US2594279A

US2594279A - Mineral oil compositions

Info

Publication number: US2594279A
Application number: US77057A
Authority: US
Inventors: Leonard E Beare
Original assignee: Sinclair Refining Co
Current assignee: Sinclair Refining Co
Priority date: 1949-02-17
Filing date: 1949-02-17
Publication date: 1952-04-29
Anticipated expiration: 1969-04-29

Description

Patented Apr. 2 9, 1952 MINERAL OIL COMPOSITIONS Leonard E. Beare, Lansing, 111., assignor to Sinclair Refining Company, New York, N. Y., a corporation of Maine No. Drawing. Application February 17, 1949, Serial No. 77,057

S'Claiins. (01. 252-463) .This'invention relates to novel lubricating oil compositions. More particularly, it is concerned with'gear oils and with, especially, universal gear lubricants.

A satisfactory universal gear lubricant'is capable of lubricating automotive and truck hypoids while performing, atthe same time, as a reasonably satisfactory lubricant for the other gears and transmissions found in such vehicles. Accordingly, the problem is' to provide a singular gear lubricating composition which is satisfactory for the conditions encountered at high speed-low torque operations on one hand, and, conversely, at low speed-high torque operations on the other. In addition, these lubricants must be 'efi'ective without objectionable channeling, rusting, corrosion, foaming, or additive separation in various environments.

Theapplications Serial No. 761,994, filed July 18, 1947, now Patent No. 2,515,222, by William S. Hoock and Milton P, Kleinholtz, and Serial No. 762,003, filed July 18, 1947, by Robert L. May, describe and claim new compositions of matter resulting from the reaction of a bieyclic terpene,

sulfur, and a phosphorus sulfide. I have now;

discovered that the compounds to which these applications are directed are especially effective in compounding highly satisfactory gear lubricating compositions when such products are used in conjunction with an organic chlorinecontaining compound.

The proportions of the addends used in the Generally, the range of the concentration of the compounds described in the aforementioned applications is most satisfactory from 4 to- 12% by weight on the compounded lubricant. How ever, I prefer andrecoznmend anaddition of about 8%.

The rangeof concentrations of the chlorinecontaining compounds is most satisfactory from about 3 to 8%, and is dependent in great part upon the chlorinated hydrocarbon employed.

The exact mechanism of the reactions orming thesecompounds is unknown, nor has amo lecular weight or structure been assigned to them because of their complexity. When normally prepared, the additive is solid at ordinary temperatures and when employed as a lubricating oil addend, it is best incorporated in the form of an oil solution having a-phosphorus content of, for example, about 1.5 to 4.0%, using asthe solvent oil a petroleum fraction whose viscosity and other characteristics are not such asto adversely affect the lubricating qualities of the compound.

Although these compounds may be prepared using any proportions of the identified reactants, Where the product is to be used in the compounding of a lubricant, as here, the most satisfactory proportions have been found to be about 3lto-5 moles of the bicyclic terpene and about0.5 to 5 atoms of sulfur, for each mole of the phosphorus sulfide.

A terpene most advantageously used is alphapinene. However, in place of alpha-pinene, a reactant comprising substantially alpha-pinene in. admixture with other related terpenes, such as camphenes and dipentenes, has been found to be satisfactory. A phorphorus sulfide productive of highly desirable addends within thescope of my invention is, for example, phosphorus pentasulfide. A light petroleum fraction that may be used to prepare an oil concentrate containing these reaction products isa Mid-Continent solvent-treated neutral.

The following examples are illustrative of, and indicate the procedure by which, these novel compositions of matter are. made.

EXAMPLE A In a five-liter, three-necked flask equipped with a mechanical stirrer anda thermometer were placed 1088 grams (8 moles) of alphapinene. An electric heating mantlewas used to heat the alpha pinene to 275 F. Theheat was turned "oil and 444 gms. (2Jmo1es) of-powdered phosphorus pentasulfide were added portionwise while maintaining vigorous stirring. The initial portions weighed approximately 40 gms. and after about half of the phosphorus pentasulfide was added, the portions were increased to about gms. each. Meanwhile the temperature :was maintained between 270 and 280 F. as regulated by the .rate of the phosphorus pentasulfide additions. After 1% hours, all the phosphorus pentasulfide had'been added and the exothermic reaction was no longer apparent. The heater was then turned on'and the temperature was maintained at 275 to 280 F. for two hours. 96 gms. (3 atoms) of powdered sulfur were added in increments of 32 gms. each at 45-minute intervals. After the second addition of sulfur, the temperature was raised to 325 to 340 F. and so maintained for 5% hours after all the sulfur had been added. The heater was turned off and the product was diluted with 2302 gms. of a Mid- Continent neutral lubricating oil. The product was filtered at a temperature of 200 F. using a commercial filter aid. Upon analysis it was found to contain 11.13% sulfur and 2.98% phosphorus. The acid number was 3.8 and the saponification number 59.

EXAMPLE B In a five-liter, three-necked flask equipped with a mechanical stirrer, a reflux condenser, and a thermometer were placed 1088 gms. (8 moles) of alpha-pinene. An electric heating mantle was used to heat the alpha-pinene to 275 F. The heat was turned off and 444 gms. (2 moles) of powdered phosphorus pentasulfide were added portionwise while maintaining vigorous stirring. The initial portions Weighed approximately 40 gms. and after about half of the phosphorus pentasulfide was added, the portions were increased to about 80 gms. Meanwhile the temperature was held at 275 F. as regulated by the rate of addition of the phosphorus pentasulfide. After 1 /2 hours all of the phosphorus pentasulfide had been added and the exothermic reaction was no longer evident. The heater was then turned on and the reactants were maintained at 275 F. for 2 hours. 192 gms. (6 atoms) of powdered sulfur were added in toto and the temperature was increased to 325 F. At this time another exothermic reaction occurred and the temperature rose rapidly to 366 F. The flask was cooled to 325, F. and maintained at this temperature for 6 hours. The heat was turned oil and the product was diluted with 2206 gms. of a Mid-Continent neutral lubricating oil. The final product was filtered at 200 F. using a commercial filter aid. It contained 12.85% sulfur and 3.08% phosphorus. The acid and saponiflcation numbers were 16.4 and 100 respectively.

EXAMPLE C In a five-liter, three-necked flask equipped with a mechanical stirrer, a reflux condenser, and a thermometer were placed 1088 gms. (8 moles) of alpha-pinene. An electric heating mantle was used to heat the alpha-pinene to 275 F. The heat was turned off and 444 gms. (2 moles) of powdered phosphorus pentasulfide were added portionwise while maintaining vigorous stirring. The first portions weighed approximately 40 gms. and after about half of the phosphorus pentasulfide was added, the portions were increased to about 80 gms. each. The addition of phosphorus pentasulfide required approximately 2 hours and the temperature was maintained at about 275 F. throughout this step. The reactants were kept at this temperature for an additional 2 hours and then 288 gms. (9 atoms) of powdered sulfur were added in three equal portions over a period of 45 minutes. After all the sulfur had been added, the temperature was raised to 325 F. The temperature wasmaintained at about 325 F. for 6 hours after the final addition of sulfur was made and then the heater was turned off and 2110 gms. of a Mid-Continent neutral lubricating oil were added. The final product was filtered with a commercial filter aid at a temperature of 200 4 F. It had an acid number of 25.4, a saponification number of 109, and contained 15.10% sulfur and 2.93% phosphorus.

EXAMPLE D In a five-liter, three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, were placed 1360 gms. (10 moles) of alphapinene. An electric heating mantle was used to heat the alpha pinene to 275 F. The heater was turned off and 444 gms. (2 moles) of powdered phosphorus pentasulfide were added in increments of 40 to gms. each at such a rate as to maintain the temperature at about 275 F. The reactants were stirred vigorously during the phosphorus pentasulfide addition. The heater was then turned on and the alpha-pinene-phosphorus pentasulfide mixture was maintained at approximately 275 F. for an additional 2 hours. 192 gms. (6 atoms) of sulfur were added in three equal increments over a period of 45 minutes. After all the sulfur had been added, the temperature was raised to 325 F. and an exothermic reaction momentarily raised the temperature to 377 F. The flask was cooled to 325 F. and so maintained for 6 hours. The product was diluted with 1934 gms. of a Mid-Continent neutral lubricating oil and, after cooling to 200 F., was filtered with a commercial filter aid. It had an acid number of 5.4 and a saponification number of 133 and contained 12.35% sulfur and 3.08% phosphorus.

EXAMPLE E In a five-liter, three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, was placed 1360 gms. 10 moles) of alpha-pinene. An electric heating mantle was used to heat the alpha-pinene to 275 F. The heater was turned off and 444 gms. (2 moles) of powdered phosphorus pentasulfide were added in increments of 40 to 80 gms. each at such a rate as to maintain the temperature at about 275 F. The alphapinene was stirred vigorously during the 1% hours while the phosphorus pentasulfide was introduced. The heater was turned on and the reactants were maintained at 275 F. for an additional 2 hours. 288 gms. (9 atoms) of sulfur were added in three equal portions over a period of 2 hours. The first portion of sulfur was added at a temperature of 275 F. and the heater was turned up until a temperature of 317 F. was reached. At this stage an exothermic reaction occurred and the heater was removed. The maximum temperature was 342 F. After addition of the balance of sulfur at about 317 F., the reaction was continued at 325 F. for 6 hours and the heater was turned off. The product was diluted with 1838 gms. of a Mid-Continent neutral lubricating oil and filtered at 200 F. using a commercial filter aid. It analyzed 15.42% sulfur and 3.14% phosphorus. The acid number was 10.4 and the saponification number 109.

EXAMPLE F In a five-liter, three-necked flask equipped with a mechanical stirrer, a reflux condenser, and a thermometer were placed 1088 gms. (8 moles) of alpha-pinene. An electric heating mantle was used to heat the alpha-pinene to 275 F. The heater was turned off and 222 gms. (1 mole) of powdered phosphorus pentasulfide were added portionwise, with stirring, at such a rate as to maintain the temperature at 275 to 285 F. during the 50 minutes required for the phosphorus pentasulfida addition. Theheater was: turned a Mid-Continent neutral oil wereadded, and the product wasfiltered at 200 F. witha commercial filter aid; It analyzed 15.93% sulfur and. 1.64% phosphorus. The-acid numberwas- 25.1.a-nd the saponification number 108.

EXAMBLE: G

In. a fiveeliter, three-necked flask equipped with a stirrer, reflux condenser, and a thermometer, were placed 1360 gms. moles) of alphapinene. An electric heating mantle was'used to heat the alpha-pinene to 275 F. 10' gms. of powdered sulfur were added with stirring and thetemperature was raised to 300'F. 10 more gms. of sulfur. were added and the temperature was raised until the alpha-pinene refluxed vigorously (310, to 316 F.). 172 gms. (to complete a total of 6 atoms) of sulfur were added and the temperature was maintained at 310 to 316 F. for 3 hours. The heater was turned off and the product was cooled to 275 F. 444 gms. (2 moles) of powdered phosphorus pentasulfide were addedportionwise. Approximately 40-gm. portions were added initially and after about half of the phosphorus pentasulfide was added, the portions were increased to about 80 gms. The temperature was controlled by the rate of the phosphorus pentasulfideadditions so that'it did not exceed 285 F.

After 1%, hours, all the phosphorus pentasulfide had been added and the exothermic reactionwas EXAMPLE H In a five-liter, three-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, were placed 1360 gms. (10 moles) of alpha pinene. An electric heating mantle was used to heat the alpha-pinene to 305 F; 40 gms. of powdered sulfur were'added, with stirring, and no evidence of an exothermic reaction was noticed. The solution was cooled to 285 F. and 248 gms. (to make a total of 9 atoms) more sulfur were added. Heat was applied and the temperature slowly rose to 305 F. After heat ing 2 hours at 305 F., the product was cooled to 275 F. and the heater turned ofi; 444 gms. (2 moles) of powdered phosphorus pentasulfide were added in increments of 40 to 80 gms. each at such a rate as to maintain the temperature at 270m 290 F. The addition of phosphorus p'entasulfide-required 1 hours. The heater was" 384' gms. (12 atoms). of: sulfur were' 6'. turned on: and-the, temperature,- was. raised. to 300 F. and maintainedtfort.hours. The'heater. was turned oif and 1838 gms. of a Mid-Continent neutral lubricating oil were added. The final product, was, filtered at 200 F. using a com mercial filter aid. It had a phosphorus content of 3.24%, a sulfur content of 15.49% and showed a saponification number of 98 and an acid numberof 35.4.

EXAMPLE I In a five-liter, three-necked flaskequipped with a stirrer, a reflux condenser, and a thermometer, were placed 1360 gms. (10' moles) of alpha-pinene and 384 gms. (12 atoms) of.pow-- dered sulfur. The stirrer wasstartediand the reactants were heated to 310 F.,by meansofj an. electric heatin mantle. After 1 hour, 9.6. gms. (3 atoms) additional sulfur were, added and the: temperature was maintained at 310 F. for 21 hours. The heater was turned off and the, reactants were cooled. to 275 F. 278 gms. (1%. moles) of powdered phosphorus pentasulfide, were then added portionwise over a period of 1%. hours: The temperature was kept at 275 to 285 F. during the phosphorus pentasulfide addition by adding the reactant in increments of 15 to 20- gms. each. The heater was turned on and the temperature was held at 300 F. for 3 hours. The heater was turned off, 2118 gms. of a Mid--- Continent neutral lubricating oil were added, and the product was filteredat200 F. with a commercial filter aid. It had a phosphorus content of 1.65%, a sulfur content of 16.17% and showed a saponification number of. 98 andan acid number of, 23.9,.

EXAMPLE J 1088 gins. (8 moles) of alpha-pinena were. charged into a five-liter, three-necked flaskv equipped with a mechanical stirrer anda thermometer. The alpha-pinene was heated to 280 F. with an electric heating mantle, and 96 gins. of sulfur (3v atoms) were added. The reaction mixture was stirred and heated at a refluxtemperature of 305 to 315 F. for 3 hours. The electric heating mantle was then removed and 444 gms. (2 moles) of phosphorus pentasulfide were added portionwise, while maintaining vigorous stirring, at a 'sufiicientrate to maintain the temperature at 275 tov 290 F. for 1 hours. The reaction mixture was heated at 275 to 285F. for an additional 2 hoursand then raised to 300 F.v for an, additional 3 hours. 2302 gms. of a Mid"- Continent solvent-treated neutral oil were then blended with the reaction mass. This oil concentrate was. allowed to stand overnight. It was thenheatedto F. and filtered with afilter aid. The product analyzed 3.46% phosphorus and 10.56% sulfur and had an acid number of 2.70 and a saponification number of, 58.6.

Various chlorine containing hydrocarbons may. be used in preparing these improvedlnoveli lubrieating compositions; the intended use of the lubricant is determinative of'the nature and char.- acteristics of these chlorinated'addends. Chlorinated naphthalenes and chlorinated paraffin waxes are illustrative of highly desirable compounds of this nature. In addition, chlorinated diphenyls may be, used. In. each case, the important considerations are the effective, amounts. of chlorine that are available and the solubility of the selected additive in oil. Generally, chlorinated naphthalenes and parafiin waxes having a minimum tendency to evolve free hydrogenchloride in storage or upon moderate heating are and tested.

compounds most advantageously employed in the preparation of the lubricants.

1 The chlorine content of the chlorinated naphthalenes and the paraffin waxes will vary greatly and amounts ranging from about 50 to 70% chlorine in naphthalenes and about 35 to 75% chlorine in paraffin waxes have been found to be satisfactory. However, the criteria for determining the eiiicacy of a chlorine-containing substance, as mentioned above, appear to be primarily dependent upon the effective amounts of chlorine available and the solubility of the compound in oil.

The range of concentration of these compounds in the improved lubricating composition is most satisfactory from about 3 to 8% by weight on the compounded lubricant. In particular, 6% of a chlorinated parafiin wax containing approximately 40% chlorine has been found to be highly satisfactory.

To further illustrate my invention, various lubricating compositions have been compounded The standard Federal-specified methods for evaluating the performance of universal gear lubricants, which I have used, are described in the Coordinating Research Council Handbook, 1946 edition. In addition, certain other tests, namely, the Timken Weed-Out Procedures, were resorted to. Essentially, these latter tests are performed as follows:

The Timken L- Weed-Out Procedure No. 1.--Timken L-20 Weed-Out Procedures employ the Timken testing machine of the Coordinating Research Councils Timken Machine Test (CRC L-18-545), with necessary modifications as required to operate under the following conditions:

Test cup speed 100 R. P. M.

Lever load 198 pounds Oil temperature 250 F.

Oil feed Rapid circulation over entire cup Duration 16 hours The total weight loss of the test cup and block are determined and these parts are examined for failure.

The Tz'mken L-20 Weed-Out Procedure N0. 2.-This test is identical to Procedure N0. 1 except that the test block is continuously moved back and forth beneath the test cup in a direction paralleling the lever arm, for a distance of 0.13 inch, four times per minute. In addition, the coefiicient of friction and sludge formation, particularly of deposits on the Timken Test Block, are recorded during the 16 hour wear test.

Additional one-hour tests are made at higher speeds. These tests indicate the maximum R. P. M., to the nearest R. P. M., at Which 198 pounds can be carried for one hour without any evidence of failure by scoring, grooving, or smearing. Timken L-20 Procedure No. 2 is preferred over Procedure No. 1 because wear occurs under line contact conditions at unit loads closely simulating those in hypoid ears under high torque conditions. Uncompounded base oils will usually fail at from 25 to of the regular 198 pound lever load. Commercial hypoid gear lubricants which meet standard specifications give from 4 to 15 mgs. of wear and a smooth bright surface. Commercial hypoid gear lubricants which pass the CRC High Speed Axle Test but fail the CRC High Torque Axle Test give from to 300 mg. of wear and heavy grooving.

The following examples illustrate various universal gear lubricating oil compositions, as well as the results of certain evaluating tests performed upon each lubricant. The compositions contain identified addends that were blended with a base oil, the characteristics of which are indicated in Table I. The pour depressant compounded into the lubricating oil compositions was an octadecyl methacrylate polymer. The antifoam agent was a silicone polymer, while the solubilizer was a 10% concentrate of calcium sulfonate in oil. This additive was included in several of the compositions primarily for its value as a solubilizer, although it has utility also as a rust and sludge inhibitor. However, the presence of this compound is not critical, since its functions are not essential to the practice of my invention. In particular, low percentages of the sulfonate concentrate, for instance, 1%, do not appreciably affect load capacity. On the other hand, appreciable amounts, for instance 5% or more, will undoubtedly decrease load capacity, chemical activity, and oxidation sludging of the lubricant.

Composition XII shows that both a chlorinated naphthalene and a chlorinated parafiin wax may be added together.

Preferred reaction products are the preparations of Examples A and D. Eight per cent of such preparations with 6% of either a chlorinated naphthalene containing 57% chlorine or a chlorinated paraffin wax containing 40% chlorine are highly preferable addition compounds when employed in the recommended base oil. The results also indicate that the chlorinated paraflin wax of 40% chlorine content and the chlorinated naphthalene of 57% chlorine content are approximate equivalents. However, the low cost and great solubility of the par-afiin wax favor its use.

Not all of the Coordinating Research Council Gear Lubricant Evaluation Tests have been per-' formed upon each of the illustrative gear oil compositions. However, a sufficient number of the more critical tests were made to show the most useful properties. In fact, essential properties of a satisfactory gear lubricant may be evaluated by the use of a singular test, namely, the Timken L-20 Weed-Out Procedure.

TABLE I Composition Mid-Continent solvent-treated neutral oil,

weight per cent 16.97 Mid-Continent solvent-treated bright stock oil, weight per cent 82.83 Pour depressant, weight per cent 0.20

Properties Flash point, F 460 Viscosity, S. U. S. at F' 1216 Viscosity, S. U. S. at 210 F 96 Viscosity index 91 Pour point, F 5 Sulfur, per cent 0.28

Composition I The lubricating oil composition was composed of by weight:

Per cent Preparation of Example D 2 57% Clz-containing naphthalene 6 solubilizer 1 Base Oil 91 Composition II .The lubricating oil composition was composed of by weight:

Per cent Preparation of Example E 2 57% Gi -containing naphthaleneun 6 Solubilizer l Base oil 91 The Timken Procedure No. 1showed a 29 mg. loss after 16 hours of wear, the surfaces being lightly grooved. The lubricant failed this test.

The copper strip was a dark peacock color after.

1 hour at 250 F. There was no'rustformation in the Rust Protection Test.

Composition III The lubricating oil composition was composed of by weight:

i V I t Per cent Preparation of Example G 2 57 cl z-containing naphthalene 6 Solubilizer 1 Base oil 91 The Timken' Procedure No; 1 showed a145 mg. loss after16 hours of wear, the surfaces being heavily grooved." The lubricant failed this test.

'The copper'strip after 1 hour at 250 F. was a light peacock color. The Rust Protection .Test showed no rust formation.

Composition IV The lubricating oil composition was composed of byweight:

1 Per cent Preparation of Example H '2 57% Gig-containing naphthalene 6 Solubilizer '1 Base o i1 9 Y The Tir'nken Procedure No. 1 showed a 15 mg. loss after 16 hours of wear, the surfaces being in good condition; the lubricant passed this test. The copper strip after 1 hour at 250 F was a light peacock color and the RustProtection' Test indicated that no rust had formed.

Composition V n The lubricating oil composition was composed of by weight:

, Per cent Preparation of Example A ,4 57% Gig-containing naphthalene 6 Solubilizer. 1

Basevoil 8.9

ThejTimk'en Procedure No. 1 revealed that there was a 6 mg. loss after 16 hours of wear. and the surfaces showed a slight trace of grooving. The

lubricant was on the bo'rderline of passing this test' The'copper strip was a light peacock color after 1 hour at 250 F., and there was no rust formation in the Rust Protection Test. The lubricant passed the High Speed Axle Test (CRC 15-19-6 15) and failed the High Torque Axle Test ('CRC L- 2p-545) because of grooving. r V

0? Composition VI The lubricating oil composition was composed of by weight:

Per cent Preparation of Example D 4 57% Clz-containing naphthalene 6 Solubilizer 1 Base oil 89 The Timken Procedure No. 1 showed a 6mg.

loss after 16- hours of wear, and the surfaces showed a trace of grooving. The lubricantreceived a borderline rating in this test. The color of the copper strip after 1 hour at 250 F. was dark peacock. No rust formed in the Rust Protection Test.

- Composition VII The lubricating oil composition was composed of by weight:

Per cent Preparation of Example J 4 57% Ch-containingnaphthalene 1 6 Solubilizer 1 Base oil 89 The Timken Procedure No. 1 indicated that there was a 3 mg; loss after1'6'hoursof wear,

and the surfaces were ingood condition As. a; result the lubricant passed this test. The copper strip was a light peacock color after 1 hourat 250 F. H The Rust Protection Test showed no rust formation.

Composition VIII A I The lubricating oil composition was composed of by weight:

' 7 Per cent Preparation of Example G 4 57% Clz-containing naphthalene 6 Solubilizer ..V 1

"Base oil 89 The'TinikenProcedure No. 1 showed a 16 mg. loss after 16 hours of wear, the surfaces being lightly grooved. Asa result, the lubricant failed this test. The copper strip was a light peacock color after 1 hour at 25051 There was no rust formation in the Rust Protection Test.

H Composition IX u The lubricating oilcomposition was composed of by weight: 1 v

Per cent Preparation of Example A 8 57% Clz-containing naphthalene 6 Solubilizer 1 Base oil TheTimken Procedure No. 1 showed an 11 mg.

loss after 16 hoursofwear, andthe surfaces were.

in goodcondition. .As. a result the lubricant passed this test. Thev color .of. the. copper strip after -1 hourat 250 F. was light peacock. .The

Rust Protection Test revealed that no rust formed.

" Compositi n X The lubricating oil composition was composed ofby'weight: r a i V v Per cent Preparation of Example A; 8 57 (Ila-containing 'naphthalene 6 Base oil 86 .The-Timken L-20 Procedure No. 2 revealed that.

there was 'a 13 mg. loss after 16 hours of W621, the surfaces being in good condition. The safe R. P; M. were and the lubricant passed this test.

There was no rust formation in the Rust Protection Test.

Composition XI The lubricating oil composition was composed of by weight:

Per cent Preparation of Example A 8 70% Clz-containing naphthalene 4 Neutral oil 15.80 Bright stock oil 71.94 Pour depressant 0.26 Antifoam agent 0.0005

The Timken Procedure No. 2 revealed an 11 mg. loss after 16 hours of wear, the condition of the surfaces being good. The safe R. P. M. were 125 and the lubricant passed this test. The Rust Protection Test showed no rust formation, while the Storage Solubility Test (CRC 11-22-445) was also passed.

Composition X1 1 The lubricating oil composition was composed of by weight:

Per cent Preparation of Example A 8 70% Clz-containing naphthalene 4 40% Ola-containing paraffin wax 1.5 Base oil 86.5

The Timken L-20 Procedure No. 2 revealed a 7 mg. loss after 16 hours of wear, the surfaces being in good condition. The safe R. P. M. were 225, and the lubricant passed this test.

Composition XIII The lubricating oil composition was composed of by weight:

Per cent Preparation of Example A 8 40% Clz-containing paraffin wax 4.5 Neutral oil 22.70 Bright stock 64.54 Pour depressant 0.26 Antifoam agent 0.0005

The Timken L-20 Procedure No. 2 showed a 14 mg. loss after 16 hours of wear, the surfaces being in good condition. The safe R. P. M. were 200 and the lubricant passed this test. The copper strip after 1 hour at 250 F. was a dark peacock color, while the Rust Protection Test revealed that no rust had formed.

Composition XIV The lubricating oil composition was composed of by weight:

Per cent Preparation of Example D 8 57% Clz-containing naphthalene 6 Solubilizer 1 Base oil 85 The Timken Procedure No. 1 showed a 4 mg. loss after 16 hours of wear, and the surfaces were in good condition. As a result the lubricant passed this test. The color of the copper strip after 1 hour at 250 F. was a dark peacock. No rust formed during the Rust Protection Test.

Composition XV The lubricating oil composition was composed of by weight:

Per cent Preparation of Example J 8 57% Ch-containing naphthalene 6 Solubilizer 1 Base oil '85 The Timken Procedure No. 1 showed a 12 mg. loss after 16 hours of wear, the surfaces being in good condition. As a result, the lubricating composition passed this test. The copper strip was a dark peacock color after 1 hour at 250 F. The Rust Protection Test showed no rust formation.

I claim:

1. A lubricating oil composition comprising predominantly a mineral oil and containing minor but effective proportions for extreme pressure properties of an oil-soluble stable chlorinated hydrocarbon containing about 35 to 75% chlorine and a composition of matter prepared by the reaction of a bicyclic terpene, sulfur, and a phosphorus sulfide in the approximate molar ratio 38:0.5-5:1, the said composition of matter containing sulfur within the range from 10.56 to 16.17 per cent by weight and containing phosphorus within the range from 1.65 to 3.46 per cent by weight.

2. A lubricating oil composition comprising predominantly a mineral oil and containing minor but effective proportions for extreme pressure properties of an oil-soluble stable chlorinated hydrocarbon containing about 35 to 75% chlorine and sulfurized condensate of alphapinene and phosphorus pentasulfide in which ratio of alpha-pinene to sulfur to phosphorus pentasulfide is approximate 3-8:0.5-5:1, the said sulfiurized condensate containing sulfur within the range from 10.56 to 16.17 per cent by weight and containing phosphorus within the range from 1.65 to 3.46 per cent by weight. I

3. A lubricating oil composition comprising predominantly a mineral oil and containing minor but effective proportions for extreme pressure properties of an oil-soluble stable chlorinated hydrocarbon containing about 35 to 75% chlorine and a reaction product of sulfurized alpha-pinene and phosphorus pentasulfide in which the ratio of alpha -pinene to sulfu'r to phosphorus pentasulfide is approximately 3-8:0.5-5:1, the said reaction product containing sulfur within the range from 10.56 to 16.17 per cent by weight and containing phosphorus within the range from 1.65 to 3.46 per cent by weight.

4. A lubricating oil composition comprising predominantly a mineral oil and containing minor but effective proportions for extreme pressure properties of an oil-soluble stable chlorinated hydrocarbon containing about 35 to 75% chlorine and a composition of matter prepared by the reaction of about 3 to 5 moles of alphapinene, about 0.5 to 5 atoms of sulfur, and about 1 mole of phosphorus pentasulfide, the said composition of matter containing sulfur within the range from 10.56 to 16.17 per cent by weight and containing phosphorus within the range from 1.65 to 3.46 per cent by weight.

5. A lubricating oil composition comprising predominantly a mineral oil and containing 3 to 8% of an oil-soluble stable chlorinated hydrocarbon containing about 35 to 75% chlorine and 4 to 12% of a composition of matter prepared by the reaction of alpha-pinene, sulfur, and phosphorus pentasulfide in the approximate molar ratio 3-8:0.5-5:1, the said composition of matter containing sulfur within the range from 10.56 to 16.17 per cent by Weight and containing phosphorus within the range from 1.65 to 3.46 per cent by weight.

6. A lubricating oil composition comprising predominantly a mineral oil and containing 3 to 8% of an oil-soluble stable chlorinated naphthalene containing about 35 to 75% chlorine and 4 to 12% of a composition of matter prepared by the reaction of alpha-pinene, sulfur, and

phosphorus pentasulfide in the approximate molar ratio 3-8:0.5-5:1, the said composition of matter containing sulfur Within the range from 10.56 to 16.17 per cent by Weight and containing phosphorus within the range from 1.65 to 3.46 per cent by weight.

7. A lubricating oil composition comprising predominantly a mineral oil and containing 3 to 8% of an oil-soluble stable chlorinated parafiin Wax containing about 35 to 75% chlorine and 4 to 12 of a composition of matter prepared by the reaction of alpha-pinene, sulfur, and phosphorus pentasulfide in the approximate molar ratio 3-8:0.5-5:1, the said composition of matter containing sulfur within the range from 10.56 to 16.17 per cent by Weight and containing phosphorus Witin the range from 1.65 to 3.46 per cent by weight.

8. A lubricating oil composition comprising predominantly a mineral oil and containing about 4 to 6% of an oil-soluble stable chlorin- 14 ated hydrocarbon containing about 35 to 75% chlorine and about 8% of a composition of mat- -ter prepared by the reaction of alpha-pinene,

sulfur and phosphorus pentasulfide in the approximate ratio of 3-8:0.5-5:1, the said composi tion of matter containing sulfur within the range from 10.56 to 16.17 per cent by Weight and containing phosphorus Within the range from 1.65 to 3.46 per cent by Weight.

LEONARD E. BEARE.

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

UNITED STATES PATENTS Sproule et al Apr. 26, 1949

Claims

1. A LUBRICATING OIL COMPOSITION COMPRISING PREDOMINANTLY A MINERAL OIL AND CONTAINING MINOR BUT EFFECTIVE PROPORTIONS FOR EXTREME PRESSURE PROPERTIES OF AN OIL-SOLUBLE STABLE CHLORINATED HYDROCARBON CONTAINING ABOUT 35 TO 75% CHLORINE AND A COMPOSITION OF MATTER PREPARED BY THE REACTION OF BYCYCLIC TERPENE, SULFUR, AND A PHOSPHORUS SULFIDE IN THE APPROXIMATE MOLAR RATIO 3-8:0''5-5:1, THE SAID COMPOSITION MATTER CONTAINING SULFUR WITHIN THE RANGE FROM 10.56 TO 16.17 PER CENT BY WEIGHT AND CONTAINING PHOSPHORUS WITHIN THE RANGE FROM 1.65 TO 3.46 PER CENT BY WEIGHT.