FR2615861A1 - Olefin polysulphide compositions with a high sulphur content and a very low chlorine content, their preparation and their use as additives for lubricants - Google Patents

Abstract

Olefin polysulphide compositions which have a high sulphur content and a very low chlorine content, which are obtained by a process in which: 1 - sulphur mono- and/or dichloride is reacted with at least one C2-C5 aliphatic monoolefin to form an addition product or "adduct"; 2 - hydrogen sulphide is reacted with an alkali metal hydroxide or ammonium hydroxide in solution in at least one substantially anhydrous C1-C4 aliphatic monoalcohol, with optional addition of elemental sulphur; 3 - the said "adduct", together with at least one monohalogenated hydrocarbon compound, is placed in contact with the alcoholic solution obtained at the end of stage 2; 4 - the mixture resulting from stage 3 is heated, the monoalcohol is removed, while water is added; and 5 - after separation and removal of the aqueous phase the organic phase, consisting at least predominantly of the required olefin polysulphide composition, is recovered. These compositions, exhibiting a sulphur content which may go up to approximately 65 % on a mass basis and a chlorine content which is generally lower than approximate 0.1 % on a mass basis, are employed especially as additives for improving the extreme-pressure properties of lubricants. Single plate to be published.

Description

The invention relates to the field of sulfur-containing organic additives used in particular for improving the extreme-pressure properties of lubricants; it relates more particularly to new products of the type polysulfurized olefins, high sulfur content and very low chlorine content, their preparation and their use as additives for mineral or synthetic lubricants.

There are described in the prior art a number of processes for the preparation of polysulfide olefins useful as extreme pressure additives for lubricants.

In particular, US Pat. Nos. 3,471,404 and 3,697,499 describe a process whose main steps are as follows: (1) sulfur monochloride is reacted with an excess of an olefin of 2 to 5 carbon atoms, in particular isobutene, at a temperature of 20 to 80 C, so as to form an "adduct"; (2) 3 "adduct" of the first step is reacted with a sulfide of.

alkali metal (preferably sodium sulphide) and elemental sulfur, used in a ratio of 1.8 and 2.2 mol of metal sulphide per gram atom of sulfur, the proportion of alkali metal sulphide being in addition 0 8 to 1.2 moles per mole of "adduct", and the reaction being carried out in the presence of an alcohol or a hydro-alcoholic solvent under reflux; and
(3) the resulting product, which contains 1-3% of chlorine, is reacted with a refluxing aqueous mineral base until the residual chlorine content of the product is less than 0.5%.

 It is stated in these prior patents that the sulfur content of the products obtained could be 40 to 60% by weight. In reality, it is most often close to 46% in mass. These products can be used as extreme pressure additives for lubricating oils, transmission fluids or greases, the lubricating bases considered consisting of mineral oils and certain synthetic oils.

In addition, U.S. Patent No. 4,204,969 discloses a relatively similar method for preparing polysulfide olefins useful as extreme pressure additives for lubricating oils. This process comprises the following main steps (1). - 100 C of sulfur monochloride with a C3 to C6 aliphatic monoolefin (usually isobutene), preferably in the presence of a lower alcohol promoter, so as to form an "adduct"; (2) this "adduct" is reacted with sulfur and sodium sulphide (prepared for example from NaOH, Na and / or H 2 S) in a ratio of 0.1 to 0.4 gram atom of sulfur per mole of sodium sulphide in a hydroalcoholic medium at a temperature ranging from 500C to reflux; and the product obtained is recovered without treatment by means of a base.

The single example indicates that the product has a sulfur content of 49% by weight and a viscosity at 37.8 C (100 F) of 8.6 mm 2 / s (cSt); but the analysis indicates that such a product still contains a residual chlorine content of about 0.25% by weight.

Examination of the prior art shows that isobutylene polysulfides, prepared in reaction mediums containing significant proportions of water, still contain amounts of residual chlorine greater than 0.1% by mass, the complete elimination of chlorine being made difficult because of the insolubility of the "adduct" in the reaction medium, or an incomplete heterogeneous phase reaction.

In the majority of the processes described, the water is generally introduced into the reaction medium, in the presence of a minor amount of an alcohol (in particular isopropanol), to dissolve the alkali metal sulphide used, which itself contains most often a significant amount of water of hydration (at least 40% by weight in the case of industrial Na2S).

It is, however, possible to increase the solvent character of the reaction medium with respect to the adduct by substituting the water of dissolution of the alkaline sulphide hydrate with a lower alcohol, but the amounts of alcohol to be used are then incompatible with economically satisfactory industrial production.

It is also known that toxicological and ecological constraints are currently driving a new legislation, concerning additives for lubricants, which will impose in the next few years for these products, a maximum chlorine content substantially less than 0.1% by mass.

It has now been found that it is economically possible to use a reaction medium in which the "adduct" is soluble, resulting in increased reactivation against the alkali polysulfide. This new reaction medium does not result in reaction volumes greater than those required by the prior art, and leads to (poly) sulfide olefin compositions which contain very high sulfur contents for very low levels of residual chlorine. and may, as such, be advantageously used as additives for lubricants, which they especially improve the extreme-pressure properties.

The appended FIG. 1 represents a continuous embodiment of the additive preparation process according to the invention.

Generally speaking, the process for the preparation of polysulfurized olefins of the invention comprises the following steps: (1) at least one compound chosen from monochloride and sodium chloride is reacted, for example at a temperature of 20 to 80 ° C. sulfur dichloride with at least one aliphatic monoolefin of 2 to 5 carbon atoms, thereby forming an adduct (2) hydrogen sulfide is reacted with an alkali metal hydroxide (sodium, potassium) or ammonium hydroxide in solution in at least one substantially anhydrous C1 to C4 aliphatic monoalcohol; elemental sulfur is optionally added, depending on whether it is desired to form a mixture of alkali metal sulphide, hydrogen sulphide and / or polysulphide (3), said "adduct" is brought into contact and, at the same time, at least one saturated monohalogenated hydrocarbon compound. unsaturated bu, as defined below, with the alcoholic solution obtained at the end of step (2), maintained at a predetermined temperature, for example from 20 to 120 ° C., during the introduction of the reagents, possibly by operating under pressure ; (4) the resulting mixture is heated for a specified time, at a temperature ranging for example from 500C to reflux temperature; the monoalcohol is removed by distillation; while adding a sufficient volume of water to keep reagents and mineral products in solution; (5) after decantation, the aqueous phase is removed and the polysulfurized olefin constituting the organic phase is recovered; and (6) optionally, the product obtained is treated with a basic compound, such as a mineral base, and washed with water.

In step (1) of the process of the invention, the starting olefins may contain from 2 to 5 carbon atoms, and may be used alone or in mixtures. Isobutylene is most often used. It is also possible to use these olefins in admixture with minor proportions of olefins having more than 5 carbon atoms (eg diisobutylene).

The olefin may be used in a proportion of 1.5 to 2.5 moles, preferably 1.8 to 2.2 moles, per mole of monochloride and / or sulfur dichloride. It is generally introduced into monochloride and / or liquid sulfur dichloride at a temperature of 20 to 80 ° C., more specifically 30 to 500 ° C.

The sulphide compound prepared in step (2) may have the proportions of a sulphide, a hydrogen sulphide and / or an alkali metal polysulfide (for example sodium or potassium) or ammonium or a mixture of these.

This is most often sodium compounds. In general, from 0.1 to 1 mole of hydrogen sulfide and preferably from 0.3 to 0.7 mole of hydrogen sulfide per mole of hydroxide is used.

It is of course possible to use a higher proportion of hydrogen sulfide, but in this case the effective proportion of hydrogen sulfide is not necessarily increased, the unreacted amount then being released.

The elemental sulfur optionally used in step (2), together with the sulfurized compound, may be with the introduced hydroxide, in a molar ratio ranging from 0 to about 3.6 / 1, more particularly from 0 to 2.5 / 1.

In step (2), the sulfur compound is formed, and elemental sulfur is optionally introduced into a light aliphatic monoalcohol containing 1 to 4 carbon atoms.

As light aliphatic monoalcohols, mention may be made of: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol, methanol being preferred; the amount involved is advantageously from 100 to 400 cm 3, preferably from 125 to 200 cm 3 per mole of hydroxide used.

In step (3) of the process, the saturated hydrocarbon compound (s)
and / or monohalogenated unsaturated used together with the "adduct"
obtained at the end of step (1), may consist of chlorides,
bromides or iodides of allyls or alkenyls, linear or
branched, from C1 to C12 (preferably C2 to C4), cycloalkyls
and / or optionally substituted C5 to C12 cycloalkenyls (from
preferably C6), or aryl and / or arylalkenyls,
optionally substituted, C6 to C12 (preferably C8 and C9).

Examples that may be mentioned include chlorides, bromides and
iodides of methyl, ethyl, isopropyl, n-propyl,
tert-butyl, isobutyl, n-butyl, tert-amyl, isoamyl,
n-amyl, n-hexyl, 2-ethylhexyl, n-octyl, cyclohexyl and
benzyl and mixtures thereof.

It may also be mentioned chloro-l ethylene, chloro-l propene,
2-chloropropene, 3-chloropropene, 1-chlorobutene-1,
chloro-1-butene-2, 2-chloro-2-butene, 3-chloro-butene-1,
chloro-1-methyl-2-propene, 3-chloro-2-methylpropene, or the
3-chloro-1-phenylpropene-1, 2-chlorophenothenone, and the
brominated and iodinated derivatives.

 Advantageously, n-butyl chloride and melthalyl chloride are used.

In the context of the invention, it is possible to replace at least
part the monohalogenated hydrocarbon compound as defined above
by at least one monohalogenated hydrocarbon compound
minus a functional group comprising one or more
heteroatoms (such as oxygen and / or nitrogen and / or sulfur).

Among these functional monohalogenic hydrocarbon compounds, one
will mainly use monochlorous or monobromous compounds; they
will advantageously be chosen from monohalogenated compounds containing at least one alcohol function and
especially ::
halides of aliphatic, alicyclic or aromatic-aliphatic monoalcohols containing, for example, from 2 to 18 carbon atoms, such as, for example, 2-chloro and 2-bromo-ethanols, chloro- and bromo-propanols, butanols, pentanols, hexanols; heptanols, octanols, nonanols, decanols, undecanol and dodecanol, and chloro or bromo-benzyl alcohols, and chloro- or bromo-phenylethyl alcohols;
polyol halides, such as, for example, 3-chloro or 3-bromo-1,2-propanediol (and the corresponding epoxy derivatives, for example 1-chloro or 2,3-bromo-2,3-epoxy propane);
- (poly) oxyalkylenated monohydric alcohols, such as, for example, chlorine and bromo- (poly) ethoxyethanols, (poly) ethoxypropanols, (poly) propoxyethanols and (poly) propoxypropanols;
monohalogenated compounds containing at least one phenol function, such as, for example, chloro and bromophenols which are unsubstituted or substituted, for example with alkyl groups, the monohalogenated compounds containing at least one carboxylic function, such as, for example, chloro and bromoacetic, propionic, butyric, valeric, benzoic and succinic; ;
the monohalogen compounds contain at least one amine function, especially aliphatic, alicyclic or aromatial-aliphatic compounds, such as, for example, chloroethylamine hydrochloride and chloro-N, N-dimethyl-, diethyl- and dipropyl-hydrochlorides; ethylamines, chloro- and bromo-benzylamines, and chloro- and bromo-phenylethylamines; monohalogen compounds containing at least one amide function, such as, for example, chloro- and bromoacetamides and propionamides; or monohalogenated compounds containing at least one thiol function, such as, for example, chloro- and bromo-mercaptobenzothiazoles, chloro- and bromo-phenylmercaptans and chloro- and bromobenzylmercaptans.

Among the compounds. functional monohalogenes having groups of several different types, there may be mentioned compounds with hydroxyl functions and carboxylic acid, such as, for example, 5-chloro-salicylic acid or 3-chloro-4-hydroxy-mandelic acid; amine and carboxylic acid-containing compounds, such as, for example, 4-chlorophenylalanine, or compounds with hydroxyl and amine functional groups.

Without departing from the scope of the invention, these functional monohalogenated hydrocarbon compounds may be used together with non-functional monohalogenated hydrocarbon compounds as defined above, and in all proportions.

In the following, the term "monohalogenated hydrocarbon compounds" will be used interchangeably to denote in a general manner the non-functional compounds and the functional compounds involved, or their mixtures.

When, in step (3) of the process of the invention, at least one functional monohalogen compound is used as defined above, it is advantageous to carry out the reaction of this step in the presence of a small amount of (For example from 0.1 to 10% by weight) of at least one phase transfer catalyst, especially a quaternary ammonium halide (for example tetrabutylammonium chloride), or an alkylphosphonium halide, or another "ethercouronne" (or cryptate).

The proportion of monohalogenated hydrocarbon compound used is generally from 1 to 70% in gram atoms of halogen relative to the total number of gram halogen atoms of the "adduct" + momohalogenated hydrocarbon compound. This proportion generally corresponds to a number of moles of monohalogenic hydrocarbon compound of about 0.015 to 1.9 per 100 g of "adduct," especially when the starting monoolefin is isobutylene.

The proportion of "adduct" and of monohalogenated hydrocarbon compound used relative to the hydroxide in question corresponds generally to a number of halogen atoms per mole of hydroxide ranging from 1/1 to 0.5 / 1, preferably from 0.85 / 1 to 0.75 / 1.

Step (3) can be carried out under low pressure, the relative pressure can be, for example, up to 1 MPa (10 bar).

The additives of the invention can also be prepared using a continuous parallel current, multi-contact process. In this case, the reaction of step (3) is generally carried out under pressure.

Such an embodiment will be described in more detail in Example 12, in relation to the appended figure.

The polysulfurized olefin compositions according to the invention may have a sulfur content of up to about 65% by weight, for particularly low residual chlorine contents generally less than about 0.1% by weight, most often less than 0.05%, and sometimes as low as about 0.01% by weight, especially in the case of the use of methanol and / or a slight reaction pressure.

The products of the invention which contain less than 50% by weight sulfur content have sufficient solubility in mineral oils to be used in the formulation of the anti-wear gear extreme pressure oils.

The products of the invention which contain sulfur contents greater than 50% up to about 65% by weight have a more limited solubility in mineral oils, but still sufficient for the applications to which they can be applied (oils for the work metals for example); in addition, they are fully soluble in common petroleum solvents such as white spirit or in petroleum cuts of a more aromatic nature.

The following examples illustrate the invention without limiting it.

EXAMPLE 1
In a 10-liter reactor equipped with a stirrer, 27DDg of sulfur monochloride S2C12 (20 moles) is introduced and then, via a dip tube, is introduced under the surface of the
S2C12 constantly stirred, 2530 g of isobutylene (48.7 moles), in which 25 g of methanol had previously been dissolved. The temperature of the reaction medium is maintained at 45 ° C. to 500 ° C. throughout the period of introduction of the isobutylene (1 hour). Thus 500D g of adduct is obtained which is designated by the term "adduct".

In a second reactor of 1 liter equipped with an agitator and surmounted by a system allowing the distillation, 98 g of sodium hydroxide in pellets (2.45 moles) and 400 cm3 of anhydrous methanol are introduced, then the mixture is agitated until at complete dissolution.

41.65 g of hydrogen sulphide (1.225 mol) are introduced through a tube immersed in the alcoholic phase for a period of 1 hour, the reaction mixture being maintained at 500 ° C. by external cooling.

14.52 g of blooming sulfur (0.45 g) are then added to the medium, and the mixture is then heated with stirring at the reflux temperature of methanol for 1 hour to promote the formation of the mixture.

sodium polysulfide.

By means of a dropping funnel, a mixture consisting of 230 g of "adduct" and 15 g (ie approximately 16.2 10 -2 mol) of sodium chloride is introduced into the alcoholic solution of sodium polysulfide. -butyl (duration of introduction: 2 hours), the reaction temperature being regulated by the reflux of methanol to boiling.
It is allowed to react at reflux for 7 hours, then the methanol is gradually removed by distillation, while, at the same time, 350 cm3 of water are gradually introduced into the boiling mixture.

After complete distillation of the methanol, the hot (upper) organic phase is separated from the aqueous phase containing the NaCl formed and the excess of sodium polysulfide.

The organic phase is treated under reflux with stirring for 3 hours with 200 g of a 10% by weight aqueous sodium hydroxide solution.

After decantation, the recovered organic phase is washed twice with 200 cm3 of water, dried over anhydrous Na 2 SO 4 and filtered. 168 g of a yellow-orange liquid are thus collected, the characteristics of which are indicated in Table 1.

EXAMPLE 2
The experiment of Example 1 is repeated by substituting the methanol with the same volume of ethanol; after reaction, treatment with sodium hydroxide and recovery treatments, 160 g of an orange liquid are collected, the characteristics of which are shown in Table 1.

EXAMPLE 3
The experiment of Example 2 is repeated by substituting one methanol for the same volume of isopropanol; 140 g of an orange-yellow liquid are collected, the characteristics of which are indicated in Table 1.

EXAMPLE 4
The experiment of Example 1 is repeated using 98 g (2.45 mol) of sodium hydroxide pellets, 41.65 g of H 2 S (1.225 mol), but using no sulfur in flower. After reaction with the chlorinated mixture (230 g of "adduct" + 15 g of n-butyl chloride) and then after distillation of methanol, the organic sulfur phase recovered is washed, dried and filtered without prior treatment with 10% sodium hydroxide. .

168 g of an orange-yellow liquid are thus collected, the characteristics of which are indicated in Table 1.

EXAMPLE 5
The experiment of Example 4 is repeated using this time 57 g of H 2 S (1.67 mol); 168 g of a yellow-orange liquid are collected whose characteristics are close to those of the additive obtained in Example 4; they are shown in Table 1.

EXAMPLE 6
The experiment of Example 1 is repeated using 98 g (2.45 mol) of sodium hydroxide pellets, 41.65 g of H 2 S (1.225 mol), 39.3 g of sulfur in flower, 400 cm 3 of methanol and a mixture of 215 g of "adduct" and 30 g of n-butyl chloride. After reaction and treatment with 10% sodium hydroxide, 195 g of an orange-yellow liquid are collected, the characteristics of which are shown in Table 1.

EXAMPLE 7
The experiment of Example 6 is repeated using 98 g (2.45 mol) of sodium hydroxide pellets, 41.65 g of H 2 S (1.225 mol), 152 g of sulfur in bloom (4.75 g). ), 400 cm3 of methanol and a halogenated mixture consisting of 110 g "adduct" and 105 g of n-butyl chloride. After reaction and distillation of the methyl alcohol, the recovered organic sulfur phase is washed, dried and filtered without prior treatment with sodium hydroxide. 218.7 g of an orange liquid are thus collected, the characteristics of which are indicated in Table 1.

EXAMPLE 8
The experiment of Example 1 is resumed by allowing the halogenated mixture to react on the alcoholic solution of sodium polysulfide for 16 hours. The additive (163 g), obtained after treatment, has the characteristics indicated in the table li
EXAMPLE 9
The experiment of Example 1 is repeated by carrying out the reaction under a pressure of 3 bars absolute (0.3 MPa) so as to maintain, for 7 hours, the reaction temperature of the halogenated mixture on the sodium polysulfide alcoholique towards 105 C. The characteristics of the additive obtained after treatment (167 g) are summarized in Table 1.

EXAMPLE 10
The experiment of Example 1 is repeated by replacing the n-butyl chloride by the same molar amount of 3-methyl-2-chloropropene (14.7 g). The additive (167 g) obtained after treatment has the characteristics indicated in Table 1.

EXAMPLE 11
The experiment of Example 1 is repeated using a halogenated mixture consisting of 162.5 g of "adduct" and 65.6 g of chloro-1-epoxy-2,3-propane (0.71 mole).

After refluxing for 7 hours, the mixture is allowed to cool and then toluene is added to extract the sulfur additive; after stirring and decantation, the recovered organic phase is washed twice with 200 cm3 of distilled water, dried over anhydrous Na 2 SO 4, filtered and then evaporated under reduced pressure to remove toluene. 157 g of a viscous brown liquid are thus recovered, infra-red analysis indicates the presence of the alcohol function and the absence of the ether function; the physico-chemical characteristics of the product are as follows (S)% mass = 41 (C1)% mass = 0.12 10H = 120
Kinematic viscosity at 1000C (mm2 / s) = 26
Solubility in
100 Neutral Sol Wind Oil: Insoluble
Benzene, Toluene, Xylene: soluble
Acetone: soluble
EXAMPLE 12
This example describes a procedure for the continuous production under low pressure of an additive containing about 46% by weight of sulfur and a residual chlorine content of 0.025% by weight.

To prepare an alcoholic solution of sodium polysulfide, 21.83 parts by weight of methanol, 6.75 parts of pelletized sodium hydroxide, 2.69 parts of H 2 S and 1 part of sulfur in bloom are introduced into a reactor R1; the mixture heated to 700C is then transferred by
line 1 in the storage bin Sl, to allow the manufacture of the next polysulfide charge;
The alcohol solution of sodium polysulfide is withdrawn from the storage tank S1 and then sent to the reactor R2 (at a pressure of 2 bar, pump P1) via line 2, at a weight rate of 2.36 parts / h.

At the same time, 1.23 parts / h of a halogenated mixture consisting of one part by weight of n-butyl chloride per 15.33 parts of "adduct" is introduced into the reactor R2 via line 3.

After an average residence time of 2 hours, the reaction mixture heated at 1050C with stirring is withdrawn continuously from the reactor R2 to be transferred via line 4 to the base of the reactor R3 ("piston" type) in which the reaction is completed, at the same temperature of 105 C, after an average residence time of 5 hours. The reaction mixture is taken up at the top of the reactor R3 via line 5 to be directed after expansion at atmospheric pressure (expander D1) to a static mixer SM, into which 1.75 parts / h of water coming from the tower is simultaneously introduced. T1, by line 6.

The mixture obtained is transferred via line 7 into a distillation column CD, at the top of which the methanol is recovered in a storage tank S2 from which, and after addition, the methanol is recycled via line 8 to the reactor R1 of manufacturing the alcoholic solution of sodium polysulfide.

The crude sulfur additive, mixed with an aqueous solution containing the excess sodium polysulfide, sodium chloride and traces of methanol is taken up at the bottom of the distillation column to be conveyed via line 9 to a decanter D2 where separates the two liquid phases at a temperature of 90 ° C.

The aqueous phase is removed at the bottom of the decanter via line 10.

The raw sulfur additive is taken up at the top of the decanter
D2 by line 11, to be directed to the base of an extraction tower
T2, in which it is brought into contact, against the current, with an aqueous solution of sodium hydroxide at 10% by mass, admitted at a flow rate of 1 part / h by line 12. The temperature in the tower T2 is 100 C.

The heavy phase, consisting of the aqueous solution of sodium hydroxide and sodium polysulfide, is removed at the base of the reactor via line 13.

The light phase, consisting of the washed sulfur additive, flows over the line 14 at the top of the washing tower T1, where it encounters, in countercurrent, an upward flow of 1.75 parts d water brought in line 15. The temperature in the T1 tower is 90 C.

The light aqueous phase recovered at the top of the scrubber is directed by line 6 to the static mixer SM, as indicated above.

The heavy phase, consisting of the sulfur-containing sulfur additive, is withdrawn at the base of the tower T1 and sent via line 16 to an evaporator
E, in which traces of water and light constituents are removed under reduced pressure at a temperature of 100 C.

The dry additive recovered at the base of the evaporator E is taken up by the line 17 to be conveyed after passing through the filter F, to the storage tank S3 via the line 18.

The characteristics of the additive thus obtained are shown in Table 1.

In Table 1, on the one hand, it is indicated the molar proportions of the rwac-b's, put into play by relating them to the quantity of soda used, (the symbol C1 representing in atoms-gram of chlorine the total quantity of chlorine. "adduct" and monohalogenic hydrocarbon compound involved) and secondly certain characteristics of the products obtained.

TABLE 1

<tb><SEP> Preparation <SEP> Product <SEP> obtained
<tb><SEP> Molar Reports
<tb> Additive <SEP> of <SEP> between <SEP><SEP> reagents <SEP> set <SEP> in <SEP> set <SEP> Sulfur <SEP> Chlorine <SEP> Viscosity
<tb> comenu <SEP> by <SEP> residue @ <SEP><SEP> c @ nemauque
<tb><SEP> Example <SEP> ClNaOH <SEP> H2S / NaOH <SEP> S / NaOH <SEP> Additive <SEP> in <SEP> to <SEP> 100 C
<tb><SEP> (% <SEP> mass) <SEP> additive <SEP> (mm <SEP> / s)
<tb><SEP> (% <SEP> mass)
<tb><SEP> i <SEP> 0.83 <SEP> 0.5 <SEP> 0.184 <SEP> 46.5 <SEP> 0.026 <SEP> 16.9
<tb><SEP> 2 <SEP> 0.83 <SEP> 0.5 <SEP> 0.184 <SEP> 43.2 <SEP> 0.040 <SEP> 16.1
<tb><SEP> 3 <SEP> 0.83 <SEP> 0.5 <SEP> 0.184 <SEP> 37.4 <SEP> 0.11 <SEP> 15.4
<tb><SEP> 4 <SEP> 0.83 <SEP> 0.5 <SEP> 0 <SEP> 47.2 <SEP> 0.025 <SEP>
<tb><SEP> 5 <SEP> 0.83 <SEP> 0.68 <SEP> 0 <SEP> 47.3 <SEP> 0.025 <SEP> 15.3
<tb><SEP> 6 <SEP> 0.83 <SEP> 0.5 <SEP> 0.184 <SEP> 47.2 <SEP> 0.031 <SEP> 12.7
<tb><SEP> 7 <SEP> 0.83 <SEP> 0.5 <SEP> 1.939 <SEP> 63.8 <SEP> 0.0125 <SEP> 12.3
<tb><SEP> 8 <SEP> 0.83 <SEP> 0.5 <SEP> 0.184 <SEP> 46.4 <SEP> 0.014 <SEP> 11.4
<tb><SEP> 9 <SEP> 0.83 <SEP> 0.5 <SEP> 0.184 <SEP> 46.6 <SEP> 0.012 <SEP> 14.2
<tb><SEP> 10 <SEP> 0.83 <SEP> 0.5 <SEP> 0.184 <SEP> 46.5 <SEP> 0.026 <SEP> 15.2
<tb><SEP> 12 <SEP> 0.83 <SEP> 0.5 <SEP> 0.184 <SEP> 46.3 <SEP> 0.025 <SEP> 15.5
<tb> (*) X-ray fluorescence assay.

SOLUBILITY OF THE ADDITIVES OF THE INVENTION
The solubility of the additives prepared according to the invention is measured at 20 ° C. and 5 ° C. in an SAE 90 mineral oil and in white spirit for concentrations equal to 5% by weight; the results obtained are collated in the following table 2
TABLE 2

<tb><SEP> Solubility <SEP> after. <SEP> 15 <SEP> days
<tb><SEP> Additive <SEP> Content <SEP> in <SEP> in
<tb><SEP> of <SEP> Sulfur
<tb> example <SEP>(9;<SEP> mass) <SEP> Oil <SEP> SAE <SEP> 90 <SEP> mineral <SEP> White spirit
<tb><SEP> 20 C <SEP> 5 C <SEP> 20 C
<tb><SEP> 1 <SEP> 46.5 <SEP> Soluble <SEP> Soluble <SEP> Soluble
<tb><SEP> 2 <SEP> 43.2 <SEP> Soil <SEP> Soil <SEP> Soil
<tb><SEP> 3 <SEP> 37.4 <SEP> Soil <SEP> Soil <SEP> Soil
<tb><SEP> 4 <SEP> 47.2 <SEP> Soil <SEP> Soil <SEP> Soil
<tb><SEP> 5 <SEP> 47.3 <SEP> Soil <SEP> Soil <SEP> Soil
<tb><SEP> 6 <SEP> 47.2 <SEP> Insol <SEP> Insol <SEP> Soil
<tb><SEP> 7 <SEP> 63.8 <SEP> Insol <SEP> Insol <SEP> Soil
<tb><SEP> 8 <SEP> 46.4 <SEP> Soil <SEP> Soil <SEP> Soil
<tb><SEP> 9 <SEP> 46.6 <SEP> Soil <SEP> Soil <SEP> Soil
<tb><SEP> 10 <SEP> 46.5 <SEP> Soil <SEP> Soil <SEP> Soil
<tb><SEP> 12 <SEP> 46.3 <SEP> 1 <SEP> Soil <SEP> Soil <SEP> Soil
<tb> (*): Insoluble at 5% mass in SAE 90
Soluble in all proportions in white spirit and aromatic oil cuts.

MEASUREMENT OF THE CORROSIVE ACTIVITY OF THE PRODUCTS ACCORDING TO THE INVENTION
Corrosion tests are carried out on the copper blade according to the standard
ASTM D 130 (NF M 07-015), from a mineral oil SAE 90 containing 5% by weight of additive.

The results obtained are collated in the following Table 3. They are expressed by a quotation comprising a number of (1 to 4), this number being followed by a letter specifying the grade of corrosion of the copper strip.

TABLE 3

<tb> Additive <SEP> of <SEP>[<SEP> S <SEP>] <SEP> 3 <SEP> hours <SEP> to
<tb> the example <SEP> in <SEP> the additive
<tb><SEP> (% <SEP> mass) <SEP> 100 C <SEP> 121 C
<tb><SEP> 1 <SEP> 46.5 <SEP> 1 <SEP> a <SEP> i <SEP> b <SEP>
<tb><SEP> 2 <SEP> 43.2 <SEP> the <SEP> 1 <SEP> b <SEP>
<tb><SEP> 3 <SEP> 37.4 <SEP> 1 <SEP> a <SEP> i <SEP> b <SEP>
<tb><SEP> 4 <SEP> 47.2 <SEP> 2 <SEP> a <SEP> 2 <SEP> b
<tb><SEP> 5 <SEP> 47.3 <SEP> 2 <SEP> a <SEP> 2 <SEP> b
<tb><SEP> 6 <SEP> 47.2 <SEP> 2 <SEP> b <SEP> 3 <SEP> b
<tb><SEP> 7 <SEP> 63.8 <SEP> 3c <SEP> 4c
<tb><SEP> 8 <SEP> 46.4 <SEP> the <SEP> i <SEP> b <SEP>
<tb><SEP> 9 <SEP> 46.6 <SEP> the <SEP> I <SEP> b
<tb><SEP> 10 <SEP> 46.4 <SEP> the <SEP> I <SEP> b
<tb><SEP> 12 <SEP> 46.3 <SEP> 1 <SEP> a <SEP> i <SEP> b <SEP>
<Tb>
For the formulation of automotive gear oils, the additives leading to a rating less than or equal to 3 (in particular at 121 ° C.) are preferably used. For the formulation of oils for metal working, it is possible to use the products prepared according to the invention and preferably those which lead to high corrosion ratings, for example those obtained in Examples 6 and 7.

EVALUATION OF EXTREME-PRESSURE PROPERTIES OF ADDITIVES ACCORDING TO
THE INVENTION
Tests were carried out demonstrating the extreme-pressure properties of the additives of the invention, on the one hand in formulations. of the gear oil type and, on the other hand, in metalworking oil type formulations.

a) The additives of Examples and 1, 8, 9, 10 and 12 were investigated using a 4-bead machine according to the procedures of ASTM D 2783 and ASTM D 2266, at the concentration of 1.5% by weight in the oil
SAE 90; the results obtained were collated in Table 4.

TABLE 4

<tb><SEP> Index <SEP> Load <SEP> of <SEP><SEP> Fingerprint <SEP>
<tb> Additive <SEP> of <SEP> load-wear <SEP> weld <SEP> balls <SEP> 1 <SEP> h <SEP> under <SEP> 40 <SEP> kgf
<tb> Example <SEP> (Kgf) <SEP> (N) <SEP> (Kgf) <SEP> (N) <SEP> (392.4N)
<tb><SEP> (mm)
<tb><SEP> without <SEP> 22.2 <SEP> 217.8 <SEP> 160 <SEP> 1569.6 <SEP> 0.80
<tb><SEP> 1 <SEP> 63.4 <SEP> 621.9 <SEP> 400 <SEP> 3924.0 <SEP> 0.62
<tb><SEP> 8 <SEP> 62.5 <SEP> 613.1 <SEP> 400 <SEP> 3924.0 <SEP> 0.65
<tb><SEP> 9 <SEP> 64.4 <SEP> 631.8 <SEP> 400 <SEP> 3924.0 <SEP> 0.67
<tb><SEP> -10 <SEP> 65.0 <SEP> 637.6 <SEP> 400 <SEP> 3924.0 <SEP> 0.62
<tb><SEP> 12 <SEP> 64.5 <SEP> 632.7 <SEP> 400 <SEP> 3924.0 <SEP> 0.65
<tb> b) Tests demonstrating the extreme-pressure properties of the additive prepared according to example 7 in a formulation of the type of metal cutting oil, using a 4-ball machine according to the procedure ASTM D 2783.

The lubricating formulation studied consisted of an oil 100
Neutral wind sol containing 3% by weight of chlorine in the form of chlorinated paraffin and 1% by weight of sulfur in the form of sulfur additive of Example 7. The results obtained are collated in Table 5 below.

The results obtained show that the additive of the invention containing more than 60% by weight of sulfur has a still sufficient solubility in a 100 Neutral mineral oil to lead to very high extreme-pressure performance, hence its interest in the formulation of metal working oils.

TABLE 5

<SEP> Solubility <SEP> in
<tb> Paraffin <SEP> Additive <SEP> S <SEP>% <SEP> mass <SEP>% <SEP> mass <SEP> oil <SEP> 100 <SE> NS <SEP> Index <SEP> Load <SEP> Charge
<sep>SEP> chlorinated <SEP> of <SEP> of <SEP> additive <SEP> of <SEP> additive <SEP> charge / <SEP> before <SEP> of
<tb> (% <SEP> mass) <SEP> the example <SEP> sulfur <SEP> in <SEP> wear <SEP> seize <SEP> weld.
<Tb>

<SEP> oil <SEP> 20 C <SEP> 0 C
<tb><SEP> kgf) <SEP> (N) <SEP> (kgf) <SEP> (N) <SEP> (kgf) <SEP> (N)
<tb><SEP> 4.62 <SEP> without <SEP> - <SEP> - <SEP> - <SEP> - <SEP> 21.4 <SEP> 209.9 <SEP> 50 <SEQ> 490, 5 <SEP> 116 <SEP> 1138.0
<tb><SEP> 4.62 <SEP> without <SEP> - <SEP> - <SEP> clear <SEP> limpid <SEP> 38.1 <SE> 373.8 <SE> 80 <SE> 784, 8 <SEP> 200 <SEP> 1962
<tb><SEP> without <SEP> 7 <SEP> 63.8 <SEP> 1.56 <SEP> limpid <SEP> clear <SEP> 44.0 <SE> 431.6 <SE> 80 <SEP> 784.8 <SEP> 315 <SEP> 3090.1
<tb><SEP> 4.62 <SEP> 7 <SEP> 63.8 <SEP> 1.56 <SEP> limpid <SEP> clear <SEP> 98.0 <SEP> 961.4 <SEP> 100 <SEP> 981.0 <SEP> 620 <SEP> 6082.2
<Tb>

Claims (18)

 1. A polysulfurized olefin composition with a high content of sulfur and very low chlorine content, characterized in that it is obtained by a process in which: (1) reacting at least one compound selected from monochloride and sulfur dichloride with at least one aliphatic monoolefin of 2 to 5 carbon atoms to form an adduct; (2) reacting hydrogen sulfide with sodium, potassium or ammonium hydroxide in solution in at least one substantially anhydrous aliphatic monoalcohol of 1 to 4 carbon atoms; (3) contacting said "adduct" formed in step (1) and at least one saturated or unsaturated monohalogenated hydrocarbon compound with the alcoholic solution obtained at the end of step (2); (4) heating the mixture resulting from step (3), removing said monoalcohol while adding water in an amount sufficient to keep reagents and minerals in solution; (5) after decantation and removal of the aqueous phase, recovering the organic phase consisting at least substantially of the desired polysulfurized olefin composition.  Composition according to Claim 1, characterized in that in step (1) 1.5 to 2.5 moles of aliphatic monoolefin are used per mole of mono and / or sulfur dichloride and a temperature of 20 to 80 ° C. 3. Composition according to one of claims 1 and 2, characterized in that, in step (2), is used from 100 to 400 cm3 of aliphatic monoalcohol and from 0.1 to 1 mole of hydrogen sulfide per mole hydroxide. 4. Composition according to Claim 3, characterized in that 125 to 200 cm 3 of aliphatic monoalcohol per mole are used. 5. Composition according to Claim 3, characterized in that 0.3 to 0.7 moles of hydrogen sulfide are used per mole of hydroxide. 6. Composition according to one of claims 1 to 5, characterized in that the aliphatic monoalcohol is methanol and the hydroxide is sodium hydroxide. 7. Composition according to one of claims 1 to 6, characterized in that, in step (2), elemental sulfur is added to the reaction mixture. 8. Composition according to claim 7, characterized in that the proportion of elemental sulfur introduced goes up to about 3.6 moles per mole of hydroxide introduced. 9. Composition according to claim 7, characterized in that the proportion of elemental sulfur introduced goes up to about 2.5 gram atoms per mole of hydroxide. 10. Composition according to one of claims 1 to 9, characterized in that in step (3) the monohalogenated hydrocarbon compound represents from 1 to 70% in gram atoms of halogen relative to the "adduct" set + monohalogenated hydrocarbon compound, said "adduct" and said monohalogenated hydrocarbon compound are used in a proportion of 1/1 to 0.5 / 1 gram atoms of halogen per mole of hydroxide, and the temperature is 20 at 120 C. 11. Composition according to one of claims I to 10, characterized in that the reaction of step (3) is carried out under a relative pressure of up to about 1 MPa. 12. Composition according to one of claims 1 to 11, characterized in that, in step (4), the temperature ranges from 500C to the reflux temperature of the medium. 13. Composition according to one of claims 1 to 12, characterized in that the process for its preparation comprises a step (6) wherein the polysulfurized olefin composition obtained is brought into contact with a basic compound and then washed with the water.  14. Composition according to one of claims 1 to 13, characterized in that the process for its preparation is carried out continuously in a parallel flow and multi-contact process.  15. Composition according to one of claims 1 to 14, characterized in that it has a sulfur content of up to 65% by weight and a chlorine content of less than about 0.1% by weight. 16. Composition according to claim 15, characterized in that its chlorine content is less than about 0.05% by weight. 17. Use of a composition according to one of claims 1 to 16, having a sulfur content of up to 50% by weight, as an additive for gear oils.  18 Use of a composition according to one of claims 1 to 16, having a sulfur content of 50 to 65% by weight, as an additive for oils for working metals.