Patented June 20, 1950 2,512,359 umreo PATENT OFFICE LUBRICANT ‘- COMBO SITIONSiCONTAINING ~ :BERYL'LIUM‘.C‘ARBQXYLATES John F. McGrogan, Philadelphia; Pa, ,assignor to The Atlantic ,‘Re?ning Company,’ Bhiladelph‘ia, Pa., a corporation of Pennsylvania Noni-owing- ‘Application October 26,1946. .> SerialrNo. 706,054 v10 Claims.“ (mag-#3217) ' , 1' , , The present invention relates to lubricants, and particularly to mineral oil lubricantshaving,‘ incorporated therein ininorquantitiesof addi erence ishadpforjmonc- Or di-salts of saturated tive materials adapted to improve lubrication aliphatiocarboxylic, acids of from 1.2 to ,18, car properties, and toinhibit or retard deposition of blpnatqms- .iHowcver, a variety of acids ‘may be employed-in the production of the beryllium saltsfiineluding, both the mono! and polycar varnish, lacquer and sludge caused by deteriora tion of the oil in normal lubrication service. > ' Commercial petroleum lubricating oils, no boxyhlcv acids which are exempli?ed by enanthic matter how highly re?ned, have. a de?nite tend ency to deteriorate under the lubricating con; a1 ditions encountered-in internal combustion en, waxes. adipic acid, :nimelic . acid, suberic acid, az'elaic acidsebacic acid; succinic acid, and other 15 Deposits, in the nature of varnish, lacquer and t sludge, are products of this deterioration, and iere with proper operation, ,ormay even cause 20 _ the,;nuclear.hydregen atoms. issu-bstituted. byan acids such as nhthalic acid gests many ways of accomplishing- these ends, - Ch 3 l ' beIiatoms; .alkylated aryl carboxylic acids in cludinebenzcic acid .in which one Qrmore of alkyl or. alkenyl group preferably of ataromatic ,‘least 6 ' . carbon-atoms; .allsylated nolycarboxylic problems oi inhibiting oil deterioration, andThe of maintaining oil cleanliness during lubrication service, are, therefore, pies; ential importance, and while the prior art sue; further improvement is desirable. acidsiof that series in which. one. or. more of the metbvlenc hydroaensare substituted by unsatu ratedhizdrocarben residues suchas polymers of presumed butvlene’having from 8 to '18 car-1 in modern engines with close clearances small amounts of these deposits may seriously._inter-. engine seizure. . .caprvlic acid, pelargonicacid, lauricacid, myristicacid, vgpalrnitic acid, stearic acid‘, acids derived. brthe oxidation of petroleum oils and gines. High crank case temperatures, and other increasingly severe requirements inengine, per formance, aggravate the rate of oil, deterioration from thermal decomposition and oxidation. 12 normal .911 basic , salts or mixtures thereofderived from 9L1? gona mixture of carboxylic acids. ' :Pref which one or more, of ethe nuclear hydrogenatoms is substituted by an allgyior alkenyl group of .6_or_rnore .carbon It is an object of this invention to‘ provide atoms; abietic acid, hydrogenated abietic, acid, particularly of from 12 to 18 carbon atoms, are excellent detergents for all common lubricating oils, and that these compounds as additives-in such as to give either'a normalor a basic salt ;Alternatiuely, a-solublev beryllium icompoundsuch small concentrations minimize .depositionof- de terioration products, and thereby improve-the solution, may be reacted with an aqueous solu narlithenicacidsl and the like > lubricating oil compositions which are eifectively The beryllium salts of the carboxylic acids may inhibited against the formation of varnish, lac beprepared by reacting a basic; beryllium com quer and sludge deposits. 30 pound, such as beryllium hydroxide or carbonate I. have fellndthat the beryllium salts. of. earwith‘the oarboxylic acid at elevated temperature, boxylic acids of from 6 to 18 carbon ‘atoms, and the ratio of hydroxide or; carbonate to acid being as the chloride, nitrate or ‘sulfate in. aqueous tiomondispersionof an alkali metal saltoi a over-all lubricating properties of the oil. Some c, ;bo_xylic_i_acld.to?give .awater-ins'oluble beryl of these salts are inherently soluble in petroleum oils in an amount su?icient to provide good. de 40 liu .carboxylate. ‘The nrcnarationof the beryl lium-salts of the carboxylic acids is effected by tergency action, and those which are less. $91.11. conventional meanseand formsllQP?-l‘t?f the ble can be readily'incorporated in oils with‘the present invention. thereieret further discussion aid of solubilizing agents, such as aliphatic acids thereof is not essential. and alcohols, alkyl esters, or other compounds The beryllium salts of the carboxylic acids known to have a solubilizing function. The may be incorporated in suitable amounts in actual amount of salt additive necessary to pro lubricating oil by simply heating the mixture vide the results intended may vary broadly with until solution or dispersion is accomplished, and in a range from about 0.1% to 5.0% by weight of thereafter cooling the product to ordinary tem-x the oil, depending upon the properties of the untreated oil base; and with the more common 50 peratures. When it is desired to increase the anti-corrosion and anti-rust properties of the commercial lubricants, additions of about 0.5% lubricant, various inhibitors may be added to to 2.0% of the beryllium salts have given very the oil containing the detergent beryllium car satisfactory results. boxylates. The anti-oxidants, anti-corrosion The beryllium salts which may be employed in accordance with this invention are either the or agents, and anti-rust agents may be incorporated in amounts varying from 0.1% to 5% by weight mass; of the lubricant, 0.5% to 2.0% being preferred. These agents include phenolic and amino com pounds such as the long-chain alkylated phenols produced by the polymerization of ole?ns or the condensation of ole?ns or halogenated hydrocar bons with aromatic hydrocarbons. and polyhydroxy aromatic compounds; aliphatic I claim: and aromatic amines; metal salts and amine salts of the acid esters of the acids ofv phosphorus, and particularly metal salts of the acid esters 1; A lubricating oil composition comprising hydrocarbon oil and a beryllium salt of a car boxylic acid containing from 6 to 18 carbon atoms, said salt being present in an amount sui?cient to improve the detergency of the oil when used in the of a thio-aoid of phosphorus such as the zinc salt of cyclohexyl acid thiophosphate; phenol sul?des and metal salts thereof; sulfurized oils and sul furized esters of carboxylic acids, such as sul-' 10 lubrication of internal combustion engines. 2. A lubricating oil composition comprising hydrocarbon oil and from 0.1% to 5% by weight furized aliphatic abietates, sulfurized higher fatty acid esters, sulfurized sperm 0'1, and the like‘. The present invention may be further illus trated by the following examples, which, however, of a beryllium salt of a carboxylic acid containing from v6 to 18 carbon atoms. ‘ - 3. A lubricating oil composition comprising are not to be construed as limiting the scope thereof: 4 oils, deasphaltized residual oils, and synthetic oils and from 0.5% to 2% by weight of a beryllium salt of a carboxylic acid containing ‘ hydrocarbon oil " For the detergency test, there is provided- a. glass test tube within which are vertically and concentrically disposed two sand-blasted open ended steel tubes. Between the steel tubes is in from 6 to 18 carbon atoms. 4. A lubricating oil composition comprising hydrocarbon oil and from 0.1% to 5% by weight of a beryllium salt of a saturated aliphatic car boxylic acid containing from 6 to 18 carbon atoms. serted a copper tube of small dimension through‘ which air is delivered to the bottom of the test 5. A lubricating oil composition comprising hydrocarbon oil and from 0.5% to 2% by weight of beryllium stearate. 6. A lubricating oil composition comprising hydrocarbon oil and from 0.5% to 2% by weight tube .below- the end of the inner steel tube. In carrying out' the test, the inner steel tube is weighed and then inserted in the testing appa-v ratus. '15 cc. of the oil to be tested is then ‘intro duced into the glass test tube and forms a pool of beryllium mono-stearate. ' covering the lower ends of the steel tubes and the 7. A lubricating oil composition comprising copper tube. The apparatus is then placed in an 30 hydrocarbon oil and from 0.5% to 2% by weight oil bath and heated to 300° F., air being injected through the copper tube and beneath the surface of beryllium di-stearate. 8. A lubricating oil composition comprising hydrocarbon oil, 0.5% to 2% by weight of beryl lium stearate, and 0.5% to 2% of a metal salt of the test oil at a rate of 30 liters per hour. After 65 hours heating and blowing, the apparatus is removed from the oil bath and cooled. The inner 35 of an acid ester of an acid of phosphorus. steel tube is withdrawn, washed with naphtha, 9. A lubricating oil composition comprising and weighed, the increase in weight being attrib hydrocarbon oil, 0.5% to' 2% by weight of beryl uted to the deposition of sludge. The smaller the lium stearate, 0.5% to 2% of a metal salt of an weight increase, the more e?ective the'detergent acid ester of an acid of phosphorus, and 0.5% to agent in the oil. The results of the tests are tab?‘ 40 2% of sulfurized ester of a carboxylic acid. ulated below. The base lubricating oil used was 10. A lubricating’ oil composition comprising a ra?inate fraction of a nitrobenzene selective hydrocarbon oil, 0.5% to 2% by weight of beryl solvent extracted distillate lubricating stock, such lium stearate, 0.5% to 2% by weight of a metal base oil having an A. P. I. gravity of 31° and a salt of an acid thiophosphate, and 0.5% to 2% by Saybolt Universal viscosity of 175 seconds at weight of sulfurized sperm oil. 100° F. JOHN F. MCGROGAN. Milligrams Lubricant sludge de . posited REFERENCES CITED The following references are of record in the Base oil ____________________________________________ . _ Base oil+0.5% beryllium mono-stearate. _ .. Base oil+l.0% beryllium mouo-stearate.Base oil+2.0% beryllium mono-srearate Base oil+l.0% beryllium di-stearate.-Base oil+2.0% beryllium di-stearate ________________ _. 63 13 . 3 ' *3 ‘ 0 1 While, in the above test, a solvent re?ned lubri cating oil was employed as the base, other hydro carbon oils may be used in lieu thereof, including ?le of this patent: UNITED STATES PATENTS Number Name Date 2,320,392 White ____________ __ June 1, 1943 2,322,307 Neely ____________ __ June 22, 1943 CTHER REFERENCES ‘The Alkaline Earth and Heavy Metal Soaps, straight-run lubricating distillates from paraf?n 00 base, naphthene base, or mixed base crude oils, ACS Monograph Series No. 103, 1946. p. 165, by acid treated oils, hydrogenated oils, clay treated Elliott.