US2363513A - Lubricating composition and the like - Google Patents

Description

' Patented Nov. 28, 1944 Bruce ,B. Farrington and James 0. Clayton,

Berkeley, and Dorr H. Etzler, Albany, Calif., assignors to Standard Oil Company of California,

., a corporation of Dela- San Francisco, Calif ware No Drawing.

Application September 15, 1942, Serial No. 458,454

21 Claims. (Cl. 252-32) This invention relates to new and useful compositions and it involves a lubricating composition-comprising a polar substituted metal alkyl carboxylate and an ester of an hydroxy substituted aliphatic carboxylic acid.

In the improvement of mineral lubricating oils, especially for use in internal combustion engines, it has been the object of long sustained research to produce an oil which does not deteriorate rapidly and which does not harmfully affect the engine; for example, an oil which does not cause fouling of pistons, sticking of piston rings and corrosion of susceptible alloy bearings; such as copper-lead and cadmium-silver bearings. Stability toward oxygen is also a desirable attribute of lubricants in general and of cable, switch and transformer oils and the like.

In the history of development of stable lubricents for internal combustion engines, it was found relatively early that certain types of oil are less susceptible to oxidation than others. Thus it was found that parafllnic oils are more stable than naphthenic oils, at least as regards atmospheric oxidation. Parafllnic oils were, therefore, at a premium and the effort was made to refine non-parafllnic oils to produce parafllnic oils. However, with the advent of Diesel and other engines operating at temperatures of 400 to 650 F. under pressures of oxidizing combustion gases of 750 to 1200 pounds per square inch, it was found that, in some respects at least, naphthenic oils are superior; for example, they were found to cause less fouling of the pistons and sticking of piston rings. 1

A marked advance was made in the improvement of mineral oils with respect to maintenance of engine cleanliness and prevention of piston ring sticking, when metal naphthenates, metal phenates and metal salts of fatty acids were advanced as lubricant additives. ,Small amounts of these additives were found greatly to improve mineral lubricating oils with respect to engine cleanliness and piston ring sticking. However, the advent of harder but more easily corrodible alloy bearings such as copper-lead and cadmiumsilver bearings, and a substantial increase in operating temperature, gas pressure and loads of engines made a greater demand upon mineral oil lubricants, a demand not entirely satisfied by the,

then known compounded lubricants.

In various of our copending applications there I are disclosed improvements 'upon the use of metal naphthenates, metal phenates and metal salts of fatty acids in lubricating oils, such improvements relating to the use in oils of various polar substituted metal alkyl carboxylates. As set forth in said applications, improvement resultsfrom the presence of a polar group in the molecule of a metal alkyl carboxylate in close proximity to a metal alkyl carboxylate group. (By alkyl carboxylic acid is meant an acid having a COOI-I group attached toan aliphatic carbon atom, and by metal alkyl carboxyla is meant a metal salt of such an acid; that is, a compound having in its molecule the group inwhichlldisamoncvalventmetalor the hydrogen equivalent of a polyvalent metal, and the carbon atom shown with free valencies is an aliphatic carbon atom, said valencies being satisfied by carbon, hydrogen or other atoms or groups of atoms. This group -COOM is referred to here as a metal alkyl carbomlate group) More specifically, in our copending application Seria1 No. 322,946, filed March 8, 1940, of which the present application is a continuation-inpart, it is disclosed that metal salts of aliphatic of certain polar substituents in positons close to I a metal alkyl carboxylate group, Preferably in the "alpha, beta or gamma position with respect to said group. There is disclosed in said copending application a large number of effective polar substituents.

In two other of our copending applications we have set forth the extension of this discovery to other and particular polar substituted metal alkyl carboxylates. These further applications, of

which the present application is also a continuation-in-part, are as follows: Serial No. 350,054,

filed August 2, 1940, now Patent No. 2,308,502, issued January 19, 1943, Certain oxygen sub-- stituted metal alkyl carboxylates; Serial No. 350.055. filed August 2, 1940, now Patent No. 2,308,503, issued January 19, 1943, Certain sulfur, selenium or tellurium substituted metal alkyl carboxylates.

The polar substituents disclosed in said copending applications, as well as other polar substituents (that is, substituents which are electronegative or electro-positive in character and impart to an otherwise non-polar molecule, such as benzene or methane, a dipole moment) possess, as we have discovered, the property of improving metal alkyl carboxylates as lubricant additives; in particular, the property of detergency in an internal combustion engine unaccompanied by, or

accompanied by relatively little corrosiveness toward susceptible alloy bearings.

We have now found, however, that polar substituted metal alkyl carboxylates can be greatly improved as hydrocarbon oil additives and as constituents of lubricants if they are employed in conjunction with esters of hydroxy substituted aliphatic carboxylic acids.

In a preferred embodiment of the invention, a polar substituted metal alkyl carboxylate and an ester of an hydroxy substituted aliphatic carboxylic acid are employed in relatively small amounts, dispersed in a hydrocarbon or mineral oil of lubricating viscosity.

Another embodiment of the invention includes the use of larger quantities of the said metal alkyl carboxylate and the said hydroxy ester, even to the exclusion of hydrocarbon oil. Thus a grease may be formed in which the polar substituted metal alkyl carboxylate constitutes all or a large part of the soap ingredient, the hydroxy ester, constitutes all or a large part of the oily ingredient, and hydrocarbon oil may be present in greater or lesser quantity or may be entirely absent, as desired.

Still another embodiment of the invention comprises the use of a viscous liquid hydroxy ester, such as amyl citrate, as the effective lubricant, to which is added a relatively small amount of a polar substituted metal alkyl carboxylate as an improvement agent.

A further embodiment of the invention comprises the use of relatively small quantities of a polar substituted metal alkyl carboxylate and of an ester of an hydroxy substituted aliphatic carboxylic acid in a non-hydrocarbon lubricant such as butyl phthalate.

I (X)A-COOM and an ester of an hydroxy substituted aliphatic carboxylic acid, which may be represented as follows:

(HO) BCOOR In both of these formulae there may be a plurality of any one or more of the groups X, COOM, COOR and OH.

In Formula I, M represents a monovalent metal or the hydrogen equivalent of a polyvalent metal, A represents an organic grouping containing an aliphatic carbon atom attached to the group COOM, and X represents a polar group which is attached to an aliphatic carbon atom close to the group COOM and preferably in the alpha,

beta or gamma position with respect to said group.

In Formula II, R represents a hydrocarbon or substituted hydrocarbon group, B represents an organic grouping containing an aliphatic carbon atom attached to the group COOR, and the OH group is attached to an aliphatic carbon atom of the group B, preferably in a position close to the group COOR, as in the alpha, beta or gamma position with respect to said group COOR With further reference to Formula I, the metal M may be any of a number of metals, such as sodium or potassium, but preferably it is a polyvalent metal such as an alkaline earth metal (magnesium, calcium, strontium and barium), aluminum, chromium, cobalt, nickel, lead, manganese, tin or zinc. Preferably a metal is used whose salts tend to be oil soluble and which does not promote oxidation of the oil or increase wear of relatively moving surfaces. The preferred polyvalent metals are the alkaline earth metals and zinc.

Numerous examples are given in application Serial No. 322,946 of the polar group X which is present in the molecule (X) ACOOM. The ethylenic and acetylenic groups are considered as polar groups effective in reducing corrosiveness if present in a position close to the group COOM, whether present in the same carbon chain as the COOM or in a side chain. Substituents X are preferred which are not readily hydrolyzable and do not split off readily to produce corrosive acids. Thus the nitrate (ONO2) sulfate (0-SO3H), and halogen (F, Cl, Br, I) groups are notpreferred, although they may be used, because they tend to hydrolyze and form corrosive acids. Also, substituents which are thermally stable, that is. which do not break down readily at normal or moderately elevated temperatures, are preferred, although in some instances a complex polar substituent will break down into a simpler polar substituent which is effective in modifying and improving the metal alkyl carboxylate.

Following are examples of polar groups that may be employed:

0 O OH Carboxyl C S OH Thionocarboxyl C O S H Thiolcarboxyl -C S S H Dithiocarboxyl O M Metallo-oxyl 0 R1 Orgeno-substltuted hydroxyl (alkoxyl, aroxyl,

cycloalkoxyl, etc.) i S H Mercapto S M Metallo-mercapto S R1 Thio (alkylthio, arylthio, cycloalkylthio, etc.) -S "R; Polythio (alkylpolythio, arylpolythio, cycloalkylpolythio, etc.) Selenium and tellurium analogues of the above mercapto, thio and polythio groups. NR1R Amino =NR Imino NO Nitroso N0z Nitro -ON Oyano NC Isocyano =N 0 R1 Oximino -N R10 R: Hydroxamino N0n Nitrato 0 ON Cyanato -NC 0 Isoeyanato S ON Thiocyanato -NC 8 Isothiocyanato -NRi.SOaRa Sullamino --SO2.NR1R2 Sulfamyl P B1B, Phosphino R, Phospbylene --P O Phosphcroso P 0 a Phospho O-Rz 0 P O Phosphate O-Rq asoaus boxylic acids that may be usedin accordance In the above table of polar groups, M represents a monovalent metal, such as sodium or potasslum, or the, hydrogen equivalent of a polyvalent metalsuch as magnesium, calcium, strontium, barium, zinc or aluminum: Rrand R2 represent the same or different groups selected from the class consisting of hydrogen and hydrocar bon or substituted hydrocarbon groups such as methyl, ethyl, butyhcetyl, phenyl, tolyl, cetylphenyl, chlorphenyl, 'benzyl or naphthyl; and R:

and R4 represent the same or diflerent groups selected from the class consisting of hydrogen,

monovalent metals (such as sodium or potassi um), the hydrogen equivalent of polyvalent metals (such as magnesium, calcium, strontium, barium, zinc or aluminum) and hydrocarbonor substituted hydrocarbon groups (such asgmeth yl, ethyl, butyl, cetyl, phenyl, tolyl,cetylphenyl,

with the invention:

The sodium, potassium, magnesium, calcium,

strontium, barium, zinc, aluminum, chromium, cobalt, lead, nickel, manganese and tin I salts (normahbasic or mixed) of alpha, beta origamma hydroxy substituted acetic, propionic, bu-, tyric, valeric, caproic, heptanoio, caprylic, capric, lauric, myristic,'.palmitic, stearic, arachidic,

oleic, ricinoleic, malonic, succinic,glutaric, adipic, pimelic, andsuberic acids; also the salts of the same metals and the same acids substituted in chlorphenyl, benzyl and naphthyl). In the gIOuDSnR-l, the subscript n is an integergrea'ter than 1. Examples of alkyl, aryl, cycloalkyl and aralkyl groups referred to in the above table in connection with the carboxyl, thlonocarboxyl, thiolcarboxyl and ,dithiocarboxyl derivatives are the methyl, ethyl, butyl, cetyl, phenyl, cetylphenyl, tolyl, chlorphenyl, naphthyl, cyclohexyl. methylcycloheiwl, and benzyl groups. Examples of metals referred to, inconnection with the carboxyl, thionocarboxyl, thiolcarboxyl, and dithiocarboxyl derivatives are sodium, potassium,

magnesium, calcium; strontium, barium, zinc and aluminum. i I V i a The group A of FormulaI above, may be any one of a number ofrgroups, either purely hydrocarbon or substituted hydrocarbon The nature of the group A and its relation to the rest of the molecule is best illustrated by the following list of metal salts of polar substituted alkyl carthe,alpha,[beta or gammaposition by anyof the following groups instead of by an hydroxy group; carboxy, metallo-carboxy, carboxy ,ester, oxyether, thio-ether, seleno-ether, mercapto, mer

captide, amino, phosphino and cyano' groups.

The metal salts of naturally occurring or com monhydroxy substituted carboxy acids, such as lactic, tartaric, citric and mucic acids, constitute excellent additives without further modification,

and greater oil solubility can be imparted thereto by incorporating a long chain alkyl. group in the molecule, as by esterii ying a carboxy group. Also,excellent additivescan be'prepared by con,- densing an olefine with maleic anhydrideand forming a metal alkenyl succinate, and in general metal saltsof aliphatic ,polycarboxylic acids having two carboxy groups separated by not more than three carbon atoms may be used in accordance with the invention. Metal alkyl carboxylates containing more than about 10 carbon atoms are preferred because of their greater oil solubility. i

With further reference to Formula II above,

as stated, the group R represents a hydrocarbon or substituted hydrocarbon group, the group B represents an organic grouping containing an aliphatic carbon atom attached to the group COOR, and the OH group is attached to an aliphatic carbon atom of the group 13, preferably in a position close to the group COOR, as in the alpha, beta or gamma position with respect thereto. Preferably theester (HO)B(COOR) is a neutral ester of a low molecular weight (Crto C6 inclusive) aliphatic alcohol and a low moor gamma hydroxy acetic, propionic, butyric,

valeric, caproic, enanthic, caprylic, capric, lauric, myristic, palmitic, stearic and arachidic acidsjas well as, the corresponding esters of glyceric, tartronic, malic, tartaric, mucic and citric acids.

The polar substituted metal alkyl carboxylates and the, esters of hydroxy substituted aliphatic carboxylic acids maybe used inwidely varying amounts, depending upon the nature of the com position desired. In the preferred embodiment of the invention, where said metal carboxylate and hydroxy ester are employed in relatively small amounts as additives for hydrocarbon oils of lubricating viscosity, these additives may each be employed in amounts ranging from 0.1% or lower to 10% or higher based on the finished oil,

propyl, isopropyl, butyl,

but the metal carboxylate is preferably employed in amounts from about 0.25 to 2% and the hydroxy ester iniamounts from about 0.1 to 2% by weight on the finished oil. In other cases, as where concentrates or greases are desired, or where the hydroxy ester constitutes the effective lubricant, much larger quantities of metal carboxylate or hydroxy ester or both will be used, for example from 10% to 50% each of metal carboxylate and hydroxy ester.

The additives of this invention may be em ployed in various types of oil, such as the more viscous petroleum distillates, petroleum residua, viscous olefin polymers, lubricating oils produced from oxides of carbon or other forms of carbon by hydrogenation, etc., the newer synthetic lubricants such as amyl naphthalene and butyl phthalate, solventrefined petroleum oils, acid refined petroleum oils, aluminum chloride refined, petroleum oils, greases, transformer, switch and cable oils, and the like.

In the first two examples below are set forth data showing the comprehensiveness of our discovery that, polar substituents greatly modify and improve the performance of metal alkyl carboxylates. In the third example are set forth data showing how the performance of polar substituted metal alkyl carboxylates is modified and improved by the employment therewith-of esters of hydroxy substituted aliphatic carboxylic acids.

5 EXAMPLE I I Ring sticking and engine cleanliness I In the tests whose results are summarized in Table I below, a single cylinder Lauson gasoline spark-ignition engine, 2% inch bore and 2 /2 inch stroke, loaded with fan dynamometers, was operated under extremely severe conditions, designed to develop fullythe tendency of the crankcase lubricant to deteriorate with gum formation and piston ring sticking: operation was at 1600 R. P. M.'; engine jacket temperaturewas maintained at 375 F.; crankcase oil temperaturewas maintained at 220 F.; at periods of 15 hours the operations were interrupted and the condition of the piston rings determined. In Table I, the base oil referred to as Western SAE 30 was an acid-refined lube stock of California origin; A. P. I. gravity 21.4"; viscosities at 100 and 210 of 622 seconds and 56.6 seconds, respectively, Saybolt Universal. To this base oil were added the various salts in the amounts indicated, by weight. The base or uncompounded oil referred to as Pennsylvania SAE 30 was a solvent refined stock of Pennsylvania origin,- A. P. I. gravity 28.6; viscosities at 100 and 210 F. of 519 and 66 seconds, respectively, Saybolt Universal.

Table I Exmu: II

Bearing alloy corrosion In the tests whose resultsare summarized in Table II, thin sheets of the indicated bearing metals were cut into strips (copper-lead, it"x 1%" x 3 2"; cadmium-silver /2" x 1%" X 1 5"), 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. -1 F., except where indicated as 325 F. Each test tube contained approximately 300 cc. of oil, and air was bubbled through each tube 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 72 hours, and the weight losses tabulated below are those found at the end of the 72 hour period.

Attention is directed to the fact that in Table II are shown corrosion results with (1) base oil, (2) base oil plus prior art additives (fatty acid, naphthenic acid and phenolic salts) and (3) base oil plus polar substituted metal alkyl carboxylates of the invention. Except for White oil No. 15 (39.0 mgms. corrosion loss with Cu-P-b) the base oil in every case exhibited very low corrosivity. Each base oil when compounded with a metal salt of an unsubstituted fatty acid (with the exception noted below) exhibited greatly'increased corrosion of both Cu-Pb and Cd-Ag strips. The metal naphthenates likewise caused considerable corrosion of both types of bearing metal, though substantially less corrosion of Cd-Ag than caused by Ca stearate. Calcium cetyl phenate caused very little corrosion of the Cd-Ag strip in Western SAE 30 but caused considerablecorrosion-of the Cu-Pb strip. In increasing order of merit, therefore, the prior art additives rank as follows: metal salts of unsubstituted fatty acids meta1 naphthenates metal phenates. In every case, however, the polar substituted metal alkyl carboxylates of the invention exhibited greatlyreduced corrosion compared tothe abovementioned prior art additives,.great reduction in corrosionwas exhibited with both Cu-Pb and Cd-Ag, and in nearly all cases the compounded oil was less corrosive than the base oil.

It will be noted that calcium acetate exhibited low corrosivity, even less than the base oil. However, as shown .by Ca silicato-tetra-acetate, Ba thiosulfatoacetate, Ca glycolate and .Ca cyanoacetate, the polar substituted acetates are even less corrosive than Ca acetate. I

. Hours to Relative cleanliness oi Oil Additive cause ring (sticking Ring slot. Piston Nil Poor Poor.

. 0.28% K cetyl tartrate 0.42% Mg cetyl tartrate at 0.50% Ga cetyl tartrate 0.52% A1 cetyl citrate 0.50% Ga alpha-cetylmalonate 0.50% Ga alpha,cetenylsucclnate Fa1r+ Do. 0.40% Ga cetyl alpha-aminosuccinate 60+ Very good... Very good. Nil 30 Poor. Poor. r

0.50% Ga cetyl tartrate 60+ Gopd Do. 0.63% Ga alpha-hydroxy steal-ate 60+ Fa1r Fain.

Table 11 strength. w re. largenun'iber oi saltsavailable, it is possible to choose a salt which isbest w i 5 for a particular-fuse upon taking into considera. i 'tion factors such as the nature of .the base oil, the 9" .fi l 5 nature of other. compoundingfagents, andfthe Cum) conditions offuse of the compounded oil. The salts of theinventionarenot equally effective in I 1 y every respect. .Some haveparticularly marked s a r of detergent properties, others have particularly 2}? gigl0 markedcorrosion or oxidation inhibiting proper: 11 1 0 119 ties, etc. The metal'of the salt, the polar sub- 5- 3 stitutent and its position, the nature of the car- 01 f 210 013 boxy acid, and the amount in which the salt is g 3%. used all. havean influence upon the final result. .0150 9.11 01315. flEximrLnIII. i

0.50 o h d 1 .11 s 0.3 i i 1 l i atz :f q 1 Combination efiect I i 't fi i 30 blend of refined paraffinic and 3%,? 9m ama ":4 3 naphthenic oils was usedas the base oil. This base 0.33%0'5 alpha hydroxystearate 10.0 12.1 oil, blends of baseoil with 'metal salts of polar g'ff W F "F substituted. alkyl carboxylic acids, and blends of .3 Y base oil with said metal salts andesters of hy- 515%.?e3iitifi tisatitasiYeast: i319 2921 dmxy se r acids, were submitted to Strip Nil A 5.5 .0 corrosion tests as follows i 300 F. corrosion test.--A clean strip of cop- 0. 3.3 +0.4 per-lead bearing metal approximately wide 3- 1%? by 2"long isweighed tothe nearest 0.1 milli- 01 0110 15.7. gram. Approximately 10 grams of steel wool and 8' 3; 22:5 a copper strip are placed in a 2" x 16" test tube 1 C t t 1; and 300 cc. of the oil to be tested are introduced i into the tube. The tube is placed in a bath main- 0.5 B h 0.5 0.3 egt ::F: 0 tained at 300 F. 12 F. The weighed strip of 0 t bearing metal is suspended from a hook on a rod 0.6 B 1511i 1! ta 0.3 0.0 -tg c a propion- 0.5 0.1 about.,3" from the bottom of the rod and-the a 6. 0.5 B in i M M rod is placed in the test tube so that it rests on 5.55.? l gfian i t atop 1.0 0.4 the steel wool. Air isblown through theoil in in 1;? 3;3 the tube at the rate of 30 :5 liters per hour.

1.4 +0.2 The strip is removed at 24 hour intervals, care- +0.2 fully cleaned of oil and weighed and is thenre- +0.0 +0.1, placed in the oil. p 3;:2; 8: 5.131535 3;: 3 325 F. cor osi n test-substantially the same 0.6% Ca a-phosphat pr pi te.. 1.4 technique is employed as in the 300? F. test, the only difierences being as follows: The temperature 3 F.- i of the bath is maintained at 325 F. :2" F.; 400 cc. Besides deterzency (inhibition of ring sticking of oil are used; air is passed through at the rate and maintenance of piston cleanliness) and corof 10:1.5 liters per hour;the steel wool is omitted rosion inhibition, shown by I'ables I and II above, and the rod rests upon the bottom of the tube.

the polar substituted metal alkyl carboxylates of Inthese tests the steel wool and copper strip the invention in many cases exhibit other value catalyze oxidation of i the oil; hence, promote able properties when added to hydrocarbon oils. formation of corrosive substances. 1 such as color stabilization, inhibition or oxida- The results of the corrosion tests are set forth in tion, reduction of wear, and improvement orfllm .Table m below, along with usedoil inspections: i 1 Table III i Corrosion (mgms. lost) Usedoilinspection Oil Additives l i Viscosity Neutral N hth a @3533? i 1 300 F. CORROSION 'rns'r Western Nil 1.2 73.3 24.10 10.0 5.40 s4.

sasao i l I blend. 1 i i i i i Do--- 0. Caootylcitrate 0.3 3.2 10.4 5.0 2.10 1 4 1 Do... 0. Decatylcitram 1.3 4.3 23.1 0.3 3.24 3 1 Do.-. 0. o. ootyl 0.0 41.0 no 4.0 2.00 i 10 Do... 0. Oaoatylcltrate+0. 7%isoamyltartrata 4.0 0.4 13.6 6.8 V2.15 27 110.-. 0. CaostylcltntoHLlflsoam matte-.. 1.3 3.0 8.1 5.1 .200 11 Do.-. 0. o 0aoetylcitrato+0.06%buty citrate .1-.. 15.2 i 4&5 80.0 3.7 1.51. 14

awnconnosron 'rns'r i i i 0.0. 9.1 27.2 7.3 3.14

. oeet i eimte... 1:: a1 5.1 3.0 2.15 14 Gaoetylcitrate i 3.4 4.8 03.0 i as 3.10 23 oeeetyiei rm i 10.1 30.0 21.4 9.2 i 3.35 43 1 c4 oetylcitmte+00$immyltartrate4 9.1 10.3 10.3 11.5 3.32 44 Caoety1citnto+0.1 isoamy tartrate.. 4.3 5.3 5.4 11.0 3.25. 35 .Oaoetyloitmte-H). isosm ltfll'tmte 2.3 4.0 '01 e0 2137 34 'OACaeatylcitrata-l-OM but citrate. 15.0 10.31 m3 a0 v432 5a .4 oeeetyieimtewz gut leimta, 13.4 14.0 i 140 3.0 2.52 31 Oa'fvisoousoiPsu 00...; 12.5 mi 13.2 as 3.2a 12 Oflvlloouso "luocimte+0.2%isoamyltartrate.. +0.8 +0.5 0.0 10.6 1.97

The isoamyl tartrate and butyl citrate referred to in Table III were the neutral esters. The calcium viscous oil" succinate of Table III was a saltprepared by condensing viscous oil butene polymers (about C20 to Cat) with maleic anhydride and forming the normal calcium salt. It was, therefore, the calcium -salt of a mixture of alkenyl su ccinic acids. v The preparations of many'of the metal salts of polar substituted alkyl carbo'x'ylic acids retion is added. The salt changes from a powder to a viscous mass. The benzene is then poured off and the residue is'washed with benzene. -'It is then 'dried and most of the HCl is removed by heating to 250 F. at mm. for two hours.

Calcium crotonate.-21.5 grams of crotonic acid are dissolved in 250 cc. of waterand the solution is neutralized with 9.0 grams of calcium hydroxide suspended in 100 cc. of -water.a-;'The

solution is filtered and evaporated to dryness.

Barium beta-phosphonatoisobutyrate. 500

' 'grams of P013 are mixed with 800 cc. of dry; al-

, water bath to remove more HCl.

' cohol-free, acetone. 'grams of AlClaare added in small portions. After rapid evolution of H01 has subsided the, mixture isj heated on a The diacetone phosphorus chloride thus formedis hydrolyzed to impure diacetone phosphonic acid which is recovered by evaporating off water and is purified by dissolving in alcohol and precipitating the ammonium salt with ammonia. The. salt ,is washed with alcohol, dissolved in water and iii- Formulae and polar groups l Compound Structural formula ggs zg Calcium ailimto-tetraaoetate 0-'-oH,.c o 0- -o o-cH,.ooo-- v-o Si CB: Si o-cmoooo O-CH1.C O O- --0 'Calcium'crotonate (CHl-CH=OH.C o 0- ,oa CH=CH Barium beta-phospho-natoisobutymte; CHi.CH.C O 0-- /0 0\' V Hr-PO\ B8: -P= /Ba 0- 1 Calcium gamma-oximinovalerate (OHa.-C.CH;.CH:.C O 0-) Ca =N 0H t .OH Barium thlosulfatoacetate (CH|.C o 0- 101- V 1 nate omorrc o 0- Calcium alpha thiocyanato-prop o I Ca SCN Barium suecinamate V (KIN-C O-CHz-CHLO 0 0-);Ba 0 ONE, 3 1 ts CHl.CH-COO I Calcium alpha nitrataprop ona (I) 08 O NO '(lglciumlevulinate HM: O.CHl.GHl.Co0),ca' -o 0.03,

late CHl(CH2)5.CH.COO- Calcium aipha-amino-capry I Ca NH,

but ate omomcmo 0 0- Calcium alpha hydrox amino yr a NHOH NHOH 1 Calcium beta-nitro-propionate oirkcmonao o 0-):Oa

Calcium cystinate N H; v

1 SCH:.( JH;COO 3 .s

Ca and on,.cn.o o o-J .-NH|

(Hoom'oo'o-j ,cB p V (NC.CH|.C O 0-3 03 CN Calcium beta-pnosphato-propionate.. 0,-CH:.CH5.CO O-- OP-O-CH:.CHa.COO-- Caz -0P=O o-omomc o olMetlwds .0 preparation 1 Calcium -silicato-tetraacetate.-l9 grams of calcium glycolate are suspended in cc. of

tered and theacid is obtained-by acidification with H01 followed by' evaporation. The solid acid is extractedwith alcohol, filtered and evapbenzene and an excess of 81014 in benzene solu- 75 orated to dryness andlit is then oxidized, first means with nitric acid and then with fuming nitric acid.

Excess nitricacid is removed on a water-bath and the resulting impure beta-phosphonatoisobutyric acid is dissolved in. water and barium hydroxide is added untilthe solution is strongly alkaline.

It is then heated to boiling andfiltered and the filtrate is discarded and the desired barium salt is recoveredirom the residue by extraction with cold water. The extractis evaporated to dryness and pure barium beta-phosphonatoisobutyrate is recovered as the residue.

Calcium gamma-oxtmluovalerata-25 grams of levulinic acid are dissolved in 250 cc. 01' water and 15 grams othydroxylamine hydrochloride are added to this solution. The solution ismade slightly alkaline with NaOH and is allowed to stand over night. It is then acidified with H=SO4 and extracted with ethyl ether. The ether is evaporated and the residue of acid is dissolved in water and neutralized with calcium hydroxideu The solution oicalcium salt is evaporate to dryness.

Barium. thiosulfatoacetate.- -19 grams of chloroacetic acid are dissolved in 100 cc. of water and neutralized with a saturated solution .of 10.6 grams of NaaCOa.

.tate pentahydrate are added to the solution and 50.3 grams of sodium thiosulthe solution is evaporated to its original volume. The barium salt is precipitated by the 1 addition of BaCla and it .is recoveredby filtration and is dried. 1

Calcium alpha thiocuanatopropionate. 20 grams of ethylalpha bromopropionate are mixed with an alcoholic solution or 10.7 grams of KSCN. The solution is; allowed to stand several days on a steam plate, and potassium bromide is then filtered oil. Excess calcium hydroxide solution is then addedand the mixture is heated. .CO2 is passed through the mixture to remove excesslime and the calcium carbonate is removed by filtration. The filtrate is evaporated to dryness.

Barium succinamate.-19.8 grams of succinimide are dissolved in water and a solution of 31.6 grams of barium hydroxide octahydrate is added. The solution is evaporated to dryness. Calcium alpha-nitratopropinate.20 grams of zinclactate are added to a mixture of 25 grams of fuming nitric acid and 40 grams of concentrated sulfuric acid. The mixed acid is kept below 40 F. while adding the zinc lactate. The solution is allowed to warm and most of the excess nitric acid is removed on a hot waterbath. The residue is poured into a large amount of cold water fromwhich a heavy oil separates. This is .neutralizedwith calcium. hydroxide solution and the water is removed on a steam plate.

Calcium leuulinate.20 grams of levulinic acid are dissolved in 500 cc. of water and the solution a is neutralized with a lime slurry. It is then heated on a steam plate, filtered and evaporated to dryness.

Calcium alpha-antinccaprylata-IS grams of alpha-aminocaprylic acid are mixed with suillcient ethyl alcohol to make a thin paste and this paste is added slowly to 500 cc. of water while stirring. A 20% KOH solution is added until solution just occurs. A solution of 5.25 grams of CaClz in a small amount of water is added while stirring. A curdy precipitate forms which is 111- tered off and dried in a desiccator.

Calcium alpha hydroxaminobuturate. 14.2 gramsot sodium are dissolved in 200 cc. oi absolute alcohol and to the solution is added a solution of 43 grams of hydroxylamine hydrochloride in 200 cc. of absolute alcohol. 21.5 grams of crotonic acid dissolved in 100 cc. of alcohol are added to the above solution and themixture is allowed to stand 3 days at room temperature. Alcohol is then evaporatedoflt, leaving a. thick, viscous residue. This is extracted with hot alcohol. The alcoholic. extract is neutralized with lime slurry and the solution of calcium salt is evaporated to dryness.

Calcium beta-nitropropiouate.-15.3 grams of beta-lodopropionic acid. are dissolved in 400 cc.

of water and the solution is cooled to 40 F. 12.23 grams of silver nitrite are added slowly to the solution and the mixture is .allowed to warm to room temperature. The solution is filtered to remove silver iodide and evaporatedunder vacuum to a volume of about 100 cc. Excess calcium hydroxide is added and the excess is removed by treating with C02 and filtering of! calcium carbonate. The filtered solution is evapevaporated to dryness. l 1

Calcium cystiuate.--12 grams of cystine and 3.7 grams of calcium hydroxide are added to 500 cc. of water. The mixtureis heated on a steam plate for hour and filtered. The residue on the filter is leached several times with hot water grams of beta-iodopropionic acid are dissolved in 200 cc. of water and 9.5 grams of silver phosphate are added. The mixture is heated hourHand the silver iodide is filtered off. Calcium hydroxide is added until the solution is neutral, and the solution is then evaporated to dryness.

We claim:

1. A composition of matter, comprising a major proportion of hydrocarbon .oil and a small amount each not less than about .l% by 'weight based on finished oil of a metal salt of an alkyl carboxylic acid and an ester of an hydroxy substituted aliphatic carboxylic acid, said :metal salt of an alkyl carboxylic acid having a polar substituent attached to an aliphatic carbon atom near enough to ametal alkylcarboxylate group to reduce substantially the corrosive tendency of said metal salt inthe absence of said polar substituent toward bearing alloys of the type represented by copper-lead and cadmium-silver bearing alloys.

2. A lubricant comprising a small amount each not less than about, .l% by weight based on finished lubricant of a polyvalent metal salt of an alkyl carboxylic acid and an ester of an hydroxy substituted aliphatic carboxylic acid, said metal salt of an alkyl carboxylic acid having a polar substitunt attached to an aliphatic carbon atom near enough to a metal alkyl carboxylate group to reduce substantially the corrosive tendency of said metal salt in the absence of said polar substituent toward bearing alloys of the type represented by copper-lead and cadmlum-sllver bearing alloys.

3. A composition of matter, comprising a major proportion of hydrocarbon 011, about 0.1 to 2% by weight based on finished oil of a polyvalent proportion of mineral oil of lubricating viscosity, about 0.1 to 2% by weight based on finished oil of a polyvalent metal salt of an alkyl carboxylic acid and about 0.25 to 2% by weight based on finished oil of an ester of a lower molecular weight hydroxy substituted aliphatic carboxylic acid, said metal salt of an alkyl carboxylic acid having a polar substituent attached to an aliphatic carbon atom near enough to a metal alkyl carboxylate group to reduce substantially the corrosive tendency of said metal salt in the absence of said polar substituent toward bearing alloys of the type represented by copper-lead and cadmium-silver bearing alloys.

5. The composition of claim 4, wherein said polar substituent is in the alpha, beta or gamma position with regard to a metal alkyl carboxylate group. 6. The composition of claim 4, wherein said metal salt is the salt of a polyvalent metal and a polycarboxylic aliphatic acid containing at least two aikyl, carboxyl groups separated by not more than three aliphatic carbon atoms.

7. The composition of claim 4, wherein said metal salt is the salt of a polyvalent metal and an alpha, beta or gamma hydroxy substituted aliphatic acid.

8. The composition of claim 4, wherein said metal salt is the salt of a polyvalent metal and an aliphatic carboxylic acid substituted in an alpha, beta or gamma position with regard to a metal alkyl carboxylate group by a substituent containing an element selected from the group consisting of oxygen, sulfur, selenium, nitrogen and phosphorus.

9. The composition of claim 4, wherein said metal salt is the salt of a polyvalent metal and an alpha, beta or gamma sulfur substituted alkyl carboxylic acid.

10. A compounded mineral lubricating oil, comprising about 0.1 to 2% by weight based on finished oil of a polyvalent metal salt of an alpha, beta or gamma polar substituted alivphatic carboxylic acid, and about 0.25 to 2% by weight based on finished oil of an ester of an aliphatic alcohol of 1 to 6 carbon atoms and an alpha, beta or gamma hydroxy substituted aliphatic carboxylic acid of 2 to 6 carbon atoms.

11. The compounded oil of claim 10, wherein said ester is the ester of an hydroxy substituted fatty acid.

12. The compounded oil of claim 10, wherein said ester is the ester of an hydroxy substituted aliphatic polycarboxylic acid. a

13. A compounded mineral lubricating oil,-comprising about 0.1-to 10 per cent by weight base'd on the finished oil of a polyvalent metal salt of an alpha, beta or gamma polar substituted ali-. phatic carboxylic acid'and about 0.1 to 10 percent by weight based on the finished oil of an ester of a C1 to C6 aliphatic alcohol and a C2 to Ca hydroxy substituted aliphatic carboxylic acid containing at least one hydroxyl substituent in an alpha position with respect to a carboxyl group.

14. The compounded oil of claim 10, wherein said ester is isoamyl tartrate.

15. The compounded oil of claim 10, wherein said ester is butyl citrate.

16. A compounded mineral lubricating oil, comprising about 0.1 to 2% by weight based on finished oil of an oil soluble polyvalent metal salt of an aliphatic polycarboxylic acid and about 0.25 to 2% by weight based on finished oil of a low molecular weight alkyl ester of an hydroxy substituted aliphatic polycarboxylic acid.

1'1. A concentrated solution in mineral oil of lubricating viscosity of a metal salt ofan alkyl carboxylic acid and an ester of a lower molecular weight hydroxy substituted aliphatic carboxylic' acid, said metal salt of an alkyl carboxylic acid having a polar substituent attached to an allphatic carbon atom near enough to a metal alkyl carboxylate group to reduce substantially the corrosive tendency of said metal salt in the absence of said polar substituent toward bearing alloys of the type represented by copper-lead and cadmium-silver bearing alloys. V

18. A grease, comprising soap, mineral oil, and an ester of an hydroxy substituted aliphatic carboxylic acid, at least part of the soap being a metal alkyl carboxylate havin a polar substituent attached to an aliphatic carbon atom near enough to a metal alkyl carboxylate group" to