NL7905011A - Dispersant-detergent additive for lubricating oils - comprises an alkaline earth metal aliphatic sulphonate and an alkenyl mono: succinimide - Google Patents

Abstract

Lubricating oil compsn. comprises an oil of lubricating viscosity and (A) 2.5-50 (10-30) millimols per kg. of an alkaline earth metal substantially satd. (>95%) 20-300C aliphatic sulphonate and (B) 0.5-20 (2-10) wt. % of a 50-300C alkenyl monosuccinimide. Also claimed is a concentrate contg. 25-100 millimols (A) and 5-80 wt. % (B) (as well as the lubricating oil). Used for I.C. engines, automatic transmissions or as hydraulic oils, heat-transfer oils etc. The combination of (A) with (B) gives a dispersant and detergent additive of superior detergency than that of conventional succinimide and sulphonate.

Description

It-i-y N.O. 27,820

Chevron Research Company, San Rrancisco, Califomia, Ter.St. v. America.

Sulfonate containing lubricating oil renarate.

The present invention relates to sulfonate additives J

for lubricating oils used together with succinimide, Mannich base, suocinate or thiophosphonate additives. !

Re-use of succinimides, succinates, Mannich bases J

and thiophosphonates as dispersants or detergents! Lubricating oils are generally known. Pink additives are often used in combination with conventional aromatic, usually petroleum-derived sulfonates. |

It has now been found that the combination of a monosuccinimide hydrocarbyl substituted succinic acid ester provides a high molecular weight Mannich base or monohydroxyalkyl substituted hydrocarbyl thiophosphonate with a hydrocarbyl thiophosphonate. alkaline earth metal substantially saturated, aliphatic sulfonate a ? lubricating oil additive of greater cleaning power than provides the combination of a dispersing or cleaning agent with the conventional sulfonate.

The present invention provides a lubricating oil composition consisting of an oil of lubricity suitable for viscosity characterized by the presence of: (a) 2.5 - 50 mmol / kg of an alkaline earth metal substantially saturated, aliphatic sulfonate, wherein the aliphatic group 20-500 carbon atoms and (b) 0.5-80% by weight of a detergent dispersant selected from the group consisting of alkenyl monosuccinimides, wherein the alkenyl group contains about 50-300 carbon atoms, 25

an ester of hydrocarbyl-substituted succinic acid, wherein the hydrocarbon group contains at least 50 carbon atoms, monohydroxyalkyl hydrocarbylthiophosphonates and a Mannich base J

790 5 0 1 1 1 -V *, -2 - I ~ '- -: High molecular weight "1" and its borate-containing complexes.

The sulfonates used according to the invention are alkaline earth metal substantially saturated, aliphatic sulfonates, which may be indicated by the formula (R-SO 4 M, wherein R 5 is a substantially saturated aliphatic substituent with about 20-300, preferably about 20-100 represents carbon atoms The term "substantially saturated" means that at least about 95% of the carbon-carbon covalent bonds are saturated Too many unsaturation sites make the molecule more oxidizable, degradable and polymerizable.

: This makes the products unsuitable for many applications "in hydrocarbon oils.

The substantially saturated aliphatic substituent may contain polar substituents. However, there should not be so many substituents that the hydrocarbon character of the radical is significantly changed. Examples of such polar substituents are chlorine, keto, alkoxy, etc. The presence of such polar groups is not preferred. The polar substituents in the radical must not be more than about 20% based on the hydrocarbon content of the radical. to shape.

The sources of the substantially saturated, aliphatic substituent include substantially enough saturated polyolefins, especially polymers of mono-olefins of about 2-30 carbon atoms. Particularly suitable polymers are the polymers of 1-mono-olefins such as ethylene, propylene, 1-butene, isobutylene, 1-hexene, 1-octene, 2-methyl-1-heptene, 3-cyolohexyl-1-butene and 2-methyl -5-propyl-1-hexene. Polymers of olefins in which the ethylenically unsaturated bond is not terminated, such as 2-butene, 3-pentene and 4-octene, are also suitable.

Copolymers of olefins as indicated above with other copolymerizable ethylenically unsaturated compounds such as 1-olefins, cyclic olefins and polyolefins can also be used. These include those prepared by polymerizing isobutene with butadiene, propylene with

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790 50 1 1. -. Isoprene, ethylene with piperylene, isobutene with ehloroprene, 1-hexene with 1,3-hexadiene, 1-octene with 1-hexene, 1-heptene with 1-pentene, 3-methyl-1-butene with 1 octene, 3-3 <3-imethyl-1-4 pentene with 1-hexene, etc.

The relative ratios of the mono-olefins to the other 5 monomers in the copolymers affect the stability and oil solubility of the final preparations. In order to achieve oil solubility and stability, the copolymer must be substantially saturated, ie it must not contain more than about 5% of the ethylenically unsaturated bonds based on the total number of carbon-carbon covalent bonds, usually each molecule would contain about one ethylenically unsaturated bond. The percentage of ethylenically unsaturated bonds should be less than about 2% of the total number of carbon-carbon covalent bonds.

Suitable examples of such copolymers include the terpolymer of 98% isobutene and 1% piperylene and 1% chlorprene, the terpolymer of 95% isobutene with 2% 1-butene and 3% 1-hexene, the terpolymer of 60% isobutene with 20 % 1-butene and 3% 1-hexene, the terpolymer of 80% 1-hexene and 20% 1-heptene, the terpolymer of 90% isobutene with 2% cyclohexene and 8% propylene and the copolymer of 80% ethylene and 20% propene.

Preferred starting materials for the aliphatic groups are polybutene, polyisobutene and polypropylene. Polyisobutene is particularly preferred.

The metal component M of the sulfonate can be formed by any metal of the group II of the Periodic System which forms a salt with the sulfonic acid part and yields a salt which can act as a cleaning agent in lubricating oil preparations. The Group II metals include magnesium, calcium, strontium, barium and zinc. Preferably the metal M is calcium or magnesium.

The hydrocarbon from the aforementioned sources can be converted to the corresponding sulfonic acid or salt thereof by many methods, two of which are described below. At 79050 11 J, ---— ..........................: .............. ..... 1 '- -}' one method is to react the hydrocarbon with a known sulfonating agent such as sulfur trioxide chlorosulfonic acid, etc. Chlorosulfonic acid is preferred.

These methods are well known in the art.

In another preparation method of the hydrocarbyl sulfonic acid, the hydrocarbon is first reacted with an alkyl bromo-1 or chlorosulfonate, optionally in the presence of a solvent such as 1,2-dichloroethane, ether and the like. The response i o. runs well at temperatures of 20 - 120 C, preferably; ! from 70 - 90 ° C, but below the decomposition point of the reagents 10! and the products. The reaction can be carried out under vacuum; atmospheric pressure or gauge pressure. For convenience, the reaction is usually carried out at atmospheric pressure.

The hydrocarbon and the alkyl chlorosulfonate are usually reacted using a slight molar excess sulfonate based on the hydrocarbon. Preferably 1.1-2 mole of alkyl chlorosulfonate per mole of hydrocarbon is used.

The alkyl of the alkyl chlorosulfonate contains 1-4 carbon. atoms. Ethyl chlorosulfonate is preferred because it is easy to prepare and reacts quickly with an ethylene. unsaturated hydrocarbon.

The alkaline earth metal salts can be prepared in any suitable manner. According to one of the methods, a basic reacting metal compound, such as the oxide or hydroxide, combined with the acid or an alkyl ester of the hydrocarboxylic sulfonic acid is prepared as described above. This is generally done in the presence of a hydroxyl-containing promoter such as water, methanol or ethylene glycol and an inert solvent for the sulfonate, for example under heating. Under these conditions, the basic reacting compound will yield the metal sulfonate. The hydroxyl-containing promoter and the solvent can then be removed to obtain the metal sulfonate.

Under certain circumstances it may be easier to saline the Group I metals of the Periodic System

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i 7905011 '*. "* * -5 - of the sulfonate" and convert this material by metathesis to the alkaline earth metal sulfonate. Using this method, the previously prepared sulfonic acid or alkyl sulfonate is combined with a Group I basic metal compound such as sodium or potassium hydroxide The resulting sodium or potassium sulfonate can be purified by water extraction, then the sulfonate of the Group I metal is combined with the alkaline earth metal salt to obtain the alkaline earth metal sulfonate The most commonly used alkaline earth metal salt is a halide For example, the sodium or potassium sulfonate is combined with an aqueous alkaline earth metal chloride solution, followed by stirring sufficiently long for the metathesis to take place, then the aqueous phase is removed and, if desired, the solvent can be evaporated.

If a sulfonate with a fully saturated hydrocarbyl group is desired, it must be hydrogenated using hydrogen and a known noble metal or precious metal oxide hydrogenation catalyst, such as platinum or platinum oxide.

The preferred sulfonates are the calcium and magnesium sulfonates.

The alkenyl monosuccinimides used according to the invention are known products, the preparation of which is described in U.S. Pat. Nos. 3 * 219,666, 3 * 172,892 and 3,272,746. These products, commonly referred to as succinimides, are prepared, for example, by the reaction of alkenyl-substituted succinic acid or anhydride with a nitrogen-containing compound. Many chemical compounds are formed by this reaction, for example, amide, imide and amidine. However, the main product is a suecinimide and this term has been widely accepted to designate the product of the reaction described.

Both mono- and bis-succinimides can be prepared by this method. Mono-succinimides have the general formula 1, while bis-succinimides have the general formula 2, in which E represents hydrocarbyl and A a bonding group.

79050 11 '"-:.':" "_6 _. . "V-" ".

Techniques drawn to those skilled in the art can prepare a predominantly mono- or bis-succinimide prodock easily. This is done by controlling the molar ratios of the reagents. For example, if 1 mole of amine is reacted with 1 mole of succinic anhydride, a 5. mainly mono-suecinimide-containing product. If 2 moles of succinic anhydride per mole of polyamine are reacted

J

, a bis-succinimide will be obtained.

Only the mono-succinimide product is suitable for the preparation f l liner of the present invention. 10. The suitable for use according to the invention with; hydrocarbon-substituted succinic acid esters are known: products disclosed in U.S. Pat. Nos. 3 * 381,022 and 3 * 522,179 * The hydrocarbon portion of the succinate has at least 50 carbon atoms and is derived from essentially the same sources as the aliphatic portion of the sulfonates concerned . The alcohols used in the preparation are described in the aforementioned U.S. Patents.

Preferably, neopentyl glycol, ethylene glycol, glycerol, pentaerythritol and sorbitol are used.

The monohydroxyalkylhydrocarbylthiophosphonates to be used in the present invention are known products and are disclosed in U.S. Patent 3 * 087 * 956 * He monohydroxyalkylhydrocarbylthiophosphonates have the general formula 1: 3, wherein R hydrocarbyl and R and R independently of one another hydrogen or an aliphatic hydrocarbon group having 1-6 carbon atoms X sulfur or a mixture of sulfur and oxygen. Preferred dispersants are those in which R represents a polyolefin, especially polybutene, having a 1 2 average molecular weight of 250 - 50,000 and R and R each represent hydrogen.

The high molecular weight Mannich bases to be used in the invention are known products, the preparation of which is described in U.S. Patent 3 * 539 * 633 * These Mannich bases are prepared by the reaction of an alkyl phenol having at least 50 carbon atoms. preferably 50-200 carbon atoms with formaldehyde and an alkylene polyamine ΗΝ (-ΑΝΞ) ηΗ,

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7905011% \. ·% -7 - wherein A represents a saturated divalent alkyl hydrocarbon of 2-6 carbon atoms and n 1-10 or of the condensation product of the alkylene polyamine with urea or thiourea.

If desired, the Mannich base can be reacted with a boron compound such as a boron halide, boric acid or an ester of boron to form a particularly suitable coordinated boron complex. In the practice of the invention, a dispersant is particularly suitable marketed under the name Amoco 9250, the borate-containing Mannich condensation product prepared from a high molecular weight alkyl phenol, formaldehyde and the condensation product of tetraethylene pentamine and urea.

The lubricating oils of the invention contain an oil of lubricating viscosity and 2.5 - 50 mmol / kg, preferably 10 - 50 mmol / kg of the alkaline earth metal, substantially saturated, aliphatic sulfonate and 0.5 - 20%. % preferably 2-10% by weight of the cleaning or dispersing agent as described above.

The invention further also relates to additive concentrates. Beze usually contains about 90-10% by weight oil of lubricity suitable viscosity and is normally formulated to contain about 10 times the additive concentration to be used in the final lubricating oil formulation. Bit is usually 25-100 mmol / kg of the alkaline earth metal sulfonate and 5-80% by weight of the succinimide. For example, the concentrates contain enough diluent to facilitate handling in shipping and storage. Suitable diluents for the. concentrates include any inert diluent, preferably an oil of lubricating viscosity, so that the concentrate can be easily mixed with lubricating oils to prepare lubricating oil compositions. Suitable lubricating oils, which can be used as diluents, have a viscosity of about 35-500 SUS at 38 ° C, although any oil of suitable viscosity for lubrication can be used. 35 Suitable lubricating oils, those for the preparation of lubricating oil 7905011

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I can use a preparation or a concentrate are oils. with lubrication suitable viscosity derived from petroleum or synthetic sources. The oils can be paraffin-like, naphthenic halogen-substituted hydrocarbons, synthetic esters or combinations thereof. Suitable oils have a viscosity of about 35 - 50 * SUS S at 38 ° C more: usually a viscosity of about 50 - 10,000 SUS at 58 ° C.

Other known additives which can be used in combination with the additive combination according to the invention are; For example, oxidation inhibitors, anti-foaming agents, viscosity • index enhancers, yield strength suppressants, and the like.

. Among these are formulations such as chlorinated wax, benzyldisulphide, sulfurized spermaceti oil, sulfurized terpene, phosphorus esters such as trihydrocarbon phosphites, metal thiocarbamates, such as methioctyldithiocarbamate, metal phosphorothioates, such as zinc diethioctylphosphoromethylphosphoromethylphosphonic acid.

The lubricating oil compositions according to the invention are suitable for the lubrication of internal combustion engines, automatic transmissions and as industrial oils such as hydraulic oils, heat transfer oils, torsion fluids, etc. These (lubricating oils can lubricate not only the engines, but also their dispersing properties help to maintain a high degree of purity of the lubricated parts

Example I.

Preparation of oaloium polyisobutyl sulfonate.

. A 38-liter enamel reactor is charged with 14,430 g of polyisobutene with a number average molecular weight of 330 and an approximate average carbon content of about 24 and with 20,600 g of 1,2-dichloroethane. 7 ^ 50 g of chlorosulfonic acid are slowly added to this mixture over a period of 1 to 1.25 hours. The reaction mixture is cooled continuously during the addition of the chlorosulfonic acid to keep the temperature at 16 ° C. After completion of the addition, the reaction mixture is heated to 60 ° C. After the temperature

S079HÖLC

790 50 1 1 of the reaction mixture at 60 ° C for 5 hours, a solution of 3200 g of NaOH in 6400 ml of methanol is slowly added over a period of 1 hour. The reaction mixture is stripped to 91 ° C under atmospheric pressure and 3,785 liters of hydrocarbon thinner and 130 g of NaOH in 260 ml of methanol are added, after which stripping is continued to 120 ° C under atmospheric pressure. The reactor contents are cooled and transferred to a larger reactor, after which sec-butanol and a solution of 6,300 g of CaCl 2 in 32 liters of water are added.

This mixture is stirred at 38-49 ° C for 45 minutes. 10

After the mixture has settled, the water layer is removed and the metathesis is repeated twice with 3900 g of CaCl 2 in 18 liters of water. The reaction mixture is then washed three times with about 15 liters of water. 1 kg of CaCOH2 is added after the first wash with water. After the water from the last wash has been drained, the above product solution is filtered through diatomaceous earth. 3000 g of diluent oil are added to the filtrate and the mixture is stripped at 158 ° C at 7> 8 kPas yield 17 070 g of calcium sulfonate concentrate containing 1.85% Ca, 4 57% S and 0.30% Cl. Neutral calcium as sulfonate determined by Hyamine titration described in "Analytic Chemistry", 26, (1954) 1492-1497 by Halph House and J.L. Darragh, is 1.81%.

Example II.

Preparation of Sodium Nol Visobuten Vlsulfonate. 25

A 38 liter enameled reactor is charged with 12000 g of polyisobutene with a number average molecular weight of 950 and an approximate average carbon number of about 68 and with 6000 g of 1,2-dichloroethane. A solution of 2100 g of chlorosulfonic acid in 6000 g of butyl ether is slowly added to this mixture over a period of 1.5 hours. The reaction mixture is cooled continuously to maintain the temperature at 4.5 ° C. After the addition is complete, the reaction mixture is heated to 40 ° C. After the temperature of the reaction mixture has been maintained at about 38 ° C. for about 5 hours, 3810 ml of 25% aqueous sodium hydroxide solution (about 1150 g NaOH) are slowly added within 2 hours. 1000 ml cabbage 7905011 --./-- './ ·; / / '; ·' ‘',, /:, /. -ίο -:. / / - / / / /.:. - '-' I -; ---; ---: - i

hydrogen diluent are added and the reaction mixture I

it is stripped at 90 ° C under atmospheric pressure. Then an additional 10 000 ml of hydrocarbon thinner are added, after which 52 090 g of product are obtained.

Example III. 5

Preparation of sodium polyisobutenyl sulfonate.

The procedure of Example II is repeated except that the reaction mixture is neutralized with a methanolic solution of sodium hydroxide prepared from 1020 g.

NaOH in 4500 ml of methanol. The product is 26 µg of sodium poly 10; i: isobutenyl sulfonate solution. 1

Example IV.

; Preparation of calcium polyisobutyl sulfonate.

To the product solutions of Examples II and III, a half volume of hydrocarbon thinner and half volume of isobutyl alcohol are added, which are mixed thoroughly. This is the feed in the continuous metathse method.

The device consists of a metathse column of 100 cm 5 cm and a wash water column of 100 x 11.5 cm, both filled with 0.655 cm Perm State filling and heated with heating belt at 40 ° C; to keep.

The metathesis column is filled with 20% aqueous CaCl 2 solution. The CaGl solution and the water are introduced into the columns up to 20 cm from the top at 40 and 80 ml per minute, respectively. The drains are close to the bottom of the columns. The height of the GaCl solution and the water level in the column 4 are controlled by increasing or decreasing the discharge of a 0.80 cm pipe connected to the bottom discharge of the columns: this height is usually 15 cm below the top.

The product feed solution is pumped into the metal column at 50 cm from the bottom at 20 ml per minute and discharged 2 cm below the top. The residence time of the product in the metathse column is 20 minutes. The metathetic product is then pumped into the wash water column 20 cm from the bottom at 20 ml per minute and discharged 2 cm from the top. 55

Sufficient Ca (OH) 2 is added to the product washed with water. added to neutralize any acid product, _____

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7 9 ^ 0 5 0 1 1 V i · '-11-' · which may be formed and enough diluent oil to give a 70% concentrate after stripping the solvent. The separated and filtered product "contains" in X-ray fluorescence analysis% calcium, 1.97% sulfur, 0.01% chlorine and 1.10% neutral calcium as sulfonate by Hyamine titration. 5

Example Y.

Preparation of Magnesium Uol Visobuten Vlsulfonate.

To a 500 ml three-necked flask filled with 100 ml of dibutyl ether are slowly added 57 S chlorosulfonic acid from a dropping funnel over a period of 5 minutes under cooling with ice-water to keep the temperature below 20 ° C. A 2-liter, four-necked nitrogen-flushing flask is charged with 300 g of polyisobutene with a number average molecular weight of 950 and with 150 ml of 1,2-dichloroethane. The chlorosulfonic acid solution is added to this mixture with a drop of funnel over a period of 10 minutes, while the temperature increases from 22 ° C to 28 ° C. The reaction mixture is kept at 40 ° C for 5 hours. A solution of 58 g of 98% sodium hydroxide granules in 150 ml of water is then added dropwise over a period of 10 minutes. During this addition, the temperature is kept below 25 ° C by cooling. 600 ml of hydrocarbon diluent and 50 nil of 2-ethyl-1-hexanol are added to this solution. The temperature is raised to 165 ° C and maintained for 1 hour. 660 ml of solution are distilled.

After cooling, 200 ml of hydrocarbon diluent, 300 ml of 2-butanol and 400 ml of water are added to the remaining reaction mixture. The mixture is stirred at 80-85 ° G for 0.5 hours, transferred to a 4 liter separatory funnel and the water layer is removed. The supernatant is added to a 2 liter four neck flask and 130 g of magnesium chloride hexahydrate in 400 ml of water are added. The mixture is stirred at 80-85 ° C for 1 hour and transferred while hot to a 4 liter separatory funnel. After storage, the aqueous layer is removed and the supernatant is transferred to a 2-liter 4-necked flask. This is repeated twice and the then remaining solution becomes three - 7905011 V ”; '; N. -12-. . :: '. Washed once with 400 ml of water. The supernatant is heated to a bottom temperature of 145 ° C under atmospheric conditions.

pressure. 375 ml of liquid are distilled. The remaining product is cooled and filtered through diatomaceous earth. The filtrate is stripped at a bottom temperature of 170 ° C below 0.8 kPa. Shortly before stripping is completed, 130 g of diluent oil are added, after which 450 g of magnesium polyisobutyl sulfonate in oil are obtained. The product contains 0.57%, neutral magnesium as sulfonate by Hyamine titration.

Mg = 0.62% according to emission spectroscopy. S = 1.88% and = mine 10 less than or equal to 0.1% according to X-ray fluorescence analysis. " ,

Example 71.

In a 500 ml 3-necked flask filled with 100 ml of dibutyl ether, 57 S chlorosulfonic acid in 50 ml 1,2-dichloroethane are slowly added over a period of 21 minutes at 22-29 ° C from a dropping funnel. A 1 liter 4-necked nitrogen-flushing flask is charged with 200 g of polyisobutene with a number average molecular weight of 950 and with 150 ml of 1,2-dichloroethane. The chlorosulfonic acid solution is added to this mixture from a dropping funnel at a temperature of from 20: 22-27 ° C within 18 minutes. The reaction mixture is kept at room temperature for 5 hours. The reaction mixture is washed once with a mixture of 25 ml of water, 600 ml of hydrocarbon; thinner and 250 ml isopropanol and twice with a mixture of 200 ml water and 200 ml isopropanol. Then add to the mixture. 50 ml of concentrated ammonium hydroxide were added, followed by 17 g of calcium hydroxide. The temperature is raised to 170 ° C and stripped to 165 ° 0 below 0.7 kPa. Shortly before stripping is completed, 150 g of diluent oil are added, resulting in 474 g of calcium polyisobutenyl sulfonate in oil. The product contains 1.0% neutral calcium as sulfonate by Hyamine titration and by X-ray fluorescence 1.08% calcium, 1.94% sulfur and 0.05% Cl.

Example YII.

A 2-liter 4-necked nitrogen-flushing flask is charged with 750 g of polyisobutene with a number average molecular weight of 950, 150 ml of 1,2-dichloroethane and 162 g of ethyl-

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7905011 Λ, 'S' '~ -13 - chlorosulfonate. The mixture is stirred at 80-85 ° C for 6 hours. 300 ml of hydrocarbon thinner are then added, followed by a dropwise addition of a solution of 146 g of potassium hydroxide in 300 ml of methanol over 15 minutes. During the addition, the temperature rises to 47 ° C. 5

The mixture is then stripped to 150 ° C under atmospheric pressure.

The mixture is transferred to a 5-liter 3-necked flask to which 500 ml of hydrocarbon diluent, 500 ml of 2-butanol and 700 ml of water are added. The mixture is heated to 85 ° C.

The water layer is removed and 147 S calcium chloride dihydrate and 700 ml of water are added. The mixture is stirred at 80 ° C for 3/4 hours, after which the water layer is separated. The addition of calcium chloride followed by heating and separation of water is repeated twice, once with 100 g of calcium chloride dihydrate in 700 ml of water and once with 500 g of calcium chloride dihydrate in 700 ml of water.

200 ml of 2-butanol are then added to the mixture and the mixture is washed with 700 ml of water. The mixture is then stripped to 1 ° 8 ° under 0.8 kPa. 340 g of diluting oil are added shortly before stripping is completed. 20

The product weighs 1136 g, has a basicity value of 2.02 and contains 1.03% calcium by Hyamine titration and by X-ray fluorescence it contains 1.04% calcium, 1.72% sulfur and less than 0.01 % chlorine.

Example Till. 25

A 3-liter 3-neck flask is charged with 528 g of polyisobutylene with a number average molecular weight of 339 and with 600 ml of 1,2-dichloroethane. To this mixture are added dropwise 280 g of chlorosulfonic acid within 1 hour and 40 minutes.

The reaction mixture is kept at 60-62 ° C for 6 hours under nitrogen purge. A solution of 100 g of sodium hydroxide in 600 ml of methanol is added to the reaction mixture over a period of 30 minutes. The mixture is then heated to 120 ° C and 500 ml of fresh water thinner are added. After heating to 150 ° C and subsequent cooling to room temperature, a solution of 12 g of sodium hydroxide in 100 ml of methanol is added. This mixture is heated to 150 ° 0, 7905011 I 1-UIK ^^^ 11 · ™ · —.1: which temperature is maintained for 45 minutes. The mixture is then cooled, after which 250 ml of hydrocarbon diluent and 50 ml of 2-hutanol are added, followed by addition of 255 S calcium chloride dihydrate and 700 ml of water. The mixture is stirred at 80-85 ° C for 1 hour. 1 liter of hot water is then added and the water layer is separated. The; The emulsion obtained is washed with hot water until practically no emulsion is present anymore. The mixture is then mixed twice! washed with 147 g of calcium chloride dihydrate. 700 ml of water and 1 * I three times with 700 ml of water. The mixture is then stripped to 10 150 ° C at 0.8 kPa for 15 minutes. 120 g of diluting oil are added to 462 g of product. To this mixture are added 550 ml of hydrocarbon thinner, 250 ml of 2-butanol, 150 ml of water and 25 g of calcium hydroxide. This mixture is stirred at slow reflux for 20 hours. The lower boiling point solvent is removed by distillation at 150 ° C, after which 550 ml of hydrocarbon thinner are added.

The temperature is maintained at 150-165 ° C for 1 hour.

The product is then filtered through diatomaceous earth and until; Stripped 167 ° C at 0.8 kPa, which temperature is maintained for 15 minutes. The product has a weight of 521 g, a basicity value of 15> 7 and contains 2.7% calcium according to: Hyamine titration and according to X-ray fluorescence 2.45% calcium, 4.55% sulfur and 0.04% chlorine.

Example IX. 25

The compositions according to the invention were subjected to a Caterpillar 1-G test, in which a 1-cylinder diesel engine with 15 cm cylinder bore and 16.5 cm piston stroke is operated under the following conditions, time control, degrees BTDC 8; mean effective braking pressure, 971> 5 kPa; braking power 50.0 kw; 50 6172 kJ per min .; speed 1800 rpm .; air supply, 180 kPa; indoor air temperature, 124 ° C; water temperature outside, 88 ° C; sulfur in fuel, 0.4 wt%. After every 12 hours of operation, a sufficient amount of oil is drained from the crankcase to add 1 liter of fresh oil. When testing the lubricating oil compositions of the present invention, the 1-G test was conducted for 60 hours. Ha de pe->

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7905011 * - ·, V * -15- \ • «* 60-hour period, the motor is dismantled and rated for purity. The ring fields are rated on a scale from 0 to 800, with 0 representing clean and 800 representing black deposits.

The ring grooves are rated on a scale of 0-100 groove filling, with 0 indicating clean. The lower head of the 5 piston is rated on a scale of 0-10, with 0 indicating dirt and 10 clean.

The base oil used in this test is a Midcontinent SAB 30 oil containing 15 mmol / kg of a zinc dihydrocarbyldithiophosphate, 31 mmol / kg of calcium phenate and the amounts of detergent or dispersant and sulfonate shown in the table.

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SC796ÖLC

7905011

Claims (13)

Lubricating oil composition, characterized by the presence of suitable viscosity and (A) 2.5 - 50 mmol / kg of an aliphatic sulfonate substantially saturated with an alkaline earth metal, wherein the aliphatic group 5 contains about 20 to 300 carbon atoms and (B) 0 5 - 80 wt% detergent / dispersant selected from the group consisting of alkenyl monosuccinimides, in which the alkenyl group contains about 50-300 carbon atoms, an ester of a hydrocarbon-substituted tartaric acid, wherein the hydrocarbon group contains at least 50 carbon atoms, monohy- hydroxyalkylhydrocarbylthiophosphonate and a high molecular weight Mannich base and their boron / rafting complexes. 2. Preparation according to claim 1, characterized in that the aliphatic group is derived from a polyolefin group. Preparation according to claim 1 or 2, characterized in that the detergent / dispersant is an alkenyl mono succinimide and is prepared from an ethylene polyamine. Preparation according to claim 1 or 2, characterized in that the detergent / dispersant is an ester of hydrocarbon-substituted tartaric acid and is prepared from an alcohol selected from neopentyl glycol, ethylene glycol, glycerol, pentaerythritol and sorbitol. 5. A composition according to claim 1 or 2, characterized in that the detergent / dispersant is a mono-hydroxyalkylhydrocarbylthiophosphonate, wherein the hydrocarbyl group is derived from a polyolefin having an average molecular weight of 250 to 50,000. 6. A composition according to claim 1 or 2, characterized in that the detergent / dispersant is a borate-containing Mannich base prepared from an alkylphenol, formaldehyde and the condensation product of tetraethylene pentamine and urea. 7. Preparation according to claim 3, characterized in that the ethylene polyamine is tetraethylene pentamine or 7905011. . 1.18-triethylene tetraamine. 8. A composition according to claim 4, characterized in that the alcohol is pentaerythritol. 9. A composition according to claim 5, characterized in that the detergent / dispersant is a mono-hydroxyethyl ethyl polybutenyl thiophosphonate. 10. A composition according to any one of claims 1-9, characterized in that the alkaline earth metal is calcium or magnesium and the aliphatic group is derived from polyisobutene of 20-100 carbon atoms. 10 Preparation according to claims 1-10, characterized in that 2.50 - 50 mmol / kg sulfonate and 0.5 - 20 wt.% Detergent / dispersant are present. 12. A composition according to claim 11, characterized in that 10-50 mmol / kg sulfonate and 2-10 wt.%> 15 detergent / dispersant are present. Full throttle preparation claims 1-10, characterized in that 25-100 mmol / kg sulfonate and 5-8% by weight of detergent / dispersant are present. '' 1 "'"> I I.— .. || , / 7905011 »JL \ N — AH A —r ^ K ° ° ^ T ~ N-A-N A X R1 R2 II I I R-P-OCH-CHOH OH 7905011