CA2044036A1 - Detergents for lubricating oils containing a phosphor organic derivative and lubricating compositions containing such detergents - Google Patents

Abstract

1 Overbased detergent for lubricating oils obtained by carbonation of a mixture containing a detergent chosen from alkali or alkaline earth sulfonates, naphthenates, salicylates, phosphonates and thiophosphonates, an alkaline or alkaline earth oxide, hydroxide or alcoholate, a nitrogen and / or oxygenated promoter, at least 3% by weight of phosphorus in the form of a non-metallic organic derivative, a hydrocarbon solvent and optionally a diluent oil and water. These detergents contain 0.5 to 10% and preferably 1 to 5 weight of phosphorus. They have very improved antiwear and antioxidant properties.

Description

20 ~ 36 SOCIETE NATIONALE ELF AQUITAINE

DEBASED DETERGENTS FOR LUBRICATING OILS CONTAINING A
ORGANIC PHOSPHORUS DERIVATIVE AND LUBRICATING COMPOSITIONS
CONTAINING SAID DETERGENTS
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This invention relates to overbased detergents for oils lubricants containing an organic phosphorus derivative.
Overbased detergents are alkali metal salts or alkaline earth organic acids overbased by carbonation with carbon dioxide. The term overbased is used to denote excess alkali metal or alkaline earth relative to the stoichiometric amount necessary to neutralize the acid.
The structure of overbased detergents is that of a colloidal dispersion of which the micelles contain the alkali or alkaline earth metal carbonate formed during carbonation. Micelles are stabilized by salts alkaline or alkaline earth detergents.
These overbased detergents are particularly useful in lubricants used in internal combustion engines from "petrol" or "diesel" type, whether engines terrestrial or marine.
Thanks to their detergent and dispersing effect they prevent formation of lacquers and varnishes on the pistons, and keep soot from combustion dispersed fuel incomplete.
Another important function of these additives is the neutralization of the acid compounds resulting from the oxidation of oil or the combustion of sulfur products brought in by the fuel. This function is particularly appreciated when using sulfur-rich fuels like for example heavy fuels used in engines sailors.

2 ~ 036 Base detergents also improve resistance to the oxidation of the oils in which they are incorporated. This function is particularly important for Lubricating formulations subject to constraints severe thermal, such as in engines highly supercharged diesel.
Overbased detergents are characterized by their value alkaline (VA) expressed in mg of KOH per gram of product.
It is determined by titration using a strong acid according to ASTM D-2896. A reserve of alkalinity significant results in a high VA.
It is also known to use in lubricants mixtures of overbased detergents and phosphorous additives or phosphosulfurized. These bring properties antiwear and antioxidants. The most commonly used are metal salts of dithiophosphoric acid and more especially the zinc salt of the acid dialkyldithiophosphoric.
Many lubricant formulations including between others, overbased detergents and metallic salts and more particularly the zinc salt of the acid dialkyldithiophosphoric, exist. They are suitable for a large number of applications, for example concerning transmission fluids (WO 88-08874-A), lubricants for land petrol or diesel engines (EP-A
225580, US 4664822, US 4525288, US 4704217), lubricants for marine engines (US 4681694) or hydraulic fluids (US 3899432).
However, it turns out that negative interactions can exist between overbased detergents and derivatives organic phosphorus, and in particular the zinc salt of dialkyldithiophosphoric acid. The competition, during adsorption on metal surfaces ~ lubricate, between overbased detergents and zinc salts or reactions between these two additives in the volume of the lubricant can cause a significant decrease in properties antioxidants e ~ antiwear.

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We have now found that by overbasing detergents in the presence of a non-organic compound metallic phosphorus, there is incorporation of phosphorus in the micelle, which also contains carbonate alkali or alkaline earth metal. So the interactions negative between overbased phenates and derivatives organic phosphorus are ~ avoided.
The invention therefore relates to an overbased detergent for oils lubricants obtained by carbonation of a mixture containing a detergent chosen from sulfonates, naphthenates, salicylates, phosphonates and alkali thiophosphonates or alkaline earth, a derivative of an alkali metal or alkaline earth chosen from oxides, hydroxides or alcoholates, a nitrogenous and / or oxygenated promoter, a solvent hydrocarbon and possibly a diluent oil and water, characterized in that the mixture contains at least 3%
weight of phosphorus in the form of an organic derivative not metallic.
The overbased detergents according to the invention contain O, S to 10% and preferably 1 to 5% by weight of phosphorus. They have greatly improved antiwear and antioxidant properties, while retaining detergency properties, dispersion and neutralization of acid compounds, unaltered.
Antiwear and antioxidant power can be further improved by the addition of zinc dithiophosphate (DTPZ). In this case, DTPZ is effective at very low concentrations, which results in a noticeable decrease in character corrosive to formulations.
Non-metallic organic phosphorus derivatives are chosen from phosphites, phosphoramides, derivatives of phosphoric, thiophosphoric, dithiophosphoric acids, trithiophosphoriques, tetrathiophos-phoriques and their salts organic.
More particularly, the phosphosulfur derivatives are used like thiophosphoric or dithiophosphoric acids and their organic salts and preferably acid derivatives dithiophosphoriques and their organic salts.

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Among the derivatives of dithiophosphoric acids used in general dihydrocarbyldithio-phosphoric acids, general formula ~ -0 ~ ~; S
~ P (I) R ~ O SH
where R and R 'identical or different represent chains linear or branched C1 to C20 alkyls, cycles aliphatic or aromatic.
Among these derivatives we can mention the acid diethyldithiophosphoric acid, diisopropyldithiophos-phoric, dicyclohexyldithiophosphhoric acid or acid dicrésyldithiophosphorique.
It is particularly advantageous to use the compounds of general formula (I) insoluble in oils. These compounds have antioxidant and antiwear properties surfactant effect. So they participate as co-surfactants stabilization of the micelles.
The methods of the prior art did not allow incorporating in overbased detergents that the oil-soluble derivatives of phosphorus. The process of the invention allows the incorporation both oil-soluble and insoluble derivatives in oils. It is particularly interesting not to not be limited in the choice of the phosphorus derivative.
Dihydrocarbyldithiophosphoric acids of formula general (I) can be prepared by the action of phosphorus pentasulfide on an alcohol or phenol of formula general R-OH or a mixture of alcohols or phenols of formula R-OH and R'-OH.
The molar ratio of phosphorus pentasulfide to alcohol or phenol must be at least 1 to 4. The reaction can be made ~ e at a temperature between 40 and 200 ~ C, ci depending on the type of alcohol or phenol chosen.
Acid preparation methods dialkyldithiophosphoriques are described in the brsvets Americans 30 ~ 9850, 3101096, 3293181 and 3489682.

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The detergents are chosen from sulfonates, naphthenates, salicylates, phosphonates and thiophosphonates of alkali or alkaline earth metal. Instead of detergents, the reaction medium may contain the precursors. In this neutralization is carried out in the reaction medium before carbonation.
Sulfonates are obtained from sulfonic acids of petroleum or synthetic origin. Sulfoni acids tankers are prepared by sulfonation of oils from petroleum distillation.
Their structure does not correspond to a well defined formula, but their average molecular weight must be at least equal to 300.
Synthetic sulfonic acids are prepared by alkylation of aromatic compounds such as benzene, toluene, xyl ~ ne or naphthalene with olefinic cuts then by sulfonation of the alkylate obtained. The structure of the chains alkyls attached to the nucleus is linear or branched, depending on the structure of olefins used for alkylation. The number of carbon atoms per alkyl chain is greater or equal to 8.
The preparation of the alkali metal sulfonate or alkaline earth is made by contacting the acid sulfonic with an alkali metal derivative or alkaline earth, preferably an oxide or hydroxide, in a hydrocarbon solvent, optionally in the presence of an alcohol.
The alkylsalicylic acids are prepared by alkylation of salicylic acid or by pressure carboxylation of alkylphenols. The alkyl chain contains a minimum of 12 carbon atoms.
The phosphonates and thiophosphonates are prepared by action of P205 or P2S5 on a polyisobutene, then neutralization by an alkali or alkaline earth oxide or hydroxide. The weight molecular of polyisobut ~ is between 300 and 2000.
All these detergents can be used in mixture with dispersants soluble in a hydrocarbon medium, for example alkylsuccinimide type or esters of alkylsuccinic acids of molecular weight of 300 and 2500.

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'. . - - - '~ ~ ~' ~: '~,''.''~''. . '' '~,' ~ ' 2 ~ 036 Among the alkali or alkaline earth metal derivatives are uses oxides, hydroxides or alcoholates. Drifts preferred are oxides and hydroxides.
These are added to the excess reaction medium stoichiometric compared to the phenolic compound. Excess stoichiometric can vary between 5: 1 and 30: 1.
The oxygenated promoter is generally an aliphatic alcohol or aromatic, an alkoxyalkanol, a glycol or even a alkanolamine. We prefer to use alcohol aliphatic in C1 to C20 or mixtures thereof. Alcohols aliphatics can be used in admixture with glycols, alkoxyalkanols or alkanolamines.
The molar ratio of the oxygen promoter to the phenolic compound is generally between 1 and 30.
The use of a nitrogenous promoter is optional. The nitrogen promoter is generally chosen from ammonia, ammonium salts, primary, secondary or tertiary in C2 to C10 and their salts, polyamines or alkanolamines as well as nitro mineral compounds.
Among the nitrogenous promoters, ammonia is preferred, carbonate and ammonium chloride, ethylenediamine, ethanolamine or diethanolamine, as well as nitrate of calcium.
The molar ratio of the nitrogen promoter to the phenolic compound is generally between 0.05 and 30.
Hydrocarbon solvent allows perfect homogenization different reagents as well as lowering the viscosity, which will facilitate recovery later solid carbonation residues. The solvent represents generally 10 to 70% by weight of the reaction mixture. The solvents used are aliphatic compounds or aromatics in C6 to C12. The preferred solvents are aromatic solvents, such as benzene, toluene, xylene, ethylbenzene and aromatic chlor ~ s. Their choice is dictated by the characteristics of the addi ~ if collected, by their boiling point and by the boiling point of azeotropes that they can form with oxygenated compounds and water.

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-,:. ,, 7 ~ 40 ~ b The handling of overbased detergents is facilitated by the addition of a diluting oil. The oil represents approximately 20 to 50% by weight of the additive obtained. This can be added to the reaction medium before carbonation or still after this, that is to say just before elimination solvents. The diluent oils used are of a nature paraffinic, type 100 or 150 Neutral Solvent on nature mostly naphthenic such as 100-150 Pale Solvent.
The carbonation reaction can be carried out after optional addition of water to the reaction medium. The bill of water is particularly beneficial when the derivative of alkali or alkaline earth metal is an oxide.
Generally the amount of water added is such that the water / metal oxide molar ratio is of the order of 5. More in detail, the process for obtaining overbased detergents consists of:
a, neutralize the detergent with an alkali metal derivative or alkaline earth, in the presence of a nitrogenous promoter and / or oxygenated, a hydrocarbon solvent and optionally an oil thinner and water, b, add a non-metallic organic derivative of phosphorus, and better a phosphosulfur derivative, then carbonate the mixture with carbon dioxide gas for a sufficient time to consume part or all of the excess metal alkaline or alkaline earth ~ x, c, remove solid residues and solvents.
A preferred implementation of the method consists in successively introduce into a reactor equipped with a agitator, temperature control, heating and evacuation:
- 0 to 700 parts by weight of a hydrocarbon solvent, - 100 ~ 400 parts by weight of a detergent or a precursor detergent, - an excess of alkali or alkaline earth metal derivative stoichiometric with respect to the detergent or its precursor This stoichiometric excess is between 5: 1 and 30: 1, - an oxygen promoter whose molar ratio to the detergent is between 1 and 30, , - ', , - '- ~ ~.

8 20 ~ 036 - possibly a nitrogenous promoter whose molar ratio detergent is between 0.05 and 30, - possibly a quantity of water such as the ratio molar water / alkali or alkaline earth metal oxide either around 0.5, - a diluting oil in quantity such as this represents 20 ~ 50% by weight of the additive recovered at the end operations, - one of the organic phosphorus compounds described previously.
In the case where a detergent precursor and a acid phosphorus organic compound, it is best to neutralize the precursor by excess derived from alkali or alkaline earth metal before introducing the organic acid phosphorus compound.
In the case where a detergent pre-ursor and a salt of an organic phosphorus compound it is better successively introduce the precursor, the salt and finally excess alkali or alkaline earth metal derivative.
The phosphorus concentration of the reaction medium must be greater than or equal to 3% by weight.
We then proceed to carbonate the excess alkali or alkaline earth metal stoichiometric at a temperature between room temperature and reflux temperature of the mixture and more particularly at a temperature between room temperature and 50C and preferably at a temperature between ~ ure 30 C and 45 C.
The molar ratio of carbon dioxide introduced to excess alkali or alkaline earth metal stoichiometric is between 0.6 and 1.2. The mixture is possibly stabilized by heating under vacuum or under a stream of nitrogen, so as to eliminate low-point oxygen promoters boiling water and added water, as well as the water produced by the carbonation reaction. Solid residues are removed, generally by centrifugation and / or filtration at of diatomaceous earth.

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20 ~ 036 If the diluent oil has not been added before carbonation, it is then added before removing the solvent hydrocar ~ oné and possibly alcohol. These last are removed by vacuum heating at temperatures of around 100 to 200C.
Note that the filtration operation can be performed after recovery of the solvent.
The overbased detergents according to the invention are clear and stable. The color is variable depending on the detergent used. The overbased sulfonates are for example colored brown-green, dark brown salicylates.
The base detergents according to the invention are entirely compatihles with hydrocarbons.
They are incorporated into the original lubricating oils natural or synthetic at a concentration between about 0.5 and 40 ~ by weight and preferably between 1 and 30%
in weight.
The lubricant compositions thus obtained can contain other additives, with antiwear effect, dispersant, antioxidant and polymers improving the index of viscosity.
The examples below illustrate the invention without, however, limit it.
In the examples, the basicity of overbased detergents is characterized by their alkaline value (VA) expressed in mg KOH / g of product. VA is determined by titration using a strong acid according to standard ASTM D-2396.
Unless otherwise indicated, all percentages are in weight.
EXAMPLE A
Preparation of dimethyldithiophosphoric acid In a 1 liter reactor fitted with a stirring system, temperature regulation, a cooler and a reagent introduction system, coupled with a system of neutralization of acid gases, we m ~ t suspended in 600ml of carbon tetrachloride, 133.45g of pentasulfide phosphorus. The suspension is cooled to 3C and 153.6g of m ~ thanol are added in 30 minutes, maintaining the temp ~ rature lower than 5C.

2 ~ 036 We then add in 60 minutes and in portions, an excess about 30% methanol based on the stoichiometry of the reaction. The mixture is then brought to re ~ lux until let it become perfectly clear.
The solution is cooled and filtered on a Millipore filter 0.22 ~ m, then the solvent evaporated.
177.6 g of dimethyldithiophosphoric acid are recovered at 75.5 of purity.
EXENPLB B
Preparation of diethYldithioPhosphoric acid We proceed as in example A, except that we use 220.8 g of anhydrous ethanol in place of methanol. We recover 211g of diethyldithiophosphoric acid at 95% purity.
EXAMPLE C
Preparation of diisopropyldithioDhosPhoric acid We proceed as in example A except that we use 288g of isopropyl alcohol.
243 g of 80% diisopropyldithiophosphoric acid are recovered of purity.
EXAMPLE D
Preparation of dicyclohexyldithiophosphoric acid We proceed as in Example A except that we use 66.7g of P2S5 and 240g of cyclohexanol.
209 g of 75% dicyclohexyldithiophosphoric acid are recovered of purity.
EXAMPLE E
Preparation of dicresyldithiophosphoric acid We proceed as in Example A except that we use 400ml of toluene in place of carbon tetrachloride, 66.7g of P2S5 and 259.2g of para-cresol.
401.2 g of 42% dicresyldithiophosphoric acid are recovered of purity.

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he EXE ~ PLB 1: Comparison In a 1 liter reactor, equipped with a regulation of temperature, refrigerant, agitation system and of a gas bubbling device, we introduce successively:
- 520ml of toluene, 131.8g of alkylxylenesulfonic acid at linear C16-C18 alkyl chain, molecular weight 430 and 96% active ingredient, 168g of 100 Neutral diluent oil solvent, 108.4 g of slaked lime at 96% purity and 80 ml of methanol.
After neutralization of sulfonic acid by lime which can possibly be carried out by heating to 60C of the reaction medium for 30 minutes, 55.2 g of carbon dioxide in the mixture maintained at a temperature of 42C.
After carbonation, the methanol and the water produced are eliminated by the reaction by heating the mixture under partial vacuum. The medium is clarified using 2% by weight of diatoms Clarcel DICS of CECA SA.
After removal of the solvent, 407 g of product are recovered containing 12.8% calcium, VA = 323.
The product is brown, clear and stable when diluted, in mineral or synthetic oils. No trouble is observed or no designation after several weeks at 60DC.
EXEMPLB 2 ~ comparative) we operate as in example 1, but we introduce 219.2 g alkylarylsulfonic acid with cha ~ ne branched alkyl (of didodecylbenzenesulfonic acid) whose molecular weight is 520 and 70% active matter.
The amount of diluent oil is 108g.
The product is in the form of a brown liquid VA = 298. It is stable when diluted in oils lubricants.

We operate as in Example 1 except that we introduce 40ml of methanol instead of 80ml, and introduce 24g of product of Example A after neutralization of the acid sulfonic.

We recover ~ re an overbased sulfonate of VA = 320, d ~ nt the content calcium is 12.8% and the phosphorus content is 1.05%. The product is stable when diluted in oil.

we operate as in Example 3, but we introduce 48g of product of Example A. An overbased sulfonate of VA = 280, stable when diluted in oil, the contents of which in calcium and phosphorus are respectively 11.8% and 2.05%.

We operate as in Example 2, but we introduce 48g of product of Example A after neutralization of the acid sulfonic. The product collected at the end of operations is stable when diluted in oil. Its VA = 295 and its contents in calcium and phosphorus are respectively 11.4% and 1.8%.

We operate as in example l except that we introduce 120ml of methanol instead of 80ml, and introduce 67.5g of the product of Example B after neutralization of the acid sulfonic.
A sulfonate of V ~ - 300 is recovered, stable when diluted in oil and whose calcium and phosphorus contents are 12, ~% and 2.45% respectively.
EXAMPLE ~ 7 we operate as in Example 1 except that we introduce 2g, 3g of 95% purity ammonium diethyldithiophosphate (JANSSEN CHIMICA) just after sulfonic acid. The rest of the procedure is identical to that of example l.
a product of VA = 330 is collected, stable in dilution in oil, whose calcium and phosphorus contents are 13%
and 1.2% respectively.

We operate as in Example 2, but we introduce 67.5 g of product of Example B after neutralization of the acid sulfonic.

20 ~ 036 At the end of the operations, a product of VA = 290 is collected, stable when diluted in oil, including calcium contents and phosphorus are 11.8 ~ and 2.2% respectively.
EXEMP ~ E g We operate as in Example 2, but we introduce 197.3g sulfonic acid instead of 219.2g. On the other hand, we add 44g of 95% ammonium diethyldithiophosphate purity (JANSSEN CHIMICA) just after sulfonic acid. The remainder of the procedure in Example 2 is not changed.
A product of VA = 330 is recovered, stable in dilution in oil e ~ whose ralcium and phosphorus contents are 12%
and 1.5% respectively.

We operate as in Example 1, but we introduce 48g of product of Example C after neutralization of the acid sulfonic.
a product of VA = 326 is collected, stable in dilution in the oil, the calcium and phosphorus contents of which are 12.6% and 1.5% respectively.

We operate as in Example 2, but we introduce 48g of product of Example C after neutralization of the acid sulfonic.
A product of VA = 302 is recovered, stable in dilution in the oil, the calcium and phosphorus contents of which are 11.8% and 1.6% respectively.

We operate as in Example 1, but we introduce 76g of product of Example D after neutralization of the acid sulfonic.
a product of VA = 303 is collected, stable in dilution in the oil, the calcium and phosphorus contents of which are 11.7% and 1.5% respectively.

We operate as in Example 2, but we introduce 76g of product of Example D after neutralization of the acid sulfonic.

14 2 ~ 3 &
A product of VA = 295 is collected, stable in dilution in the oil, the calcium and phosphorus contents of which are 11.5% and 1.5% respectively.

We operate as in Example 1, but we introduce 80g of product of Example E after neutralization of the acid sulfonic.
A product of VA = 303 is collected, stable in dilution in the oil, the calcium and phosphorus contents of which are 11.8% and 0.9% respectively.

We operate as in Example 2, but we introduce 80g of product of Example E after neutralization of the acid sulfonic, and except that we use 113.2g of lime off instead of 108.4g.
A product of VA = 280 is collected, stable in dilution in the oil, the calcium and phosphorus contents of which are 10.9% and 0.8 ~ respectively.
EXENPLB 16 comparison We operate as in Example 1, but we introduce in the 312 g (C14-C18 alkyl) salicylic acid reactor, 37.5 g of slaked lime, 150ml of methanol and 100g of diluent oil.
After neutralization and carbonation at 42 C with 7.65 g of C2 we ra ~ oute 30g of lime which we carbonate with 10g CO2.
a stable dark brown additive is collected in the oils. Its calcium content is 7.6% VA = 205.

we operate as in example 16, but we introduce 44g of ammonium diethyldithiophosphate (JANSSEN CHIMICA) after neutralization.
The procedure is then identical to that of Example 16.
a black additive is collected, stable in dilution in VA oil = 210. Its phosphorus content is 1.5%.

The performance of new overbased detergents containing an organic phosphorus compound are examined on laboratory, wear, friction, oxidation and corrosion.

~ '' 2 ~ 4036 The test matrices correspond to lubricants for land engines on the one hand and for marine engines on the other go.
The products are first tested in a formulation API-SG type lubricant for petrol engine.
So that the performances of the different formulations are comparable, we establish compositions of the same level of VA
by substitution of the overbased detergent, and of the same content phosphorus, by subtracting from the initial amount of zinc dithiophosphate (DTPZ) of the formulation, the quantity of DTPZ whose phosphorus content corresponds to the content of phosphorus provided by the organic compound of phosphorus enclosed by the base detergent.
The formulations contain 1.4% overbased detergent and their phosphorus content, provided on the one hand by DTPZ and on the other hand by the organic compound of phosphorus from overbased detergent, is 1.3%.
URU ~ E EB8AI
(Lubricant for petrol engines) l. FALEX test (according to ASTM 26703 The test is carried out under the following conditions:
. Running-in: 5 minutes under 200 lbs (normal load) . 3 hours trial under 540 lbs (normal load) 16 2 ~ 4036 As an example, Table I gives some results showing that an overbased detergent containing a organic phosphorus compound has antiwear properties equivalent or improved compared to the overbased detergent of reference described in Example 1, or in relation to a sulfonate commercial overbased.
TABLE I

PHOSPHORUS CONTENT PRODUCT (ppm) FALEX RESULT
PROVIDED BY

Wear Weight loss (No. of teeth) (mg) DTPZ Detergent on the base Sulfonate1300 O 16 18.7 commercial Example 11 300 0 15 17.5 (comparative) Example 6900 340 9 10.5 2. Test on a 4-ball machine (according to ASTM 2783-71) The test conditions are as follows:
- speed: 1,500 rpm - duration: 1 hour - load: 60 Kg The quotation is obtained by determining the diameter imprint. This footprint diameter is even smaller that the anti-wear power of the formulation is important.

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Table II gives some results showing the effect beneficial use of overbased detergents containing a organic phosphorus compound on antiwear performance lubricant.

TABLE II

DIAMETER PHOSPHORUS CONTENT PRODUCT
EXAMPLE (ppm3 PROVIDED BY FOOTPRINT
(mm) -DTPZ Overbased detergent l (comparative) 1300 O 0.72 960 340 0.56 7 1130 170 0.69 1090 210 0.57 12 1090 210 0.57 14 1,170 130 0.70 -(Lubricant for petrol engines) On the same lubricant formulas, an oxidation test is performed at 165C with an air flow of 1.7 liters / minute for a period of 64 h and in the presence of a catalyst oxidation (ac ~ iron tylacetonate). This test allows partially simulate the conditions under which the oil can be submitted in a gasoline engine.
Table III gives the values of the variation in viscosity samples at the end of the 64 hours of the test (increase in dynamic viscosity in%). The increase in viscosity is the lower the resistance of the lubricant to oxidation is important.

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Overbased detergents containing an organic compound of phosphorus have resistance to oxidation significantly higher than that of overbased detergents of reference described in Examples 1 and 2.
TABLE III

PRODUCT ~ E PHOSPHORUS CONTENT VARIATION OF
THE EXAMPLE (ppm) PROVIDED BY VISCOSITY
(increase in ~) DTPZ Overbased detergent l (comparative) 1300 0 309 6,980,320,154 lloO 200 181 11 1090 ~ 10 112 . . . _. . .

ZF corrosion tests are carried out on the same lubricant formulations. According to the procedure, a plate of Iron and a copper plate are immersed for 24 hours in a sample containing 1% water and maintained at 95C.

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Table IV gives the visual rating results and shows the beneficial effect of the overbased detergent containing a organic compound of phosphorus. Lubricating formulations are less aggressive towards copper, because the content of DTPZ is lower.
TABLE IV
. _. . _. . . _. . . _ PRODUCT QUOTATION Cu QUOTATION
Fe (ASTM D 130) ____________________________________________________________ 4A Traceless Commercial Sulfonate Example l (comparative) without trace 4 ~
Example 6 without trace lA

WEAR TEST
Overbased detergents containing an organic compound of phosphorus are then tested in a formulation lubricant for marine engine (cylinder oil).
The basicity of the oil is 70 mg KOH / g of which only 20gKOH / g provided by the overbased detergent.
The test is carried out under the following conditions:
- running-in: 5 minutes under 300 lbs (Normal load)

- 3 hours of test under 900 lbs (Normal load) These conditions are close to extreme pressure.
Table V shows that the cylinder oil for marine engine formulated with detergents according to the invention significantly reduces wear.

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In addition, we observe that this performance gain is accompanied, in some cases, a gain in stability of the formulation.
TABLE V
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PRODUCT OF THE FALEX EXAMPLE RESULT

Wear Weight loss (NB of teeth) (mg) 1 (comparative) 183 197 1 ~ 1.5 ~ of DTPZ 82 92 (large deposit) , - ',,' ~ ''

Claims (14)

1 1 - Overbased detergent, for lubricating oils, obtained by carbonation of a mixture containing a detergent chosen from sulfonates, naphthenates, salicylates, alkaline phosphonates and thiophosphonates or alkaline earth, a derivative of an alkali metal or alkaline earth, chosen from oxides, hydroxides or alcoholates, a nitrogenous and / or oxygenated promoter, a solvent hydrocarbon and possibly a diluent oil and water, characterized in that the mixture contains less 3% phosphorus as an organic derivative non-metallic. 2 - Detergent according to claim 1 characterized in that that it contains 0.5 to 10% and preferably 1 to 5% by weight phosphorus. 3 - Detergent according to claim 1 or 2 characterized in what the non-metallic organic derivative of phosphorus is chosen from phosphites, phosphoramides, derivatives of phosphoric and thiophosphoric acids, dithiophosphoriques, trithiophosphoriques, tétrathiophos-phorics and their organic salts. 4 - Detergent according to claim 3 characterized in that the organic phosphorus derivative is a derivative phosphosulfurized like thiophosphoric acids or dithiophosphoriques and their organic salts and preferably derivatives of dithiophosphoric acids and their organic salts. 5 - Detergent according to claim 4 characterized in that the dithiophosphoric acid derivative is a derivative dihydrocarbyldithiophosphoric acid of formula general (I) where R and R 'identical or different represent linear or branched alkyl chains in C1 to C20, the aliphatic or aromatic cycles. 6 - Detergent according to claim 5 characterized in that dihydrocarbyldithiophosphoric acid is the acid diethyldithiophosphoric acid, diisopropyldithiophos-phoric, dicyclohexyldithiophosphoric acid or dicrésyldithiophosphorique acid. 7 - Detergent according to one of claims 1 to 6 characterized in that the alkali metal derivative or alkaline earth is an oxide or hydroxide. 8 - Detergent according to one of claims 1 to 7 characterized in that the oxygenated promoter is chosen among aliphatic or aromatic alcohols, alkoxyalkanols, glycols, alkanolamines or their mixtures. 9 - Detergent according to one of claims 1 to 8 characterized in that the nitrogenous promoter is chosen among ammonia, ammonium salts, amines primary, secondary, or tertiary in C2 to C10 and their salts, polyamines, alkanolamines or nitro mineral compounds. 10- Detergent according to one of claims 1 to 9 characterized in that the diluting oil is of a nature paraffinic or naphthenic. 11- Detergent according to one of claims 1 to 10 characterized in that the hydrocarbon solvent is a C6 to C12 aliphatic or aromatic compound and preferably an aromatic solvent such as benzene, toluene, xylene, ethylbenzene and the compounds chlorinated aromatics. 12- Lubricating composition characterized in that it contains a lubricating oil of natural origin or synthetic and 0.5 to 40% by weight and preferably 1 to 10%
weight of a detergent according to claims 1 to 11. 13- Composition according to claim 12 characterized in that that it contains anti-wear additives, dispersant, antioxidant and enhancing polymers the viscosity index. 14- Composition according to claim 12 or 13 characterized in that it contains dialkyldithiophosphate zinc.