US2363511A - Compounded oil - Google Patents

Description

Patented Nov. 28, 1944 COMPOUND 01L Bruce B. Farrlngton and James 0. Clayton,

Berkeley, and Dorr H. Etsler, Albany, Calil., aeeignors to Standard Oil Company of California,

San Francisco, Calii'.,

a corporation or Delaware No Drawing. Application September 15, 1842, Serial No. 458,451

1! Claims. (Cl. 252-39) This invention relates to the improvement of hydrocarbon oils and the like, in particular, mineral lubricating oils.

This application is a continuation-in-part of our copending application Serial No. 322,946, filed in the case of transformer oils and switch oils,

results in the gra'duai formation of acidic oxidation products and the depomtion of sludge. Use of a lubricating oil in the ordinary gasoline engine, as in motor cars, results in a more rapid deterioration of the oil with deposition of sludge and the formation of "varnish" on cylinder walls. Use of a lubricating oil in Diesel engines, which operate at higher temperatures and pressures than ordinary gasoline engines, results in even more rapid deterioration with resultant greater disadvantages. The temperatures and pressures involved in Diesel engine operation, around 400"- 650 F. and 750-1200 pounds per square inch, cause deposition from ordinary lubricating oils on the moving parts of the engine, such as pistons, piston rings and piston ring slots, of carbonaceous matter of such a cementitious character as to cause sticking of piston rings and greatly to reduce the eillciency oi the engine.

It has been found heretofore that some improvement of hydrocarbon oils. especially lubricating oils, can be effected by incorporating therein a small amount of a soap of a fatty acid, such as a sodium, calcium or magnesium soap of butyric, capric, palmitic. stearic or oleic acid. Such soaps, among other things. reduce piston ring sticking in internal combustion engines, especially Diesel engines, apparently by loosening the cementitious deposits described above, or by inhibiting the formation of such deposits, or both. The action of the added soaps, by virtue of the analogy to the common cleansing or detergent action of soaps, came to be known as a "detergent" action and the soap additives came to be known as "detergents."

The use of these soaps or detergents is not,

however, without disadvantage. Among other 60 m things they are corrosive to certain alloy bearings. such as copper-lead and cadmium-silver alloy bearings. which are commonly used in internal combustion engines. 80 destructive are certain of the leave to these alloy bearings that they cannot be used satisfactorily in lubricating oils for internal combustion engines.

It is an object achieved by the present inven tion to provide a valuable class of additives for lubricating oils, transformer and switch oils, and the like.

It is a further object achieved by the present invention to improve the use of soap-like or metal alkyl carboxylate additives in viscous hydrocarbon oils.

It is a still further and a. particular object achieved by the present invention to provide a class of soap-like or metal alkyl carboxylate additives for lubricating oils which are non-corrosive, or substantially less corrosive than prior soap additives, such as calcium stearate, toward alloy bearings.

Other objects achieved by the invention will be apparent from the description and the claims.

We have discovered that substantial advantages result from incorporating in a hydrocarbon oil or the like, especially a hydrocarbon lubricating oil, a polar substituted metal alkyl carboxylate wherein the substituent is of a certain class and is in an alpha, beta or gamma position with respect to a metal alkyl carboxylate group.

The substituents that have been found to be desirable are those substituents containing at least two dissimilar atoms selected from the group consisting or nitrogen, oxygen and sulfur. That is, we add to and use in hydrocarbon oils or the like, alpha, beta or gamma substituted metal alkyl carboxylates, the alpha, beta or gamma substituent being a nitrogenand oxygen-, a nitrogen- 5 and sulfur-, or a sulfurand oxygen-containing radical. Preferably those suimituents are used wherein a nitrogen, oxygen or sulfur atom is directly bonded to the alkyl group of the metal alkyl carboxyiate.

The additives of our invention may also be characterised by the following formulae:

-o-coou wherein H is a metal (or the hydrogen equivalent of a polyvalent metal). the carbon atoms shown attached to CO0]! are aliphatic carbon atoms. and x is a subetituent containing at least two dissimilar elements of the group nitrogen. oxygen and sulfur. The unsatisfied carbon valencies shown may be satisfied by hydrogen or hydrocarbon groups (e. g. alkyl groups) by polar groups (including polar groups of the type represented by X, and/or other polar groups), etc.

It will be apparent that three principal constitutional factors may be varied in the additives of this invention: (1) the nature and amount of the substituent X (2) the nature of the alkyl carboxylic acid which is substituted and whose salt is formed; and (3) the nature of the metal M. These factors are discussed in more detail immediately below.

(1) The substituent X.-'1"he following substituents are illustrative:

Nitroso Sulionyl In the above, R represents hydrogen, hydrocarbon group (alkyl, aryl, etc.), metal, or other atoms or groups. More than one 01 the above or other like substituents may be present in the molecule. and at least one such substituent is present in the alpha, beta or gamma position, as indicated, first preference being given to the alpha position. secnd to the beta position and third to the gamma position. As stated. other substituents, including polar substituents. may be present in the alkyl chain of the metal alkyl carboxylate, either in the indicated alpha, beta or gamma position or in positions further removed from the metal alkyl carboxylate group.

Those substituents are preferred which do not hydrolyze readily to produce corrosive acids. However, insofar as certain of the advantages of the metal alkyl carboxylates of the invention are concerned, even those polar substituents which hydrolyze readily to produce corrosive acids are eilective; for example, as long as the hydrolyzable polar group remains attached to the metal alkyl carboxylate, it inhibits corrosion.

(2) The alkyl carboxylic acids-For simplicitys sake, reference is made to the free, unsubstituted acids, and it is to be understood that in the practice of the invention a substituent will be included and a metal salt formed, as indicated hereinabove.

Monoand polybasic acids may be employed, and although open chain acids are preierred, cycloaliphatic acids and aliphatic acids having an aromatic substituent attached to the alkyl chain (preferably removed by three or more carbon atoms from the alkyl carboxyl group) are comprehended by the invention. In all cases, however, the acid contains at least one carboxyl group attached to one alkyl or aliphatic carbon atom. By the term alkyl carboxylic acid is meant a carboxylic acid in which a COOH group is attached to an aliphatic carbon atom, and by the term metal alkyl carboxylate" is meant the metal salt of such an acid.

Illustrative of suitable acids are the following:

Acids of the acetic series. such as propionic, butyric, isobutyric, valeric, isovaleric, alphamethylbutyric, pivoalic, caproic; alpha, alphadimethylbutyric; alpha, beta-dimethylbutyric. alpha-ethylbutyric; alpha-ethyl, alpha-methylbutyric, capric, lauric, myristic, palmitic, stearic, etc: also, unsaturated and/or.hydroxy and other substituted members of the same series such as oleic, linoleic. linolenic, licanic, lactic and ricinoleic acids.

Acid: 0! the oxalic acid series, such as malonic. succinic, isosuccinic, glutaric, adipic. etc.; also unsaturated dibasic acids, such as maleic and iumaric; also hydroxy dibasic acids, such as malic, mucic and tartaric.

Tribasic acids, such as citric and agaric acids.

Preference is given to those acids, generally the longer chain alkyl carboxylic acids, whose salts are oil soluble, although the lower acids, even acetic, when properly substituted and used in the form of appropriate metal salts, greatly improve the stability of hydrocarbon oils and inhibit ring sticking and associated phenomena. C10 and higher acids provide adequate oil solubility.

(3) The metal M.Any monoor polyvalent metal capable of forming a sumciently stable salt with the acid chosen may be used. Metals which do not exhibit adverse catalytic activity (such as promoting oxidation) and whose use does not result in excessive wear are preferred. Examples of metals whose salts may be formed and used in accordance with this invention are lithium, sodium, potassium, calcium, barium, strontium, beryllium, magnesium, aluminum, zinc, cadmium, tin, lead, chromium, molybdenum, tungsten, manganese, iron, cobalt. nickel, vanadiumand bismuth. Basic and mixed, as well as normal simple salts may be employed.

Examples of substituted metal alkyl carbonylates contemplated by this invention are sodium. potassium, calcium, barium, aluminum, magnesium, zinc and nickel alpha, beta and gamma nitroso butyrates; the corresponding alpha. beta and gamma nitroso valerates. caproates, caprates, iaurates, palmitates, stearates, myristates, acry lates, crotonates, angelates, oleates, lactates, malonates, succinates, glutarates, adipates, maleates, fumarates, malates and citrates; also the corresponding nitro, cyanato, isocyanato, thiocyanato, isothlocyanato, sulflnyl, sulionyl, thiosulfato, thiolcarboxyl, thionocarboxyl, sulflno. sulfo, sulfato, sulfito, sul! amino and suli'amyl substituted salts (that is, the salts formed by substituting nitro, cyanato, etc., for nitroso).

It will be apparent to one skilled in the art that all of the possible substituents X cannot be introduced into each of the positions alpha, beta and gamma of every alkyl carboxylic acid. Thus the presence in an alkyl carboxylic acid of an alpha. beta or gamma substituent, for example an hydroxyl substituent, may hinder the further substitution of the alpha, beta or gamma position by a certain substituent X oi the present invention. In such case, a diil'erent substituent X within the scope oi the invention, or a different position in the alkyl carboxylic acid, or a different alkyl carboxylic acid may be chosen ior substitution; or the hindering alpha, beta or gamma group, such as an hydroxyl group, may be replaced by the desired substituent.

Various methods of forming the metal salts may be employed, one such method being to form an alkali metal salt (as by neutralizing the acid. or saponifying the corresponding ester, with an alkali metal hydroxide) and using the alkali metal salt per se or converting it into a polyvalent metal salt by adding to an aqueous solution of the alkali metal salt. a water soluble salt of a polyvalent metal, thus producing double decomposition and precipitation oi the polyvalent metal salt.

The substituted metal alkyl carboxylates of this matter at the conclusion of each test, were also measured. The results of the test are set forth in Table I below, the additives referred to having been used in the amount of 0.5% by weight based detergent eflect, unaccompanied by corrosion or 5 on the oil:

Table I Fresh all Used oil Ou-Pb strip Cd-Ag strip viscosity viscosity Neu- ASTM no htha on Additive zation mgolw 24 4s 72 24 4s 72 100 210 100 210 jf' bles hrs. hrs. hrs. hrs. hrs. hrs. F. F. r. F. 6

None 0. 8 l. 6 5. 5 0. 0. 0 0. O 632 57. 0 1, 041 66. 6 2. 00 109 cabutyl'atuvflnnnnv 3.9 13.3 37.4 0.0 15.5 45.8 628 57.1 Ca 2-ethy1 butyrate 2. 44.0 117. 0 0.0 17.0 47.1 632 57. 0 1, 442 76. 6 4. 97 1B9 Calsurate 14.2 67.2 97.9 12.4 16.3 15.7 630 57.3 1,148 70.1 4.49 143 Cs palmitate 47. 3 125. 0 106. 4 9. 5 38. 2 90. 2 632 67. 0 1 361 75. 5 3. 07 221 Ca steal-ate 84. 4 152. 5 5'08. 1 0. 6 34. B 82. 0 653 57. 5 1, 340 75. 0 4. 02 248 Ca gamma-oximino valeratc +0. 1 0. 0 +0. 3 0.0 0. 0 0. 2 630 57. 0 40 62. 5 l. 02 72 Ba thiosulfatoacetate 0. 0 0. l 0. 3 il. 0 0. U 0. 0 680 57. 0 847 62. 6 l. 05 I4 Ca alpha-thiocyarmtopropionate. 0.5 0. 7 (1.6 0.0 0.0 0. l 63l 57.0 878 63. 6 3.05 39 C8 alpha-nitratopm innate 0. 3 i]. 5 1. 0 0. l D. 3 0. 4 635 57. 3 918 64. 1 2. 06 70 Ca alpha-hydroxam no butyrate. 1.0 0. 0 l. 4 0.0 +0. 1 +0. 2 630 57. l 809 61. 5 0. 48 18 C8 beta-nitropropionate. 1.0 1. 0 1. 5 0.0 0. 0 +0. 2 631 57. 2 1. 111 69. 1 3. 61 201 Ba succinamste 0. 2 0. 2 0. 3 0. 0 0. 0 0. 0 630 57. 0 800 61. 6 2. 85 14 accompanied by relatively little corrosion of hard alloy bearings. This contrasts with excessive corrosion of similar bearings when prior art soaps. such as calcium stearate and calcium naphthenate are used. Also, used oil inspections fsuch as increase in viscosity, increase in neutralization number. and increase in naphtha insoluble matter in the used oil) are benefited by the presence of small amounts of the substituted metal alkyi carboxylates of the invention, or at least are not as adversely affected as by the commoner soaps and unsubstituted metal aikyl carboxylates. Moreover, the metal alkylcarboxylates of the invention render oils more stable toward oxidation than the ordinary soaps. and they produce still other advantageous efiects.

The following specific examples will show how a number 01' properties of hydrocarbon oils are benefited by. and will provide a comparison for judging the relative utility of. the substituted metal alkyl carboxylates of the invention.

Example I.A base oil (an SAE 30 blend of 70% Western acid treated naphthenic base oil and 30% Western paraflinic base oil) was tested.

with and without the presence of metal alkyl carboxylate additives. to determine its corrosiveness to various alloys of the type used in bearings 01' internal combustion engines. The Strip corrosion test" was employed in these determinations. this test being as follows:

'I'hin sheets of the indicated bearing metals were cut into strips (Copper-lead, 1%" x 1%" J: Jr": cadmium-silver, x 1%" x 1 and these strips were immersed in the exemplified oils carried in 2" x 20 glass test tubes; these test tubes were carried in an oil bath maintained at 300 F. .tl" F. Each test tube contained approximately 300 cc. of oil, and air was bubbled through each tub at the rate of 10 liters per hour. At the end of each of three 24-hour periods. the strips were removed from the oils,

washed with petroleum ether and carefully wiped with a soft cotton cloth; weight losses of the strips were measured in connection with the weight of each individual strip. The duration of the tests was 'l2 hours, and the weight losses tabulated below are those found at the end of each 24-hour period.

The increase in viscosity of the oil, the neutralization number or the oil at the conclusion of each test. and th amount of naphtha insoluble Example II.-Oi1 was placed in a beaker in contact with air, maintained at a given temperature, and protected against drafts until darkening due to oxidation had occurred. A sample of the original oil was placed in a glass cell 50 mm. square by 7 mm. thick, and an equal sample 01' the exposed oil was placed in a second similar glass cell. The glass cells were placed equidistant from an electric light. The light that passed through each glass cell was caused to impinge on a photoelectric cell. The two photoelectric cells were mounted in two arms of a Wheatstone bridge. The difference in light transmissions, caused by the different colors or the oils, was thus registered on the Wheatstone bridge. The readings of the bridge were calibrated against the standard ASTM color numbers, and from this the readings of the bridge could be converted into ASTM color numbers (Method D-34T).

A base oil (Western parafllnlc SAE 30) and the same base 011 plus 0.5% by weight of inhibitor were tested, various substituted and unsubstituted metal alkyl carboxylates being used as the inhibitor. The results are set forth in Table II below:

The substituted metal alkyl carboxylates ot the invention may be advantageously added to any hydrocarbon oil or lubricating oil, such as the more viscous distillates and residues from petroleum oil, viscous olefin polymers, and viscous oils derived from oxides of carbon or other forms 01' carbon by hydrogenation, and they may be added with advantage to of any the newer synthetic lubricants, such as. amyl naphthalene. The additives of our invention may be used in viscous hydrocarbon oils ranging in viscosity from about 60 SSU or lower at 100 1". to SSU or higher at 210' 1". The metal alkyl carboxylate may be used, in the finished oil, in amounts ransins from 0.1% oriess to 10% or more by weight based on the finished oil, but preferably it is used in amounts of about 0.1 to usually 0.5 to 2%. Concentrates may be prepared containing more than and up to 50% or more of the metal alkyl carboxylate of the invention, alone or tosether with another additive or other additives. and the concentrate may be diluted with more oil when it is desired to produce the finished oil.

The substituted metal alkyl carboulates oi the invention, as is clear from the examples, are multifunctional in character, and an oil containin: one or more of the additives of this invention is improved in several respects. However, the additives or the invention may be advantageously combined in hydrocarbon oils with one or more other additives, such as other antioxidants or corrosion inhibitors, other detergents or anti-ring sticking agents, pour point inhibitors, viscosity and viscosity index improvement agents, oiliness. wear, and dim strength agents, etc. Specifically. the additives of this invention may be used in mineral or hydrocarbon oils in combination with any one or more or the following:

(1) Unsubstituted or corrosive carboxylate salts such as the calcium, barium and aluminum salts of lauric, palmitic, stearic, arachidic, naphthenic, phenyi stearic, benzal stearic; dihydroabietic, oleic, linoleic and alkylated aromatic acids; also various polar substituted metal carboxylates, such as metal salts or chloro stearic, hydroxy stearic, licanic, cetyl hydroxybenzoic, mercaptostearic, cetyl tartaric, cetyl cystine and dcdecyl aminobenzoic acids.

(2) Metal phenates such as the calcium, barium and aluminum salts or cetyl phenol, cetyi chlorphenoi and cetyl thiophenol.

(3) Metal salts oi organo-substituted 0117- and thio-acids oi phosphorus, such as calcium cetyl phosphate, aluminum lauryi phosphate and calcium cetyl phenyl phosphate. i

(4) Carboxylate esters having an alkyl hydroiw substituent (an hydroiw substituent attached to an alkyl carbon atom) near a, carbonyl group of the ester, such as the methyl, ethyl, propyl, butyi, amyl, hexyl, heptyl, octyl, nonyl, lauryl, dodecyl, tetradecyL'cetyl and octadecyl esters of alpha, beta or gamma hydro'xy propionic acid, and the corresponding esters of alpha, beta or gamma hydroxy butyri valeric, caproic, enanthic, caprylic, capric, lauric. myrlstic, palmitic, stearic, and arachidic acids, as well as thecorre aizisding esters of tartonic, tartaric and citric The structural formulae and preparation of typical additives capable of use in accordance with this invention are given below:

Calcium oammo-orimino tolerate The structural formula o! this substance is as follows:

added to this solution. The solution is then trade slightly alkaline with No.03 and allowed to stand over night. It is then acidified with suliuricacid and extracted with ethyl ether. The ether is evaporated and the residue or acid is dissolved a,ses,su

and the solution oi calcium gamma-oximino valerateisevaporatedtodrynesstorecoverthedesired calcium salt as residue.

Barium thtosulldto acetate The structural formula 01' this substance is I! follows:

(BaO:CH:.COO) Ba 19 grams of chioro acetic acid are dissolved in 100 cc. of water and the solution is neutralized with a saturated solution oi 10.0 grams of sodium carbonate. 50.3 grams of. sodium thiosuiiate pentahydrate is added to the neutralized solution and the solution isevaporated to about one-half 0! its original volume. The barium salt is then precipitated by adding barium choiide and is illtered 0i! and dried.

Calcium alpha-tniocvonotopropionate The structural formula of this substance is as follows:

CHnCECOO A Ca Calcium olpho-nitrotopropionate The structural formula of this substance has follows:

CH|.CH.COO i NO: 2

, Calcium olpho-hydrozominobittilrote The structural formula or this substance is as follows:

(CHaGHpCBflOO) HOE 2 14.2 grams of metallic sodium are dissolved in 200cc. oi absolute alcohol and to the rcsultinl a0 iution a solution 0! 43 gramsoi hydroxylamine hydrochloride in 200cc. of absolute alcohol is added. 21.8 grams of crotonic acid are dissolved in 100 cc.

, of alcohol and the solution is added to the above in naiand neutralized with calcium hydroxide rs solution and the mixture is allowed to stand for three days at room temperature. The alcohol is then evaporated oil and the viscous residue is extracted with hot alcohol. The hot alcohol solution is neutralisedwith a slurry of lime and the solution or calcium-salts is evaporated to dryness. The residue isthedesiredcalcium alphahydroaaniino butyrate.

aseasn Calcium beta-nitropropionate The structural formula of this substance is as follows:

(omcmcrncoo) 2C8 vacuum. Excess calcium hydroxide is added and the excess removed by treating with carbon dioxide and filtering oil the calcium carbonate. The filtered solution is evaporated to dryness.

Barium succinamate The structural formula is as follows:

(H2N.CO.CH2.CH2.COO) :Ba

19.8 grams of succinimide are dissolved in water and a solution of 31.6 grams of barium hydroxide octahydrate are added. The solution is evaporated to dryness.

Calcium hydantoate The structural formula is:

(NH2.CO.NH.CH2.COO) :Ca

grams of glycine are mixed with 12 grams of urea and the mixture is heated on a steam plate over night. Excess barium hydroxide solution is then added to the mixture and it is heated further until no odor of ammonia is noticeable. The excess urea is thus destroyed and barium hydantoate is formed. The excess barium hydroxide is precipitated with carbon dioxide and the resulting barium carbonate is removed by liltration. A silver nitrate solution is added to the solution of barium hydantoate, causing precipitation of insoluble silver hydantoate. This is filtered ofi, washed with cold water and suspended in water. Hydrogen sulfide is passed through the suspended salt causing precipitation of silver sulfide which is then removed by filtration. The filtrate is evaporated to asyrupy consistency. and allowed to crystallize. The crystals are filtered. washed and dissolved in water and neutralized with calcium hydroxide.

The formula (OCN) as used in the claims is inclusive of the normal and isocyanate radicals and the formula (SCN) as used in the claims is infiuslve of the normal and isothiocyanate radica We claim:

1. A composition of matter, comprising a major proportion of hydrocarbon oil and a small amount, not less than about 0.1% by weight based on finished oil, of a polyvalent metal alkyl carboxylate substituted on an alpha, beta or gamma alkyl carbon atom with respect to a metal alkyl carboxylate group by a substituent containing at least two dissimilar elements selected from the group consisting of nitrogen, sulfur and oxygen.

2. A composition of matter, comprising a major proportion of an oil of lubricating viscosity and a small amount, not less than about 0.1% by weight based on finished oil, of a polyvalent metal alkyl carboxylate substituted on an alpha, beta or gamma alkyl carbon atom with respect toa metal alkyl carboxylate group by a substituent containing at least two dissimilar elements selected from the group consisting of nitrogen, oxygen and sulfur, said substituent being attached to ll said alkyl carbon atom through one of said elements.

3. The composition of claim 2, wherein said 4 substituent contains .nitrogen and sulfur.

4. The composition of claim 2, wherein said substituent contains nitrogen and oxygen.

5. The composition of claim 2, wherein said substituent contains sulfur and oxygen.

6. The composition of claim 2, wherein the metal alkyl carboxylate is an alkaline earth metal allcyl carboxylate.

7. A composition of matter, comprising a major proportion of a hydrocarbon oil of lubricating viscosity and a small amount, sufficient to improve the oil, of an oil-soluble polyvalent metal alkyl carboxylate substituted on an alpha, beta or gamma alkyl carbon atom with respect to a metal alkyl carboxylate group by a radical derivable from. an oxy-acid of nitrogen.

8. A composition of matter, comprising a major proportion of a hydrocarbon oil of lubricating viscosity and a small amount, sufficient to improve the oil, of an oil-soluble polyvalent metal alkyl carboxylate substituted on an alpha, beta or gamma, alkyl carbon atom with respect to a metal alkyl carboxylate group by a radical derivable from an oxy-acid of sulfur.

9. A'lubricating oil comprising a hydrocarbon oil of lubricating viscosity and a small amount,

sulficient to improve the oil as a lubricant, of an carbon atom with respect to a metal alkyl carboxylate group by a substituent lravlng the formula (OCN).

10. A petroleum lubricating oil comprising about 0.1 to 5 per cent by weight based on finished oil of a polyvalent metal salt of a fatty acid containing not less than ten carbon atoms and substituted on an alpha, beta or gamma alkyl carbon atom with respect to the metal carboxylate group by a substituent containing at least two dissimilar elements selected from the group consisting of nitrogen, oxygen and sulfur, said substituent being attached to said alkyl carbon atom through one of said elements.

11. The oil of claim 10, wherein said polyvalent metal is an alkaline earth metal.

12. A composition of matter, comprising a concentrated solution in viscous mineral oil of a metal alkyl carboxylate substituted on an alpha, beta or gamma alkyl carbon atom with respect to a polyvalent metal alkyl carboxylate by a substituent containing at least two dissimilar elements selected from the group consisting of nitrogen, oxygen and sulfur.

13. A composition of matter, comprising a major proportion of a hydrocarbon oil of lubricating viscosity and a small amount, sufficient to improve the oil, of a metal alkyl carboxylate substituted on an alpha, beta or gamma alkyl carbon atom with respect to a metal alkyl carboxylate group by a substituent having the formula (SCN).

14. A lubricating oil comprising a hydrocarbon oil of lubricating viscosity and about 0.1 to 5 per cent by weight based on said lubricating oil of a polyvalent metal salt of an alpha, beta or gamma monothiocarboxyl substituted aliphatic carboxylic acid.

15. A lubricating oil comprising a hydrocarbon oil of lubricating viscosity and about 0.1 to 5 per cent by weight based on said lubricating oil of a polyvalent metal salt of an alpha, beta or gamma thiocyanato substituted aliphatic carboxylic acid.

16. A lubricatina oil comprislns a hydrocarbon k oil'oi lubrlcatinl viscosity and about 0.1 to 5 per cent by welsht based on said lubricatlns oil of a polyvalent metal salt of an alpha, beta or gamma cyanato substituted aliphatic carboxylic acid.

17. A petroleum lubricating 011 comprising a.

small amount of each of a metal salt of a phenol and a metal alkyl carboxylate substituted on an 'aipha, beta or gamma alkyl carbon atom by a substituent containing at least two dissimilar elements selected from the group consisting of nitro gen. oxygen and sulfur, said substituent belnt attached to said alkyl carbon atom through one of said elements, said salt of phenol and sold carboxylate being present in respective amounts and in relative proportions sufllcient to provide a lubricant of enhanced detergency and low corrosivity in the crankcase of an internal ccmbustion engine. 1

1s. The 011 of claim 11, wherein said metal salt CERTIFICATE OF CORRECTI ON Patent Nos 2, 5 65 511 November 28 19141;.

BRUCE B. FARRI NGTON, ET' AL.

It-is' hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 5, seeand column, line 55, claim 12, strike out the word "polyvalent" and insert the same before "metal" in line 51, same claim; and that the said Letters .Patent should be read this correotion therein that the same may confomto the record of the case in the Patent Office.

Signed and sealed this 5th day of June, A. p. 1915.

(Seal) 1 Leslie Frazer Acting Commissioner of Patents.

16. A lubricatina oil comprislns a hydrocarbon k oil'oi lubrlcatinl viscosity and about 0.1 to 5 per cent by welsht based on said lubricatlns oil of a polyvalent metal salt of an alpha, beta or gamma cyanato substituted aliphatic carboxylic acid.

17. A petroleum lubricating 011 comprising a.

small amount of each of a metal salt of a phenol and a metal alkyl carboxylate substituted on an 'aipha, beta or gamma alkyl carbon atom by a substituent containing at least two dissimilar elements selected from the group consisting of nitro gen. oxygen and sulfur, said substituent belnt attached to said alkyl carbon atom through one of said elements, said salt of phenol and sold carboxylate being present in respective amounts and in relative proportions sufllcient to provide a lubricant of enhanced detergency and low corrosivity in the crankcase of an internal ccmbustion engine. 1

1s. The 011 of claim 11, wherein said metal salt CERTIFICATE OF CORRECTI ON Patent Nos 2, 5 65 511 November 28 19141;.

BRUCE B. FARRI NGTON, ET' AL.

It-is' hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 5, seeand column, line 55, claim 12, strike out the word "polyvalent" and insert the same before "metal" in line 51, same claim; and that the said Letters .Patent should be read this correotion therein that the same may confomto the record of the case in the Patent Office.

Signed and sealed this 5th day of June, A. p. 1915.

(Seal) 1 Leslie Frazer Acting Commissioner of Patents.