BE486220A - - Google Patents

Description

       

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  "IMPROVEMENTS IN LUBRICATING COMPOSITIONS"
The present invention includes improvements to lubricating compositions and relates more especially, but not exclusively, to compositions for use in internal combustion engines, which may be powered by gasoline or oil. In the latter case, the invention is applied to lubricating oils known as “high load oils” used in diesel engines and other oil engines.



   It is an object of the invention to provide a lubricating composition in which the lubricant has the tendency to form products which corrosively act on metals (e.g. metal bearing surfaces or bearings), and to form harmful oxidation products. in the lubricant are neutralized, and it is another object to provide a composition which also has detersive properties.

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   These latter properties aim to ensure the cleanliness of the engine during the use of the lubricant, by preventing the deposition of gums or lacquers on the lubricated parts or components, and by keeping in suspension the solid particles and the sludge (formed in portions of the engine or in the lubricant). Such properties are of particular importance in oil engines such as diesel engines.



   The present invention contemplates the use, in a lubricating composition, of a metal derivative of an organic substituted dithiophosphate; a few examples of the latter type of compound have already been proposed with a view to incorporation into lubricating oils.



   According to the invention a lubricating composition comprises a lubricating oil base and a minor proportion: (a) of the tin salt of an oil soluble petroleum sulfonic acid and (b) of a. polyvalent metal salt (which is soluble in base oil) of an organic dithiophosphoric acid.



   It has already been proposed to add various metal salts of organic dithiophosphoric acids to oils.



   These additions are generally known to give the oil good resistance to oxidation and to prevent, to a greater or lesser extent, the formation of products with corrosive action on the seats or bearings of composite metal.



  Some of these additions also possess "detergent" or "sludge dispersing" properties, and in this connection especially effective are the alkaline earth metal salts of dithiophosphoric chain acids. a line with ten or more carbon atoms.



   These relatively high molecular weight dithiophosphates have, however, been found to be much less effective as and oxidation / corrosion inhibitors or bearings than those with low molecular weight which, however, are relatively ineffective as detergents and dispersants. sludge.

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   An advantage of the invention lies in the fact that by the use of the combination of additions which is defined herein, lubricating compositions possessing all these properties to a high degree can be formed.



   Another advantage of the compositions of the present invention lies in the fact that they provide better protection of ferrous metal surfaces against rust (and the resulting wear) due to the presence of condensed water, carbon dioxide, d hydrobromic acid, etc., normally present in small amounts in the combustion space.



   The additions of the present invention also provide the base oil with improved film breaking strength.



   The combination of desirable characteristics provided by the lubricating compositions of the invention cannot be obtained by the arbitrary choice of any compound having detersive properties with any oxidation or corrosion inhibitor, since very often the presence of Detergent works against the normal action of the inhibitor, making it relatively ineffective, possibly preventing it from forming a film on the surfaces of metal catalysts that may be present.



   In addition, many of the detersive compounds previously proposed as additions to lubricants are themselves corrosive to composite metals, for example copper-lead seats or bearings.



   It is a feature of the present invention that not only does neither of the two additions interfere with the normal action of the other, but also that in many cases they cooperate to provide improved results over and beyond. those obtained with one or the other addition used alone.



   In accordance with one form of the present invention, a lubricating composition comprises a lubricating oil base and a minor proportion of both the tin salt of an oil-soluble petroleum sulfonic acid, and a metal salt (which is solu-

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 ble in the base oil) of an organic di-substituted dithiophosphoric acid derived, at least in part, from an alkylated phenol.



  Such a di-substituted salt can be represented by * the general formula:
 EMI4.1
 in which n represents the valence of a metal M; R1 is any suitable organic radial, and R2 is an alkylated aromatic radical.



   The R2 radical of the general formula given above is advantageously such that it has not less than five carbon atoms in the alkyl group and can be derived, for example, from p-tert-amylphenol, p-octylphenol or octylcresol. The radical R1 is such that it provides an oil soluble product and can be derived, for example, from an aliphatic alcohol (for example butyl, amyl or lauryl alcohol), from a cyclic alcohol (for example). example cyclohexanol or methyl-cyclohexanol), a phenol (for example cresol or octylcresol), or an aromatic alcohol such as benyl alcohol.



   It should be understood that suitable radicals for R1 and R2 in the general formula given above should always be such that the di-substituted metal salt is soluble in the lubricating base oil.



   Although, as already indicated, it is preferable to employ compounds in which R2 contains at least five carbon atoms in the alkyl group, it is within the scope of the invention to use compounds in which the alkyl group of R2 is short, or even absent, provided that R1 is such as to give the metal salt adequate solubility in oil.



   Typical preferred examples of di-substituted dithiophosphoric acids of which a metal salt is used according to

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 the invention, are the acids: di (octyl-cresyl) dithiophosphoric acid "octyl-cresyl cresyl" "octyl cresyl 2-ethyl hexyl dithiophosphoric" di (p-octyl phenyl) dithiophosphoric "di (t-butyl cresyl)" "octyl cresyl n-butyl "" octyl cresyl cyclohexyl "
The preparation of such metal salts is advantageously carried out by first reacting the alkylated phenol with phosphorus pentasulfide, in the presence or absence of a suitable organic hydroxyl compound intended to react simultaneously in order to produce a mixed di-substituted dithiophosphate.



   The acid is advantageously neutralized with caustic soda and a desired metal salt is obtained by adding a suitable salt of said metal.



   In accordance with another form of the present invention, the lubricant composition mentioned last is modified by the incorporation into the lubricating oil base, (either as a replacement or in addition to the organic di-substituted dithiophosphate derived from a phenol alkyl) of a minimal proportion of an oil-soluble metal salt of an organic di-alkyl or di-cyclo-alkyl dithiophosphoric acid. This last salt is represented by the general formula:
 EMI5.1
 in which R1 and R2 are alkyl or cyclo-alkyl groups having at least five and preferably not more than ten carbon atoms, either in a straight chain or a branched chain or in the ring, and in which n is the valence metal M.



   The radicals R1 and R2, of the formula indicated above,

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 are preferably, but not necessarily, analogs, and may, for example, be derived from amyl alcohol, hexyl alcohols such as n-hexyl alcohol, methyl-isobutyl carbinol, and 2-ethyl butanol , 2-ethyl hexanol, nonyl alcohol, cyclohexanol and methyl cyclohexanol.



   Typical preferred examples of di-alkylated or di-cyclo-alkylated dithiophosphoric acids of which a metal salt is used in accordance with the invention are the acids: din-hexyl) dithiophosphoric acid "di (2-ethyl hexyl) dithiophosphoric" di ( methyl cyclohexyl) dithiophosphoric "di amyl dithiophosphoric" di (-methyl isoamyl) dithiophosphoric.



   It will be understood, however, that mixed dithiophosphoric acids can be employed in the preparation of the oil soluble salts.



   The preparation of the dialkyl or dialkyl dithiophosphates can be accomplished by first reacting an appropriate alcohol or mixture of alcohols with phosphorus pentasulfide to generate thiophosphoric acid, from which the desired metal salt can be prepared. by first neutralizing the acid with caustic soda and then adding an appropriate salt of the metal from which it is desired to obtain the dithiophosphate.



     However, it is possible to prepare certain salts, for example those of zinc, by direct reaction of an oxide of the metal with dithiophosphoric acid.



   In accordance with one form of the invention, a chromium salt of the organic di-substituted dithiophosphate is used, the advantage of using organic compounds of tin and chromium in a lubricating composition having already been demonstrated. Other dithiophosphate salts can however be used, such as those of barium, calcium, strontium, magnesium, zinc, aluminum, nickel, cobalt, tin, cadmium and manganese.

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   Also according to the invention, the lubricating compositions of the type referred to above may also comprise in their composition, (1) a thio-ether and, or hydroxy-substituted aromatic di- or polysulphide, and, or (2) an aromatic ester phosphite or thiophosphite derived from such an aromatic thio-ether and, or di- or polysulfide. As a replacement for, or in addition to, ingredients (1) and (2), another ingredient, namely (3) a tri-aryl phosphite can be incorporated into the lubricating composition.



   As examples of the third addition agent, there may be mentioned the compounds:
 EMI7.1
 (1) di (3-carbomethoxy-4-hydroxyphengrl) thioether, disulfide or polysulfides; (2) di (3-carbomethoxy-4-hydroxyphenyl) thioether cresyl phosphite; (3) triphenyl phosphite, tri (p. T-amyl phenyl) phosphite.



  Example 1
Preparation of chromium di (octyl-cresyl) dithiophosphate.



   88 grams of octyl cresol (a mixture of di-isobutyl cresols available in commerce) are placed in a round-bottomed flask of 250 cc, heated to 130 ° C. and treated with 24.3 grams of pentasulfide. powdered phosphorus, added in small portions over 30 minutes with mechanical stirring, the temperature being maintained at 130 - 140 C until almost the evolution of hydrogen sulfide is almost complete and most of the phosphorus pentasulfide has disappeared,
The reaction is then completed by heating slowly to 150 ° C. and maintaining this temperature with stirring for five minutes.



   After cooling, the product is dissolved in petroleum ether and separated by filtration from a little sulfur and unreacted phosphorus pentasulfide, the solvent then being distilled off under reduced pressure, to give a viscous liquid am -

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 The acidity of the product, determined by titrating an alcoholic solution with a standard caustic soda solution in the presence of phenolphthalein as an indicator, corresponded to an apparent molecular weight of 529 compared to a molecular weight. Theoretical 533 for di (octyl cresyl) dithiophosphoric acid.



   This product is mixed with nine times its weight of water in a flat-bottomed vessel or test tube, heated to 40-50 C and neutralized by gradually adding caustic soda solution, while mixing, until alkaline reaction occurs. 'phenolphthalein indicator.



   This sodium salt solution is then heated to 90 ° C. and a small additional quantity of caustic soda is added, obtaining a clear solution which is exactly alkaline with phenolphthalein.



   To this solution is added rapidly, while stirring, a 10% aqueous solution of chromium alum (at 90 ° C.) containing 15% excess relative to the theoretical chromium, with precipitation of chromium violet dithiophosphate in the form of a viscous liquid.



   After cooling, the aqueous solution is decanted from this liquid which is then dissolved in petroleum ether, dried over amhydrous sodium sulfate, filtered and freed from the solvent by distillation. A theoretical yield of 82% of the product is obtained.



   Of a number of products prepared by this method, a typical large-scale product roughly corresponds to the following analysis:
Chromium 1.20% Sulfur 8.4% Phosphorus 4.3%
43%
Chromium salt of di (octyl-cresyl) dithiophosphoric acid,
Sodium salt of "" "" "5%
Free di (octyl-cresil) dithiophosphoric acid 29%
Octyl-cresol and other neutral products 23%.



   (The molecular weight of the free acid in this case was 600).

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   The mixed product obtained by this method will be called subsequently: chromium di (octyl-cresyl) dithiophosphate "A".



  Example 2.



   Using the method of Example 1, except that the precipitation temperature of the chromium salt is 50 - 60 C instead of 90 C, and the concentration of the sodium salt solution is 5% instead of 10 %, products with a higher chromium salt concentration are obtained.



   Such a product, prepared from a free acid with a molecular weight of approximately 675, gives the following analysis:
Chromium 1.86% Phosphorus 4.34% Chromium salt of di (octyl-cresyl) dithiophosphoric acid 72% Sodium salt of "" il "13% Free di (octyl-cresyl) dithiophosphoric acid 15%
The product will be called subsequently: di (octyl-cresyl): chromium "B" dithiophosphate.



   It should be understood that in employing the compounds of the invention, either pure metal salts or mixtures can be used, such as the products of Examples 1 and 2. Although the presence of small amounts of free dithiophosphoric acids and their sodium salts do not give rise to objection, it is preferable to use materials containing not more than about 20% free acid 4 and preferably less) and not less than about 65% of the salt of the polyvalent metal .



   If desired, the residual free acid can be substantially neutralized by heating the product (preferably in an oil solution) with a metal oxide or hydroxide (such as zinc oxide or calcium hydroxide or barium), in order to produce, for example, a mixture of chromium and zinc salts, in combination with a small amount of sodium salt.



  Example 3.



   Using the method of Example 1, 1170 grams of 2-ethyl hexanol are reacted with 500 grams of phosphorus pentasulfide, a reaction temperature of 100 to 110 ° C. suitable,

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 and the reaction being terminated by heating to 1300 C. A dark liquid is obtained having a molecular weight of 380 compared to a theoretical molecular weight of 354 for di (2-ethyl hexyl) dithiophosphoric acid.



   The zinc salt of the latter acid is prepared in the present example by heating a mixture of 101 grams of acid and 11.1 grams of zinc oxide, for half an hour, from 120 to 1300 C. reaction product is dissolved in petroleum ether, separated by filtration from the excess zinc oxide and the solvent is removed by distillation to give a yellow viscous liquid holding 8.30% by weight of zinc compared to an amount Theoretical 8.22% for zinc .dioctyl dithiophosphate.



  Example 4.



   Octyl-cresyl 2-ethyl hexyl dithiophosphoric acid tin salt.



   Using the method of Example 1, from a mixture of 330 grams of octyl cresol and 195 grams of 2-ethyl hexanol, 647 grams of phosphorus pentasulfide are obtained by the action of 166.5 grams grams of a viscous amber liquid, representing a yield of 97%.



   This product has a molecular weight of 540 compared to a theoretical value of 444.



   Using the method of Example 2, from 42 grams of this material, and 12.4 grams of tin chloride in concentrated cold aqueous solution, 34.6 grams (72%) of a Extremely viscous brown liquid, containing 12.5% tin.



  Example 5.



   Mixed chromium-zinc salt of di (2-ethyl hexyl) dithiophosphoric acid.



   19 grams of di (2-ethyl hexyl) dithiophosphoric acid (of molecular weight 380) prepared as described in Example 3 are mixed with stirring for 20 minutes at 70-80 C with

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 Freshly moist chromic hydroxide will precipitate from a 10% aqueous solution containing 4.2 grams of chromium alum by the addition of ammonia. Then 1.5 grams of zinc oxide are added and heating is continued for another 15 minutes, after which the temperature is slowly raised to 1300 ° C. to complete the reaction and remove the water formed.



   The product, after dissolution in petroleum ether, filtration, and removal of the solvent, contained 1.30% chromium and 5.10% zinc, the composition being approximately as follows: Chromium salt of di (2-ethyl hexyl) dithiophosphoric acid 29% Zinc salt of "" "" "67% Free di (2-ethyl hexyl) dithiophosphoric acid 3%
Other known methods for the preparation of metal dithiophosphates of the invention can also be used:

   for example, the direct reaction between the free acid and a metal oxide in an alcohol-benzene solution at 40 - 50 C (especially applicable to salts of alkaline earth metals and magnesium), or the direct reaction between a metal hydroxide , such as barium hydroxide and free acid, by heating them together in a solution of mineral oil in the presence of a stream of air to remove the liberated water.



   Alternatively, the metathesis can be carried out in an alcoholic solution between an alkali metal salt of a dithiophosphoric acid and a metal salt soluble in alcohol.



   A large number of the salts can be prepared with good yield by the method of Example 2, the conversion of the metal to salt being carried out in many cases (for example for tin, cadmium, nickel, cabalt) of a more satisfactorily than in the case of chromium. A better transformation is also obtained in the case of the dialkylated dithiophosphates than for the aryl alkylated dithiophosphates.



  Example 6.



   The tin salt of petroleum sulfonate for use in conjunction with the product of Examples 1-5 is prepared as follows;

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1816 grams of an oil concentrate containing 45% petroleum-sodium sulfonate (derived from so-called "mahogony acids" with a molecular weight equal to 400 - 420) are mixed with 15.9 liters of water and heated at 90 C, obtaining a milky solution. To this solution is added, while stirring, a cold solution of 227 grams of stannous chloride (SnCl2, 2H20) in 500 cc. of water, and a precipitate of petroleum tin sulfonate in oil solution is obtained.



   After cooling, the aqueous solution is decanted and the product is washed by boiling it with 4.5 liters of water.



  The mixture, after boiling, is mixed with 1816 grams of mineral oil and the resulting composition is passed through a Laval centrifuge. The oil concentrate, freed from most of the water, is heated to 121 C in a stream of air to remove the remaining moisture.



   By this process, 3.360 kilograms (representing a yield of 96) are obtained of a solution of petroleum-tin sulphonate oil which, on analysis, shows a content of 21% petroleum-tin sulphonate and 2 , 74% tin by weight. The product is sodium-free and can be used as an oil solution, in an appropriate amount, with a lubricating oil base, with a view to the introduction into the latter of petroleum tin sulfonate.



  Proportions.



   Although the expression "minimal proportion" generally covers the use of the additions of the invention, the following proportions give an indication of the values envisaged.



   Metal dithiophosphate 0.1 - 2% (preferably 0.2 - 1%)
Petroleum tin sulfonate 0.05 - 2% (preferably 0.1 - 1%)
The third addition 0.01 - 1% (preferably 0.05 - 0.5%)

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Test results.



   Numerous examples of the invention are given below, together with the results of tests which serve to illustrate, from various points of view, why the lubricating compositions provided by the invention are desirable.



   For the purpose of comparison, the test results include those relating to the lubricating base oils employed, in the examples of compositions proposed by the invention as well as, in certain cases, those relating to compositions not comprising. only one of the additions.



   The constituents of said compositions are given in weight percentages in all tests.



   Test # 1.



   Resistance to oxidation.



   As a means of examining the oxidation resistance of the compositions provided by the invention, a variation of the well known oxidation test from the British Air Ministry was used.



   In this test 40 oc. of the oil are oxidized by heating to 160
0 for two periods of 6 hours, in glass tubes, in the presence of a current of air which is passed at a speed of
15 liters per hour. Lubricating compositions were oxidized under standard conditions of the British Air Ministry oxidation test except that the temperature employed was.
160 C, and the presence of a copper catalyst consisting of a polished rolled sheet, 56.4 x 25.4 m / m. The catalyst was replaced with a new one at the end of the first period of
6 hours of oxidation.



   The test results are as follows:

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 EMI14.1
 
<tb>
<tb> Es- <SEP> Lubricant <SEP> composition <SEP> Increase- <SEP> Acidity <SEP>% <SEP> insoluble
<tb> sai <SEP> ment <SEP> of <SEP> (mgs of <SEP> in <SEP> ether
<tb> n. <SEP> viscosity <SEP> KOH <SEP> by <SEP> of <SEP> oil
<tb> (%) <SEP> gram) <SEP> (boiling point <SEP> <SEP> <<SEP> 40 C)
<tb> 1 <SEP> oil <SEP> "B" <SEP> ¯-¯¯¯ <SEP> 33.6 <SEP> 1.00 <SEP> 0.45
<tb> 2 <SEP> oil <SEP> "B" <SEP> + <SEP> 0.5% <SEP> di <SEP> ([alpha] <SEP> -methyl <SEP>)
<tb> isoamyl))
<tb> dithiophosphate)
<tb> of <SEP> zinc) <SEP> 25.0 <SEP> 0.45 <SEP> 0.34
<tb> + <SEP> 0.2% <SEP> sulfonate <SEP> of)
<tb> petroleum-tin <SEP>) <SEP>
<tb> 3 <SEP> oil <SEP> "B" <SEP> + <SEP> 0.6% <SEP> di (octyl <SEP> cresyl)
<tb> dithiophosphate)
<tb> from <SEP> chrome <SEP> "B" <SEP>)

   <SEP> 21.5 <SEP> 0.56 <SEP> traces
<tb> + <SEP> 0.2% <SEP> sulfonate <SEP> of)
<tb> petroleum-tin <SEP>) <SEP>
<tb> 4 <SEP> oil <SEP> "B" <SEP> + <SEP> 0.6% <SEP> di (octyl <SEP> cresyl)
<tb> dithiophosphate) <SEP> very <SEP> led <SEP> zinc <SEP> 22.7 <SEP> 0.56 <SEP> managed <SEP> tra-
<tb> + <SEP> 0.2% <SEP> sulfonate <SEP> of) <SEP> these
<tb> petroleum-tin <SEP>) <SEP>
<tb>
 
 EMI14.2
 5 oil "B" + 0.6% di (2-ethylpl)
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<tb>
<tb> dithiophosphate)
<tb> of <SEP> chrome <SEP> 19.3 <SEP> 0.56 <SEP> light
<tb> + <SEP> 0.2% <SEP> sulfonate <SEP> of) <SEP> traces
<tb> petroleum-tin <SEP>) <SEP>
<tb> 6 <SEP> oil <SEP> "B" <SEP> + <SEP> 0.5% <SEP> di-n-hexyl
<tb> dithiophosphate)
<tb> of <SEP> zinc <SEP> 17.5 <SEP> 0.45 <SEP> light
<tb> + <SEP> 0.5% <SEP> octyl <SEP> cresyl <SEP> traces
<tb> cresyl <SEP> di- <SEP>)
<tb> thiophosphate <SEP>)

   <SEP>
<tb> from <SEP> chrome)
<tb> + <SEP> 0.2% <SEP> sulfonate <SEP> of <SEP>)
<tb> petroleum-tin <SEP>) <SEP>
<tb> 7 <SEP> oil <SEP> "B" <SEP> + <SEP> 1 <SEP>% <SEP> octyl <SEP> cresyl <SEP> n-)
<tb> butyl <SEP> dithio- <SEP>) <SEP>
<tb> phosphate <SEP> of)
<tb> cobalt) <SEP> 19.3 <SEP> 0.56 <SEP> traces
<tb> + <SEP> 0.5% <SEP> sulfonate <SEP> of)
<tb> petroleum-tin <SEP>) <SEP>
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It appears that while all of the compositions tested exhibit greatly improved resistance to oxidation as compared to the base oil, those comprising metal salts of alkylated aromatic dithiophosphates are especially effective, especially in inhibiting the formation of sludge Test 2. - Corrosion of bearings or bearings.



   The following test was performed to obtain indications as to the corrosion tendency of seats or bearings made of composite metals.

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 tes, in particular copper-lead bearings, when using lubricating compositions provided by the invention.



     .400 oc. lubricant are distributed in deep vases or test tubes of 1500 cc., without lips and made of glass, of which eight of them are heated in a circular oil bath, electrically heated, and controlled by thermostat to maintain the temperature lubricant at 140 C. The test pieces are fitted with aluminum lids which fit tightly, presenting central slots or slides which are normally closed but which can be opened for the introduction of specimens to be tested. However, the closed slots or slides leave sufficient passage for the steel stirrer rods, placed in the middle, to rotate freely.

   These rods are electrically driven from a common drive shaft, rotating at 400 ¯ 40 revolutions per minute and have at their lower end slotted brackets to which lead test pieces are attached with screws. . For the test pieces, rectangular plates, pure lead, 44.5 x 25.4 m / m, are mounted vertically exactly below the surface of the lubricant, their major axis being horizontal. Strips of copper, used as catalysts, 12.7 m / m wide and curved into a semicircle 95 m / m in diameter are placed entirely below the surface of the lubricant and held in place with wires vertical copper to cork stoppers mounted in the lids of the test tubes. Each test piece is also provided with a thermometer.



   The tests are carried out in a total time of 30 hours, in six hour periods, the copper and lead specimens being removed every two hours and replaced by

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 new clean specimens. The copper catalysts were cleaned with carborundum powder and washed in petroleum ether. The lead specimens were flattened, scraped using special Skartsen scrapers and finally brushed in one direction using a stiff bristle brush called a "card", before washing with benzene and weighing. After a period of two hours, another benzene wash, brushing with a camel hair brush and reweighing were performed.



   At any time, the total corrosion is calculated by adding together the weight losses of the lead specimens after each two hour period.



   These total losses were shown in a diagram with respect to time, and from the curves obtained, the times necessary to obtain determined corrosion losses were deduced.



   The following results were obtained:

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 EMI17.1
 
<tb>
<tb> Es- <SEP> Lubricant <SEP> composition <SEP> Specimens <SEP> in <SEP> Time <SEP> for
<tb> sai <SEP> lead <SEP> -loss <SEP> losses <SEP> of
<tb> n. <SEP> of <SEP> weight <SEP> in <SEP> weight <SEP> of <SEP>: <SEP>
<tb>
 
 EMI17.2
 mgrs. after:

   ¯¯¯¯¯¯¯¯¯¯
 EMI17.3
 
<tb>
<tb> 12h. <SEP> 18h <SEP> 20 <SEP> 50 <SEP> 100 <SEP> mgs
<tb>
<tb> 8x <SEP> oil <SEP> "B" <SEP> 283 <SEP> 4 <SEP> 6 <SEP> 8
<tb> 9 <SEP> oil <SEP> "B" <SEP> + <SEP> 0.5% <SEP> of <SEP> sulfonste <SEP> of
<tb> petroleum-tin <SEP> 113- <SEP> 4 <SEP> 6 <SEP> 10
<tb> 10x <SEP> oil <SEP> "B" <SEP> + <SEP> 0.3% <SEP> of <SEP> di (octyl <SEP> cresyl)
<tb> dithiophosphate
<tb> of <SEP> chrome <SEP> "B" <SEP> 20 <SEP> 281 <SEP> 12 <SEP> 14 <SEP> 15
<tb> llx <SEP> like <SEP> in <SEP> test <SEP> n <SEP> 10
<tb> + <SEP> 0.2% <SEP> of <SEP> sulfonate <SEP> of
<tb> petroleum-tin <SEP> 24 <SEP> 63 <SEP> 10 <SEP> 17 <SEP> 20
<tb> 12x <SEP> like <SEP> in <SEP> test <SEP> n <SEP> 10
<tb> + <SEP> 0,

  2% <SEP> of <SEP> sulfonate <SEP> of
<tb>
 
 EMI17.4
 petroleum-calcium 15 143 13 15 17
 EMI17.5
 
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<tb> 13 <SEP> like <SEP> in <SEP> test <SEP> n <SEP> 10
<tb> ¯ <SEP> 0.2% <SEP> of <SEP> sulfonate <SEP> of
<tb> petroleum <SEP> -sodium <SEP> 19 <SEP> 83 <SEP> 12 <SEP> 16 <SEP> 18
<tb>
 
 EMI17.6
 14 oil "B" <- 0.5% di (<- methyl)
 EMI17.7
 
<tb>
<tb> isoamyl) <SEP> dithio- <SEP>) <SEP> more
<tb> phosphate <SEP> of <SEP> zinc) <SEP> 19 <SEP> 25 <SEP> 16 <SEP> 26 <SEP> of <SEP> 30
<tb> + <SEP> 0.2% <SEP> of <SEP> sulfonate <SEP> of <SEP>) <SEP>
<tb> petroleum-tin <SEP>)
<tb> 15 <SEP> oil <SEP> "B" <SEP> + <SEP> 0.4% <SEP> of <SEP> di (p-octyl <SEP>)
<tb> phenyl) <SEP> dithio- <SEP>) <SEP>
<tb> phosphate <SEP> of)
<tb> chrome) <SEP> 20 <SEP> 142 <SEP> 12 <SEP> 15 <SEP> 17
<tb> + <SEP> 0.1% <SEP> of <SEP> sulfonate <SEP> of <SEP>)

   <SEP>
<tb> petroleum-tin
<tb> 16 <SEP> oil <SEP> "B" <SEP> + <SEP> 0.4% <SEP> of <SEP> di (2-ethyl <SEP> he-)
<tb>
 
 EMI17.8
 l) dithiophospha4
 EMI17.9
 
<tb>
<tb> te <SEP> of <SEP> magnéoium <SEP>) <SEP> 37- <SEP> 11 <SEP> 12 <SEP> 14
<tb> + <SEP> 0.4% <SEP> of <SEP> sulfonate <SEP> of <SEP>) <SEP>
<tb> petroleum-tin
<tb> 17 <SEP> oil "B" <SEP> + <SEP> 0.3% <SEP> of octyl <SEP> cresyl <SEP>)
<tb> cyclohexyl <SEP> di- <SEP>)
<tb> thiophosphate <SEP> from <SEP>) <SEP>
<tb> cadmium <SEP>) <SEP> 16 <SEP> 203 <SEP> 13 <SEP> 14 <SEP> 16
<tb> + <SEP> 0.1% <SEP> of <SEP> sulfonate <SEP> of <SEP>) <SEP>
<tb> petroleum-tin
<tb> 18 <SEP> oil <SEP> "B" <SEP> + <SEP> 0.5% <SEP> di <SEP> di (methyl <SEP>)
<tb> cyclohexyl) <SEP> di- <SEP>) <SEP>
<tb> thiophosphate <SEP> from <SEP>) <SEP> more
<tb> nickel) <SEP> 14 <SEP> 18.5 <SEP> 22 <SEP> of <SEP> 30
<tb> + <SEP> 0,

  2% <SEP> of <SEP> sulfonate <SEP> of <SEP>) <SEP>
<tb> petroleum-tin
<tb> 19 <SEP> oil <SEP> "B" <SEP> + <SEP> 0.6% <SEP> of <SEP> di (ter <SEP> butyl <SEP>) <SEP>
<tb> cresyl) <SEP> dithio- <SEP>) <SEP>
<tb> phosphate <SEP> of)
<tb> manganese <SEP>) <SEP> 35 <SEP> 103 <SEP> 9 <SEP> 16 <SEP> 28
<tb> + <SEP> 0.4% <SEP> of <SEP> sulfonate <SEP> of <SEP>)
<tb> petroleum-tin
<tb>
 

 <Desc / Clms Page number 18>

 
 EMI18.1
 
<tb>
<tb> Es- <SEP> Lubricant <SEP> composition <SEP> Specimens <SEP> in <SEP> Time <SEP> for
<tb> sai <SEP> lead <SEP> -loss <SEP> losses <SEP> of
<tb> n. <SEP> of <SEP> weight <SEP> in <SEP> weight <SEP> of <SEP>:

   <SEP>
<tb> mgrs. <SEP> after <SEP>:
<tb> 12h. <SEP> 6 p.m. <SEP> 20 <SEP> 50 <SEP> 100mgrs7
<tb>
 
 EMI18.2
 --- "##" ### - # "# # - # # ### # # - ### <## - # #i. * os> ## m H e> .e #., # ------------- ----------------
 EMI18.3
 
<tb>
<tb> 20 <SEP> oil <SEP> "B" <SEP> + <SEP> 0.8% <SEP> of octyl <SEP> cresyl <SEP>) <SEP>
<tb> 2-ethyl <SEP> hexyl)
<tb> dithiophosphate <SEP>) <SEP> more
<tb>
 
 EMI18.4
 tin) 17 24 15 of 30 - + 0.2i $ sulfonate)
 EMI18.5
 
<tb>
<tb> petroleum-tin <SEP>)
<tb> 21 <SEP> oil <SEP> "B" <SEP> + <SEP> 2 <SEP>% <SEP> of <SEP> di <SEP> (2-ethyl <SEP>)
<tb> hexyl) <SEP> dithio- <SEP>) <SEP> more
<tb> phosphate <SEP> of <SEP> zinc) <SEP> 10 <SEP> 13 <SEP> 29 <SEP> of <SEP> 30
<tb> + <SEP> 0.2% <SEP> of <SEP> sulfonate <SEP> of <SEP>) <SEP>
<tb> petroleum-tin
<tb> + <SEP> 0.2% <SEP> of <SEP> sort (p-ter <SEP>)

  
<tb> amyl <SEP> phenyl) <SEP>)
<tb> phosphite)
<tb> 22 <SEP> oil <SEP> "B" <SEP> + <SEP> 0.5% <SEP> of <SEP> di (methyl <SEP> cy-)
<tb> olo / hexyl) <SEP> <SEP> zinc <SEP> dithiophosphate <SEP>)
<tb> + <SEP> 2 <SEP>% <SEP> of <SEP> sulfonate <SEP> of <SEP>) <SEP>
<tb> petroleum-tin <SEP>) <SEP> 47.5 <SEP> 8 <SEP> 12 <SEP> 16
<tb> + <SEP> 0.5% <SEP> of octyl <SEP> oresol <SEP>) <SEP>
<tb> thioether <SEP>)
<tb>
 Note.



   The x's indicate that these are average values of 2 or 3 trials.



   The compound known as octyl cresol thioether of test n 22 was prepared by the action of sulfur dichloride on octyl oreol in solution in carbon tetrachloride.



   It appears that in order to obtain the most effective inhibition of corrosion, the amount of petroleum tin sulfonate employed should not exceed that of metal dithiophosphate.



   It emerges from the results of previous tests, and in particular of tests 8 -13, that a higher degree of protection against the. corrosion by the use of the combination of additions of the invention than that which would be obtained by the use of one or the other addition employed separately in comparable proportions and, in addition, that the use of sulfonate of petroleum-tin gives superior results than those obtained by the use of other metallic petroleum sulphonates, such as those of calcium and sodium, with regard to the delay in the rate of increase of corrosion in the later stages of the test.

   Other test results are shown to give an idea of the wide range of compounds

 <Desc / Clms Page number 19>

 and in proportions which can be used in order to obtain lubricating compositions having a high degree of resistance to the formation of corrosive products with respect to seats or bearings of composite metal.



  Test 3. - Protection against rust.



   A simple test was set up to demonstrate the effectiveness of the lubricating compositions of the invention in the protection against rust of ferrous metal surfaces in the presence of humidity and carbon dioxide.



   Rectangular plates of mild steel 75 x 25 m / m, polished with emery cloth and washed with petroleum ether, are weighed and completely immersed in the tested oil, for five seconds, at the temperature of d. flat, drained in a vertical position for 15 minutes and placed horizontally across two small glass rods in the bottom of a glass tray 100 m / m in diameter.



   The tray is then filled with distilled water saturated with carbon dioxide so that the steel is approximately 12 m / m below the surface of the water, and left open, exposed to air, the level being kept approximately constant,, After one month, the plates are removed, freed of loose rust by rubbing them with a muslin, and weighed.



   The following results were obtained:
 EMI19.1
 
<tb>
<tb> Test <SEP> Oil <SEP> used <SEP> Loss <SEP> of <SEP> weight
<tb> n <SEP> of the <SEP> plates
<tb> (mill <SEP> igram <SEP> s) <SEP>
<tb> 23 <SEP> oil <SEP> "B" <SEP> 41.7
<tb> 24 <SEP> oil <SEP> "B" <SEP> + <SEP> 0.5% <SEP> of <SEP> di <SEP> -methyl <SEP> isoamyl))
<tb> Zinc <SEP> <SEP> <SEP> dithiophosphate <SEP>)
<tb>
 
 EMI19.2
 * 0.2% di (octyl, cresyl) di-)
 EMI19.3
 
<tb>
<tb> chromium <SEP> thiophosphate <SEP> <SEP>)
<tb> "B" <SEP>)
<tb> + <SEP> 0.2% <SEP> of <SEP> sulfonate <SEP> of <SEP> petroleum- <SEP>) <SEP> 3.1
<tb> tin <SEP>)
<tb>
 
 EMI19.4
 +0.05.

   di (3-carbomethoxy-4-)
 EMI19.5
 
<tb>
<tb> hydroxyphenyl) <SEP> thioether)
<tb> cresyl <SEP> phosphite)
<tb>
 
The water in test 23 was filled with red rust, while in test 24 it was only slightly modified.

 <Desc / Clms Page number 20>

 Test 4- - Protection against rust in the presence of hydrobromic acid.



   The UK Ministry of Supply method - D.T.D. specification is used. 698, (Annex 1).



   This method, in which strips of mild steel, sandblasted, are immersed first in a solution of hydrobromic acid in kerosene, then in the tested oil (diluted with 15% of 'petroleum ether) and finally suspended for 24 hours in a closed container above a saturated solution of zinc sulphate, was devised to simulate the conditions existing in an internal combustion engine where, after a period of operation, the engine is left idle.

   Corrosion of cylinder walls, with the resulting loss of power due to excessive piston clearance, tends to occur there due to the presence of condensed water, carbon dioxide and products of fuel combustion, among which hydrobromic acid produced in small quantities by the combustion of ethylene dibromide normally present in lead-loaded fuels.



   The following results were obtained.
 EMI20.1
 
<tb>
<tb>



  Test <SEP> Oil <SEP> used <SEP> Gain <SEP> of <SEP> weight <SEP> of
<tb> n <SEP> steel <SEP> strips <SEP> due
<tb> to <SEP> the <SEP> training <SEP> of
<tb> rust
<tb> (milligrams)
<tb> 25X <SEP> oil <SEP> "B" <SEP> 20.7
<tb> 26X <SEP> oil <SEP> "B" <SEP> + <SEP> 0.6% <SEP> of <SEP> di <SEP> (octyl <SEP> oresyl)
<tb>
 
 EMI20.2
 clithiophosphaze
 EMI20.3
 
<tb>
<tb> chrome <SEP> "B" <SEP> 12.2
<tb> 27X <SEP> like <SEP> in <SEP> the <SEP> tests <SEP> 26
<tb> + <SEP> 0.2% <SEP> of <SEP> sulfonate <SEP> of
<tb> petroleum-tin <SEP> 5.4
<tb>
 the x's indicate that these are the average values of at least three trials.



  Test 6. - Test at the Lauson engine.



   Tests were carried out in standard Lauson engines, type H-2, under the following conditions: temperature of the jacket 99 C t loti "of the oil pan 138 C ¯ 1, 1
Duration of the test 60 hours .., ¯

 <Desc / Clms Page number 21>

 
 EMI21.1
 
<tb>
<tb> The <SEP> results <SEP> are <SEP> as <SEP> follows <SEP>: <SEP>
<tb> Es- <SEP> Lubricant <SEP> Evaluation <SEP> of <SEP> Loss <SEP> Analysis <SEP> oil <SEP> used
<tb> Sai <SEP> lacquering <SEP> or <SEP> en- <SEP> weight <SEP>% <SEP> increased- <SEP>% <SEP> in- <SEP> aci-
<tb>
 
 EMI21.2
 no.

   Grassroots will pay sow so. d it é
 EMI21.3
 
<tb>
<tb> piston <SEP> mgrs. <SEP> viscosity <SEP> ether
<tb> Pevisual <SEP> evaluation <SEP> <SEP> C.R.C, <SEP> trole
<tb>
 
 EMI21.4
 ------------------------- ------------- ----- ------- - ------ ----,
 EMI21.5
 
<tb>
<tb> P.E <SEP> <<SEP> 40 C
<tb> 28 <SEP> oil "B" <SEP> (average <SEP> of <SEP> plus <SEP> 6.2 <SEP> 92 <SEP> 39.9 <SEP> 0.94 <SEP> 1 , 04
<tb> of <SEP> 20 <SEP> tests)
<tb> 29 <SEP> oil "B" <SEP> + <SEP> 0.6% <SEP> of
<tb> di <SEP> (octyl <SEP> cresyl) <SEP> dithiophosphate.- <SEP> of <SEP> chrome <SEP> "B" <SEP> 7.3 <SEP> 5 <SEP> 20.4 <SEP> 0.64 <SEP> 0.28
<tb> 30 <SEP> like <SEP> in <SEP> test <SEP> 29
<tb> + <SEP> 0.2% <SEP> of
<tb> sulphonate <SEP> of petroleum <SEP>
<tb> tin <SEP> 8.4 <SEP> 10 <SEP> 28 <SEP> 0.62 <SEP> 0.53
<tb> 31 <SEP> oil "B" <SEP> + <SEP> 0,

  6% <SEP> of
<tb> di <SEP> (octyl <SEP> cresyl) <SEP> chrome <SEP> dithiophosphate <SEP> <SEP> "A" <SEP> 8.5 <SEP> 39 <SEP> 33.3 <SEP > 0.70 <SEP> 0 <SEP> 60 <SEP>
<tb> + <SEP> 0.2% <SEP> of
<tb> sulphonate <SEP> of petroleum <SEP>
<tb> tin.
<tb>



  32 <SEP> like <SEP> in <SEP> test <SEP> 31
<tb> + <SEP> 0.2% <SEP> of
<tb> di <SEP> (3-carbomethoxy-4-
<tb>
 
 EMI21.6
 hydroxyphenyl) thioeliher
 EMI21.7
 
<tb>
<tb> cresyl <SEP> phosphite <SEP> 7.9 <SEP> 7 <SEP> 33.8 <SEP> 0.61 <SEP> 0.63
<tb> 33 <SEP> like <SEP> in <SEP> test <SEP> 31
<tb> + <SEP> 0.1% <SEP> of
<tb> di <SEP> (3-carbomethoxy-4hydroxyphenyl) polysulfide <SEP> 8.5 <SEP> 17 <SEP> 34.5 <SEP> 0.94 <SEP> 0.39
<tb> 34 <SEP> oil "B" <SEP> + <SEP> 0.5% <SEP> of
<tb> di <SEP> [alpha] -methyl <SEP> isoamyl)
<tb> zinc <SEP> <SEP> <SEP> <SEP> 7.5 <SEP> 5 <SEP> 16 <SEP> 0.41 <SEP> 0.28
<tb> 35 <SEP> like <SEP> in <SEP> test <SEP> 34
<tb> + <SEP> 0.5% <SEP> of <SEP> petroleum-tin <SEP> <SEP> <SEP> 9 <SEP> 8 <SEP> 23.6 <SEP> 0.10 < SEP> 0,

  28
<tb> 36 <SEP> like <SEP> in <SEP> test <SEP> 34
<tb> + <SEP> 1 <SEP>% <SEP> of
<tb> petroleum-tin <SEP> sulfonate <SEP> <SEP> 9.5 <SEP> 17 <SEP> 19 <SEP> 0 <SEP>, 06 <SEP> 0.45
<tb> 37 <SEP> like <SEP> in <SEP> test <SEP> 34
<tb> + <SEP> 0.2% <SEP> of
<tb> petroleum-tin <SEP> <SEP> <SEP> <SEP> 9 <SEP> 6 <SEP> 13.8 <SEP> 0.12 <SEP> 0.21
<tb> + <SEP> 0.2% <SEP> of
<tb> di <SEP> (octyl <SEP> cresyl) <SEP> dithiophosphate <SEP> from <SEP> chrome <SEP> "B"
<tb> 38 <SEP> oil "B" <SEP> + <SEP> 0.6% <SEP> d '
<tb> octyl <SEP> cresyl <SEP> 2-ethyl <SEP> hexyl
<tb> Zinc <SEP> <SEP> <SEP> <SEP> 8.7 <SEP> 18 <SEP> 16.4 <SEP> 0.17 <SEP> 0.39
<tb> + <SEP> 0,

  2% <SEP> of
Petroleum-tin <tb> <SEP> sulfonate <SEP>
<tb>
 

 <Desc / Clms Page number 22>

 
 EMI22.1
 
<tb>
<tb> Es- <SEP> Lubricant <SEP> Evaluation <SEP> of <SEP> Loss <SEP> Analysis <SEP> oil <SEP> used
<tb> sai <SEP> lacquering <SEP> or <SEP> and * - <SEP> weight <SEP>% <SEP> increased- <SEP> in- <SEP> aci- <SEP>
<tb> n <SEP> fouling <SEP> of the <SEP> bearings <SEP> sow <SEP> solsdadipiston <SEP> mgrs, <SEP> viscosity <SEP> ether <SEP> tee.
<tb>



  Evaluation <SEP> of <SEP> p- <SEP>
<tb> visual <SEP> C.R.C. <SEP> trole
<tb>
 
 EMI22.2
 ############################ ------------- ----- ---- ---- ------ -----
 EMI22.3
 
<tb>
<tb> P.E <40 C
<tb>
 
 EMI22.4
 39 hui1effB "+ 0.6 di
 EMI22.5
 
<tb>
<tb> octyl <SEP> cresyl <SEP> 2-ethyl
<tb> hexyl <SEP> dithiophosphate
<tb> from <SEP> chrome <SEP> 8,6 <SEP> 6 <SEP> 20 <SEP> 0.14 <SEP> 0.42
<tb> + <SEP> 0.2% <SEP> of
<tb> sulphonate <SEP> of petroleum <SEP>
<tb> tin
<tb> 40 <SEP> oil "B" <SEP> + <SEP> 0.6% <SEP> of
<tb> di <SEP> (2-ethyl <SEP> hexyl) <SEP> chromium <SEP> dithiophosphate <SEP> <SEP> 7.7 <SEP> 7 <SEP> 25.6 <SEP> 0.05 <SEP> 0.34
<tb> + <SEP> 0.2% <SEP> of
<tb> sulphonate <SEP> of petroleum <SEP>
<tb> tin
<tb>
 
The C.R.C.

   is carried out according to the method indicated for the 36-hour test l-4 / the so-called "Co-operative
Research Committee "for the evaluation of piston cleanliness in the Chevrolet Standard, in which a clean piston would have an evaluation value of 10.



   The majority of values shown are averages of at least two tests.



   It emerges from the results of tests 29 and 30, and 34 to 37 that the combination of two additions according to the invention gives, as regards the cleanliness of the pistons, results superior to those obtained by the use of dithiophosphate alone.



   The hard-third addition advantage as proposed by the invention is demonstrated by the results of tests 31 to 33, in which the dithiophosphate was present in an insufficient amount to ensure by itself adequate protection of the bearings against corrosion.



   The result of test 37 confirms the results of the oxidation tests already indicated, namely that some further improvement in the oxidation of the oil can be expected from use, with petroleum tin sulfonate of a metal alkyl dithiophosphate and a metal alkyl aryl dithiophosphate.

 <Desc / Clms Page number 23>

 Additional tests were carried out in standard Lauson / type H-2 engines under different conditions, as follows:
Oil pan temperature 177 C "107 C
Duration 100 hour s.



   These tests were more especially intended to illustrate the effectiveness of the lubricating compositions of the invention under "high load" conditions such as in high speed diesel engines operating under heavy load.



   The test results are as follows:
 EMI23.1
 
<tb>
<tb> Es- <SEP> Lubricant <SEP> Evalua- <SEP> Scrub <SEP> Loss <SEP> Analysis <SEP> of used oil <SEP>
<tb> sai <SEP> tionla- <SEP> seg- <SEP> weight <SEP> after <SEP> 100 <SEP> hours
<tb>
 
 EMI23.2
 n quages pa- increase-% i rj, 4 9aci-
 EMI23.3
 
<tb>
<tb> piston <SEP> will bind <SEP> sement <SEP> in <SEP> 1 '<SEP> diEvalua- <SEP> mgrs. <SEP> viscose <SEP> ether <SEP> tee
<tb> tion <SEP> vi- <SEP> té <SEP>% <SEP> de <SEP> pésuelle <SEP> CR.C.

   <SEP> trole
<tb> P.E <SEP> <<SEP> 40 C
<tb> 41 <SEP> oil "B" <SEP> 1.5 <SEP> 1 <SEP> 118 <SEP> 176.1 <SEP> 0.32 <SEP> 0.45
<tb> 42 <SEP> oil "B" <SEP> (repetition
<tb> test) <SEP> 1.5 <SEP> 2 <SEP> 109 <SEP> 197 <SEP> 0.39 <SEP> 0.45
<tb> 43 <SEP> oil <SEP> "B" <SEP> + <SEP> 0.7% <SEP> of
<tb> di <SEP> ([alpha] -methyl <SEP> isoamyl)
<tb> <SEP> zinc <SEP> dithiophosphate <SEP> 3.2 <SEP> 1 <SEP> 12 <SEP> 137.1 <SEP> 0.09 <SEP> 0.28
<tb> 44 <SEP> oil "B" <SEP> + <SEP> 0.5% <SEP> of
<tb> di <SEP> ([alpha] -methyl <SEP> iaoamyl)
<tb> zinc <SEP> dithiophosphate <SEP> <SEP> 7.5 <SEP> none <SEP> 14 <SEP> 107.6 <SEP> 0.06 <SEP> 0.28
<tb> + <SEP> 0.5% <SEP> of
<tb> sulphonate <SEP> of petroleum <SEP>
<tb> tin.
<tb>
 



   The considerable superiority of the combination of the additions of the present invention has thus been fully demonstrated.



  Test 7.- Chevrolet test 36 hours.



   Tests were carried out on a standard type 6 cylinder chevrolet engine, in accordance with standard process L.4 of the "Co-operative Research Committee"
 EMI23.4
 
<tb>
<tb> Es- <SEP> Composition <SEP> oil <SEP> Corrosion <SEP> Evaluation <SEP> Evaluation <SEP> Evaluation
<tb> sai <SEP> average <SEP> varnishing <SEP> varnishing <SEP> mud
<tb> n <SEP> loss <SEP> by <SEP> piston <SEP> total <SEP> total
<tb> landing
<tb>
 
 EMI23.5
 integer ¯¯¯¯¯¯¯ ¯¯¯¯¯¯¯ ¯¯¯¯¯¯¯
 EMI23.6
 
<tb>
<tb> 45 <SEP> oil <SEP> "B" <SEP> 0.856 <SEP> 8.4 <SEP> 48,

  4 <SEP> 46
<tb>
 

 <Desc / Clms Page number 24>

 
 EMI24.1
 
<tb>
<tb> Es- <SEP> Composition <SEP> oil <SEP> Corrosion <SEP> Evaluation <SEP> Evaluation <SEP> Evaluation
<tb> sai <SEP> average <SEP> varnishing <SEP> varnishing <SEP> mud
<tb> n <SEP> loss <SEP> by <SEP> piston <SEP> total <SEP> total
<tb> --- <SEP> landing
<tb> integer
<tb>
 
 EMI24.2
 46 oil "B" + 0.6% of
 EMI24.3
 
<tb>
<tb> di <SEP> (octyl <SEP> cresyl) <SEP> di- <SEP>)
<tb> thiophosphate <SEP> from <SEP> chro- <SEP>) <SEP>
<tb> me <SEP> "A" <SEP>)
<tb> + <SEP> 0.2% <SEP> of)
<tb> sulfonate <SEP> of <SEP> petroleum- <SEP>)
<tb> tin <SEP>)
<tb> + <SEP> 0.2% <SEP> of)
<tb> di <SEP> (3-carbomethoxy-4- <SEP>) <SEP> 0.109 <SEP> 9.2 <SEP> 49.4 <SEP> 47.4
<tb> hydroxyphenyl) <SEP> thioether <SEP>) <SEP>
<tb> cresyl <SEP> phosphite)
<tb> 47 <SEP> oil <SEP> "B" + <SEP> 0.5% <SEP> of)

  
<tb> di <SEP> ([alpha] -methyl <SEP> isoamyl) <SEP>) <SEP>
<tb> <SEP> zinc <SEP> dithiophosphate <SEP>) <SEP> 0.192 <SEP> 8.95 <SEP> 48.95 <SEP> 46.4
<tb> + <SEP> 0.5% <SEP> of)
<tb> sulfonate <SEP> of <SEP> petroleum- <SEP>)
<tb> tin)
<tb> 48 <SEP> oil "B" <SEP> + <SEP> 0.5% <SEP> of)
<tb>
 
 EMI24.4
 di (.

   -methyl isoamyl)
 EMI24.5
 
<tb>
<tb> Zinc <SEP> <SEP> dithiophosphate <SEP> <SEP>) <SEP>
<tb> + <SEP> 0.2% <SEP> of)
<tb> sulfonate <SEP> of <SEP> petroleum- <SEP>)
<tb> tin)
<tb> + <SEP> 0.2% <SEP> of)
<tb> di <SEP> (octyl <SEP> cresyl) <SEP> di- <SEP>) <SEP> 0.127 <SEP> 8.85 <SEP> 48.85 <SEP> 43.9
<tb> chromium <SEP> thiophosphate <SEP> <SEP>) <SEP>
<tb> "B" <SEP>)
<tb> + 0.05% <SEP> of)
<tb> di <SEP> (3-carbomethoxy-4- <SEP>)
<tb> hydroxyphenyl) <SEP> thioether)
<tb> cresyl <SEP> phosphite <SEP>)
<tb>
 Used oil analysis (36 hours)
 EMI24.6
 
<tb>
<tb> Test <SEP> n <SEP> Increase <SEP>% <SEP> insoluble <SEP> in <SEP> acidity <SEP> (mgs <SEP> KOH
<tb>% <SEP> of <SEP> viscosi- <SEP> ether <SEP> of <SEP> petro- <SEP> by <SEP> gr.)
<tb> tee <SEP> on
<tb> P.E.

   <SEP> <<SEP> 40 <SEP> C
<tb> 45 <SEP> 52.3 <SEP> 0.85 <SEP> 0.62
<tb> 46 <SEP> 59.1 <SEP> 0.68 <SEP> 0.75
<tb> 47 <SEP> 24.1 <SEP> 0.37 <SEP> 0.45
<tb> 48 <SEP> 22.1 <SEP> 0.32 <SEP> 0.22
<tb>
 
In all the preceding examples, the petroleum-tin sulfonate employed is prepared as described in example 6.



   It should be understood that in all the previous tests the additions of metal dithiophosphates were used such as

 <Desc / Clms Page number 25>

 prepared by the methods already illustrated, some being relatively pure organic compounds and others being combined with various small amounts of other compounds, in particular free dithiophosphoric acids and their sodium salts.



   The invention is to be understood as encompassing an addition for use in a lubricating oil base, this addition comprising in admixture of petroleum-tin and dussl metal sulfonate, soluble in oil, of an organic dithiophosphoric acid di. -substituted.



   CLAIMS.



   1. A lubricating composition comprising a lubricating oil base and a minimal amount of: (a) the tin salt of an oil soluble petroleum sulfonic acid and (b) a polyvalent metal salt (which is soluble in base oil) of an organic dithiophosphoric acid.



   2. A lubricating composition comprising a lubricating oil base and a minor proportion of both the tin salt of an oil soluble petroleum sulfonic acid and a metal salt (which is soluble in the base oil. ) a di-substituted organic dithiophosphoric acid derived, at least in part, from an alkylated phenol.



   3. A lubricating composition as claimed in claim 2, modified by the incorporation into the lubricating oil base (either in replacement of or additionally to the di-substituted organic dithiophosphate derived from an alkylated phenol) of a minimum proportion of a metal salt, soluble in oil, of an organic dithiophosphoric acid di-alkyl or di-cycloalkyl.



   4. A lubricating composition as claimed in any one of the preceding claims, which still contains a minimal amount of a thioether and, or hydroxy-substituted aromatic disulfide or polysulfide.

** ATTENTION ** end of DESC field can contain start of CLMS **.


    

Claims (1)

5. A lubricating composition as claimed in claim 1, 2 or 3, which further contains a minor proportion of an aromatic phosphite or thiophosphite ester derived from a thioether and, <Desc / Clms Page number 26> or aromatic disulfide or polysulfide. 6. A lubricating composition as claimed in any one of the preceding claims, which further contains a minimal amount of a tri-aryl phosphite. 7. A lubricating composition as claimed in any one of the preceding claims, in which a chromium salt of an organic dithiophosphoric acid is used. 8. The method of preparing an addition for use in a lubricating oil composition, as described in any of the examples given. 9. The lubricant composition comprising a mineral release oil, a salt of a polyvalent metal, soluble in oil, of an organic dithiophosphoric acid and petroleum-tin sulfonate, in the proportions indicated in any one of the examples. given.