US2656317A - Lubricating oils containing metal salts of a condensation product of a substituted phenol and an allyl compound - Google Patents

Description

Patented Oct. 20, 1953 LUBRICATING OILS CONTAINING METAL SALTS OF A CONDENSATION PRODUCT OF A SUBSTITUTED PHENOL AND AN ALLYL COMPOUND Loren L. Neif, Long Beach, Calif., assignor to Union Oil Company of California, Los Angeles, Calif., a corporation of California No Drawing. Application July 17, 1950,

Serial No. 174,368

This invention relates to lubricating oil addition agents having exceptional anti-corrosion and detergent characteristics when added to mineral lubricating oil, and to lubricating oils containing such addition agents with and without supplemental detergents. More particularly, the invention relates to oil-soluble metal salts of the condensation products obtained by condensing hydrocarbon substituted phenols with allyl compounds as will be described herein and to lubricating oils containing such metal salts.

The ,present trend in internal combustion engines, ;'particularly of the diesel engine type, is in the direction of higher compression ratios, higher operating temperatures and thus higher horse power output per unit weight of the engine. ,Moreover, it is the trend to operate engines of this type for longer periods without oil change so that oils which are satisfactory for use in the present-day high output diesel engines, for example, must have not only an initially high detergency and initially high anti-corrosion characteristics but these properties must be retained under severe conditions of use for relatively long periods of use in an engine. To further complicate the preparation of a satisfactory oil for the lubrication of such engines the fuels available often contain higher proportions of sulfur than those Which have been used in the past and it is well recognized that high sulfur fuels tend to produce'corrosive conditions in an engine which must be overcome by the lubricating oil employed, otherwise not only does corrosion take place in the engine but wear rates are sufficiently high that frequent overhaul and replacement of parts becomes necessary, thereby unduly increasing engine operation cost.

In order to prepare oils which may be used in engines of the character described it has been the practice to merely increase the percentage of additive materials which have been used in the past in ordinary diesel engines, automative engines and the like, hoping to gain the extra protection necessary by the use of these larger pro-- portions.

It is an object of this invention to prepare a lubricating oil which will operate satisfactorily in internal combustion engines and particularly in the high output diesel engines over relatively long periods of service. It is another object to prepare such lubricating oils which will protect engines of this type operating under severe conditions even while using a fuel containing as high as 1% or more of sulfur.

It is found that these and other objects can be obtained by adding to mineral lubricating oil relatively small amounts of an oil-soluble metal salt of the condensation product of a hydrocarbon substituted phenol and an allyl compound of the type described hereinbelow.

Claims. (Cl. 252--33.4)

Thus the invention resides in lubricating oils containing between about 0.05% and about 10% or as high as about 20% by weight of an oilsoluble metal salt of the condensation product obtained by condensing a hydrocarbon substituted phenol wherein the hydrocarbon substituent or substituents contain between about 4 and about 30 carbon atoms with an allyl compound of the class consisting of allyl alcohol, allyl ethers and allyl esters of hydrohalogen acids and fatty acids. These condensation products are acidic and capable of reacting with metal bases, as for example, metal oxides, hydroxides and carbonates, under appropriate conditions to form the corresponding metal salts. The term hydrohalogen acids is used herein in its usual sense and includes hydrogen chloride, hydrogen bromide, hydrogen fluoride and hydrogen iodide. These acids may also be termed hydrogen halides.

A typical oil-soluble metal salt is produced by reacting approximately one molecular proportion of octyl phenol with one molecular proportion of allyl acetate. The phenol and acetate are dissolved in about 2 parts by volume of a petroleum naphtha and to the solution is added about 2 parts by volume of a condensation catalyst, e. g. sulfuric acid. The catalyst is added slowly and the temperature of the reaction mixture is maintained at a point such that the allyl acetate is not vaporized excessively. Preferably, the reaction mixture is maintained at a temperature between 60 C. and 72 C. and under these conditions the reaction is found to be complete in about 3 hours. Since the reaction is exothermic, completion of the reaction can be determined by following the temperature of the reaction mixture. Thus. whereas during the early part of the reaction cooling is necessary in order to maintain the temperature within the desired range, toward the end of the reaction heat may be necessary in order to maintain this temperature. Following the completion of the reaction the product is cooled and water washed until free of mineral acid. Upon evaporation of the solvent naphtha employed there remains a resinous material having a dark brownish color. The resin may be converted into its metal salt, as for example the barium salt, by treatment of a solvent solution, as for example a naphtha or a hydrocarbon lubricating oil solution, of the resin with barium hydroxide octa-hydrate or with anhydrous barium hydroxide, in which latter case it is necessary to add small amounts of Water during the neutralization. Where the metal salt is the desired product, the solvent solution of the condensation product is mixed with the desired metal base and, after neutralization and elimination water, the solvent is evaporated leaving the metal salt of the condensation product. The barium salt of the above condensation product is a semisolid to solid resin of brownish color. Where it is desirable to prepare a lubricating oil concentrate of the metal salt of the condensation prod.-v uct the neutralization is preferably effected in mineral oil solution. In this case the condensation product or the solvent solution -of the con-v densation product is dissolved in about 1 to about volumes of mineral lubricating oil and the desired metal base and Water is added The resulting product is agitated and heated sufficiently to effect complete neutralization and subsequently filtered to remove solid impurities. The resulting product will be referred to as an oil concentrate of an oil-soluble metal salt of the. gondensa tion product of a hydrocarbon substituted phenol and an allyl compound of the class described.

gHyd'rocarbo'n substituted phenols which are .usefulin the preparation of the oil-soluble metal ts of this invention include the phenols havalkyl, cyc'loalkyl, 'aryl, aralkyl and alkar y'l ituents. The .substituents may be in the ,e ho., metaor para.- positions. Preferably the b mpo'und will have either an orthoanda para- .p itio'n free of substituents, or if the para-posi- (ti n 'isqsubsftituted then preferably both orthoiaos'itiiiii's should be free of substituents. Alkyl increments "include the butyl, amyl, iso-amyl', h'xyl, heptyl, .octyl, .Iauryl, .cetyl and like radi- "The'se radicals may'be normal or branched groups and thephenol may contain one or ji ore these substituents. Moreover, the alkyl substituent's inelude, the .so-called wax radicals, he. radi s "derived from paraflin wax which may conta nasjhigh as or more carbon atoms... wax 'phe'nolsare. well known in the art Jand lmaybe prepared by reacting phenol with ;1nated.parafi in,.wax .in the presence of a E (Kiel-( Shaftv Catalyst. Cycloalkyl substituents includecyclohexyl, .methylcyclohexyl, cyclopeninmates/ ethyl and propyl cyclopentyl radicals and the like. ,Aryl radicals include the phenyl fr dic'al, 'asifor example ,phenyl phenol. Aralkyl if icals "include the. benzyl radical and thus .benjzyl phenol. Alka'ryl radicals. include the fradicals such as methylphenyl, 'ethylphenyl and theflik v 'Allyl cdnp'ounds which are'useful in preparing the condensation products. include allyl aljc'ohol, the lower molecular weight allyl ethers', asffoifljexallilple diallylljether, allyl ethyl Ethel,

allyhpropyl'ether andthe like and aim esters.

J1 egau'yl' esters, include 'the..allyl hydrohalogen ,e'cm esters, "as for. example allyl .ehlor'ide, allyl hr mide and auy iodide and..thejlowerQmoleom is ightcarboxyiic acid esters,- particularly V tyQacid esters, as. forfexample allyl acerate; llyl 'propiona'te, allyl butyrate and thelike. Generally the carboxylic or. fatty acidfradica fp L t in the. ester will contain '1.to..5 .or 6 .carbon atemfs. and preferably 2.700. '4 carbonatoms. The 'molar ratio of. hydrocarbon substituted .phenol- .tb allylf compound to be ,used in preparing sesame condensation products will be between laboutl..0.5.. and about 3 to l. Preferably this rat i0 Will fall between. about 0.8 and about jzg'tlj Particularl satisfactory results. have been obtained. using approximately equal .molecular fproportions of phenol andallylcompound. Catalystsfor condensation agents which may .be employediand which serve toeiiect the de- .s ired condensation reaction include the acid catalysts si m l f ri aci nd. P 195." Jphoric .a idas Well as h e Q -Cm t ty .catalysts. i udin um num chl i e, boron trifluoride, zinc. chloride and; the like. In the case of boron trifiuoride, this compound is generally employed in the form of its complex with .diethyl ether. The complex is known as boron trifiuoride etherate and has a boiling point of about C. The amount of catalyst to be employedwill generally be between about 0.5% and 10% "by weight of the total reactants. However, as much as 20% may be employed if desired, with satisfactory results.

Although the condensation reaction will take place in the absence of solvent or diluent, it is generally desirable to employ a solvent during the-condensation reaction. Solvents which may be employed include those which do not react with phenols or with the allyl compounds under the conditions of condensation, Such solvents include the hydrocarbon naphthas or thinners, aromatic solvents, as for example benzene, toluene, and xylene, and the like as well as chlorinated solvents such as chloroform, carbon tetrachloride and the like. Also, the condensation is satisfactorilyv effected using mineral oil as the :solvent or diluent. Thus, the solvent can be the .oil to be used in the preparation of the final lubricating oil composition. The amount of solvent or diluent to be employed may be widely varied, although generally between 0.5 and 5 ,volumes of solvent per volume of reactants is 'found to. give satisfactory results. v

The temperature of reaction will depend upon the reactants involved but will generally be between about -20 C. and about 200 C. and preflerably between about 0 C(and about 100 C. or C. The temperatureemployed will depend 'to some extent upon the volatility of the allyl compound employed and also. upon the reactivity of theallyl compound. With the more volatile compounds, as for example allyl chloride, lower temperatures are generally preferred and pressures up to 3 or ,4 atmospheres may be employed .if desired in order to maintain the reactants in ,solution or in liquid condition at the temperatures employed. ,7

The time of reaction is dependent upon the ,'particular reactants. and upon the temperature ,and condensation agentemployed, although generally it is found thatfbetwjeen about 1 hour'and e'or '5'hours. suffices to effectthe desired extent of condensation. However, entirely satisfactory condensation products, have been prepared when the reaction conditions were maintained for as long as 24 hours. Products soobtained are found .to be oil-soluble. and metal salts derived from the condensation products. are also oil-soluble.

The lnietals tobe employed in preparing metal salts, of the condensation products are preferably. the polyvalent metals, although the monovalent alkali; metals are satisfactory .in some instances. Thus the sodium, potassium and lithium salts are found to be oil-soluble and have the desired characteristics when added "to mineral lubricating oils. Of the. polyvalent metals, thealkaline. earth lmetals calcium, magnesium, barium and'strontium are particularly elfective. However, the zinc, lead and aluminum salts are suitable andin somecases chromium, iron, nickel, cobalt, mercury, tin and other polyvalent metal salts have utility and, are to be considered part of this invention, although'this latter group ofpolyvalent metal salts are not to be considered equivalent to the alkali and alkaline earth metals and zinc, lead and aluminum salts. .Inbr paring; metal. salts of the acidic condensation products a solvent solution ora lubricating oil solution of the condensation product produce outstanding lubricating oils.

5 is heated with the desired metal base, i. e. oxide, hydroxide or carbonate, in the presence of a small amount of water or in the presence of a small amount of alcohol. The mixture is agitated and heated to eliminate water and effect neutralization. In the case of the more weakly basic metal the metal salt is preferably made by a method involving first preparing the alkali metal salt, as for example the sodium salt, and subsequently metathesizing the alkali metal salt with an inorganic salt of the desired metal. This metathesis is carried out in alcoholic solution in order to prevent hydrolysis which would occur in aqueous solution. Methods of metathesizing weak acid salts are well known in the art and therefore need no further description here. This same method of preparation may be employed in producing any of the polyvalent metal salts if so desired.

the oil containing the metal salt to a temperature of 100 C. to 150 C. and agitating the solution to effect rapid and complete solution and/or dispersion. Lubricating oils which may be employed include substantially all types of mineral lubricating oils. Thus the oil may be one having a viscosity index of or even lower or it may be a 'paraflinic type oil having a viscosity index in the neighborhood of 100. Particularly satisfactory results have been obtained using a solvent treated Western paraffinic mineral lubrieating oil having a viscosity index of between about 85 and 95.

Although lubricating oils containing the additive of this invention as the only additive material are particularly effective, it is often de- --'sirable, particularly where the oil is to be used under severe service conditions, to incorporate in theoil relatively small amounts, as for example 0.5% to 8 or 10% by weight, of a supplemental detergent. It is found, for example, that oil-soluble metal sulfonates and particularly the oil-soluble metal salts of mahogany sulfonic facids obtained by treating lubricating oil fractions of petroleum with sulfuric acid, $03 or chlorosulfonic acid, which methods of preparation are well known in the art, appear to cooperate with the additives of this invention to Thus by adding between about 0.5 and 5% by weight of a metal petroleum sulfonate it is found that the detergency of the oil is improved without adversely aifecting the anti-corrosion or antioxidation characteristics of the oil.

Another detergent which appears to cooperate with the additives of this invention is a modified sulfonate prepared by heating an oilsoluble metal petroleum sulfonate with an inorganic base to solubilize the base in the sulfonate. Thus, mahogany sulfonic acids may be reacted with inorganic bases as, for example,

with metal oxides, hydroxides, carbonates and Cir indicates a completely clean engine. volume of carbon present in the top ring groove 6 and these materials are found to impart 'excep tional detergency characteristics to lubricating oils containing the condensation product salts of this invention. Such oil-soluble complexes of sulfonic acids and metal hydroxides, oxides, carbonates and the like which may be employed together with the additive of this invention are those described by Mertes in U. S. Patents Nos. 2,501,731 and 2,501,732.

The metals to be employed as constituents of the sulfonate or modified sulfonate supplemental detergents are the same as those described hereinabove as being useful as constituents of the condensation products.

Two different engine tests have been employed in the evaluation of lubricating oils containing the oil-soluble metal salts of this invention. These tests have been carried out in Lauson single cylinder engines and a single cylinder Caterpillar Diesel standard test engine. The tests are referred to as the Lauson engine test and the Caterpillar test, respectively.

Tests in the Lauson single cylinder test engines are carried out in such a manner that the oil is subjected to severe service conditions. This test is employed to determine the corrosion tendencies of the oil and to determine the tendency for the oil to deposit resinous and lacquer-like materials in the engine. In carrylllg out the Lauson engine test the engine is operated for a total of 60 hours under a load of about 3.5 horsepower, with a coolant temperature of about 295 F. and an oil temperature of about 280 F. At the end of the test the cleanliness of the engine is observed and the oil is given a numerical detergency rating between 0% and where 100% indicates aperfectly clean engine. Thus, a detergency rating of 100% would indicate that during the test with a given oil there were substantially no lacquer or varnish-like deposits within the engine. The corrosivity of the oil is measured by determining the loss in weight of corrosion-sensitive copperlead bearings during the period of test. Generally, the bearings are removed and weighed after 20, 40 and 60 hours of operation.

In those cases in which corrosion is extremely severe and there appears to be danger of engine failure due to excessive corrosion of the bearings asindicated by an examination made at the 40-hour period, the copper-lead bearings are replaced with babbitt bearings in order to complete the 60-hour test. The results of such engine tests are shown in connection with some of the examples presented hereinbelow. I

In the Caterpillar test which is employed to determine the detergency of an oil, i. e., the ability of the oil to prevent lacquering of the engine, the engine is operated for a period of 240 hours under a load of about 19.8 horsepower with a coolant temperature of about 175 F. and an oil temperature of about 145 F. The fuel employed is a diesel fuel containing 1% by weight of sulfur. After hours and at the end of the test a numerical detergency rating" is as-.- signed. The method of rating is similar to that employed in the Lauson engine test and 100% Also the behind the ring is determined and this result is expressed at per cent by volume of the space behind the top ring at the start of the test.

The following examples illustrates some modifications of the invention, however it is to be realized that various modifications of the de- 7 scribed methods of preparation and thedescribed condensation product: salts'come within the scope of. the invention.

Example I ,A 206 g. portion of octylphenol 'is'dissolved in 1500 m1, of .alight paraifinic' naphtha boiling in the range 60-100 'C. and to this solution. is added 68 ml. of allyl alcohol. This mixture is placed in 'ailask; equipped with a. stirrer,- thermometer and reflux-condenser.

Sulfuric acid .(98% concentration) is added drop-wise through the reflux condenser untila total of 54 ml. has been added. During the initial addition the temperature rises to apoint of rapid reflux (about 72C.), and the addition is continued at a rate such that refluxing continues. Eollowing the addition of the sulfuric acid ,the mixture is heated at its reflux temperature for hours and then cooled. washed with water until free of acid and then heated to 125 C. to evaporate the naphtha. A 75 g. portion of the product is dissolvedin 925 g. of an SAE 30 solvent extracted Western mineral lubricating oil by heating to 140 C. with stirring. To this solution is added 56 g. of anhydrous barium hydroxide and'150 ml. of water. The water is added drop-wise at 140 C. The resulting mixture is heated to 175 C., and filtered while hot using a filter aid. This product is an oil concentrate. containing approximately 12% by ,weightoi the barium salt of the condensation product of octylphenol with allyl alcohol. This product without further dilution operates satisiaetorilyin a Lauson engine, giving a high detergency and very low bearing weight losses.

A lubricating oil is prepared by dissolving 32 partsby weight of the above oil concentrate and about. 3.7 parts by weight of an -oil concentrate of calcium petroleum sulfonate in 64.3 parts by I weight of the same SAE 30 mineral lubricating oil described above. The resulting oil containing approximately 3% by weight of the barium salt and having a calcium sulfate ash due to calcium sulfonate of approximately 0.24%is tested in a Caterpillar engine as described above, using a fuel. containing 1% of sulfur. This oil has a detergency rating of over 95% at 240 hours.

In comparison, the base oil without additives cannot be tested in this engine using a 1% sulfur .fuel for the reason that the deposits are so great as to. cause piston and ring sticking. at far less. than 120 hours to such an, extent that it is impossible to complete thetest. Thebase oil, i. e.

the oil withoutadditives, run in the same engine using a low sulfur .fuel has a detergency rating of. approximately 55% at 120 hours. V

Tests on the base oil, on the oil concentrate as produced'abovaand on the oil prepared for testing in the Caterpillar test engine are as follows:

, =a g. (.1, mol)- portion of p-octylphenol' and .25 (0.2 mol) of boron trifiuoride etherate'are dissolved in 1 liter'of light petroleumnaphtha.

The product is L The solution is placed in afiask fitted with-areflux condenser and maintained at"about"26". To this solution, 81.5 ml.v (Imol) ofallyl chloride is added slowly'with stirring. Thetemperature does not change'upon addition of the chloride but the solution darkens. The mixture'is heated at its reflux temperature; about 67C., for 8.5 hours. During this heating HCl is'evolved.

"The product is washed free of mineral "acid with water, evaporated to eliminate the naphtha and chilled with'ice whereupon crystalsiofflunreacted octy lphenol form. The crystallized phenol is removed by filtration. Vacuum distillation' of the filtrate removes additional quantities of unreacted phenol. The'bottoms fraction from the distillation, consisting of'the condense.- tion product'of octylphenol-vinyl chloride condensation product, is a clear brown resinous material.

The above condensation product isxconverlted into. its barium salt by dissolving 7.5 'pai'tsby weight of the condensation product in92.5" parts by weight of the lubricating oil described in 'Example I and adding the equivalent amount of barium hydroxide, together with a small'amount of water. The mixture is heated to 175 C. and filtered using a filter aid to yield an oil concentrate of the barium salt of octylphenol-vinyl chloride condensation iproduct'having 'a soap number of 3.77 mg. KOH/g.

A lubricating oil containing'20%.'by weight of the above oil concentrate and by weight of an SAE 30 solvent refined'pa'rafiinic'lubricating oil has good detergency and anti-corrosion characteristics as shown by Lausonenginel tests.

Eromple in To a mixture of 440g. of p-nonylphenol and- 144 g. of allyl acetate is added 54 ml. of 98% sulfuric acid. The acid is added slowly while-maintaining the reaction mixture at about 25 C. by external cooling. The reaction mixture is maintained at this temperature with stirring'for 3' hours and then dissolved in 1.5 liters of lightpetroleum naphtha and the solution water washed to remove free mineral acid. An oil solution of the condensation product is-"prepared lay-dissolving the naphtha solution in 3500g. of mineral lubricatingoil of the type described in Example 'I'and topping the mixture to C. to remove the naphtha.

Approximately one-third of the above-oil solution is treated. with 164 g. or lead" oxideand 150 ml. of water- The mixture is gradually :heated to C. and filtered hot through filter aid' to obtain as filtrate anroil: concentrate of the lead salt of nonylphenol allyl *acetateconden'sation product.

The remaining 'two thirds of'the oil-solution of condensation product isneutralized with 59g. of sodium hydroxide in the form of a 25% aqueous solution. The mixture isgra'dual-ly heated to 200 C. and filtered hot using afil'ter aid" to obtain as filtrate an oil concentrate if the'sodium'salt ofignonylphenol-allyl'acetate condensation 'produc Approximately" one-half of the "oil concentrate of the sodium" salt produced as indicated in the preced'ing'paragraph is diluted vvith 3 liters of -7.0 petroleum naphtha andtreat'ed'with a solution of100'g. of anhydrous zinc chloridein 600ml. 'of isopropyl alcohol. The mixture is stirred for "3 hours and then topped to remove the'alcoh'ol and naphtha. The topped material "is filtered to remove solids and consists of an oil' concenadded 108 ml. of allyl acetate. added slowly with stirring and the temperature 9 trate of the zinc salt of nonylphenyl-allyl acetate condensation product.

Oil concentrates of each of the three metal salts produced as described above incorporated in additional quantities of the same lubricating oil to give oils containing 3% by weight of the metal salt in each instance impart detergency and anti-corrosion characteristics to the oil.

Example IV To a mixture of 175 g. of o-cyclohexylphenol and 112 ml. of allyl ethyl ether in 1.5 liters of naphtha is added 54 ml. of concentrated sulfuric acid. The sulfuric acid is added slowly with stirring and the mixture is refluxed at a temperature of about 80 C. for 4 hours and then water washed to remove free mineral acid. The resulting naphtha solution of condensation product is dissolved in 1000 g. of mineral lubricating oil of the type described in Example I and to this solution is added 46 g. of lithium hydroxide monohydrate and 100 ml. of water. The resulting mixture is heated gradually with stirring to 175 C. and filtered to obtain as filtrate an oil concentrate of the lithium salt of cyclohexylphenol-allyl ethyl ether condensation product.

A lubricating oil prepared by dissolving by weight of the above oil concentrate in additional quantities of the same mineral lubricating oil used in the preparation of the concentrate has a detergenoy above 88% in the Lauson test engine and a bearing weight loss of less than 400 mg. at 60 hours.

Example V To a solution of 170 g. of p-phenylphenol and '38 ml. of boron trifluoride etherate in 2 liters of light petroleum naphtha maintained at C. is The acetate is and neutralized with 41 g. of calcium hydroxide using 100 ml. of water. The mixture is gradually heated to 175 C. and filtered hot to obtain as filtrate an oil concentrate of the calcium salt of phenylphenol-allyl acetate condensation prodduct. This concentrate may be employed as a lubricant for internal combustion engines and 'furnishes exceptional protection to the engine.

Example VI A paraffin wax having an average molecular weight of about 350 is treated with gaseous chlorine to obtain a. chlorinated parafiin wax containing approximately one atom of chlorine per molecule of the wax. This product is condensed with phenol in the presence of anhydrous aluminum chloride to obtain a wax substituted phenol having a molecular weight of approximately 450.

About 900 g. of the wax substituted phenol prepared as just described is dissolved in 1000 g. of an SAE' 10 solvent refined mineral lubricating oil and the mixture heated to 40 C. To this solution is added 102 ml. of allyl alcohol and 54 ml. of concentrated sulfuric acid is added slowly while maintaining a temperature between 40 C. and C. This temperature is maintained for a period of about 5 hours and the mixture water washed to remove mineral acid.

To approximately one-third of the above oil solution of wax phenol-allyl alcohol condensation product is added 231 g. of barium hydroxide octahydrate and the mixture heated to 175 C. and filtered to obtain as filtrate an oil concentrate of the barium salt of wax substituted phenol-allyl alcohol condensation product. A lubricating oil containing 10% by weight of this oil concentrate in an SAE 30 mineral lubricating oil having a viscosity index of 55 operates satisfactorily in the Lauson test engine.

The remaining two-thirds of the oil solution of condensation product produced as above described is neutralized with potassium hydroxide using 82 g. of KOH in the form of a 50% aqueous solution. The mixture is heated to 200 C. and filtered hot to obtain as filtrate an oil solution of the potassium salt of a wax substituted phenolallyl alcohol condensation product.

To approximately one-half of the oil concentrate of the potassium salt described in the preceding paragraph is added one liter of petroleum naphtha and a solution of 95 g. of nickel chloride in one liter of isopropanol. The mixture is agitated vigorously for 3 hours and then heated to 150 C. to vaporize naphtha and isopropanol and filtered to obtain as filtrate an oil concentrate of the nickel salt of a wax substituted phenol-allyl alcohol condensation product. This concentrate, when added to mineral lubricating oils in amounts between 5% and 15% by weight, imparts detergency and anti-corrosion characteristics to the oil.

Example VII To a mixture of 305 g. of m-pentadecylphenol and 119 m1. of diallyl ether is added 5.4 ml. of

concentrated sulfuric acid. The acid is added slowly while maintaining a temperature below about 150 C. This temperature is maintained for a period of approximately one hour. The reaction product is dissolved in one liter of naphtha and washed free of mineral acid with water.

To approximately one-half of the naphtha solution prepared as above is added 23 g. of lithium hydroxide monohydrate and 10 ml. of

water and the mixture is refluxed for 3 hours.

At this time a water trap is placed in the reflux line and refluxing continued until no further quantities of water are recovered in the water trap. The product is cooled and filtered and the filtrate topped to C. to remove naphtha and leave the lithium salt of pentadecylphenol-diallyl ether condensation product.

To the remaining one-half of the naphtha solution of condensation product produced as above is added 1500 g. of the lubricating oil described in Example I and to this oil solution is added 16 g. of freshly precipitated magnesium hydroxide and 20. ml. of Water. The mixture is heated to C. and filtered hot using a filter aid to obtain as filtrate an oil concentrate of the magnesium salt of pentadecylphenol-diallyl ether condensation product.

Lubricating oils containing, respectively, 2.5% by weight of the above lithium salt and 11% by weight of the oil concentrate of magnesium salt are found to have exceptional detergency and anti-corrosion characteristics as shown by Lauson engine tests.

It is to be pointed out that the preceding examples are illustrative of the invention and are not to be considered as limiting because the phenols having one or more of the other hydrocarbon substituents described herein and other allyl compounds described herein are found to conamsegen dense under similar" conditions to formz come parable" condensation products; Moreover, :the other metals described herein as being" useful; in preparing the metal salts 'of the-condensation products maybe substitutedIfor=thef metals em ployed' in the examples to give-salts which; ".21 6 effective as detergents and anti-:corrosion1:agents when added to mineral lubricatingcoilsz Iclaim:

1. A mineral'lubricating oil containing-she tween about 0.05 and.- about 20%rby'weight"of an' oil-soluble metal sa'lt of the acidic condensa tion product of 1 a hydrocarbon substituted phenot; in "which the: hydrocarbon substituent con-'- tains between about l and a'boutiio :carborratoms, and an' allyl" compound selected from: the class consisting of allyl alcohol; diallyl ether; allyl ethyl ether, allyli-propyl ether, allylestersof hydrohalogenacids and allyl esters ofzfatty acids containing between 1 and t6 carbon atoms in the fattyacid radical, saidcondensatiorrproduct' be; ing :obtained by condensing 'saidrphenolzwithfisaid allyl compound'in' themolarwratio of between Ofrand '3 to 1 at=-temperatures -between.- about -20 C. and:about=l5.0C'.-

2; A- mineral lubricatingwilt-containing.be tweeri about005 and=about 20%- -by weight of anoil-soluble alkaline earth metal' salt of the acid-ic'condensati'on product of a hydrocarbon substituted phenol, in 1 which thehydrocarbon substituent' contains between about 4 and about 30 carbon atoms, and an allyl compoundz'selected from the class consistingsof-allyl alcohol, allyl ether, allyl ethyl ether, allyl propyl ether, allyl esters of hydrohalogen .acids and allyl esters of fatty acidsicontainingJbetween 1 and6 carbon atoms in the fattyiacid radical, said condensation product being obtained "by condensing said phenoLwith said allyl compound in the molar ratio of between 025 .and'S to' 1" attemperatures between about'0 C. and about "100'"'C.1

3. A mineral lubricating" oil containing be tween about 0.05 and about. 20% by weiglifof an oil solublealkali metal salt ofth'e' a'ci'diccondensation product ofa hydrocarbon substituted phenol in which the hydrocarbon substit'uent contains between about 4": and" about '30 carbon atoms and an allyl compound selected from the. class consisting of allyl alcohol; allylfetli'er, allyl ethyl ether, allylLpropyl ether, allyl esters of hydrohalogen' acidsandiallyl esters of fatty acids containing between 1 and 6 carbon atoms in the fatty acid radical, saidtondensation prod: uct being obtained by condensing saidI phenol with said allyi compoundin the molar" ratio of between 0.5'-andf3 to. .1; at' temperatures between about-20C. and about 15s c:

.4; Amineral lubricatingoil according to claim 11 in which the molar-ratio of phenol to allyl compoundis between 0.8"an'd' 2 to 1.

,A mineral lubricating .oil according 'ito 'claim 2 ,intwhich said'alkaline earth metal'salt is a barium salt.

6. A mineral lubricating oil'according to claim 2.in which said alkaline earth metal salt is a calcium salt.

'7. A lubricating oil according to claim 3 in which said alkali metallsalt is a lithium salt.

lubricating oil according to claim 3. in which said alkali metal salt?is a;sodiumisalt;

9 A: mineral lubricating oilpcontainingbetween about 0.05 and-about 20 by weight of an oil-' soluble .tmeta'l salt ofvtthe acidic reaction product obtainedi by condensing at a temperature F138- tween' 0 C and. C.'a hydrocarbonrsubstituted phenol inawhich: the hydrocarbon; substituent contains between about .4 and about 30 carbon atoms with allyl acetate using a molar ratio of phenol to allyl'acetate of between 018' and i-Z' to 1.

10 A mineral lubricating oil containing between'about'0.05% and about 20% by weight of oil-soluble metal'salt of the acidic reaction product obtain'ed' by: condensing a hydrocarbon substitutedphenol in wh'ich'the hydrocarbon substituent' contains 'between about 4 and about T30 carbonfi-atoms with allyl alcohol using a:molar ratio of phenol to. allyl alcohol of between 0.8 and 2"to 1, the condensation being: efiected :at temperatures between: 0 C. and 100 C.

11-. A'-. mineral lubricating oil containing: be tweenab'out 0.05 :'and'.about"20% by'fweight of an oil-soluble m'etallsalt of the acidic: reaction product obtainedbycondensing a; hydrocarbon substituted phenol in' which the hydrocarbon-sub stituent contains between about 42andiabout 30 carbonatoms'withzallyl chloride, atra-zltemperature 'betweenabout 0 C. and about100"C., using amolar. ratio'aof iphenotto allylchloride: between 0&8 andi2ft'ml.

12." mineral lubricating: oil 2 containing "be; tween about 0.5% and about 10% by weight of the barium salt of the: acidic icondensation product obtained by-condensing at temperatures-between about 0 CQ-and about 100 0;, -approximately equal molarproportions ofi'an alkyllsubsti'tuted phenol and allyl aceta'te, the alkyl substituent of said-phenol containingbetween about 4iand about 30 carbon atoms.

13. A mine'ral lubricating oil containing. between about 0.5% and about 10%' b"y. weight of thebarium sa'lt'of the acidic condensation prodnot obtained 'by condensing.approximately equal molarflprop'ortions of -.octylphenol and allyl alcohol at temperatures between about 0C; and about 100 CV '14; A mineral lubricating oil accordingito claim 1 containing also between" about 0.5" and about '10 by. weight of an oil-soluble --meta1 sulfonate.

"151 A mineral lubricating .oil according to claim 1' containing also between05 and"1'0% of a modified sul'fonateprepared by"heati ng an oil-soluble" metalsulfonate with an inorganic base selected from the classconsisting of metal oxides, hydroxides, carbonates and bicarbonates to solubilize said base, said modified sulfonate having a. ratio of equivalents ofmetal-to equivalents of sulfonicracidsbetween 1.1 and 3 to l.

LOREN L. NEFF;

ReferenceaCitedin the file of this patent UNITED STATES- PATENTS

Claims (1)

1. A MINERAL LUBRICATING OIL CONTAINING BETWEEN ABOUT 0.05 AND ABOUT 20% BY WEIGHT OF AN OIL-SOLUBLE METAL SALT OF THE ACIDIC CONDENSATION PRODUCT OF A HYDROCARBON SUBSTITUTED PHENOL, IN WHICH THE HYDROCARBON SUBSTITUENT CONTAINS BETWEEN ABOUT 4 AND ABOUT 30 CARBON ATOMS, AND AN ALLYL COMPOUND SELECTED FROM THE CLASS CONSISTING OF ALLYL ALCOHOL, DIALLYL ETHER, ALLYL ETHYL ETHER, ALLYL PROPYL ETHER, ALLYL ESTERS OF HYDROHALOGEN ACIDS AND ALLYL ESTERS OF FATTY ACIDS CONTAINING BETWEEN 1 AND 6 CARBON ATOMS IN THE FATTY ACID RADICAL, SAID CONDENSATION PRODUCT BEING OBTAINED BY CONDENSING SAID PHENOL WITH SAID ALLYL COMPOUND IN THE MOLAR RATIO OF BETWEEN 0.5 AND 3 TO 1 AT TEMPERATURES BETWEEN ABOUT -20* C. AND ABOUT 150* C.