EP0598646A1 - Colloidal products containing sulphur und/or phosphorus, and/or boron, their preparation and their use as additives for lubricants - Google Patents

Abstract

Colloidal products are described containing an element chosen from sulphur and phosphorus and optionally boron, as well as an element chosen from alkali and alkaline-earth metals and zinc, micellised within at least one detergent agent. They can be obtained in micellar form by reaction of at least one inorganic or organic acid containing sulphur and/or phosphorus and optionally an acid containing boron, these acids being introduced directly or formed in situ, with at least one basic derivative containing an alkali metal and/or an alkaline-earth metal and/or zinc, in the presence of at least one surface-active agent. These colloidal products can be employed as antiwear and extreme-pressure additives in lubricants.

Description

The invention relates to new colloidal products compatible with lubricating oils, their preparation, their use as additives with antiwear and extreme pressure action in mineral and synthetic oils, for example in engine lubricants, gear oils, fluids. hydraulic, metalworking oils, greases, etc.

These new products contain at least one element chosen from sulfur and phosphorus and optionally boron, as well as an element chosen from calcium, magnesium and zinc, all of these elements being in the colloidal state.

Overbased detergent additives have been known for a long time. Some of them and their preparation have been described for example in US patents 2,865,956, 3,150,088, 3,537,996, 3,830,739, 3,865,737, 3,953,519, 3,966,621 4,148,740, and 4,505,830 and the French patent 2,101,813. There are variants of the overbasing reaction which use in particular preformed carbonates from alkoxides and CO₂ before being brought into contact with the alkaline or alkaline earth salt of the acid compound; they are described in particular in US patents 2,956,018, 3,932,289 and 4,104,180.

It is also known to modify overbased detergent additives by incorporating boron derivatives, as described for example in US patents 3,907,691, 3,929,650, 4,965,003 and 4,965,004.

Finally, the modification of overbased detergent additives by certain carboxylic acids, boric acids or phosphoric acids has also been described in US patent 4,328,111, as well as in the published French patent application 2 689031 (to which the application corresponds European published 0562912.

Furthermore, in French patent application FR-A-2,645,168, the preparation of thiophosphorus compounds is described by reaction of at least one phosphorus sulfide with at least one so-called "overbased" detergent additive.

It has now been discovered that it is possible to prepare colloidal products containing sulfur and / or phosphorus and optionally boron, by reaction of at least one mineral or organic acid containing sulfur and / or phosphorus and optionally at least one mineral acid containing boron, with at least one basic metal derivative, alkaline or alkaline-earth or zinc, in the presence of at least one surfactant.

In general, the preparation of the colloidal products of the invention can be carried out as follows:

In the presence of at least one surfactant, at least one mineral or organic acid is reacted (which is introduced directly or which is formed in situ ) , with a basic non-micellized derivative of alkali or alkaline earth metal or zinc, the reaction temperature being for example between room temperature (20 ° C) and 140 ° C, for a period ranging for example from 30 minutes to 7 hours.

The reaction medium generally contains a solvent, for example an aliphatic or cycloaliphatic hydrocarbon (such as for example hexane, cyclohexane, heptane, octanes or nonanes), an aromatic hydrocarbon (such as toluene or xylenes ), tetrahydrofuran, or carbon sulfide, and optionally a dilution oil. As a product micellization promoter, an amine (such as triethylamine), a quaternary ammonium compound, for example a salt (such as methyltrioctylammonium chloride), hydrazine or an aliphatic monoalcohol can be used. such as for example methanol.

The reaction is generally followed by filtration of the solids present in the medium and the elimination of the solvent (s) used.

The surfactant used in the preparation of the colloidal products of the invention is generally a sulfonic acid, such as alkylarylsulfonic acids or their salts.

The acids involved in the preparation of the products of the invention can be introduced directly into the reaction medium, or be formed therein ( in situ) by appropriate reaction.

As regards the acids used directly in the reaction medium, mention may be made of sulfur carboxylic acids corresponding to the general formula:

X-R¹- Sx-R³-Sy-R²-COOH in which R¹ and R² each represent a divalent hydrocarbon radical, for example an alkylene radical of 1 to 6 carbon atoms, or a phenylidene radical, R³ represents a single bond or a divalent hydrocarbon radical, for example an alkylene radical of 1 to 4 carbon atoms, X represents a hydrogen atom or a carboxylic group; x and y each have an average value of 1 to 4 when R³ is a divalent hydrocarbon radical and the sum (x + y) has an average value of 1 to 4 when R³ represents a single bond.

More particularly, when R³ is a single bond and X represents COOH, the sulfur carboxylic acids are of the form

HOOC-R¹-S _{(x + y)} -R²-COOH


and there may be given as examples thio-, dithio-, trithio- and tetrathiodiglycolic, dipropionic and dibutyric acids, as well as 2,2 '-dithio dibenzoic acid.

When R³ is a divalent hydrocarbon radical and X a carboxylic group, the acids are of the form

HOCO-R¹-Sx-R³-Sy-R²-COOH


and we can give as examples: methylene- and ethylene-bis (thio-, dithio- and trithioacetic) acids and methylene- and ethylene-bis (thio-, dithio, and trithiopropionic acids).

Finally, when R³ is a single bond and X a hydrogen atom, the acids are of the form

HR¹-S _{(x + y)} -R²-COOH


and we can give as examples the ethylthio-, dithio- and trithioacetic, -propionic and -butyric acids.

Methods for preparing these sulfur carboxylic acids have been described in French patent application 2689031 already cited above.

When in the preparation of the colloidal products of the present invention, acids formed in situ are brought into play, these acids can be formed more particularly between on the one hand, the phosphorus sulfides, in particular P₄S₁₀, and their derivatives and on the other hand, water and / or an aliphatic monoalcohol such as for example methanol.

The organic acids containing sulfur introduced directly and the mineral acids containing sulfur and phosphorus formed in situ can be used in conjunction with at least one acid containing phosphorus or boron introduced directly or formed in situ from the corresponding oxides. Thus, in this case, orthoboric and metaboric acids or phosphoric acid H₃PO₄ and its derivatives can be brought into play directly, or acids formed in situ between on the one hand a phosphorus oxide such as P₂O₅ and / can be brought into play. or a boron oxide such as B₂O₃ and on the other hand water and / or at least an aliphatic alcohol such as for example methanol.

The alkali or alkaline earth derivatives used in the preparation of the colloidal products of the invention may more particularly consist of oxides, hydroxides, carbonates or hydroxycarbonates. Mention may be made, for example, of oxides of calcium, of magnesium, hydroxides of calcium, or of magnesium, hydroxycarbonates of calcium and magnesium, and carbonates of calcium and magnesium. Zinc oxide can still be used.

• leur teneur en soufre peut aller jusqu'à environ 30% en masse ; leur teneur en phosphore, jusqu'à environ 15% en masse; et leur teneur éventuelle en bore, jusqu'à environ 10% en masse;
• leur teneur en calcium peut aller par exemple jusqu'à environ 25 % en masse, leur teneur en magnésium jusqu'à environ 20 % en masse et leur teneur en zinc jusqu'à environ 25 % en masse.

The colloidal products obtained are stable, soluble in mineral and synthetic lubricants and are characterized by their sulfur and / or phosphorus and optionally boron content, and by their calcium, magnesium, and / or zinc content:

• their sulfur content can range up to about 30% by mass; their phosphorus content, up to about 15% by mass; and their possible boron content, up to about 10% by mass;
• their calcium content can range, for example, up to approximately 25% by mass, their magnesium content up to approximately 20% by mass and their zinc content up to approximately 25% by mass.

The colloidal nature of the products of the invention is checked by dialysis through a latex membrane. The sulfur and / or phosphorus and possibly boron analyzes locate these elements in the fraction that has not dialyzed (concentrate), which constitutes the colloidal part of the additive.

The colloidal compounds containing sulfur and / or phosphorus and optionally boron according to the invention constitute excellent antiwear and extreme pressure additives. Antiwear and extreme pressure additives are incorporated into lubricants when they are intended to lubricate organs subjected to significant mechanical stresses, such as distribution in heat engines, gears, bearings or stops. Significant mechanical stresses also appear during the machining of metals, whether cutting or forming.

In addition, the colloidal compounds containing sulfur and / or phosphorus and possibly boron according to the invention are endowed with a great thermal stability which authorizes their use in lubricants subjected in service at very high temperatures which can reach 160 °. C, as in some severe engine housings, in heavily loaded transmissions or high speed metal cuts.

In the use of the products of the invention as additives for lubricating oils and greases, they can be incorporated into them, for example at a concentration of 0.1 to 25% by mass, preferably from 1 to 15% by mass .

Lubricating oils (or greases) also generally contain one or more other additives such as additives improving the viscosity index, additives for lowering the pour point, antioxidants, anti-rust, anti-corrosion additives of copper, detergents, antiwear, antifoam, dispersants, friction reducers, with which the products of the invention are compatible.

The following examples illustrate the invention without limiting it.

Ca =

4,62 % en masse

S =

7,40 % en masse

Example 1 : 32.0 g of an alkylarylsulfonic acid with an equivalent molar mass equal to 700, 20.0 g of 100 Neutral oil, 15.4 g of lime CaO, 5 are introduced into a reactor equipped with an agitator. g of methanol, 1g of water and 75 ml of tetrahydrofuran. After stirring for 30 minutes, 15.6 g of dithiodiglycolic acid previously dissolved in 50 ml of tetrahydrofuran are introduced over 5 hours. The mixture is brought to 50 ° C. for 2 hours with stirring, then, after returning to ambient temperature, the reaction medium is filtered. After evaporation of the solvents under reduced pressure, 56 g of a homogeneous, clear product are collected, which contains:

Ca =

4.62% by mass

S =

7.40% by mass

Ca =

6,40 % en masse

P =

4,05 % en masse

S =

3,80 % en masse

Example 2 30.0 g of an alkylarylsulfonic acid with an equivalent molar mass of 700.30.0 is introduced into a reactor equipped with an agitator, a Dean and Stark separator and a dropping funnel. g of 130 Neutral oil, 15.0 g of lime CaO 13.21 g of phosphorus pentasulfide, 400 ml of xylene and 100 ml of tetrahydrofuran. After mixing, a solution of 9.64 g of water in 150 ml of tetrahydrofuran is introduced dropwise, at a temperature not exceeding 50 ° C. The medium is then brought to a temperature between 50 ° C and 70 ° C for 2 hours and then, after removal of the tetrahydrofuran and water by distillation, the medium is heated at the reflux temperature of xylene for 2 hours. After returning to ambient temperature, the medium is filtered, then the filtrate is evaporated under reduced pressure. 70 g of a homogeneous, clear and liquid product are collected, which contains:

Ca =

6.40% by mass

P =

4.05% by mass

S =

3.80% by mass

Ca =

8,40 % en masse

P =

4,04 % en masse

S =

4,50 % en masse

Example 3 20.0 g of an alkylarysulfonic acid with an average molar mass equivalent to 700.20.0 g are introduced into a reactor equipped with an agitator, a Dean and Stark separator and a dropping funnel. 130 Neutral oil, 20.0 g of lime Ca (OH) 2, 15.0 g of phosphorus pentasulfide and 300 ml of xylene. After mixing, the mixture is introduced dropwise at a temperature between 50 ° C and 70 ° C for 2 hours then, after removal of the tetrahydrofuran and water by distillation, the medium is heated at the xylene reflux temperature for 2 hours. After returning to ambient temperature, the medium is filtered, then the filtrate is evaporated under reduced pressure. 49.6 g of a homogeneous, clear and liquid product are collected, which contains:

Ca =

8.40% by mass

P =

4.04% by mass

S =

4.50% by mass

Ca =

13,60 % en masse

P =

4,90 % en masse

S =

9,60 % en masse

EXAMPLE 4 20.0 g of an alkylarysulfonic acid with an equivalent molar mass of 700.20.0 g are introduced into a reactor equipped with an agitator, a Dean and Stark separator and a dropping funnel 130 Neutral oil, 25.0 g of CaO lime 15.0 g of phosphorus pentasulfide, 350 ml of xylene and 100 ml of tetrahydrofuran. After mixing, a solution of 12.20 g of water in 80 ml of tetrahydrofuran is introduced dropwise, at a temperature not exceeding 50 ° C. The medium is then brought to a temperature between 50 ° C and 70 ° C for 5 hours then, after removal of the tetrahydrofuran and water by distillation, the medium is heated at the reflux temperature of xylene for 2 hours. After returning to ambient temperature, the medium is filtered, then the filtrate is evaporated under reduced pressure. 55.7 g of a homogeneous, clear and liquid product are collected, which contains:

Ca =

13.60% by mass

P =

4.90% by mass

S =

9.60% by mass

Ca =

10,85 % en masse

P =

4,45 % en masse

S =

10,50 % en masse

EXAMPLE 5 20.0 g of an alkylarylsulfonic acid with an equivalent molar mass equal to 700.20 g are introduced into a reactor equipped with an agitator, a Dean and Stark separator and a dropping funnel 130 Neutral oil, 26.4 g of lime Ca (OH) 2, 15.0 g of phosphorus pentasulfide, 300 ml of xylene, 40 ml of tetrahydrofuran and 50 ml of carbon sulphide. After mixing, a solution of 12.16 g of water in 40 ml of tetrahydrofuran is introduced dropwise, at a temperature not exceeding 50 ° C. The medium is then brought to a temperature between 50 ° C and 70 ° C for 2 hours, then after removal of the sulfide carbon tetrahydrofuran and water by distillation, the medium is heated at the reflux temperature of xylene for 2 hours. After returning to ambient temperature, the medium is filtered, then the filtrate is evaporated under reduced pressure. 54.9 g of a homogeneous, clear and liquid product are collected, which contains:

Ca =

10.85% by mass

P =

4.45% by mass

S =

10.50% by mass

Ca =

9,40% en masse

P =

5,70 % en masse

S =

9,90 % en masse

EXAMPLE 6 20.0 g of an alkylarysulfonic acid with an equivalent molar mass equal to 700.20.0 is introduced into a reactor equipped with an agitator, a Dean and Stark separator and a dropping funnel g 130 Neutral oil, 15.4 g CaO lime, 15.0 g phosphorus pentasulfide, 700 ml xylene and 50 ml carbon sulfide. After mixing, a solution of 12.16 g of water in 50 ml of tetrahydrofuran is introduced dropwise at a temperature not exceeding 50 ° C. The medium is then brought to a temperature between 50 ° C and 70 ° C for 2 hours, then, after removal of the carbon sulfide from tetrahydrofuran and water by distillation, the medium is heated to the reflux temperature of xylene during 2 hours. After returning to ambient temperature, the medium is filtered, then the filtrate is evaporated under reduced pressure. 56.1 g of a homogeneous, clear and liquid product are collected, which contains:

Ca =

9.40% by mass

P =

5.70% by mass

S =

9.90% by mass

Ca =

12,20 % en masse

P =

4,55 % en masse

S =

12,20 % en masse

EXAMPLE 7 Into a reactor equipped with an agitator, a Dean and Stark separator and a dropping funnel, 20.0 g of an alkylarylsulfonic acid with an equivalent molar mass equal to 700.20.0 are introduced. g 130 Neutral oil, 22.7 g CaO lime, 5 ml methanol and 450 ml xylene. The medium is brought to 50 ° C. for 30 minutes, then the methanol and the reaction water are removed by distillation. After returning to ambient temperature, 18.0 g of phosphorus pentasulfide are introduced into the reactor, which is dispersed in the medium. A solution of 12.16 is then introduced drop by drop, at a temperature not exceeding 50 ° C. g of water in 50 ml of tetrahydrofuran. The medium is then brought to a temperature between 30 ° C and 50 ° C for 3 hours then, after removal of the tetrahydrofuran and water by distillation, the medium is heated at the reflux temperature of xylene for 2 hours. After returning to ambient temperature, the medium is filtered, then the filtrate is evaporated under reduced pressure. 55.1 g of a homogeneous, clear and liquid product are collected, which contains:

Ca =

12.20% by mass

P =

4.55% by mass

S =

12.20% by mass

Ca =

4,05 % en masse

P =

4,60 % en masse

S =

8,25 % en masse

Example 8 : In a reactor equipped with an agitator, a Dean and Stark separator and a dropping funnel, 20.0 g of an alkylarylsulfonic acid with equivalent molar mass equal to 700, 20.0 are introduced. g of 130 Neutral oil, 20.0 g of CaO lime, 14.8 g of phosphorus pentasulfide and 300 ml of xylene. After mixing, 2.2 g of phosphoric acid and 2.0 g of hydrazine are introduced, then a solution of 9.60 g of water in 9.60 g of water is introduced dropwise at a temperature not exceeding 50 ° C. 50 ml of tetrahydrofuran. The medium is then brought to a temperature between 50 ° C and 70 ° C for 3 hours then, after removal of the tetrahydrofuran and water by distillation, the medium is heated at the reflux temperature of xylene for 2 hours. After returning to ambient temperature, the medium is filtered, then the filtrate is evaporated under reduced pressure. 50.3 g of a homogeneous, clear and liquid product are collected, which contains:

Ca =

4.05% by mass

P =

4.60% by mass

S =

8.25% by mass

Ca =

4,86 % en masse

P =

0,69 % en masse

S =

5,60 % en masse

EXAMPLE 9 20.0 g of an alkylarylsulfonic acid with an equivalent molar mass of 700.20.0 is introduced into a reactor equipped with an agitator, a Dean and Stark separator and a dropping funnel g of 130 Neutral oil, 40.5 g of calcium carbonate, 15.0 g of phosphorus pentasulfide, 300 ml of xylene and 100 ml of tetrahydrofuran. After mixing, a dropwise introduction is carried out temperature not exceeding 50 ° C, a solution of 12.16 g of water in 50 ml of tetrahydrofuran. The medium is then brought to a temperature between 50 ° C and 70 ° C for 2 hours then, after removal of the tetrahydrofuran and water by distillation, the medium is heated at the reflux temperature of xylene for 2 hours. After returning to ambient temperature, the medium is filtered, then the filtrate is evaporated under reduced pressure. 34 g of a homogeneous, clear and liquid product are collected, which contains:

Ca =

4.86% by mass

P =

0.69% by mass

S =

5.60% by mass

Mg =

5,5 % en masse

P =

7,1 % en masse

S =

3,7 % en masse

EXAMPLE 10 20 g of an alkylarylsulfonic acid with an equivalent molar mass equal to 700.20 g of oil are introduced into a reactor equipped with an agitator, a Dean and Stark separator and a dropping funnel 130 Neutral, 25 g of magnesia Mg (OH) 2, 15.0 g of phosphorus pentasulfide, 200 ml of xylene and 100 ml of tetrahydrodurane. After mixing, a solution of 12.2 g of water in 70 ml of tetrahydrofuran is introduced dropwise, at a temperature not exceeding 50 ° C. The medium is then brought to a temperature of between 50 ° C. and 70 ° C. for 2 hours then, after elimination of the tetrahydrofuran and of the water by distillation, the medium is heated at the reflux temperature of xylene for 2 hours. After returning to ambient temperature, the medium is filtered, then the filtrate is evaporated under reduced pressure. 45 g of a homogeneous, clear and liquid product are collected, which contains:

Mg =

5.5% by mass

P =

7.1% by mass

S =

3.7% by mass

Ca =

7,6 % en masse

P =

5,8 % en masse

S =

1,9 % en masse

EXAMPLE 11 20.0 g of an alkylarylsulfonic acid with an equivalent molar mass of 700.20.0 is introduced into a reactor equipped with an agitator, a Dean and Stark separator and a dropping funnel g of 130 Neutral oil, 22.7 g of CaO lime, 15.0 g of phosphorus pentasulfide, 6.9 g of phosphorus pentoxide, 450 ml of xylene and 100 ml of tetrahydrofuran. After mixing, a dropwise introduction is carried out, at a temperature not exceeding 50 ° C. solution of 12.16 g of water in 50 ml of tetrahydrofuran. The medium is then brought to a temperature between 50 ° C and 70 ° C for 2 hours then, after removal of the tetrathydrofuran and water by distillation, the medium is heated at the reflux temperature of xylene for 2 hours. After returning to ambient temperature, the medium is filtered, then the filtrate is evaporated under reduced pressure. 48 g of a homogeneous, clear and liquid product are collected, which contains:

Ca =

7.6% by mass

P =

5.8% by mass

S =

1.9% by mass

Ca =

9,7 % en masse

P =

3,7 % en masse

S =

7,5 % en masse

B =

1,0 % en masse

EXAMPLE 12 30.0 g of an alkylarylsulfonic acid with an equivalent molar mass equal to 700.30.0 is introduced into a reactor equipped with an agitator, a Dean and Stark separator and a dropping funnel g of 130 Neutral oil, 30.0 g of CaO lime 17.5 g of phosphorus pentasulfide, 400 ml of xylene and 100 ml of tetrahydrofuran. After mixing, a solution of 14.19 g in 150 ml of tetrahydrofuran is introduced dropwise, at a temperature not exceeding 50 ° C. The medium is then brought to a temperature between 50 ° C and 70 ° C for 2 hours. After removing the tetrahydrofuran and water by distillation, 5.0 g of orthoboric acid H3BO3, 2.5 ml of methanol, 5.0 g of lime CaO are introduced, then the temperature is maintained at 45 ° C for 7 hours. After returning to ambient temperature, the medium is filtered, then the filtrate is evaporated under reduced pressure. 79 g of a homogeneous, clear and liquid product are collected, which contains:

Ca =

9.7% by mass

P =

3.7% by mass

S =

7.5% by mass

B =

1.0% by mass

Ca =

4,8 % en masse

P =

1,0 % en masse

S =

5,4 % en masse

Example 13 : In a reactor equipped with an agitator, a Dean and Stark separator and a dropping funnel, 20.0 g of an alkylarylsulfonic acid with an equivalent molar mass equal to 700.20.0 is introduced. g 130 Neutral oil, 25.0 g CaO lime, 15.0 g phosphorus pentasulfide, 350 ml of xylene and 100 ml of tetrahydrofuran. After mixing, a solution of 8.54 g of water and 6.51 g of methanol in 80 ml of tetrahydrofuran is introduced dropwise, at a temperature not exceeding 50 ° C. The medium is then brought to a temperature between 50 ° C and 70 ° C for 5 hours then, after removal of the tetrahydrofuran and water by distillation, the medium is heated at the reflux temperature of xylene for 2 hours. After returning to ambient temperature, the medium is filtered, then the filtrate is evaporated under reduced pressure. 41.0 g of a homogeneous, clear and liquid product are collected, which contains:

Ca =

4.8% by mass

P =

1.0% by mass

S =

5.4% by mass

Example 14 : Examination of the products by dialysis in heptane through a latex membrane.

The products of Examples 1 to 7 and 11 above are subjected to dialysis in solution in normal heptane through a latex membrane. For each test, the mass fraction having dialyzed (dialysate) and that having not dialyzed (concentrate) are determined, the latter constituting the colloidal part. The phosphorus and / or sulfur concentration is also determined for each fraction. The results are shown in Table I below.

Examination of the results indicates that the sulfur and phosphorus contained in the products of the invention are found in full after dialysis in the concentrate (that is to say in the colloidal fraction), and are absent from the dialysate.

EXAMPLE 15 Evaluation of the Antiwear and Extreme Pressure Properties

The products of Examples 2 to 4, 8 and 12 are evaluated for their antiwear and extreme pressure properties in a 130 Neutral mineral oil.

The antiwear and extreme pressure performances are evaluated on a 4-ball machine according to the procedure ASTM D 2783. The results are shown in table II below. Table II Example product CONCENTRATION / OIL (% by mass) ANTI - WEAR AND EXTREME -PRESSURE PERFORMANCE ON 4 BALL MACHINES Additive It Load / wear index (daN) Welding load (daN) Footprint diameter after 1 hour under 40 daN (mm) 2 10 0.64 42 250 0.45 3 10 0.99 60 315 0.46 4 5 0.61 47 250 0.47 4 10 1.22 73 400 0.47 8 10 0.40 70 400 0.46 12 10 1.03 56 400 0.50 Comparative examples Basic Ca sulfonate with 11.90% Ca 5 0.59 29 170 0.75 10 1.19 36 200 0.36

The additives according to the invention have marked antiwear and extreme pressure properties. The performances obtained are higher than those noted for formulations containing conventional overbased colloidal additives.

Claims (15)

1- Colloidal product containing at least one element chosen from sulfur and phosphorus and possibly boron as well as at least one element chosen from magnesium, calcium and zinc, all these elements being present in micellized compounds within at least one surfactant, characterized in that it is obtained in micellar form by reaction of at least one organic or inorganic acid with at least one basic non-micellized derivative of at least one metal chosen from magnesium, the calcium and zinc in the presence of at least one surfactant, said acid being chosen from sulfur-containing carboxylic acids corresponding to the general formula

X-R¹-Sx-R³-Sy-R²-COOH

wherein R¹ and R² each represent a divalent hydrocarbon radical, R³ represents a single bond or a divalent hydrocarbon radical, X represents a hydrogen atom or a carboxylic group; x and y each have an average value of 1 to 4 when R³ is a divalent hydrocarbon radical and the sum (x + y) has an average value of 1 to 4 when R³ represents a single bond and acids containing sulfur and phosphorus formed in situ between on the one hand a phosphorus sulfide and on the other hand water and / or an aliphatic monoalcohol. 2- colloidal product according to claim 1, characterized in that said sulfur carboxylic acid is chosen from thio-, dithio-, trithio- and tetra thio-diglycolic, -dipropionic and -dibutyric acids, acid 2, 2'- dithio dibenzoic acid, methylene- and ethylene-bis (thio-, dithio- and trithio acetic acids), methylene- and ethylene-bis (thio-, dithio- and trithio propionic acids) and ethyl-thio-, dithio- acids , and trithio-acetic, -propionic and -butyric. 3- colloidal product according to claim 2, characterized in that said sulfur carboxylic acid is dithiodiglycolic acid. 4- colloidal product according to claim 1, characterized in that said acid is formed in situ between phosphorus sulfide P₄S₁₀ on the one hand, and water or methanol on the other hand. 5- colloidal product according to one of claims 1 to 4, characterized in that said acid is brought into play together with at least one additional acid containing phosphorus or boron introduced directly or formed in situ from the corresponding oxides. 6- colloidal product according to claim 5, characterized in that said additional acid introduced directly is chosen from orthoboric and metaboric acids, phosphoric acid H₃PO₄ and derived acids, and said additional acid formed in situ is chosen from the acids formed between a phosphorus oxide and / or a boron oxide on the one hand, and water and / or an aliphatic monoalcohol on the other hand. 7- colloidal product according to claim 6, characterized in that said additional acid introduced directly is phosphoric acid H₃PO₄ or boric acid H₃BO₃ and said additional acid formed in situ is formed between phosphorus pentoxide P₂O₅ and water. 8- colloidal product according to one of claims 1 to 7, characterized in that said basic derivative is an oxide, a hydroxide, a carbonate or a hydroxycarbonate of magnesium or calcium, or zinc oxide. 9- colloidal product according to one of claims 1 to 8, characterized in that said surfactant is a sulfonic acid, such as an alkylarylsulfonic acid, and / or a salt derived therefrom. 10- Colloidal product according to one of claims 1 to 9, characterized in that the reaction is carried out in the presence of at least one solvent chosen from aliphatic or cycloaliphatic hydrocarbons, aromatic hydrocarbons, tetrahydrofuran, carbon sulfide and a dilution oil. 11- Colloidal product according to one of claims 1 to 10, characterized in that one operates in the presence of a micellization promoter chosen from amines, quaternary ammonium compounds, hydrazine and aliphatic monoalcohols. 12- colloidal product according to one of claims 1 to 11, characterized in that the reaction takes place at a temperature of 20 to 140 ° C for a time of 30 minutes to 7 hours. 13- colloidal product according to one of claims 1 to 12, characterized in that it contains 30% by mass of sulfur and / or up to approximately 15% by mass of phosphorus and optionally up to approximately 10% by mass of boron, as well as up to approximately 25% by mass of calcium, and / or up to approximately 20% by mass of magnesium and / or up to approximately 25% by mass of zinc. 14. A lubricant composition characterized in that it comprises a major proportion of at least one mineral or synthetic lubricant and a minor proportion of at least one colloidal product according to one of claims 1 to 13. 15- lubricating composition according to claim 14, characterized in that the colloidal product is incorporated therein a concentration of 0.1 to 25% by mass.