US2993858A

US2993858A - Metalworking lubricant

Info

Publication number: US2993858A
Application number: US727532A
Authority: US
Inventors: Louis H Sudholz
Original assignee: Socony Mobil Oil Co Inc
Current assignee: ExxonMobil Oil Corp
Priority date: 1958-04-10
Filing date: 1958-04-10
Publication date: 1961-07-25
Anticipated expiration: 1978-07-25

Description

United States Patent ()ifice 2,993,858 Patented July 25, 1961 METALWORKING LUBRICANT Louis Sudholz, Flushing, N.Y., assignor t Socony MObll Oil Company, Inc., a corporation of New York No Drawing. Filed Apr. 10, 1958, Ser. No. 727,532 9 Claims. (Cl. 252-325) This invention has to do with lubricants and, more particularly, with compositions especially adapted for lubricating metals during processing operations such as cutting including broaching, turning, threading, drilling, tapping, and milling, and operations such as grinding, drawing, rolling and the like. These are generally referred to in the art as metal processing oils.

Such oils are used by flowing over the tool and the work in a steady stream, and function to dissipate the heat from both the tool and the work; improve tool life; improve the quality of the surface produced; lubricate the surfaces in contact between the tool and the work; wash away the chips; decrease tool wear; decrease friction between chip and tool; and provide lubrication between the chip and the tool, thus reducing the effect of the high pressure of the chip on the tool. There is ordinarily an enormous pressure exerted between the cutting edge of the tool and the metal being machined and in addition, due to the inherent resiliency of the metal, heavy pressures are maintained between the work and the surf-ace of the tool just under the cutting edge and between the chips and the surface of the tool just back of the cutting edge. Therefore, it is requisite that a lubricant be provided which is capable of affording a high load-carrying lubricant film between the cutting tool, chip and the work being machined.

Dependent upon the type of metals being processed or the design of the machine used, a corrosive oil or a noncorrosive oil is utilized. That is, with copper, brass or bronze, a non-corrosive lubricant should be selected, because corrosive lubricants stain such metals. When wrought iron or steel is concerned, a corrosive lubricant can be used. Machines having bronze gibs and slides which would be exposed to the action of the lubricant, require non-corrosive lubricants when in use, since corrosion would cause the slides to stick; the machines would then have to be shut down and cleaned.

Corrosive cutting oils can be defined as those which cause more than a slight discoloration in the copper strip test. This test involves immersion of a copper strip in the test oil or composition for three hours at 212 F. Non-corrosive cutting oils can be defined as those which cause no more than slight discoloration of a copper strip under such test conditions.

It has heretofore been the practice to improve the film strength of corrosive and non-corrosive cutting oils by the incorporation therein of various compounds of sulfur, phosphorus, chlorine, metal, fatty materials or combinations thereof. Such additive materials, however, have not been found to be entirely satisfactory because of a variety of shortcomings. Materials containing high concentrations of active sulfur are disadvantageous since they tend to cause corrosion and/or staining of certain metals when in contact therewith at relatively low temperatures. Halogen-containing additives, particularly chlorinated materials, may cause staining under humid conditions and often lose halogen (as chlorine) during use. Many phosphorus-containing additives, such as acid esters of phosphorus, combine with iron fines during use (particularly grinding operations) and form iron soaps which increase the viscosity of the oil and promote excessive foam formation.

Accordingly, it is an object of the present invention to provide improved lubricants for lubrication during metal processing operations, such lubricants being free of the aforementioned shortcomings.

Another object is to provide cutting oils characterized by a high degree of machining efiiciency. A further object is to provide improved non-corrosive type cutting oils. Still another object is to provide corrosive cutting oils. Other objects will be apparent from the following description.

The foregoing objects are realized with a mineral oil composition containing in combination a corrosive sulfurcontaining extreme pressure agent or a non-corrosive extreme pressure agent, and an oil-soluble, phosphorus-, sulfurand metal-containing reaction product prepared by: (1) forming a mixture of a hydrocarbon material, such as a petroleum oil, and a metal hydroxide; (2) contacting said mixture with an oxidizing gas at a temperature of from about C. to about 325 C. to provide a metalcontaining oxidized hydrocarbon product; (3) reacting the metal-containing oxidized hydrocarbon product with a phosphorus sulfide to provide a metal-, phosphorusand sulfur-containing oxidized hydrocarbon product; (4) forming a mixture of the product produced in (3) with water and a metal hydroxide, at a temperature below the boiling point of water; (5) substantially completely dehydrating the mixture formed in (4); and (6) filtering the dehydrated mixture from (5) to remove insolubles therefrom.

Details for the character and preparation of the aforesaid reaction product are provided in application Serial No. 554,390, filed December 23, 1955 by H. G. Berger et al., now issued as Patent No. 2,830,949, and such details are incorporated herein by reference. For the sake of brevity, it may be pointed out that the hydrocarbon starting materials thus incorporated herein by reference may be briefly characterized as petroleum oils having a molecular weight of from about 200 to 1000 and which are selected from the group consisting of aliphatic hydrocarbons and aromatic hydrocrabons having at least one nuclear hydrogen atom substituted by an aliphatic radical to provide a total of at least 8 aliphatic carbon atoms per molecule therein, and mixtures thereof. However, a typical and preferred reaction product is described in detail hereinafter by way of illustration. These reaction products have an unusually high metal content, and were found by Berger et al. to exhibit exceptional detergent properties as well as antioxidant activity.

As indicated above, in addition to the high metalcontent reaction product present in the cut-ting oils of this invention, there is also present one or more other characterizing extreme pressure components depending upon the desired character of the lubricant-that is, corrosive or non-corrosive. Corrosive cutting oils as contemplated herein will contain one or more sulfur-containing organic compositions in which the sulfur is loosely bound. As considered herein loosely bound sulfur is that which will cause more than a slight discoloration on a copper strip in the copper strip test identified above. It is to be understood that in addition to having looselybound sulfur, the sulfur-containing organic compositions can contain one or more other characterizing elements such as bromine, chlorine, phosphorus, oxygen and nitrogen.

Representative of corrosive, sulfur-containing organic compositions in which sulfur is loosely-bound" are the following: sulfurized animal, marine and vegetable oils containing from about 12 to about 20 percent of sulfur; sulfurized mineral oil containing up to about 5 percent of added sulfur; sulfurized terpenes, organic polysulfides and mercaptans. Of such agents, particularly preferred are sulfurized lard and sperm oils containing about 15 percent by weight of sulfur.

It is also to be understood that the mineral oil base of the cutting oil can be sulfurized such that the sulfur therein is loosely-bound, in which case the cutting oil will be corrosive. When such a sulfurized mineral oil base is used, the cutting oil need not, but may, contain a separate sulfur-containing extreme pressure agent. Illustrative of such sulfurized base oils are parafiinic and naphthenic oils having viscosities from about 40 to about 300 seconds (SUS) at 100 F., and sulfurized to contain between about 0.1 and about 5 percent of sulfur.

Non-corrosive cutting oils of this invention contain non-corrosive extreme pressure agents which are characterized by firmly-bound sulfur, phosphorus, and/or halogen such as chlorine and bromine. Typical of such agents are: sulfurized animal, marine and vegetable oils containing up to about percent by weight of sulfur; dibenzyl disulfide; chlornaphtha xanthate; chlorinated fatty materials such as chlorinated stearic acids; chlorinated waxes; organic phosphorus compounds such as thiophosphates; etc. Preferred of such agents are sulfurized lard and sperm oils containing about 10 percent by weight of sulfur.

Illustrative and preferred of the high metal content reaction products identified above, is the following product described in Example 1.

EXAMPLE 1 Two thousand grams of a percolated, solvent refined Mid-Continent type bright stock (average molecular weight, about 800) and 200 grams (9.1 weight percent) of hydrated lime (available calcium oxide, 70% minimum) weremixed and then charged to an electrically heated glass column (60 feet in length, 3 inches in diameter). The column has a fritted glass disc sealed in the bottom for air dispersion. The contents of the column were heated rapidly to 425 F. Air was introduced through the glass frit at a rate of 3 liters per hour per 100 grams of oil for about 21 hours. The product thus formed was filtered. The filtrate has a calcium content from about 1.5-1.7 percent by weight.

The filtered oxidized oil is charged to a glass flask equipped with a stirrer, thermometer and a nitrogen inlet tube. The oil was diluted with an equal weight of a dilution oil; this is a paraffinic oil having: an A.P.I. gravity of 27.5; an S.U.S. viscosity at 100 F. of 100-110; a flash (C.O.C., F.) of 350, minimum; and a color (A.S.T.M.) of 2, maximum. About 10 percent by weight of P 8 based upon the bright stock charge, is added to the diluted oxidized oil, and the resulting mixture was reacted at 300 F. for 2 hours in an atmosphere of nitrogen. Following this, the reaction mixture was cooled to 170- 180 F. and was treated with 10 percent by weight of water, and then with 10 percent by weight of hydrated lime; the quantities of water and of lime are based upon the bright stock charge. The mixture thus formed was dehydrated when heated to a temperature of 300 F.; it was maintained at 300 F. for one hour. Five percent by weight of Hyflo (filter aid) was added and the product was filtered hot through a Hyflo coated, electrically heated funnel. The filtrate, representing the desired reaction product in the dilution oil (1:1 dilution), has an analysis of the following character:

Percent Calcium 1.5-2.8 Phosphorus 0.9-1.4 Sulfur 1.5-3.0

A reaction product so prepared is shown in several tests hereinafter and is identified as Reaction Product A.

It has also been found that the dehydrated product can be used in the cutting oils of this invention, thus dispensing with the filtration step.

Although a wide range of mineral lubricating oils can be used as the base for the cutting oils described herein, in general the oil is one having a Saybolt Universal viscosity at 100 F. in the range of from 40 to about 500 seconds and an A.P.I. gravity of 15 to 36. However, in preparing the new compositions, it is preferred to use one having a viscosity range of 50-350 seconds and a gravity range of l8-36. Correspondingly, with corrosive cutting oils having a sulfurized mineral oil base, it is preferred that the base oil contain from about 0.1 to about 5% by weight of loosely bound" sulfur and be one prepared by sulfurizing a mineral oil having a viscosity range of 40- 300 seconds at 100 F. and a gravity range of 18-36.

The concentration of the high metal-content reaction product in the cutting oils of this invention, is such as to improve the machining efiiciency thereof and can be varied considerably in accordance to the use to which they are put. When the cutting oils are employed as coolants, as well as lubricants and are applied by a circulating pump or the like, the reaction product should ordinarily be present in a concentration of from about 1 percent to about 9 percent by weight. Where the cutting oils are applied to the work and tool by brushing or the like, the reaction product will be present in a concentration of from 10 percent to 20 percent by weight.

The compositions of this invention, therefore, comprise the combination of the following components:

Broad Preferred range, range.

weight weight percent percent Corrosive cutting oils:

(a) Mineral oil 60-98 94 Corrosive extreme pressur agent 1-20 3 Reaction product A 1-20 3 (b) Sulfurized mineral oil cont loosely-bound sulfur -90 94 Reaction product A 1 -20 6 (c) sulfurized mineral 011 containing "loosely-bound" sulfur 60-98 J4 Corrosive extreme pressure agent 1-20 3 Reaction product A l-20 3 Non-corrosive cutting oils:

) Mineral oil 80-93 1:4

N on-corrosive extreme pressure agent... 1-10 3 Reaction product A i-lt) 3 The foregoing concentrations are balanced in order that the cutting oils have the desired combination of properties. That is, if too little, less than about one percent by weight of reaction product is present in the corrosive and noncorrosive cutting oils, the said cutting oils are deficient in certain machining operations such as tapping efiiciency. correspondingly, when too large a concentration of extreme pressure agent and reaction product is used, machining efficiency is lowered. This is illustrated hereinafter by test data.

The compositions of this invention have proven to be advantageous in a number of respects, as is shown by the following tests and test data.

Almen pin test This test is described in Proc. A.P.l., 1932, pages 118- 130.

Tapping efiiciency In the measurement of tapping efficiency of an oil, a series of holes is accurately drilled in a test metal,

namely SAE 1020 hot rolled steel. These holes are subsequently tapped with a series of taps in a drill press equipped with a table, which is free to rotate about the center, being mounted on ball bearings. A torque arm is attached to this floating table and this arm in turn actuates a spring scale so that the actual torque during tapping with the oil being evaluated is measured directly. The same taps used in evaluating the test oil are employed in tapping with a standard reference oil, which has arbitrarily been assigned an efiiciency of 100 percent. The average torque for the test oil is compared to that of the standard and a relative efliciency is calculated on a percentage basis. For example,

Torque with standard reference oil 19.3 Torque with test oil 19.8

Relative efiiciency of test oil This test is described by C. D. Flemming and applicant in Lubrication Engineering, vol. 12, No. 3, May- June 1956, pages 199-203.

Test results correlate well with actual field conditions.

Falex snap test This test is described in Bulletin No. 3, Faville Le Vally Corporation, Chicago, Illinois.

TABLE I NON-CORROSIVE CUTTINGOOIILLS, ADDITIVES IN MINERAL Cone, Tapping Falex Almen Additives pereifisnap, pin,

cent ciency, lbs. p.s.l. wt. percent None 60 1, 000 1, 000 Reaction product A. 3 69 3, 000 4, 000 Non-corrosive sulfurized fat 3 75 2, 750 8, 500 R 1111). .ENFX. g 79 3, 375 17, 500

eac on pro uc Non-corrosive sulfurized fat 3 82 30'000+ Brigzgt stock, 135 secs. g 60 1, 000 2,000

o. Non-corrosive sulfurizcd fat 3 74 750 000 B Non-corrosive sulfurized fat is a sulfurized lard 011 containing 10 percent by weight of sulfur.

b Bright stock is a solvent-refined paraffimc oil having a viscosity of 135 seconds (SUB) at 100 F.

TABLE II OORROSIVE CUTTING OILS, ADDITIVES IN SULFURIZED MINERAL OIL Cone, Tapping Falex Almen Additives pereifisnap, pin,

cent clency, lbs. p.s.1. wt. percent None 90 1, 750 15, 000 Bright stock, 135 secs. 3 93 1, 875 16, 000 Oxidized bright stock plus Ca 3 99 1, 750 30, 000+ Reaction product A.-- 3 100 2, 175 30, 000+ D 6 104 2, 000 30, 000+ Corrosive sulfurized fat 3 104 2, 760 500 Do 6 108 3, 125 20,000 Commercial heavy duty sulfurized-chlorinated cutting oil 1 104 2, 775 30, 000+ Reaction product A 3 Corrosive sulfurizcd fat 3 n5 250 000+ b Identified in Table I.

B Snlfurized mineral oil is a naphthenic oil having a viscosity of 150 secpnds (S.U.S.) at 100 F., suliin-ized to contain one percent of added an or.

Oxidized bright stock plus Ca is an intermediate product formed in the pi lgaration of Reaction Product A; it is the product which is reacted With 2 5.

Corrosive suliurized fat is a sulfurized lard oil containing 15 percent by weight of sulfur. v I

f Commercial heavy duty sulfnrized-clilorinated cutting 011 comprises snliurized mineral oil (c), 5 percent by weight of chlorinated parafiin wax (10 1pei cent chlorine content) and 2 percent by weight of hydroabietyl a co As mentioned above, the reaction products and the extreme pressure agents of the new compositions are used 6 in proper concentrations in order to obtain the desired results. This is illustrated in Table III below:

TABLE III CORROSIVE CUTTING OILS, ADDITIVES IN SULFURIZED MINERAL OIL Reaction Conc., Corrosive Cone, Tapping product wt. sulfurized wt. etficiency,

A percent fat 8 percent percent I 6 111 v 1 v 6 113 M 3 6 115 v 6 6 110 e Identified in Table II.

In addition the foregoing test data, one experimental corrosive cutting oil has been tested extensively for pipe threading in a commercial pipe shop. The experimental oil has outperformed a black pipe threading oil which had been used commercially for many years with success. Very little wear of the threading tool (chaser) resulted. The experimental oil has been used on many sizes of pipe, ranging from /2 inch to 2 inch, and on many types of pipe, such as galvanized, black iron, malleable iron and brass. The experimental oil comprises: 94 percent by weight of sulfurized mineral oil, 3 percent of Reaction Product A and 3 percent of corrosive sulfurized fat. The sulfurized mineral oil and sulfurized fat are the same as those identified above in Table II.

The same experimental oil used in pipe threading, was used in tapping of stainless steel (type 321). High speed steel taps (2 inch) were used. With this oil, tapping speeds five to ten times the speeds recommended by the tool manufacturer were realized. At the end of one months operation with the oil, there was no wear on the tool. In a three week test involving thread grinding of inch-20 high speed steel taps, the experimental oil was found to be at least equivalent to more expensive connnercial oils in regard to finish of the tap and low grinding wheel wear. The experimental oil was superior, however, in that no foaming thereof occurred during use, whereas some other oils foamed.

I claim:

1. Cutting oil composition consisting essentially of about 94. percent by weight of mineral oil, about 3 percent by weight of (A) a sulfurized lard oil containing about 15 percent by weight of sulfur, and about 3 percent by weight of (B) an oil-soluble, phosphorus-, sulfurand calcium-containing oxidized hydrocarbon reac-- tion pro-duct produced by the method which comprises the steps of: (1) forming a mixture comprising (a) a petroleurn oil having a molecular weight of from: about 200 to 1000 and which is selected from the group consisting of aliphatic hydrocarbons and aromatic hydrocarbons having at least one nuclear hydrogen atom substituted by an aliphatic radical to provide a total of at least 8 aliphatic carbon atoms per molecule therein, and mixtures thereof, and (b) from about 0.5 percent to about 25 percent, based on the weight of said petroleum oil, of calcium hydroxide; (2) contacting said mixture with air at a temperature of from about C.to about 325 C. to eifect oxidation of said petroleum oil and reaction of said calcium. hydroxide with the oxidized petro leurn oil; (3) continuing the oxidation for a time sufficient to incorporate from about 0.05 percent to about 3.0 percent by weight, of calcium into the oxidized petroleum oil; (4) reacting the product from (3 with from about 5 percent to about 20 percent by weight, based on the weight of the petroleum oil charged in (l), of P 3 at a temperature of from about 75 C. to about 150 C. to form a phosphorus-, sulfurand calciumcontaining product; (5) providing a mixture ofthe reaction product from (4) with from about 2 percent to about 25 percent by weight, based on the petroleum oil charged in 1), of calcium hydroxide, and water, at a temperature below the boiling point of water; (6) substantially completely dehydrating the mixture formed in (5); and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

2. Cutting oil composition consisting essentially of a sulfurized mineral oil containing from about 0.1 to about 5 percent by weight of sulfur, in loosely-bound form adapted to effect a substantial discoloration of a copper strip when said strip is immersed in the composition for three hours at 212 F., and having incorporated therein from about 1 to about 20 percent by weight of the oil soluble, phosphorus-, sulfurand calcium-containing reaction product defined as (B) in claim 1.

3. Cutting oil composition consisting essentially of about 94 percent by weight of a sulfurized mineral oil containing about one percent by weight of sulfur, in loosely-bound form adapted to effect a substantial discoloration of a copper strip when said strip is immersed in the composition for three hours at 212 F., and having incorporated therein about 3 percent by weight of (A) a sulfurized lard oil containing about percent by weight of sulfur, and about 3 percent by weight of (B) an oilsoluble, phosphorus-, sulfurand calcium-containing oxidized hydrocarbon reaction product produced by the method which comprises the steps of: (1) forming a mixture comprising (a) a petroleum oil having a molecular weight of from about 200 to 1000 and which is selected from the group consisting of aliphatic hydrocar hens and aromatic hydrocarbons having at least one nuclear hydrogen atom substituted by an aliphatic radical to provide a total of at least 8 aliphatic carbon atoms per molecule therein, and mixtures thereof, and (b) from about 0.5 percent to about 25 percent, based on the weight of said petroleum oil. of calcium hydroxide; (2) contacting said mixture with air at a temperature of from about 125 C. to about 325 C. to effect oxidation of said petroleum oil and reaction of said calcium hydroxide with the oxidized petroleum oil; (3) continuing the oxidation for a time sufficient to incorporate from about 0.05 percent to about 3.0 percent by weight, of calcium into the oxidized petroleum oil; (4) reacting the product from (3) with from about 5 percent to about percent by Weight, based on the weight of the petroleum oil charged in (l), of P 8 at a temperature of from about 75 C. to about 150 C. to form a phosphorus-, sulfurand calcium-containing product; (5) pro viding a mixture of the reaction product from (4) with from about 2 percent to about percent by weight, based on the petroleum oil charged in 1), of calcium hydroxide, and water, at a temperature below the boiling point of water; (6) substantially completely dehydrating the mixture formed in (5); and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

4. Cutting oil composition consisting essentially of mineral oil having incorporated therein from about 1 to about 20 percent by weight of (A) an oil-soluble, sulfurcontaining, non-corrosive organic film strength agent selected from the group consisting of animal, marine, and vegetable oils, each containing about 1 to 10 percent by weight of sulfur in firmly bound form adapted to effect no substantial discoloration of a copper strip when said strip is immersed in the composition for three hours at 212 F., and from about 1 to about 20 percent by weight of (B) the oil-soluble, phosphorus-, sulfurand calciumcontaining reaction product defined as (B) in claim 1.

5. Cutting oil composition consisting essentially of a sulfurized mineral oil containing from about 0.1 to about 5 percent by weight sulfur, in loosely-bound form adapted to effect a substantial discoloration of a copper strip when said strip is immersed in the composition for three hours at 212 F., and having incorporated therein from about 1 to about 20 percent by weight of the oil-soluble, phosphorus-, sulfurand calcium-containing reaction product defined as (B) in claim 1, and from about 1 to about 20 percent by weight of an oil-soluble, corrosive extreme pressure agent selected from the group consisting of a parafi'inic oil having a viscosity of about 40 to 300 seconds (SUS) at F., and sulfurized to contain between about 0.1 and about 5 percent of sulfur, a naphthenic oil having a viscosity of about 40 to 300 seconds (SUS) at 100 F. and sulfurized to contain between about 0.1 and about 5 percent of sulfur, an animal oil containing about 12 to about 20 percent of sulfur, a marine oil containing about 12 to about 20 percent of sulfur and a vegetable oil containing about 12 to about 20 percent of sulfur.

6. Cutting oil compositon as defined by claim 5 wherein the extreme pressure agent is a sulfurized sperm oil containing about 15 percent by weight of sulfur.

7. Cutting oil composition as defined by claim 5 wherein the extreme pressure agent is a sulfurized lard oil containing about 15 percent by weight of sulfur.

8. Cutting oil composition consisting essentially of about 94 percent by weight of a sulfurized mineral oil containing about 1 percent by weight of sulfur, in loosely-bound form adapted to effect a substantial discoloration of a copper strip when said strip is immersed in the composition for three hours at 212 F., and having incorporated therein about 6 percent by weight of (B) an oil-soluble, ph0sphorus-, sulfurand calcium-containing oxidized hydrocarbon reaction product produced by the method which comprises the steps of: (l) forming a mixture comprising (a) a petroleum oil having a mo lecular weight of from about 200 to 1000 and which is selected from the group consisting of aliphatic hydrocarbons and aromatic hydrocarbons having at least one nuclear hydrogen atom substituted by an aliphatic radical to provide a total of at least 8 aliphatic carbon atoms per molecule therein, and mixtures thereof, and (b) from about 0.5 percent to about 25 percent, based on the weight of said petroleum oil, of calcium hydroxide; (2) contacting said mixture with air at a temperature of from about C. to about 325 C. to effect oxidation of said petroleum oil and reaction of said calcium hydroxide with the oxidized petroleum oil; 3) continuing the oxidation for a time sufficient to incorporate from about 0.05 percent to about 3.0 percent by weight,-

of calcium into the oxidized petroleum oil; (4) reacting the product from 3) with from about 5 percent to about 20 percent by weight, based on the weight of the petroleum oil charged in (l), of P 8 at a temperature of from about 75 C. to about C. to form a phosphorus-, and sulfurand calcium-containing product; (5) providing a mixture of the reaction product from (4) with from about 2 percent to about 25 percent by weight, based on the petroleum oil charged in (1), of calcium hydroxide, and water, at a temperature below the boiling point of water; (6) substantially completely dehydrating the mixture formed in (5); and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

9. Cutting oil composition consisting essentially of about 94 percent by weight of a mineral oil and having incorporated therein about 3 percent by weight of (A) a non-corrosive, sulfurized lard oil containing about 10 percent by weight of sulfur and adapted to effect no substantial discoloration of a copper strip when said strip is immersed in the composition for 3 hours at 212 F., and about 3 percent by weight of (B) an oil-soluble, phosphorus-, sulfurand calcium-containing oxidized hydrocarbon reaction product produced by the method which comprises the steps of: (1) forming a mixture comprising (a) a petroleum oil having a molecular weight of from about 200 to 1000 and which is selected from the group consisting of aliphatic hydrocarbons and aromatic hydrocarbons having at least one nuclear hydrogen atom substituted by an aliphatic radical to provide a total of at least 8 aliphatic carbon atoms per molecule therein, and mixtures thereof, and (b) from about 0.5 percent to about 25 percent, based on the weight of said petroleum oil, of calcium hydroxide; (2) contacting said mixture with air at a temperature of from about 125 C. to about 325 C. to effect oxidation of said petroleum oil and reaction of said calcium hydroxide with the oxidized petroleum oil; (3) continuing the oxidation for a time sufiicient to incorporate from about 0.05 percent to about 3.0 percent by weight, of calcium into the oxidized petroleum oil; (4) reacting the product from (3) with from about 5 percent to about 20 percent by weight, based on the weight of the petroleum oil charged in (1), of P 3 at a temperature of from about 75 C. to about 150 C. to form a phosphorus, sulfurand calcium-containing product; (5) providing a mixture of the reaction product from (4) with from about 2 percent to about 25 percent by weight, based on the petroleum oil charged in (1), of calcium hydroxide, and water, at a temperature below the boiling point of water; (6) substantially completely dehydrating the mixture formed in (5); and (7) subjecting the dehydrated mixture to filtration to remove insolubles therefrom.

References Cited in the file of this patent UNITED STATES PATENTS 2,631,129 Waugh Mar. 10, 1953 2,773,861 Musselman Dec. 11, 1956 2,830,949 Berger et al. Apr. 15', 1958 2,864,846 Gragson Dec. 16, 1958

Claims

1. CUTTING OIL COMPOSITION CONSISTING ESSENTIALLY OF ABOUT 94 PERCENT BY WEIGHT OF MINERAL OIL, ABOUT 3 PERCENT BY WEIGHT OF (A) A SULFURIZED LARD OIL CONTAINING ABOUT 15 PERCENT BY WEIGHT OF SULFUR, AND ABOUT 3 PERCENT BY WEIGHT OF (B) AN OIL-SOLUBLE, PHOSPHORUS-, SULFUR- AND CALCIUM-CONTAINING OXIDIZED HYDROCARBON REACTION PRODUCT PRODUCED BY THE METHOD WHICH COMPRISES THE STEPS OF: (1) FORMING A MIXTURE COMPRISING (A) A PETROLEUM OIL HAVING A MOLECULAR WEIGHT OF FROM ABOUT 200 TO 1000 AND WHICH IS SELECTED FROM THE GROUP CONSISTING OF ALIPHATIC HYDROCARBONS AND AROMATIC HYDROCARBONS HAVING AT LEAST ONE NUCLEAR HYDROGEN ATOM SUBSTITUTED BY AN ALIPHATIC RADICAL TO PROVIDE A TOTAL OF AT LEAST 8 ALIPHATIC CARBON ATOMS PER MOLECULE THEREIN, AND MIXTURES THEREOF, AND (B) FROM ABOUT 0.5 PERCENT TO ABOUT 25 PERCENT, BASED ON THE WEIGHT OF SAID PETROLEUM OIL, OF CALCIUM HYDROXIDE; (2) CONTACTING SAID MIXTURE WITH AIR AT A TEMPERATURE OF FROM ABOUT 125*C. TO ABOUT 325*C. TO EFFECT OXIDATION OF SAID PETROLEUM OIL AND REACTION OF SAID CALCIUM HYDROXIDE WITH THE OXIDIZED PETROLEUM OIL; (3) CONTINUING THE OXIDATION FOR A TIME SUFFICIENT TO INCORPORATE FROM ABOUT 0.05 PERCENT TO ABOUT 3.0 PERCENT BY WEIGHT, OF CALCIUM INTO THE OXIDIZED PETROLEUM OIL; (4) REACTING THE PRODUCT FROM (3) WITH FROM ABOUT 5 PERCENT TO ABOUT 20 PERCENT BY WEIGHT, BASED ON THE WEIGHT OF THE PETROLEUM OIL CHARGED IN (1), OF P2S5, AT A TEMPERATURE OF FROM ABOUT 75*C. TO ABOUT 150*C. TO FORM A PHOSPHORUS-, SULFUR- AND CALCIUMCONTAINING PRODUCT; (5) PROVIDING A MIXTURE OF THE REACTION PRODUCT FROM (4) WITH FROM ABOUT 2 PERCENT TO ABOUT 25 PERCENT BY WEIGHT, BASED ON THE PETROLEUM OIL CHARGED IN (1), OF CALCIUM HYDROXIDE, AND WATER, AT A TEMPERATURE BELOW THE BOILING POINT OF WATER; (6) SUBSTANTIALLY COMPLETELY DEHYDRATING THE MIXTURE FORMED IN (5), AND (7) SUBJECTING THE DEHYDRATED MIXTURE TO FILTRATION TO REMOVE INSOLUBLES THEREFROM.