

Fast; and Gatterman in the Ber. 28, 2877, has disclosed that thiobenzophenone is obtained when benzophenone in benzene solution is heated with P285 for several hours at C. in a bomb. It

would appear that the reaction products from which the ammonium and'metal salts of this invention are prepared are new; and consequently, it would appear that said ammonium and metal salts are new. I

The ammonium and metal salts of this invention are prepared by reacting the aforesaid acidic,

phosphorus. .and sulfur-containing reaction products with ammonia or with a suitable metal compound, such for example as a hydroxide, oxide, alcoholate, etc. It will be understood that acidic, neutral and basic polyvalent metal salts of said reaction products will be prepared by using a 135 C. for 3 hours.

suitable metal compound. While all metals are contemplated as constituents of these metal salts, the metals of group IIof the periodic table are preferred, and of these barium is particularly preferred.

deleterious by-products and unreacted P285. The

reaction was considered complete when a pol- Although the salts of this invention are generally prepared as described above, several modifications may be made in the foregoing methods in order that particularly desirable ammonium and metal salts may be obtained. For example, we have found that the use of a non-oxidizing or inert gas, for providing a non-oxidizing atmosphere above the reaction mixture of P285 and said ketone, is beneficial in that the intermediate reaction products obtained therefrom are characterized by increased stability and lighter color; and the ammonium and metal salts thereof are similarly characterized. Illustrative of inert gases which may be used for this purpose are nitrogen, carbon dioxide, etc. A second modification which may be resorted to involves the use of a substantially inert diluent in the preparation the preparation of the corresponding ammonium and metal salts. Representative of such diluents are acid treated kerosene and tetra chlor ethane. Diluents of this type may be removed after the formation of acidic reaction product or may be removed after the formation of said salts by any suitable means, such as by distillation. In this connection, a substantially inert mineral oil may be used as the diluent and in such case the acidic reaction productwill be obtained in a mineral oil blend or concentrate. Correspondingly, when such a mineral oil diluent is used in the preparation of the corresponding salts, mineral oil blends or concentrates of the desired salts will be obtained. A further modification in the preparation of a salt rom one of the aforesaid reaction products involves the use of a carrier which combines with the water of the reaction; carriers such as butyl alcohol, ethyl alcohol, ,etc., are satisfactory for this purpose.

The following examples, in which a particularly preferred ketone-oleone-is used, are shown below in order to illustrate typical metal salts and typical procedures for their preparation.

EXAMPLE ONE NEUTRAL BARIUM SALT or PzSs-OLEONE REACTION Pnonucr (a) Preparation of Pzss-Oleone Reaction Product Grams Oleone 100 Pass 12 Nitrogen gas.

One hundred grams of oleone, 12 grams of P235 (a 4:1 radio of oleone to Pass) and 200 grams of a mineral oil diluent (Saybolt Universal viscosity-S. U. V.-of 45 seconds at 210 F.) were charged to a reaction vessel equipped with a me-, chanically driven stirrer, an upright Liebig condenser, a thermometer, and an inlet tube which extended to within a few inches above the reaction mixture. The atmosphere above the mixture was constantly swept with nitrogen, which was introduced through the inlet tube, so as to maintain the mixture in a non-oxidizing atmosphere. The reaction mixture was stirred and heated at It was then filtered through Hi-Flo, a chemically calcined natural, diatomaceus silica filter aid of the finest pore size, on a steam heated Buchner funnel to remove any ished copper strip immersed in a 3 per cent blend of the reaction product-that is, a 1 per cent blend of the concentrate-in mineral oil for 3 hours at 150 C. showed only a slight tarnish or discoloration. The reaction product in the mineral oil diluent is a light green-brown oil and contains 0.96 per cent phosphorus and 2.2 per of the aforesaid acidic reaction product and in cent sulfur, and has a neutralization number (N. N.) of 20.0.

(b) Preparation of neutral barium salt of (a) Two hundred and seventy-six grams of the reaction product obtained in (a) were mixed with 20 grams of Ba(OH) 2.8H2O, suilicient to neutralize the acid constituent or constituents of the acidic reaction product and 100 mls. of butyl alcohol in a reaction vessel equipped with a mechanically-driven stirrer, a Liebig condenser in an inclined position, a thermometer and an inlet tube (for nitrogen) extending to within a few inches of the reaction mixture. The mixture was stirred and heated at about 155 C. for 1 hour. During this time water and alcohol which are present are distilled off through the inclined condenser. The remaining reaction mixture is diluted with an equal volume of benzol and filtered through Hi-Flo" to remove any deleterious materials that may have formed. Benzol is then reaction product is identified hereinafter as Prodduct one.

EXAMPLE 'IWO Tm: Basic BARIUM SALT or PzSe-OLEONE REACTION Pxonucr Two hundred and twenty grams of the reaction product prepared as described in Example one (a) were mixed with 18 grams of Ba(OH) 2.8H2O and mls. of butyl alcohol and worked up as described in Example one (a). The reaction product, the basic barium salt of the aforesa d Passoleone reaction product in mineral oil is a light green oil containing 2.32 per cent barium, 2.44 percent sulfur and 0.84 per cent phosphorus, and is slightly alkaline. This product is designated Product two.

EXAMPLE THREE BARIUM SALT or PaSa-SULI'URIZED Omsom: REACTION Pnonuc'r (0) Preparation of PaSa-sulfurized oleone reaction product 170 C. for 3 hours and the reaction product so obtained is a sulfurlzed oleone.

The reaction product obtained in (a) is allowed I (b) Preparation-of barium salt of (a) up as described in Example .one. The reaction product is a brown viscous oil containing 0.96 per cent barium, 4.7 per cent sulfur and 0.62 per cent phosphorus, and has a neutralization number of 1.1. This corresponds to the barium salt of (a) in mineral oil; this is referred to hereinafter as.

. Product three.

EXAMPLE FOUR Ammonium SALT or PzSs-OLEONB REACTION PRonUcr Preparation OfPaSs-Oleone reaction product Copper strip tests were made on the reaction products obtained in Example four (a), (b), (c)

This reaction product is obtained as described in Example one (a) hereinabove.

(1)) Preparation of ammoniumsalt of (a) the Pzss-oleone reaction product in mineral oil.

This blend contains 0.66 per cent nitrogen, 3.0 per cent sulfur and 0.9 per cent phosphorus, and has a neutralization number of 12.5; this is Product four (17) Grams Oleone -1 Pass 10.5 Mineral oil '75 Nitrogen gas.

The apparatus described in Example one was and (d) by immersing a polished copper strip in a 3 per cent mineral oil blend in such products and heating the same for 3 hours at C. While the reaction products of Example four (a) and (0) did not tarnish the polished copper strip, the

mineral oil blends became slightly cloudy, darker in color, and a small quantity of material precipitated out in each case. In contrast to these tests, the reaction products of Example four (b) and (d) did not become cloudy, nor dark, and there was no, precipitation in either case; and such reaction productsdid not tarnish the polished copper strip immersed therein.

CORROSION TEST Motor oils especially those refined by certain solvent-extraction methods tend to oxidize when submitted to high temperatures and to form prodducts corrosive to metal bearings. This corrosive action may be quite severe with certain bearings such as those having the corrosion susceptibility of cadmium-silver alloys; and may cause their failure within a comparatively short time. The following test was used to determine the corrosive action of motor oil on an automotive connecting rod bearing. h

The oil used was a Pennsylvania solvent refined oil having an S. U. V. of 53 seconds at 210 F. The oil was tested by adding a section of a bearing containing a cadmium-silver alloy surface weighing about 6 grams and heating it to 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 is a measure of the amount of corrosion that has taken place. A sample of the oil containing a stabilizing agent was run at the same time as a sample of the straight oil and the loss in weight of the bearing section in the inhibited oil can used in this preparation and the procedure of Example one was followed with the exception that the reaction mixture was slowly heated and held constant at that temperature for 3 hours. The

reaction mixture in mineral oil is an amber col- 7 ored oil and contains 1.1? per cent phosphorus and 4.1 per cent sulfur. This product is referred to hereinafter as Product four (c).

(d) Ammonium salt of (c) 1 thus be compared directly with the loss of the section in the uninhibited oil. The results obtained in this test are set forth in Table one i below.

TABLE Om:

Bearing loss, milligrams Per cent Improving agent cone Inhibited oil g Product one 8:2 8 53 0.76 0 34 Product three 0.375 0 34 I 0. 1875 l 2; Product iou'r (b) 8: 53

ACCELERATED UNDERWOOD oxipa'nou TEST This test is used to determine the corrosive nature of lubricating oils under simulated oper-v ating conditions. The apparatus used consists of a circulating arrangement whereby an oil at 325 F., under a pressure of 10 pounds per square inch, is sprayed against a. standard cadmiumnickel bearing for a period of 5 hours. amount of oil under constant circulation in the system is 1500 cc. 1 In passing through the system.

the oil under test comes in contact with cast iron, steel, stainless steel, copper and the aforesaid cadmium-nickel bearing, and is also exposed to aeration. The oil used in this test contains a zssmall amount of an accelerator, namely, iron The grams of the cadmium-nickel bearing, and the percentage of viscosity increase.

The specific base oil used in this test was a solvent refined oil having a S. U. V. of 65 seconds at 210 F. and containing 0.17 per cent Nuodex; and the oil blend under test contained a small amount of Product one in this base oil. The results of these tests are shown in Table two below:

TABLE Two Bearing Per cent Initial Per cent A ddition agent mm N. N. vis' hm loss.

. grams After 5 hours UntrcaVd oil O. 25 8. 8 l26 0. 446 Product one 3.0 0. 25 0. 55 4. 8 0.003 Product for (b). 3.0 0.37 0. 40 2. 7 0.001

After hours Untreated oil 0.25 Product one 3. 0 0. 25 0. 77 9. 0 0. 003 Product four (0).... 3.0 0. 37 0. 50 5. 9 0. 001

After hours Untreated oil 0. 25 Product one 3. 0 0.25 l. 23 14. 0 0. 003 Product four ((7).. 3. 0 0.37 0. 72 13. 0 0.001

C. F. R. BEARING CORROSION TEST In this test, a C. F. R. fuel test engine, from which all equipment applying only to fuel test work has been removed, is used. 011 at a controlled temperature is delivered by a metering pump from an external heating sump to the test connecting rod bearing, through the drilled crankshaft. All other engine parts are lubricated with oil drawn from the same external sump by a double capacity C. F. R. oil pump. A copper-lead alloy test bearing is placed in the large end of the connecting rod. The jacket temperature is maintained at about 212 F., and the oil temperature at about 285 F. During the test, the compression ratio and engine speed are maintained at 5.5 and 1200 R. P. M., respectively. The engine is operated for a standard time which has been taken as the time (in hours) required for a loss of 0.200 gram of the copper-lead alloy test bearing when a blank oil is used. The eflectiveness of an oil addition agent is measured-by the time required for a similar loss when a blend of the same oil and an addition agent is used; and is rated in terms of a ratio, defined as the ratio of the hours for the oil blend for standard 0.200 gram corrosion to the hours for the blank oil for the same corrosion.

A solvent refined oil having an S. U. V. of 55 seconds at 210 F.the blank oil--and a blend of the same oil and a small amount of Product three were tested in the engine described above. The neutralization numbers (N. W.) of the blank oil and of the oil blend were determined after Ratio=75:38=2:l (approin).

. OPERATION TESTS We have also carried out tests of an oil and oils blends containing representative ammonium and metal salts of the type contemplated herein to determine the comparative behavior of the of the test bearings. The results are shown below in Table three wherein it is evident that the oil blend is greatly superior to the blank oil.

unblended oil and the improved oil compositions under actual operating conditions.

(a) Lauson engine test In this test, a single-cylinder-Lauson engine was operated with an oil temperature of 290 F. and a jacket temperature of 212 F. The oil used was an S. A. E. 10 motor oil, solvent refined, and the oil blends used were blends of said oil and typical metal and ammonium salts, Product two and Product four (d), respectively. The neutralization number (N. N.) and viscosity in centistokes at 210 F., of the blank oil and the oil (b) Ring-stickin;test

This test was carried out in a single-cylinder C. F. R. engine cooled with a diethylene glycolwater mixture held at a temperature of about 390 F. The oil temperature was held at about 150 F. during the test. The engine was operated continuously over a time interval of 28 hours at a speed of about 1200 R. P. M., which is equivalent to a road speed of about 25 miles per hour.

The conditions observed at the end of the test were (a) the extent to which the piston rings were stuck, (b) the extent to which the slots in the oil rings were filled with deposits, (0) the amount of carbonaceous deposits on the piston and (d) the neutralization number (acidity) of the oil, at the end of the test. The oil used was a lubricating oil having an S. U. V. of seconds at 210 F. and the results, which are recorded in Table live below, show a marked improvement in mineral oil compositions of the type contemplated herein over the oil above.

. In running these tests a comparative run was made with a sample of the blank oil and a sample of the oil containing the improving agent. In

Table five, Product one is the barium salt of an acidic, phosphorusand sulfur-containing reaction product of P285 and oleonc prepared above.

Turn Fm:

Bingoondition I Cone. Grams Per cent Improving per Degrees stuck carbon IN. N.

agent cent deposits None 360 360 300 360 300 30 40 20 12.4 1.4 Produotone 3 60 0 0 0 0 0 tr 0 7.0 1.0

(tr-trace).

The foregoing test results show that these new I ammonium and metal salts prevent the corrosion of inert metal bearings and inhibit the development of acids, the increase in viscosity and the formation of gummy deposits in'engines during use. The great effectiveness of these salts is indicated by the small amounts necessary to stabilize petroleum oils. They may be used in varying concentrations of.from about 0.05 per cent to per cent or more depending upon the type of oil, the conditions under which the blend is to be used, etc. In general, however, concentrations of from about 0.5 per cent to about 3.0 per cent of said salts will be suflic'ient to effect substantial improvement of the oil in which they are incorporated. They may be used either in straight petroleum oils or in oils containing other improving agents that have been added for other purposes, such, for example, as pour point depressants, viscosity index improvers, etc., in which case they serve to stabilize the resulting blends'without detracting from the advantages 7 of one or more of the addition agents.

It is, of course, to be understood that while :we have described certain typical procedures in making the oil addition agents contemplated herein and have referred to certain specific ammonium and metal salts and to specific mineral oils, the invention is not to be interpreted as being limited to these specific features of the foregoing descriptive material. Therefore, this invention is to be interpreted as inclusive of procedures which will be apparent to those skilled in the'art and correspondingly inclusive of other typical amselected from the group consisting of ammonium and metal salts. 1

2. An improvedmineral oil composition comprising a viscous mineral oil fraction and in admixturetherewith a minor proportion from about 0.5 per cent to about 3.0 per cent of a salt of an acidic, phosphorusand sulfur-containing reaction product, said reaction product being selected from the group consisting of a reaction product obtained by reaction, at a temperature between about 135 C. and about 200 C., of substantially one mol of Past and four mols of an unsaturated ketone; a reaction product obtained by reaction.

at a temperature between about 135 C. and about 200 C., of substantially one mol of PaSs and four mols of a sulfurized ketone, said sulfurized ketone being obtained by sulfurizing: an unsaturated ketone with elementary sulfur ata temperature above about 150 C.; and a reaction product obtained by sulfurizing, with elementary sulfur at a temperature above about 150 C., an intermediate acidic, phosphorusand sulfur-containing reaction product obtained by reaction of substantially one mol of Pass and four mols of an unsaturated ketone at a temperaturebetween about 135 0. and about 2ooc.; said salt -being selected from the group consisting of ammonium and metal salts.

monium and metal salts and other petroleum products coming within the scope of the appended claims.

We claim:

1. An improved mineral oil composition comprising a viscous mineral oil fraction and in admixture therewith a minor proportion, sumcient to stabilize said oil fraction, of'a salt of an acidic, phosphorusand sulfur-containing reaction product, said reaction product being selected from the group consisting of a reaction product obtained by reaction, at a temperature between about 135 C. and about 200 C., of substantially one mol of P285 and fourmols of an unsaturated ketone; a reaction product obtained by reaction, at a temperature between about 135 C. and about 200 C., of substantially one mol of P285 and four mols of a sulfurized ketone, said sulfuriz'ed ketone being obtained by sulfurizing an unsaturated ketone with elementary sulfur at a temperature above about 150 C.; and a reaction product obtained by sulfurizing, with elementary sulfur at a temperature above about 150'C., an intermediate acidic, phosphorusand sulfur-containlng reaction product obtained by reaction of substantially one mol of Past and four mols of an I unsaturated ketone at a temperature between t 3. An improved mineral oil compositioncomprising a viscous mineral oil fraction and in admixture therewith a minor proportion, sufficient to stabilize said oil fraction, of a salt of an acidic, phosphorusand sulfur-containing reaction product obtained by reaction of substantially one mol of P285 and four mols of an unsaturated ketone at a temperature between about C. and I about 200 C., said salt being selected'from the group consisting of ammonium and metal salts.

4. -An improved mineral oil compositioncomprising a viscous mineral oil fraction and in admixture therewith a minor proportion, sufilcient to stabilize said oil fraction, of a salt of an acidic, phosphorusand sulfur-containing reaction product obtained by reaction of substantially one mol of Past and four mols of an unsaturated ketone at a temperature between about 135 C. and about 200 C. in the presence of a nonoxidizing gas, said salt being selected from the group consisting of ammonium and metal salts.

5. An improved mineral oil composition comprising a viscous mineral oil fraction and in admixture therewith a minor. proportion, sufficient to stabilize said all fraction, of a salt of an acidic, phosphorusand sulfur-containing reaction product obtained by reaction of substantially one mol'of Pass and four mols of an unsaturated ketone at a temperature between about 135 C. and about 200 C., in the presence of nitrogen, said salt being selected from the izroup consisting of ammonium and metal salts.

6. An improved mineral oil composition comprising a viscous mineral oil fraction and in ad- 'mixture therewith a minor proportion, sufllcient to stabilize said oil fraction, of a salt of an acidic, phosphorusand sulfur-containing reaction product obtained by reaction of substantially one mol of P2S5 and four mols of an unsaturated ketone at a temperature between about 135 C. and about 200 0., in the presence of a substantially inert diluent, said salt being selected from the group consisting of ammonium and metal salts.

7. An improved mineral oil composition comprising a viscous mineral oil fraction and in admixture therewith a minor proportion, sufllcient to stabilize said oil fraction, of a salt of an acidic, phosphorusand sulfur-containing reaction product obtained by reaction of substantially one mol of P235 and four mols of dioleyl ketone at a temperature between about 135 0. and about 200 0., said salt being selected from the group consisting of ammonium and metal salts.

8. An improved mineral oil composition comprising a viscous mineral oil fraction and in admixture therewith a minor proportion, suflicient to stabilize said oil fraction, of a salt of an acidic, phosphorusand sulfur-containing reaction product obtained by reaction of substantially one moi of P2S5 and four mols of dioleyl ketone at a temperature between about 135 C. and about 200 0., said salt being selected from the group consisting of ammonium and metal salts.

9. An improved mineral oil composition comprising a viscous mineral oil'fraction and in admixture therewith a minor proportion, suflicient to stabilize said oil fraction, of a salt of an acidic, phosphorusand sulfur-containing reaction product obtained by reaction of substantially one mol of P285 and four mols of dioleyl ketone at a temperature of about 135 0. in the presence of nitrogen and in the presence of a substantially inert diluent, said salt being selected from the group consisting of ammonium and metal salts.

10. An improved mineral oil composition comof substantially one mol of P285 and four mols o1 sulfurized dioleyl ketone being obtained by s'ulf-urizing dioleyl ketone with about 10 per cent by weight of elementary sulfur at a temperature of about 170 0., and said salt being selected from the group consisting of ammonium and metal salts.

13. An improved mineral oil composition co prising a viscous mineral oil fraction and in admixture therewith' a minor proportion, sumcient to stabilize said oil fraction, of a salt of an acidic, phosphorusand sulfur-containing reaction product obtained by sulfurizing, with elementary sulfur at a temperature above about 150 0., an intermediate acidic, phosphorusand sulfur-containing reaction product obtained by eaction of substantially one mol of P285 and four, mols of an unsaturated ketone at a temperature between about 135 C. and about 200 0.; said salt being selected from the group consisting of ammonium and metal salts.

14. A 'mineral oil concentrate containing a minor proportion of a. salt of an acidic, phosphorusand sulfur-containing reaction product, said concentrate being selected from the group consisting of: a concentrate obtained by reacting substantially one mol of P285 and four mols of prising a viscous mineral ofl fraction and in admixture therewith a minor proportion, sufllcient to stabilize said oil fraction, of a salt of an acidic, phosphorusand sulfur-containing reaction product obtained by reaction, at a temperature between about 135 C. and about 200 0., of substantially one mol of P285 and four mols of a sulfurized ketone, said sulfurized ketone being obtained bysuliurizing an unsaturated ketone with elementary sulfur at a temperature above about 150 0., and said salt being selected from the group consisting of ammonium and metal salts.

11. An improved mineral oil composition comprising a viscous mineral oil fraction and in admixture th'erewith a minor Proportion, suflicient to stabilize said oil fraction; of a salt of an acidic, phosphorusand sulfur-containing reaction product obtained by reaction, at a temperature between about 135 C. and about 200 0., of substantially one mol of P235 and four mols of a sulfurized ketone, said sulfurized ketone being obtained by sulfurizing an unsaturated ketone with from about 5 per cent to about 15 per cent by weight of elementaryfsuliur at a temperature above about 150 0., and said salt being selected from the group consisting of ammonium and metal salts.

12. An improved mineral oil composition comprising a viscous mineral oil fraction and in admixture therewith a minor proportion, sufllcient to stabilize said oil fraction, of a salt of an acidic, phosphorusand. sulfur-containing reaction product obtainedby reaction, at about 135 0.,

an unsaturated ketone at a temperature between about 135 C. and about 200 .C. in the presence of a substantially inert mineral oil and substituting the P255 reaction mixture so obtained with a salt group; a concentrate obtained by reacting, at a temperature between about 135 C. and about 200 0., in the presence of a substantially inert mineral oil, substantially one mol of P285 and four mols or a sulfurized ketone, and substituting the P255 reaction mixture so obtained with a salt group, said sulfurized ketone being obtained by sulfurizing an unsaturated ketone with elementary sulfur at a temperature above about 150 0.; and a concentrate obtained by sulfurizing, with elementary sulfur at a temperature above aboutl 0. and in the presence of a substantially inert mineral oil, an intermediate acidic, phosphorusand sulfur-containing reaction product obtained by reaction of substantialiy one mol of P235 and four mols of an unsaturated ketone at a temperature between about C. and about 200 0. in the presence of said mineral oil, and substituting the sulfurized reaction product so obtained with a salt group; said salt being selected from the group consisting of ammonium and metal salts, and said salt group being selected from the group consisting of ammonium and metal.

15. An improved mineral oil composition comprising a viscous mineral oil fraction and in admixture therewith a minor proportion, sufllcient to stabilize said oil fraction, of a barium salt of an acidic, phosphorusand sulfur-containing reaction product obtained by reaction oi substantially one moi of P2S5 and four mols o1 dioleyl ketone at about 135 C. in the presence of a substantially inert mineral oil.

16. An improved mineral oil composition comprising a viscous mineral oil fraction and in admixture therewith a minor proportion, suflicient to stabilize said oil fraction, of an ammonium salt of an acidic, phosphorusand sulfur-com taining reaction product obtained by-reaction of substantially one mol of P235 and four mols of dioleyl ketone at about 135 0. in the presence 0! a substantially inert mineral oil.

17. An improved mineral oil composition comprising a viscous nuneral oil traction and in admixture therewith a minor proportion, sufllcient to stabilize said 011 traction, of a barium salt of an acidic, phosphorusand sulfur-containing reaction progluct obtained by reaction at about 140 C. of substantially one moi of P18 and tour mole of a suliurized dioleyl ketone in the presence of a substantially inert mineral oil, said sulfurized dioleyl ketone being obtained by sulfurizing' dioleyl ketone with elementary sulfur at about 170 C. in the presence of said mineral oil.

FERDINAND P. OTTO. RONALD E. 7 ROBERT C. MORAN.