US2392252A - Lubricant - Google Patents

Description

Patented Jan. 1, 1946 UNITED STATES PATENT OFFICE LUBRICANT tion of Maine No Drawing. Application July 14, 1943.

Serial No. 494,69

Claims.

This invention relates to a lubricating 011 composition having improved characteristics especially with respect to oxidation and corrosion.

In my co-pending application Serial No. 494,689, filed concurrently herewith, issued August 15, 1944, as Patent 2,356,073, I have described and claimed a novel class oi materials resulting from the reaction of an aliphatic alcohol with the condensation product of a terpene, such as present in turpentine, and phosphorus pentasulfide, P255. The turpentine-P285 condensation product is the subject of my co-pending application Serial No. 494,688, also filed concurrently herewith.

I have now discovered that the materials to which my first said application is directed, particularly those prepared by reacting an aliphatic alcohol with a condensation product of turpentine and P235, are especially effective in repressing or inhibiting the deterioration of lubricating oil compositions and the corrosion of metal parts in contact therewith.

I am at present unable definitely to identify by chemical formula either the condensation products of turpentine and P285 or the products resulting from the reaction of said condensation products with the alcohol. For brevity, I shall herein refer to the former as the turpentine- P255 condensation product and to the products resulting from the reaction of said condensation products with the alcohol as my inhibitor.

The characteristics of the inhibitor used in the compounding of the lubricating oil composition of my present invention vary somewhat depending upon the characteristics of the turpentine-P285 condensation product and the nature and proportions of the alcohol used in its preparation. Generally, these compounds are relatively acidic and are highly soluble in mineral oils.

The lubricating oil composition of my present invention may consist solely of the lubricating oil constituent and my inhibitor. However, the inhibitors of my present invention have been found to be compatible with other desirable lubricating oil addends and the inclusion of such other addends, especially addends of the type known as detergents, is within the contemplation of my present invention and constitutes an important aspect thereof.

The inclusion of certain so-called detergents, for instance, in internal combustion engine lubricants, has been found highly advantageous. An especially effective lubricating oil composition for the lubrication of internal combustion engines and the like contemplated by the present invention is one comprising, in addition to the lubricating oil fraction and my inhibitor, a minor proportion of the calcium salt of iso-octyl salicylate, or the calcium salt of capryl salicylate. These calcium salts have been found particularly efiective as detergents in lubricating oil compositions used in internal combustion engines, as more fully described in the patents, 2,347,547 and 2,339,692, issued April 25, 1944, and January 18, 1944, respectively, on applications of Willard L. Finley.

A further highly eflective lubricating oil composition contemplated by my present invention is one comprising, in addition to the lubricating oil constituents and my adden i, a calcium etroleum sulionate, as a detergen' Other detergents which may be used with advantage include the barium phenolate o1 sulfurized diamyl phenol, such as currently marketed under the trade name Aerolube B, metallic phenolates of sulfurized tertiary amyl phenol, such as currently marketed under the trade names "Calcium Paranox" and "Barium Paranox," and various metallic soaps, either basic or neutral, metallic sulfonates, alcoholates and alkoxide and metallic derivatives oi alkylated salicylic acid.

When used in conjunction with these detergents, particularly the calcium salts, including the calcium petroleum suli'onates previously mentioned, these detergents and my inhibitors have been found to complement each other so that the effectiveness of each is promoted. For example, the phosphorus acidity of the inhibitor appears to be neutralized by the calcium, thus minimizing any tendency of the former to promote sludge formation. Further, the tendency of the detergents to promote oxidation of the oil at the termination of its oxidation induction period is also minimized by the presence of my inhibitor. Each of these desirable ends is accomplished without destroying the effectiveness of either the detergent or the inhibitor.

The proportions of the inhibitor used in the compounding of my improved lubricating oil compositions may be varied somewhat but, in any case, only a minor proportion is used. In the absence of a detergent such as previously mentioned, generally satisfactory results have been obtained by using proportions within the range of about 0.05% to about 1% based on the weight of the lubricating oil constituent. In special cases. for example where such calcium salt detergents are present, somewhat higher proportions, say from about 0.25% to about 2%. may be used with advantage. However, these inhibitors are acidic phosphorus derivatives and phosphorus acidity has been found to have a general tendency to promote polymerization and sludge formation in mineral lubricating oils. In internal combustion engine lubricants, where sludge formation must be minimized, the use of the inhibitor in proportions exceeding about 1% by weight, in the absence of detergents such as previously noted, is not generally advisable. However, proportions within the indicated range have not been found to cause noticeable or objectionable sludging under such conditions. In gear lubricants, for example, where polymerization and sludging is less critical, larger proportions of the inhibitor may be employed.

For optimum results, when used in conjunction with one of the previously-noted calcium detergents, the proportion of the inhibitor should not exceed that which will be neutralized by the cal cium salt detergent, for, with an excess of the inhibitor, residual phosphorus acidity will remain with its characteristic tendency to promote sludge formation. The optimum ratio of the inhibitor to the detergent will depend upon the basicity of the detergent and upon the amount of P235 equivalent used in the preparation of the inhibitor and may be determined for any particular set of conditions by simple test.

Various petroleum lubricating oil fractions may be used, for instance solvent-treated Mid-Continent neutrals or a blend of such Mid-Continent neutrals with bright stock or a solvent-refined lubricating oil fraction from a Pennsylvania crude. Characteristics of two such oils which have been used with advantage, and which were used in the compounding of the lubricants hereinafter set forth as illustrative of my invention, appear in the following Table I, in which base oil A is a solvent-treated MidContinent 250 neutral oil and base oil B is a solvent-refined Mid-Continent S. A. E.-30 oil.

Table I Gravity. A. P. l Flash, "F

Viscosity at 100 F. SUS Viscosity at 210 F. BUS...

Viscosity index I I Pour, "F -l0 Carbon residue 0. 009 0. 03

The invention will hereinafter be illustrated by specific examples of my improved lubricating oil composition. Since the characteristics of the inhibitor are to a substantial extent affected by the characteristics of the turpentine-Piss condensation product used in its preparation and the nature and proportions of the alcohol reacted therewith, the illustrations of my lubricating oil compositions will include a description of the preparation of the particular inhibitor used.

In the preparation of the intermediate turpentine-Pass condensation product to be used in preparing my inhibitor, the ratio of turpentine to P18: used is with advantage within the range from approximately 1:1 to about 3 parts of turpentine to 1 part P285. Where ratios higher than I about 3:1 are used, the condensation product has been found to contain considrable unreacted turpentine. Ratios 01' about 3:2 have generally been found to be particularly satisfactory for this purpose.

The reaction of turpentine with P285 is highly exothermic and proceeds spontaneously after being initiated by slight heating. A desirable method of effecting the reaction is to heat the turpentine in a vessel to about 200' l. or slightly higher and then, without further heating, slowly stirring in the phosphorus penta-sulilde in the powdered term. The heat of the reaction is great and, consequently, the addition should be made slowly so as to avoid the possibility of the reaction's becoming uncontrollable. The characteristics of the inhibitor are favorably affected by the use in its preparation of the turpentine- P285 condensation product in the preparation of which th temperature during the mixing was not permitted to exceed about 250 It, although higher temperatures are permissible.

After the addition is completed, it is usually necessary to apply heat externally to complete the reaction. The temperature during this last stage is preferably maintained at about 300 I".. though temperatures of about 200 F. to 400 I". may be employed. This second stage 01' the operation should be continued until all of the P285 is dissolved. The material thus prepared is a viscous liquid at elevated temperatures which solidifies on cooling to room temperature.

The turpentine-Pass condensation products, thus prepared, are, in the absence of excess turpentine, brittle, resinous solids which dissolve readily in lubricating oils or in excess turpentine to form liquids. Such solutions 01' high concentration are relatively viscous. However, the viscosity of the solution decreases rapidly as the proportion of the solvent is increased from 25% to 75%.

In general, my inhibitor may be prepared by adding the alcohol gradually to the turpentine- P285 condensation product prepared as previously described. Such addition is advantageously at a temperature of about 250 F. In reacting the alcohol with the turpentine-Piss condensation product, very little heat is evolved. After the alcohol has been added the mixture is maintained at an elevated temperature, advantageously about 200 F. to 220 F., for about 2 hours with stirring. The nature and proportions of the alcohol added may be varied over a considerable range without loss of the effectiveness of the resulting inhibitor. The optimum proportion of alcohol used is dependent upon the ratio of turpentine to Pass used in the preparation of the intermediate condensation product. Particularly desirable results have been obtained using about 2 moles of P285, 5 moles o1 turpentine and 3 moles of alcohol, assuming the molecular weight of the turpentine to be 136.

In the preparation of the turpentine-P285 condensation product used in preparing the inhibitor, I have found it desirable that no unreacted P285 remain in the product, as in the treatment or the condensation product with the alcohol. any unreacted Pass present has been found to react with the alcohol to form esters or thinphosphorlc acid.

Aliphatic alcohols generally hav been found suitable for use in the preparation of my improved inhlbitor. For example, aliphatic aloohols ranging from methyl to octadecyl alcohol, 1. e. containing from 1 to 18 carbon atoms per molecule, including secondary alcohols of 5 to 8 carbon atoms and branched chain primary alcohols containing 5 to 6 carbon atoms, have been used with advantage. Lubricating oil compositions in which the inhibitor is prepared by reactlug capryl alcohol, i. e. octanol-2, or normal hexyl alcohol or lauryl alcohol with the turpentine-Pass condensation product, have been found to have particularly desirable properties. Generally, aliphatic alcohols having or more carbon atoms per molecule are preferred.

In the preparation of the tUrPentlIle-PaSs condensation product, either steam-distilled wood turpentine or gum spirits may be used. Such turpentine consists mainly of alpha pinene, a iii-cyclic terpene having the empirical formula CisH'is. Pure alpha pinene and other more costly terpenes will react similarly with P285 but, for reasons including economic considerations, I preier to use the more readily availabl turpentines. The turpentine used in the specific examples herein was a technical grade steam-d stilled wood turpentine comprising about 90% alpha pinene.

The following specific examples of inhibitors used in the compounding oi my improved lubricating oil compositions and the procedure by which such inhibitors may be prepared. are given as illustrative of my invention. It will be understood. however, that my invention is not limited to lubricating oil compositions containing the particular inhibitors illustrated.

Exsisrts I In a 8-liter, 3-necked flask equipped with a stirrer, a thermometer and a funnel, there was placed 1360 grams moles) of steam-distilled wood turpentine. The turpentine was heated to about 200' 1"., by means oi an electric heater placed under the flask. The heat was then turned 08, the stirrer started and 888 grams (4 moles) of powdered phosphorus pentasulfide was added portionwise. About 30 to 40 gram portions of the suliide were added at first and, after about half the sulfide was added, the portions were increased to about 100 grams. The temperature was controlled by the rate of addition of the phosphorus pentasulfide so that it did not exceed 250' I. When all the phosphorus pentasulfide had been added and the exothermic reaction had stopped, as shown by a dropping of the temperature, the heater was again turned on and the mixture stirred and heated slowly to 300 F., and maintained at that temperature for about 4 hours. At the end of this period all of the phosphorus pentasulflde was dissolved an the product was a viscous amber-colored liquid. The heater was then turned off and the mixture allowed to cool to 250 F., and, while at this temperature, 780 grams (6 moles) of capryl alcohol (octanol-2) was added slowly over a period of 30 minutes. The heater was again turned on and the temperature held at 200-220 F. for 2 hours.

The resultant product was found by analysis to have an acid number of 71, a. saponification number of 182.9 and to contain 8.07% phosphorus and 20.3% sulfur, each by weight,

Exams: II

In a 5-liter flask, similar to that used in Example I, there was placed 2040 grams moles of steam-distilled wood turpentine. The turpentine was then heated to about 200 F., by means of an electric heater placed under the flask. Thereafter, the heat was turned off and 1332 grams (6 moles) of powdered phosphorus pentasuliide was added portionwise and stirred into the turpentine. The first half 0! the phosphorus pentasuiflde was added in about 50 gram portions and the second half in about -150 m portions. The rate of addition was controlled so that the temperature of the reaction did not exceed 300 F. When the last of the sulfide was added and the heat of the reaction began to subside, the heater was again turned on and the reaction mixture stirred and heated to about 300 F., and maintained at this temperature for about 4 hours while stirring. At the end of this period, the phosphorus pentasulfide was dissolved. The heater was then turned off, the contents oi the flask permitted to cool to 250 R, and, while at this temperature, 1170 grams (9 moles) of capryi alcohol was slowly added. After all the alcohol had been added. the temperature of the mixture was maintained at 200 to 220 F., for about 2 hours.

The product resulting from the above-described procedure was found by analysis to have an acid number oi 64.9, a saponiiication number 0! 156.8 and to contain 8.2% phosphorus and 20.8% suiiur by weight.

Exams!!! 680 grams 5 moles) of turpentine was placed in a 2-liter flask such as previously described and stirred while being heated to 225 F. 444 grams of powdered phosphorus pentasulflde was then added to the turpentine at such a rate that the temperature did not rise about 250 F. After all the sulfide had been added, the temperature of the mixture was raised to 300 F. and maintained at that temperature for about 3 hours, at the end 0! which period all of the phosphorus .pentasulfide was dissolved. The mixture was then permitted to cool to 250 F. and 264 grams of Pentasol," a commercial mixture of amyl alcohols, was added. The temperature was then maintained at 220 F. for an additional hour.

The product was found by analysis to have an acid number of 74.6 and a saponiiication number of 181.1 and to contain 9.23% phosphorus and 21.57% sulfur by weight.

EXAMPLE IV The process of Example III was repeated using 444 grams (2 moles) of P285. 666 grams (4.9 moles) of turpentine and 403 grams (3.1 moles) of capryl alcohol and the resultant product was found by analysis to have an acid number of 71.1 and a saponification number of 138.8 and to contain.

8.04% phosphorus and 20.4% sulfur by weight.

Ensures V A 3-liter, round-bottomed flask, fitted with a stirrer, was charged with 680 grams of turpentine. The turpentine was heated to 200 F., the heating discontinued and 444 grams of .powdered phosphorus pentasulfide was added, with stirring, in portions of about 25 to 30 grams each, and at such a, rate that the temperature did not rise above 250' F. After all oi the phosphorus pentasulflde had been added, the temperature was raised to 300 F., and maintained at that temperature for 3 hours, at the end of which period all of the sulfide was dissolved. Thereafter, the mixture was cooled to 250 F. and 306 grams of normal hexyi alcohol was added and the temperature of the mixture held at about 200 F. for 1 hour.

The product was found by analysis to have an acid number of 74.0 and a saponiflcation number of 172.1 and to contain 8.20% phosphorus and 21.57% sulfur by weight.

Emma

680 grams moles) of steam-distilled wood turpentine was placed in a. 3-liter flask. such as previously described. and heated to 225 F. There was then added 444 grams (2 moles) of powdered phosphorus pentasulfide. in to gram portions. at such a rate as to hold the temperature below 250 F. No external heat was applied during this addition. When all of the phosphorus pentasulflde was added, the mixture was heated to 300 F. and maintained at this temperature for 3 hours. at the end of which period the phosphorus pentasulfide had dissolved. The mixture was then cooled to 250 F.. and 306 grams (3 moles) of 2-ethyl butanol-l was added over a period of 30 minutes with continuous stirring. The temperature was held at about 200 to 220 F. for 1 hour after the addition of the alcohol.

The product was found by analysis to have an acid number of 74.9 and a saponification number of 176.2 and to contain 8.96% phosphorus and 22.1% sulfur by weight.

Exam: VII

340 grams 2.5 moles) of turpentine was heated to 200 F. and 222 grams (1 mole) of powdered phosphorus pentasulfide was added slowly as previously described. After the phosphorus pentasulflde was all dissolved. 2'79 grams (1.5 moles) of "L-orol. a commercial mixture of alcohols made from hydrogenated fatty acid esters from palm oil and containing from 10 to 14 carbon atoms per molecule. was added and the mixture maintained for 1 hour at a temperature of 220 F.

The product was found by analysis to have an acid number of 67.2 and a saponiflcation number of 147.3 and to contain 7.18 phosphorus and 19.80% sulfur by weight.

Exam VIII To a turpentine-P255 condensation product prepared as in Example VII, there was added 405 grams (1.5 moles) of octadecyl alcohol and the mixture maintained at 220 F. for 1 hour. The product was found by analysis to have an acid number of 57.2 and a saponification number of 131.6 and to contain 6.52% phosphorus and H.209; sulfur by weight.

Exmts 1K in a 3-liter flask. such as used in Example I. 1360 grams (10 moles) of turpentine was placed and heated to 200 F. 888 grams (4 moles) of powdered phosphorus pentasulflde was then P slowly added to the heated turpentine under conditions described in Example 1. After the phosphorus pentasulfide was dissolved. 1300 grams (10 moles) of capryl alcohol (octanol-2) was added and the mixture stirred and heated as in Example I. The product was found by analysis to have an acid number of 114.2 and a saponification number of 146.9 and to contain 7.09% phosphorus and 17.4% sulfur, by weight.

Exunm: X

The procedure of Example IX was repeated. substituting methyl alcohol for the capryl alcohol and the product was found by analysis to have an acid number of 100.8 and a saponification number of 213.9 and to contain 10.9% phosphorus and 26.5% sulfur. by weight.

For the purpose of further illustrating my invention and the advantages derived therefrom, I have hereinafter set forth the results of convenaseaaca tional oxygen absorption tests and Chevrolet engine tests as applied to various of my improved lubricating oil compositions.

The advantages of my present invention with respect to oxidation and corrosion characteristics of my improved lubricating oil compositions are illustrated by their mean oxygen absorption rates as compared with the oxygen absorption rate of the base oil and the corrosion losses of bearing metal in contact with the respective lubricants.

For example, by the incorporation of 0.2% of the inhibitor of Example IV, the mean rate of oxygen absorption of the base oil A was reduced from 2.8 to 1.8 cc. per minute. By increasing the proportions of the inhibitor to 0.5%. the mean oxygen absorption rate was reduced from that of the base oil but to a less extent. The mean oxygen absorption rate of the base oil A in the presence of copper-lead bearing metal was 25.6 and, by the addition of 0.5% of the inhibitor of Example IV. the mean oxygen absorption rate was reduced to 2.7 cc. per minute. Further, the corrosion loss of the copper-lead bearing metal in the presence of the base oil was 5.8 milligrams while in the presence of the base oil compounded with 0.5% of the inhibitor of Example IV. no bearing corrosion loss was apparent.

The calciuni lso-octyl sallcylate and calcium capryl salicylate, previously noted as detergents. are themselves effective anti-oxidants over a. conslderable period. However, at the termination of their oxidation induction period, these calcium salts, in the presence of copper-lead bearing metal. have a tendency to act as pro-oxidants. This tendency to act as pro-oxidants upon the termination of a protective period is a characteristic of many of these so-called detergents. One aspect of my invention relates particularly to lubricating oil compositions including such detergents.

By compounding with such lubricating oil compositions a minor proportion of the inhibitor of my present invention, the pro-oxidant characteristics of these detergents. and especially the calcium salt detergents previously noted, following the induction period, is materially repressed and in eiiect the induction period is eliminated or substantially prolonged i. e. the oxygen absorption rate continues to rise gradually over a. considerably prolonged period instead of a marked increase at the end of the induction period. The proportions of the inhibitor required to produce optimum results in this respect depend upon the characteristics of the particular detergent and of the inhibitor employed.

For example, the oxidation induction period of a 1% blend of the calcium salt of iso-octyl salicylate in base oil A was approximately minutes. By the addition of 0.5% of the inhibitor of Example IV, the mean oxygen absorption rate. over a period of 518 minutes, was only 1.9 cc. per minute. the induction period being substantially eliminated. The oxidation induction period of the blend in the presence of copper-lead bearing metal was likewise substantially eliminated by the addition of 0.5% of the inhibitor of Example IV. and the mean rate of oxygen absorption was only 2.6 cc. per minute. The bearing corrosion loss of the blend in the absence of the inhibitor was 11 milligrams but, with 0.5% of the inhibitor included in the composition, no bearing corrosion loss was apparent. When the proportion of the inhibitor was reduced to about 0.3%. very little change in the induction period was observed. However. the bearing metal corrosion loss was L'II aseaass 5 reduced from iimiiligramstoosmilllgramsby the inclusion of only 0.3% of the inhibitor.

Iron naphthenate is known to have strong prooxidant action for mineral oil. I have found that this pro-oxidant action of iron naphthenate is substantially repressed by the lubricating oil composition or my present invention. For example, the presence of iron naphthenate in an amount equivalent to 0.01% FeaO: was neutralized by the presence of 0.5% of this inhibitor, the mean rate of omen absorption being reduced from 45.6 to 3.5 cc. per minute.

The results of other oxidation and corrosion tests of my improved lubricating oil compositions compounded with various inhibitors described herein, as compared with the oxidation and corrosion characteristics of the base oil, are set forth in the following Table II. In these tests no detergent was present. These tests as well as those previously described were carried out at a temperature of 360 F. Copper-lead bearing metal was present in the oil during the respective tests, The identity of the particular inhibitor used has reference to the specific examples of my inhibitor reviously set forth herein. Table II Inhibitor M t r em ra e Test Base 0: absorp; gg g gg No. oil PropnrtiomocJm I m 8 Identity tion. 100 gms. g

per cent A None 25. 6 5.8 A Ex. IV... 0. 6 2. 7 None A Bx. I11...- 0. 2. 5 None A Ex. VI... 0. t 2. 8 None A Ex. V.. 0. 5 2.0 None A Ex. VII-.- 0. 5 4.! None A El. VIIL- 0. 6 B. 4 3.8 A Ex. VIIL. 0. 75 6. 6 None A Ex. X.---. 0. 5 2. l None This base oil A compounded with 1% of the calcium salt of iso-octyl salicylate, previously referred to herein as a detergent, had an oxidation induction period of 107 minutes in the presence of copper-lead bearing metal and the corrosion loss of the bearing was 11 milligrams, as previousis noted. By the addition of various inhibitors or my present invention in proportions as indicated in the following Table III, the oxidation induction periods and corrosion losses were as therein indicated. The identity of the particular inhibitor used has reference to the specific examples of my inhibitors previously set forth herein.

In tests #1 and #2 of Table III, the oxidation induction period was completely eliminated, i. e. the calcium of the detergent was completely deactivated by the inhibitor, and the mean oxygen absorption rates were, respectively, 2.3 cc. per minute and 2.9 cc. per minute. The results of tests #5 and #6 indicated that complete protection against corrosion was not obtained where only 0.5% of the inhibitor was used. However, these tests #5 and #6 were repeated using 0.75% of the respective inhibitors. In test #5, thus repeated, no corrosion loss was apparent while in test #6, thus repeated, the corrosion loss was only 0.1 milligram. In tests #3 to #7 inclusive, though the induction period was not completely eliminated, the rate of oxygen absorption progressively decreased toward the end of the tests indicating that calcium was being deactivated.

Tests of my improved lubricating oil compositions have consistently shown them effectively to inhibit the pro oxidant characteristics of wellknown oxidation catalysts such as iron naphthenate and copper-lead bearing metal as well as that of detergents such as previously noted following their respective induction periods.

The desirable characteristics of my improved lubricating oil compositions also appear from results of tests made in accordance with the procedure of the American Society of Testing Materials, published October 1942 and entitled Proposed method of test for oxidation characteristics of heavy duty crankcase oils, conventionally known as the Chevrolet Engine Tests. These tests were run on the base oil alone and also on lubricating oil compositions of my present invention consisting of such base oil compounded with my inhibitors and various detergents.

Results, representative of such tests, are set forth in the following Table IV. In test #1, the base oil alone was used. The lubricating oil composition used in test #2 was prepared by compounding this same base oil with the indicated proportions of my inhibitor and of the detergent previously identified herein by its trade name Aerolube B. In the compounding of the lubricating oil composition used in test #3, the same base oil was used together with the indicated proportions of my inhibitor and of the detergent previously identified herein as the calcium salt of capryl salicylate. The engine cleanliness rating, analysis of the lubricants at the end of the tests and the corrosion losses per half bearing of copper-lead bearing metal during the tests, were as indicated.

Table IV Test No.-

0. 93 0. 29 14 None out. No 0. 50 0. 28 Brg. metal corrosion loss ..gms-. 0. 124 0. 091

The acid number of the base oil was originally 0.05 and its sulfur content, 0.24%.

From the results of these tests, it appears that though the base oil had a high corrosion rate and a moderately high oil deterioration rate, the lubricating oil compositions prepared therefrom in accordance with my present invention show much lower corrosion losses and oil deterioration rates while the engine cleanliness ratings were not materially changed.

I claim:

1. A lubricating oil composition comprising a petroleum lubricating oil and a proportion effective to retard oxidation of the composition of an inhibitor such as results irom the reaction of a monohydroxy aliphatic alcohol with a condensation product of turpentine and phosphorus pentasulflde.

2. A lubricating oil composition comprising a petroleum lubricating oil and about 0.05% to about 2%. based on the weight of the oil constituent, or an inhibitor such as results from the reaction of a monohydroxy aliphatic alcohol with a condensation product of turpentine and phosphorus pentasulflde.

8. A lubricating oil composition comprising a petroleum lubricating oil and about 0.05 to about 1%, based on the weight of the oil constituent, 01' an inhibitor such as results from the reaction of a mcnchydroxy aliphatic alcohol with a condensation product of turpentine and phosphorus pentasulflde.

4. A lubricating oil composition comprising a petroleum lubricating oil, a calcium salt-oi! an octyl salicylate as a detergent and from about 0.25 to about 2%, based on the weight of the oil constituent, oi an inhibitor such as results from the reaction of a monohydroxy aliphatic alcohol with a condensation product of turpentine and phosphorus pentasulflde.

5. A lubricating oil composition comprising a petroleum lubricating oil and a proportion efi'ective to retard oxidation of the composition of an inhibitor such as results from the reaction of a monohydroxy aliphatic alcohol containing not less than 5 carbon atoms per molecule with a condensation product of turpentine and phosphorus pentasulflde.

6. A lubriicating oil composition comprising a as petroleum lubricating oil. a calcium petroleum sulphonate detergent and a proportion eflective to retard oxidation of the composition 01' an inhibitor such as results from the reaction oi a monohydroxy aliphatic alcohol of not less than 6 carbon atoms per molecule with a condensation product of turpentine and phosphorus pentasulfide.

7. A lubricating oil composition comprising a petroleum lubricating oil and a proportion eflective to retard oxidation or the composition oi an inhibitor such as results from the reaction of capryl alcohol with a condensation product or turpentine and phosphorus pentasulflde.

8. A lubricating oil composition comprising a petroleum lubricating oil and a proportion eilective to retard oxidation of the composition of an inhibitor such as results from the reaction of normal hexyl alcohol with a condensation prodnot 01' turpentine and phosphorus pentasulflde.

9. A lubricating oil composition comprising a petroleum lubricating oil and a proportion eilective to retard oxidation of the composition or an inhibitor such as results from the reaction 0! lauryl alcohol with a-condensation product cl turpentine and phosphorus pentasulfide.

10. A lubricating oil omposition comprising a petroleum lubricating oil, a calcium derivative of alkylated salicylic acid as a detergent, and a proportion, eflective to retard oxidation or the composition, of an inhibitor such as results from the reaction or a monohydroxy aliphatic alcohol of not less than 5 carbon atoms per molecule with a condensation product of turpentine and phosphorus pentasuliide.

ROBERT L. MAY.

CERTIFICATE (F CORRECTION.

Patent No. 2,592,252.

January 1, 1946- ROBERT L. HAY.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 1, second column, line 25, for "alkoxide" read --a1koxides--; page 2, first column, line 71;, for "considrable" read --considerab1e--;

page 6, first column, line 35,

man, line 31, for "about" read -aboveclaim 6, for lubrficatirg" read --1ubrioating--; and second column, line 26, claim for "imposition" read --composition--; and

page 5, second colflint the said Letters Patent should be read with this correction therein that the antenna conform to the record of the case in the Patent Office.v Signed and sealed this 9th day of April, A. o. 19%.

(Seal) Leslie Frazer First Assistant Omissioner of Patents.

inhibitor such as results irom the reaction of a monohydroxy aliphatic alcohol with a condensation product of turpentine and phosphorus pentasulflde.

2. A lubricating oil composition comprising a petroleum lubricating oil and about 0.05% to about 2%. based on the weight of the oil constituent, or an inhibitor such as results from the reaction of a monohydroxy aliphatic alcohol with a condensation product of turpentine and phosphorus pentasulflde.

8. A lubricating oil composition comprising a petroleum lubricating oil and about 0.05 to about 1%, based on the weight of the oil constituent, 01' an inhibitor such as results from the reaction of a mcnchydroxy aliphatic alcohol with a condensation product of turpentine and phosphorus pentasulflde.

4. A lubricating oil composition comprising a petroleum lubricating oil, a calcium salt-oi! an octyl salicylate as a detergent and from about 0.25 to about 2%, based on the weight of the oil constituent, oi an inhibitor such as results from the reaction of a monohydroxy aliphatic alcohol with a condensation product of turpentine and phosphorus pentasulflde.

5. A lubricating oil composition comprising a petroleum lubricating oil and a proportion efi'ective to retard oxidation of the composition of an inhibitor such as results from the reaction of a monohydroxy aliphatic alcohol containing not less than 5 carbon atoms per molecule with a condensation product of turpentine and phosphorus pentasulflde.

6. A lubriicating oil composition comprising a as petroleum lubricating oil. a calcium petroleum sulphonate detergent and a proportion eflective to retard oxidation of the composition 01' an inhibitor such as results from the reaction oi a monohydroxy aliphatic alcohol of not less than 6 carbon atoms per molecule with a condensation product of turpentine and phosphorus pentasulfide.

7. A lubricating oil composition comprising a petroleum lubricating oil and a proportion eflective to retard oxidation or the composition oi an inhibitor such as results from the reaction of capryl alcohol with a condensation product or turpentine and phosphorus pentasulflde.

8. A lubricating oil composition comprising a petroleum lubricating oil and a proportion eilective to retard oxidation of the composition of an inhibitor such as results from the reaction of normal hexyl alcohol with a condensation prodnot 01' turpentine and phosphorus pentasulflde.

9. A lubricating oil composition comprising a petroleum lubricating oil and a proportion eilective to retard oxidation of the composition or an inhibitor such as results from the reaction 0! lauryl alcohol with a-condensation product cl turpentine and phosphorus pentasulfide.

10. A lubricating oil omposition comprising a petroleum lubricating oil, a calcium derivative of alkylated salicylic acid as a detergent, and a proportion, eflective to retard oxidation or the composition, of an inhibitor such as results from the reaction or a monohydroxy aliphatic alcohol of not less than 5 carbon atoms per molecule with a condensation product of turpentine and phosphorus pentasuliide.

ROBERT L. MAY.

CERTIFICATE (F CORRECTION.

Patent No. 2,592,252.

January 1, 1946- ROBERT L. HAY.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 1, second column, line 25, for "alkoxide" read --a1koxides--; page 2, first column, line 71;, for "considrable" read --considerab1e--;

page 6, first column, line 35,

man, line 31, for "about" read -aboveclaim 6, for lubrficatirg" read --1ubrioating--; and second column, line 26, claim for "imposition" read --composition--; and

page 5, second colflint the said Letters Patent should be read with this correction therein that the antenna conform to the record of the case in the Patent Office.v Signed and sealed this 9th day of April, A. o. 19%.

(Seal) Leslie Frazer First Assistant Omissioner of Patents.