DE2926069A1 - LUBRICATING OIL - Google Patents

Description

Our no. 22 478 D / 'wl

Chevron Research Company San Francisco, CA, V. St. A.

Lubricating oil

A lubricating oil with an extraordinary cleaning effect that an aliphatic alkaline earth metal sulfonate and a detergent or contains dispersants.

909882/0945

The invention relates to the use of sulfonates as additives for lubricating oils, the sulfonates in combination with succinimides, Mannich bases, succinic acid esters or Thiophosphonates are used.

The use of succinimides, succinic acid esters, Mannich bases and thiophosphonates as dispersants or detergents in lubricating oils are known. These additives are often used in combination with conventional aromatic, sulphonates usually made from petroleum products are used.

It has now been found that the combination of a monosuccinimide, Hydrocarbon-substituted succinic acid ester, a high molecular weight Mannich base or one li.onohydroxyalkyl-substituted hydrocarbyl thiophosphonate with a substantially saturated aliphatic alkaline earth metal sulfonate gives a lubricating oil additive which improved Detergent action as a combination of the dispersant or detergent with conventional sulfonates.

The sulfonates used according to the invention are essentially saturated aliphatic alkaline earth metal sulfonates of the formula (R-SO ^) ₂ M, where R 1 means ³³ essentially saturated aliphatic substituents having about 20 to 300, and preferably about 20 to 100 carbon atoms. The term "substantially saturated" means that at least about 95 % of the carbon-carbon covalent bonds are saturated. Too many unsaturated sites mean that the molecule can be easily oxidized, broken down and polymerized. This makes the products unsuitable for a wide variety of uses in hydrocarbon oils.

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The substantially saturated aliphatic sub-substituent can carry polar substituents. However, there should not be so many substituents that the hydrocarbon character of the residue is noticeably changed. Such polar substituents include, for example, chlorine, keto groups, alkoxy groups, and the like. The presence of such polar groups is not a preferred embodiment. The polar substituents should not be more than about 10 percent based on the hydrocarbon content of the remainder.

The precursors of the substantially saturated aliphatic substituents mainly include those which are substantially saturated Polyolefins, especially polymers of monoolefins of from about 2 to about 30 carbon atoms. Particularly suitable polymers are the polymers of 1-monoolefins such as Ethylene, propene, 1-butene, isobutene, 1-hexene, 1-octene, 2-methyl-1-heptene, 3-cyclohexyl-1-butene and 2-methyl-5-propyl-1-hexene. Also polymers of olefins whose double bond is not terminal is, such as 2-butene, 3-pentene and 4-octene, are suitable.

Furthermore, interpolymers of olefins, for example the above, with other interpolymerizable olefinic substances such as 1-olefins, cyclic olefins and polyolefins can be used. Examples of this are products which are obtained by “polymerizing isobutene with butadiene, propene with isoprene, of ethylene with piperylene, of isobutene with chloroprene, of 1-hexene with 1,3-hexadiene, from 1-octene with 1-hexene, from 1-heptene with 1-pentene, from 5-methyl-1-butene with 1-octene, from 3,3-dimethyl-1-pentene with 1-witches and the like.

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The proportions of monoolefins to other monomers in the interpolymers influence the stability and oil solubility of the end product. With regard to the oil solubility and stability, the interpolymers should be essentially saturated, that is to say they should not contain more than about 5% double bonds, based on the total number of covalent carbon-carbon bonds. Usually each molecule has about one double bond. The percentage of double bonds should be less than about 2 % of the total number of carbon-to-carbon covalent bonds.

Specific examples of such interpolymers are a terpolymer composed of 98 % isobutene, 1 % piperylene and 1 % chloroprene, a terpolymer composed of 95 % isobutene, 2 % 1-butene and 5 % 1-hexene, a terpolymer composed of 60 % isobutene, 20 <jo 1 -butene and 3% of 1-hexene, a polymer of 80% 1-hexene and 20% 1-heptene, a terpolymer of 90% of isobutene with 2% of cyclohexene and 8% of propene, and a copolymer of 80 # of ethylene and 20 $ propene.

Preferred starting materials for the production of the aliphatic radical are polybutene, polyisobutene and polypropylene, in particular the polyisobutylene.

The metal M of the sulfonate can be any metal of the Group II of the periodic table, which forms a salt with the sulfonic acid residue, which is used as a detergent in lubricating oils is effective. Group II metals include magnesium, calcium, strontium, barium, and zinc. Preferably that exists Metal M from calcium "or magnesium.

The hydrocarbons produced from the above precursors can be converted into the corresponding

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Sulphonic acids or their salts are converted. Two methods are described below. In one proceeding is the hydrocarbon with a conventional sulfonating agent such as sulfur trioxide, or chlorosulfonic acid the like reacted, with chlorosulfonic acid being preferred. Corresponding processes are known.

In a further process for the preparation of the hydrocarbylsulfonic acid, the hydrocarbon is first reacted with an alkyl bromo- or chlorosulfonate, optionally in the presence of a solvent such as 1,2-dichloroethane, ether or the like. The reaction proceeds satisfactorily at temperatures from 20 to 120 ⁰ C, preferably at 70 to 90 ⁰ C j, but below the decomposition point of the subscriber React ions and products. The reaction can be carried out under reduced pressure, normal pressure or elevated pressure. However, it is usually expedient to work at normal pressure.

Hydrocarbon and alkyl chlorosulfonate are generally used in a slight molar excess of the sulfonate, based on the amount of hydrocarbons, implemented. It is preferred to use 1.1 to 2 moles of alkyl chlorosulfonate per mole of hydrocarbon.

The alkyl portion of the alkyl chlorosulfonate contains 1 to 4 carbon atoms. It is preferred to use ethyl chlorosulfonate as this substance is easy to prepare and easy to use olefinic hydrocarbons reacts.

The alkaline earth metal salts can be produced in any way. will be presented. One method is to have a basic reacting metal compound such as, for example, the oxide or hydroxide with the one prepared in the above manner

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Reacts hydrocarbylsulfonic acid or its alkyl ester. In doing so, "generally works in the presence of a promoter such as Water, methanol or ethylene glycol and an inert solvent for the sulfonate; typically “toeχ this one Implementation heated. Under the conditions mentioned, the basic compound gives the metal sulfonate, the obtained after removal of the promoter and solvent.

In certain circumstances it may be appropriate to prepare salts of metals from group I of the periodic table and then convert them into the alkaline earth metal sulfonates by metathesis. In this case the sulfonic acid becomes or the alkyl sulfonate with a basic Group I metal compound such as sodium or potassium hydroxide implemented. The sodium or potassium sulfonate can be purified by extraction with water. Then it will be the metal sulfonate with the alkaline earth metal salt to the alkaline earth metal sulf onat implemented. The most common alkaline earth metal salt here is a halide, especially that Chloride, typically sodium or potassium sulfonate stirred with an aqueous alkaline earth metal chloride solution until metathesis has taken place. Then the separated aqueous phase and optionally evaporated the solvent.

If you want a sulfonate with a fully saturated hydrocarbyl radical on, so must with hydrogen and a conventional noble metal or noble metal oxide hydrogenation catalyst, for example with platinum or platinum oxide.

The preferred sulfonates are the calcium and magnesium sulfonates.

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The present invention Alkenylmonosuccinimide used are known compounds whose preparation is besehrieben 3,219,666 ₁ 3 Yji 892 and 2272 JH6 in US-PSS. These compounds, commonly referred to as succinimides, are obtained by reacting, for example, an alkenyl-substituted succinic acid or its anhydride with a nitrogen-containing compound. Various substances, for example amides, imides and amidines, are formed in this reaction, but the main product is a succinimide. It is therefore generally accepted Piacis to use this designation for the product of the above reaction.

According to the method mentioned, both mono- and Bis-succinimide can be produced. Possess mono-succinimide the formula

-AH

and bis-succinimide the formula

AT

where R is a hydrocarbyl radical and A is a link «

A product can be produced in a manner familiar to the person skilled in the art which mainly contains mono- or bis-succinimide, by adjusting the molar ratios of the reactants accordingly. For example, 1 mole of amine is used If 1 mole of succinic anhydride is reacted, then mainly monosuccinimide is formed. Become 2 moles of succinic anhydride

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reacted with 1 mole of polyamine, a bis-succinimide is formed.

Only the product of the monosuccinimide type is suitable for the purposes according to the invention.

The hydrocarbon-substituted ones which can be used according to the invention Succinic acid esters are known substances which are described in US-PSS J5,381,022 and 3,522,179. Of the The hydrocarbon portion of the ester has at least 50 carbon atoms and is essentially of the same origin as the aliphatic part of the sulfonates used according to the invention. The alcohols used to prepare the esters are mentioned in the above US patents. Are particularly preferred Neopentyl glycol, ethylene glycol, glycerin, pentaerythritol and sorbitol.

The monohydroalkyl hydrocarbyl thiophosphonates which can be used according to the invention are known substances, they are described in US Pat. No. 3,087,956. They correspond to the formula

XR ¹ R ² ti 1 t

R_P_ OCH - CHOH

OH 12

wherein R is a hydrocarbyl radical, R and R, independently of one another, Hydrogen or aliphatic hydrocarbyl radicals with 1 to 6 carbon atoms and X sulfur or a mixture represent from sulfur and oxygen. Preferred dispersants are those in which R is a polyolefin radical, preferably the polybutene radical with an average molecular

1 2

weight from 250 to 50,000 and R and R represent hydrogen.

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High molecular weight Mannich bases which can be used according to the invention are compounds the preparation of which is described in U.S. Patent 3,539. They are obtained by taking an alkyl phenol having at least 50 and preferably 50 to 200 carbon atoms with formaldehyde and an alkylene polyamine of the formula HN (ANH) H, where A is a saturated, divalent one Alkyl hydrocarbon radical with 2 to 6 carbon atoms and η represent a number from 1 to 10, or the condensation product of the alkylene polyamine with urea or Thiourea converts. Optionally, the Mannich base can be mixed with a boron compound such as a boron halide, boric acid or a boric acid ester, a particularly useful boron complex being formed. Particularly suitable for use according to the invention is a dispersant, which is sold under the trade name "AMOCO 9250" will. It consists of the borated Mannich condensation product of a high molecular weight alkylphenol with formaldehyde and the condensation product of tetraethylene pentamine and Urea.

The inventive lubricating oils containing an oil of lubricating viscosity and 2.5 to 50 M ± llimol / kg, preferably 10 to 30 millimoles / kg of the substantially saturated aliphatic alkaline earth metal sulfonate and from 0.5 to 20, and preferably 2 to 10 wt.% Of the above- detergent or dispersant described.

The invention also relates to additive concentrates. They usually contain about 90-10% by weight of an oil of lubricating viscosity and are usually formulated to contain about ten times the additive concentration of a lubricating oil. This usually means 25 to 100 millimoles / kg alkaline earth metal sulfonate, and 5 to 8θ wt.% Succinimide. the

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Concentrates contain sufficient amounts of diluent that they can be easily handled during shipping and storage. Suitable diluents for such concentrates are all inert diluents, preferably oils of lubricating viscosity, which ensure that the concentrate can be easily mixed with the lubricating oil. Suitable diluents suitable lubricating oils typically have viscosities in the range of about 35 have to about 500 Saybolt Universal Seconds (SUS) at 38 ⁰ C. However, it can also be any other oil of Schmierviskos χ did use.

Oils suitable for making a lubricating oil or lubricating oil concentrate are oils of lubricating viscosity, the source of which is petroleum or a synthetic process. The oils can be paraffinic, naphthenic, or halogen-substituted hydrocarbons, synthetic esters, or mixtures thereof., Oils of Sehmier viscosity have viscosities in the range of 35 to 50,000 SUS at 38 ° C, and more usually, from about 50 to 10,000 SUS at 38 ° C ⁰ C

Conventional additives, which together with the inventive Combinations of additives that can be used are oxidation inhibitors, antifoams, improvers Viscosity index, pour point depressant, and the like. These include substances such as chlorinated waxes, benzyl disulphide, sulphated spermacet oils, sulphurised terpene, phosphorous acid esters such as trihydrocarbyl phosphites, metal thiocarbamates such as zinc dioctyldithiocarbamate, dithiophosphorous acid salts such as zinc dioctylphosphorodithioate, polyisobutylene with an average molecular weight of 100,000 and the like.

9098S2 / 094S

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The lubricating oils according to the invention are suitable for lubrication of internal combustion engines, automatic engines and as technical oils, such as hydraulic oils, heat transfer oils, Rotary shafts and the like. Not only can they lubricate the motors, they also wear them because of their dispersing properties helps to keep the lubricated parts largely clean.

Example 1: Manufacture; of calcium polyisobutenyl sulfonate

14,430 g of polyisobutylene of average 330 with an average of 24 carbon atoms and 20,600 g of 1,2-dichloroethane are poured into a 38 liter reaction vessel lined with glass. To this mixture 7650 g of chlorosulfonic acid are added slowly over 1 1/4 hours. Zugegeben- During the addition of the chlorosulfonic acid, the reaction mixture is continuously cooled to maintain the temperature at ⁰ C l6. After completion of the addition, the mixture is heated to 60 ⁰ C. After 5 1/2 hours at 60 ° C., a solution of 3,200 g of sodium hydroxide in 6,400 ml of methanol is slowly added over the course of 1 hour. Then, the Reaktionsgemiseh at 9I ° C and normal pressure is stripped, followed by 3 * 785 1 hydrocarbon diluent and 130 g of sodium hydroxide are added in 260 ml of methanol, whereupon further stripped at 120 ⁰ C and atmospheric pressure. The contents of the reaction vessel are cooled and transferred to a larger vessel, then secondary butyl alcohol and a solution of 6300 g calcium chloride in 32 l water are added. The mixture is stirred at 38 to 49 ° C. for 45 minutes. After settling, the aqueous phase is drawn off, the metathesis is carried out twice with 3,900 g of calcium chloride in 18 l of water

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wfderholt. The reaction mixture is then washed three times with about 15 liters of water. After the first wash with water, 1 kg of calcium hydroxide is added. As soon as the water from the last washing process has been drained off, the supernatant product solution is filtered through diatomaceous earth. 3,000 g of thinner oil are added to the piltrate and the mixture is stripped to 138 ° C. at 60 mm Hg, 17 070 g of calcium sulfonate concentrate with 1.85 % calcium, 4 * 57 % sulfur and 0.30 % chlorine being obtained. The value for neutral calcium as sulfonate (determined by hyamin titration, see Ralph House and J. Ii? _ Därragh) - ^: Γ Analytic Chemistry, Vol. 26, (195 ² O p. 1492 - 1497) is 1.81 % .

Example 2: Production of sodium polyisobutenyl sulfonate

Ih become a 38 liter reaction vessel lined with glass 12,000 .g polyisobutylene with an average molecular weight (numerical

mxttel) __ ^

950 filled with an average of 68 carbon atoms and 6,000 g of 1,2-dichloroethane. A solution of 2,100 g of chlorosulfonic acid in 6,000 g of butyl ether is slowly added to this mixture in the course of 11/2 hours. The reaction mixture is continuously cooled to keep the temperature at 4.5 ° C. When the addition is complete, the reaction mixture is heated to 40.degree. After about 5 hours at about 38 ° C., 3810 ml of a 25 # aqueous sodium hydroxide solution (about 1 150 g sodium hydroxide) are slowly added over the course of 2 hours. Then 1,000 ml of hydrocarbon thinner are added and the mixture is ^{stripped off at 90 °} C. and normal pressure. With a further 10,000 ml of hydrocarbon thinner, a total of 32,090 g of product is then obtained.

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INSPECTED

Example j5:

Herst e Settin g of Natriumpolyisobutenylsulfonat

The procedure of Example 2 is repeated with the difference, that the reaction mixture is neutralized with a methanolic sodium hydroxide solution, which consists of 1 020 g Sodium hydroxide and 4,300 ml of methanol. The product obtained is 26,780 g of sodium polyisobutenyl sulfonate solution.

Example 4i Manufacture of calcium polyisobutenyl sulfonate

1/2 volume of hydrocarbon diluent and 1/2 volume of isobutyl alcohol are added to the product solutions of Examples 2 and 3 added and mixed vigorously. This feed is used in the continuous metathesis process.

The device consists of a metathesis column of 100x5 cm dimension and a wash column of 100x11,5 cm, both of which are packed with "Penn State" -Füllkörpern of 0.635 cm and maintained with a heating band at 40 ⁰ C. The meta thesis column is filled with 20 # aqueous calcium chloride solution. The calcium chloride solution and water are fed into the columns at a height of 20 cm from the upper end in amounts of 40 and 80 ml / minute, respectively. The outlet is at the bottom of the columns. The level of calcium chloride solution and water in the columns is controlled by increasing or decreasing the outlet of the 0.80 cm hose connected to the lower outlet of the columns, usually 15 cm below the top of the column.

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The Beschiekungslösung is 20 cm above the lower End at 20 ml / min, pumped into the metathesis column and 2 cm below the top. The residence time of the product in the column is 20 minutes. The product is then pumped 20 times above the bottom outlet at a rate of 20 ml / min into the wash column and there peeled off 2 cm below the upper end.

Sufficient calcium hydroxide is then added to the water-washed product to neutralize acidic product components. Sufficient diluent oil is also added so that a 70 # concentrate is obtained after stripping off the solvent. Stripped and filtered product contain, according to X-ray fluorescence analysis, 1.31 % calcium, 1.97 % sulfur, 0.07 % chlorine and 1.10 % neutral calcium as sulfonate (hyamin titration),

Example 5:

Manufacture of magnesium polysobutenyl sulfonate

In a 500 ml three-necked flask containing 100 ml of dibutyl ether, 57 g of chlorosulfonic acid are slowly added from a dropping funnel in the course of 5 minutes. The temperature is kept below 20 ° C. by cooling with ice water. A 2 liter four-necked flask with nitrogen flushing is charged with 300 g of polyisobutylene with an average molecular weight of 950 ⁷ UnO ¹ i ^ Ö ^ rnl ^e '1,2-dichloroethane. The chlorosulfonic acid solution is added dropwise to this mixture from a dropping funnel in the course of 10 minutes, the temperature rising ^{from 22 to 28 ° C.} The reaction mixture is held for 5 h. At 40 ⁰ C, is .then a solution of 58 g sodium hydroxide pellets in 98 #igen I50 ml of water over 10 min. Was added dropwise. During the encore

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the temperature is kept below 25 C by cooling. 600 ml of hydrocarbon diluent and 50 ml of 2-ethyl-1-hexanol are added to this solution. The mixture is heated to 165 ° C. and kept at this temperature for 1 hour. 66O ml of solution are distilled off overhead. After cooling, 200 ml of hydrocarbon thinner, ^ 00 ml of 2-butanol and 400 ml of water are added to the remaining reaction mixture. The mixture is stirred for 1/2 hour at 80 ° to 85 ° C. and transferred into a 4 liter separation funnel, in which the aqueous phase is drained off. The supernatant is transferred into a 2 1 four-neck flask with 130 g of magnesium chloride hexahydrate ', in 400 ml of water verSefcfc-fc * - The mixture is 1 hr and stirred at 80 to 85 ⁰ C then still hot to a 4. 1 -Separating funnel transferred. After calming, the aqueous layer is drawn off and the supernatant liquid is poured into a 2 liter four-necked flask. This procedure is repeated two more times, then the remaining solution is washed three times with 400 ral of water. The supernatant liquid is heated to 145 ° C. pot temperature at normal pressure, with 375 ml of liquid distilling over. The residue is cooled and filtered through diatomaceous earth. This filtrate is stripped off at 6 mm Hg to 170 ° C. pot temperature. Shortly before the end of the stripping, 1 ^ 0 g of thinner oil are added, 450 mg of magnesium polyisobutenyl sulfonate in oil being obtained. The product contains 0.57 % neutral magnesium as sulfonate (hyamin titration), Mg = 0.62 # (emission spectroscopy), S = 1.88 % and Cl = less than or equal to 0.1 $ (in each case by X-ray fluorescence analysis).

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Example 6

57 g of chlorosulfonic acid in 50 ml of 1,2-dichloroethane are slowly added dropwise from a dropping funnel over the course of 21 minutes at 22 to 29 ° C. into a 500 ml three-necked flask containing 100 ml of dibutyl ether nitrogen purge is charged with 200 grams of polyisobutylene of average molecular weight 950 / Uend 150 πίί 1,2-Diehlorethan charged. to this mixture, the chlorosulfonic acid in the course of l8 min. at 22 is added to 27 ⁰ C from a dropping funnel. the reaction mixture is 5 hours. kept at room temperature and then washed once with a mixture of 250 ml of water, 600 ml of hydrocarbon diluent and 250 ml of isopropyl alcohol and twice with a mixture of 200 ml of water and 200 ml of isopropyl alcohol. 50 ml of concentrated ammonium hydroxide solution and then 17 g are added to the mixture calcium hydroxide is added. It is then heated to I70 ⁰ C and stripped at 5 MTNL Hg and I65 ⁰ C. to I50 g Verünneröl Shortly before the end of stripping train etch and 474 g of calcium polyisobutenyl sulfonate are obtained in oil. The product contains 1.0 % neutral calcium as sulfonate (hyamine titration) and, according to X-ray fluorescence, 1.08 % calcium, 1.94 % sulfur and 0.05% chlorine.

Example 7

7.50 g of polyisobutylene with an average molecular weight of 950, 150 ml of 1,2-dichloroethane and 162 g of ethyl chlorosulfonate are poured into a 2 liter four-necked flask under nitrogen. The mixture is stirred for 6 hours at 80 to 85 ^° C., then 500 ml of hydrocarbon diluent are added. A solution of

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146 g of potassium hydroxide in 500 ml of methanol are added. During the addition, the temperature rises to 47 ^° C. The mixture is then stripped down ^{to 150 ° C. at normal pressure.} It is then transferred to a 5 l three-necked flask and mixed with 500 ml of hydrocarbon thinner, 500 ml of 2-butanol and 700 ml of water. The resulting mixture is heated to 85.degree. The aqueous phase is drawn off, then 147 g of calcium chloride dihydrate and 700 ml of water are added. The mixture is then stirred for a further 3/4 hours at 80 ^° C., after which the aqueous phase is removed. The addition of calcium chloride with subsequent heating and removal of the water is repeated twice, once with 100 g of calcium chloride dihydrate in 700 ml of water and once with 50 g of calcium chloride dihydrate in 700 ml of water.

200 ml of 2-butanol are then added to the resulting mixture

What ε he added and the mixture is washed with 700 ml. It is then stripped down ^{to 168 °} C. at 6 mm Hg. Shortly before the end of the stripping process, 340 g of thinner oil are added - The product weighs 1156 g, the alkali value is 2.02, the calcium content by hyamine titration is 1.05 $> - According to X-ray fluorescence , it contains 1.04% calcium, 1.72 % sulfur and less than 0.01 % chlorine.

Example 8

A 3 liter three-necked flask is filled with 528 g of polyisobutylene with a number average molecular weight of 339 and 600 ml of 1,2-dichloroethane. 280 g of chlorosulfonic acid are added dropwise to this mixture in the course of 1 hour and 40 minutes. ^{The reaction mixture is kept at 60 to 62 °} C. for 6 hours while flushing with nitrogen. then

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a solution of 100 g of sodium hydroxide in 600 ml of methanol is added to the reaction mixture over the course of 50 minutes. The mixture is heated to 120 ° C. and 500 ml of hydrocarbon thinner are added. After heating to 150 ⁰ C and cooling to Rcumtemperatür a solution of 12 g sodium hydroxide in 100 ml of methanol is added * · · This mixture is heated to 150 ⁰ C and held for 45 min. At this temperature. It is then cooled and 250 ml of hydrocarbon diluent, and 500 ml of 2-butanol are added, followed by addition of a solution of 255 g of calcium chloride dihydrate in 7OO ^m l of water. The resulting mixture is 1 hour at 80 to

ο
Stirred at 85 C, then 1 liter of hot water is added

Water. The aqueous phase is drawn off and the resulting emulsion is washed with hot water until there is practically no more emulsification. The mixture is then washed twice with 147 g of calcium chloride dihydrate in 700 ml of water and three times with 700 ml of water. The resulting mixture is stripped at 6 mm Hg to 165.degree. C. and held at that temperature for 15 minutes. 120 g of thinner oil are added to the 462 g of product. 350 ml of hydrocarbon diluent, 250 ml of 2-butanol, 150 ml of water and 25 g of calcium hydroxide are added to this mixture. The mixture is stirred at low reflux for 20 hours. The lower-boiling solvent is distilled off at 150 ° C., then 550 ml of hydrocarbon thinner are added. The temperature is kept at 150 to 16> ° C. for 1 hour. The product is then filtered through diatomaceous earth and stripped at 6 mm Hg to I67 ⁰ C and held for 15 min. At this temperature. The resulting product weighs 521 g, the alkali value is Ij5.7, calcium content by hyamine titration 2.7 %. The X-ray fluorescence analysis shows 2.4 % calcium, 4.35 % sulfur and 0.04 % chlorine.

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Example 9

The lubricating oil mixtures according to the invention were tested in a Caterpillar 1-G test. It was a single cylinder diesel engine with 15 cm bore and l6.5 cm stroke length below operated under the following conditions:

Control 8 BTDC; Average effective braking force 8.46 atmospheres · Braking power 42 HP; 1,558 kcal / min (5,850 BTU / min), speed 1,800 rpm; Air pressure 1J54.6 cm Hg absolute, air inlet temperature 124 C, water outlet temperature 88 ⁰ Cj, sulfur content of the fuel 0.4% by weight . After every 12 hours of operation, enough SI is removed from the crankcase that 1 liter of new oil can be added. To assess the lubricating oils according to the invention, the 1 G test is carried out for 60 hours. After these 60 hours, the engine is disassembled and the cleanliness is assessed. The ring ridges are rated on a scale from 0 to 800, where 0 means clean and 800 means black deposits. The piston grooves are rated on a scale from 0 to 100, where 0 means clean and 100 means the piston groove is full. The bottom of the piston is rated on a scale from 0 to, where 0 means dirty and 10 means clean.

An SAE 30-01 was selected as the base oil in these tests North American crude oil that is 15 millimoles / kg of a zinc dihydrocarbyl thiophosphate, 3> 1 millimole / kg of one Calcium phenate and the amounts given in the table of detergent or dispersant and sulfonate.

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i-G CATERPILLAR TEST

Sulfonate

Mol / kg dispersant grooves Bridges

Pistons

commercial
süfonat off Calcium
Petroleum 1 10 90988 commercial petroleum and
synthetic alkylaromatic.
Sulfonates 4th 10 K>
■> «. according to example 4th 10 O
CO according to example 4th 10 according to example 4th 10 according to example 6th 10 according to example 7th 10 according to example 8th 10 according to example 10 according to example 10

1.5

(D

1.5

(D

1.5 1.5 1.5

!, 5

(2) 58-4-0.6-0.5
40- $ - 1.2-0.6

50-6-0.6-0.7

21-6-1.2-0.7

58-6-1.0-0.6
36-10-0.5-0.5

35-10-0.5-0.5
57-2.4-0.5-0.5
42-6.2-0.6-0.5
41-6-0.7-0.8

49-0.7-0.6-0.6
35-5-0.5-0.6

25-3-0.6-0.6
35-3-0.7-0.7

160-310-215 4.8 285-180-75 4.0

390-120-515 4.8

265-30-20 4.6

220-20-20 2.9

315-10-15 5.2

200-20-20 1.5

30-10-10 1.9

85-25-35 3.7

195-20-20 Μ, *

225-IO-I5 I, °

105-20-15 s, ϊ

I85-25-35. ^S <V

I8O-2O-2O Q _t o

CO N) O) O O CO

- 2k ■

(1) Commercially available monosuccinimide from C _q g (mean) -

Alkenyl succinic anhydride and tetraethylene pentamine

(2) Lz 936, evdrocarbylsuccinic acid ester made with pentaerythritol

TLA 202j monohydroxyalkyl polybutylene thiophosphonate

Amoco 9250, borated Mannich base, made from an alkylphenol, tetraethylene pentamine, urea and formaldehyde

For: Chevron Research Company

San Francisco, Ca., V.St.A.

Dr.H.J.Wolff Attorney at Law

909882/0945

Claims (1)

Patent claims: 1. Lubricating oil, characterized by an oil with a hatching (A) 2.5 to 50 millimoles / kg of a substantially saturated one aliphatic alkaline earth sulfonate, the aliphatic group of which has about 20 to 300 carbon atoms contains and (B) 0.5 to 80 wt. $ Alkenyl monosuccinimide with a Alkenyl radical with about 50 to 300 carbon atoms, Hydrocarbon-substituted succinic acid ester with a hydrocarbon radical with at least 50 carbon atoms, monohydroxyalkyl hydroearbyl thiophosphonate or high molecular weight Mannich base or their boron complexes, as detergent-effective Dispersants. _, .., or, lube concentrate 2. Lubricating oil according to claim I, characterized in that the aliphatic radical of the alkaline earth metal sulfonate is formed from a polyolefin residue. , _M ", or, lube concentrate 3. Lubricating oil according to claim 2, characterized in that the dispersant is one made from an ethylene polyamine Is alkenyl monosuccinimide. , or lubricating oil concentrate 4. Lubricating oil according to claim 2, characterized in that the dispersant with neopentiyl glycol, ethylene glycol, Glycerol, pentaerythritol or sorbitol is produced hydrocarbon-substituted succinic acid ester. «! ^ _M , öd§P, lubricating oil concentrate 5. gchjaisFÖi risen claim 2, characterized in that E> tj5p # Pgi # rmtfcteX a monohydroxyalkyl-hydrocarbylthio- isfc, whose hydrocarbyl radical is from a polyolefin j »it has a molecular weight of 250 to 50,000. 809882 / 09A5 r _n . . ... or, SciisiieröJlcDiizentrat; , _,. , ο. Schmxerol according to Claim 2, characterized in that the dispersant is a borated Mannich base produced from an alkyl phenol, formaldehyde and the condensation product of tetraethylene pentamine and urea. ". .., or lubricating oil concentrate 7 · Lubricating oil according to claim j5, characterized in that that the dispersant is an alkenylmpnosuccinimide prepared with tetraethylene pentamine or triethylene tetramine is. ο r. τ. ., .. ^ or. Lubricating oil concentrate,. . . o. Lubricating oil according to claim 4, characterized in that the dispersant is a pentaerythritol ester. r * c f. λ ", or. Schinierölpnzentra-b,. . . 9 · Lubricating oil according to claim 5 *, characterized in that the dispersant is a monohydroxyethyl polybutenyl thiophosphonate. or lubricating oil concentrate 10. Lubricating oil according to one of claims 1 to 9, characterized characterized that the alkaline earth sulfonate is a calcium or magnesium salt and the aliphatic radical of a polyisobutylene having 20 to 100 carbon atoms originates. 11. A lubricating oil according to any one of claims 1 to 10, characterized by 2.50 to 50 millimoles / kg sulfonate and 0.5 to 20 wt.% Of the detergent-active dispersing agent. 12. Lubricating oil according to claim 11, characterized by 10 to 30 millimoles / kg of the sulfonate and 2 to 10 wt. £ des Detergent-effective dispersant. 909882/0946 13 · lubricating oil according to any one of claims 1 bts 10, characterized by 25 to 100 millimoles / kg sulfonate, and 5 to 8 wt.% Of the detergent-active dispersing agent. 909882/0965