JPH0586836B2 - - Google Patents

Description

[Detailed description of the invention]

FIELD OF INDUSTRIAL APPLICATION The present invention relates to the field of organic sulfide type additives used to improve the particularly polar properties of lubricants, and more particularly for the production of polysulfide olefin type additives. and the products obtained by this method. PRIOR ART In the prior art, several processes have been described aimed at producing polysulfided olefins that can be used as extreme pressure additives for lubricants. In particular, the main steps of the method described in US Pat. Nos. 3,471,404 and 3,697,499 are as follows.
(1) Monochlorosulfur is reacted with excess olefin having 2 to 5 carbon atoms, especially isobutylene, at a temperature of 20 to 80°C to form an adduct. (2) 1.8 to 1.8 metal sulfides per gram atom of sulfur
The adduct of the first step is reacted with an alkali metal sulfide (preferably sodium sulfide) and elemental sulfur used in a ratio of 2.2. Furthermore, the proportion of alkali metal sulfide is per mole of adduct.
0.8 to 1.2, and the reaction is carried out under reflux in the presence of an alcohol or alcoholic hydrogen solvent. and (3) reacting the resulting product containing 1-3% chlorine with the mineral base in an aqueous solution under reflux until the residual content of chlorine in the product is below 0.5%. let Although it has been shown in these prior patents that the sulfur content of the resulting product may be between 40 and 60% by weight, in practice most often
This is close to 46%. These products may be used as extreme pressure additives for lubricating bases consisting of lubricating oils, transmission fluids or greases, mineral oils and some synthetic oils. Additionally, US Pat. No. 4,204,969 describes a fairly similar process for the production of polysulfurized olefins that can be used as extreme pressure additives for lubricating oils. This method includes the following main steps. (1) At about 30-100℃, convert monochlorosulfur into a _C3 - _C6 aliphatic monoolefin (generally isobutene).
The reaction is then carried out in the presence of a co-catalyst, preferably consisting of a lower alcohol, to form an adduct. (2) This adduct is combined with sulfur and sodium sulfide (e.g. NaOH, NaHS and/or _H2S ).
(adjusted from ) in a proportion of 0.1 to 0.4 gram atoms of sulfur per mole of sodium sulfide in an alcoholic hydrogen medium at temperatures up to 50° C. under reflux. The product obtained without treatment with a base is then recovered. In the only heavy example, the sulfur content of the product produced was 49% by weight and the viscosity was 37.8℃
(100〓), it is shown to be 8.6 mm ² /s (cSt). Problem to be Solved by the Invention However, using the methods described in the prior art, the sulfur content of the additive can be reduced by increasing the proportion of elemental sulfur relative to the sulfide or alkali hydrogen sulfide used. Attempts to increase the yield result in products that are no longer sufficiently soluble, even in synthetic or mineral lubricating oils, for example of the multi-alphaolefin type, which cannot be used as extreme pressure additives. Moreover, the viscosity of the products thus obtained is generally very high. The present invention provides a new process for producing products which do not exhibit the above-mentioned disadvantages even when the proportion of elemental sulfur is increased. Another advantageous aspect of the process according to the invention is that in the second step the sulfidation reactants (sulfide or alkali hydrogen sulfide and in most cases elemental sulfur)
It is possible, for example, when desirable for economic reasons, to shorten the introduction time of the addition product olefin + sulfur chloride obtained in the first stage into the reaction medium containing This means that the product does not exhibit too high a viscosity or become insoluble in synthetic oils of the polyalphaolefin type, for example. Means for Solving the Problems The method for producing a polysulfide olefin according to the present invention comprises: (1) at least one compound selected from monochloro and dichloro sulfur with 2 to 5 carbon atoms;
(2) reacting with at least one monoolefin of 1.5 to 2.5 moles of monoolefin per mole of sulfur monochloride and/or sulfur dichloride to produce an addition product or adduct; _C1 ~ _C12 alkyl, _C5 ~
at least one halogenated hydrocarbon selected from chloride, bromide and iodide of C ₁₂ cycloalkyl or substituted cycloalkyl, C ₆ to C ₁₂ arylalkyl or substituted arylalkyl (the halogenated alkyl (corresponds to 1 to 70% of halogen gram atoms with respect to the total number of halogen gram atoms formed from the adduct and the halogenated hydrocarbon), an alkali metal used in a proportion of about 0.4 to 0.8 moles per gram atom of halogen in the total and 0 to 7 gram atoms of elemental sulfur per mole of said sulfur compound;
ammonium or alkaline earth metal sulfides,
(3) contacting at least one sulfur compound selected from hydrosulfides and polysulfides in a medium consisting of water or a mixture of water and an aliphatic monohydric alcohol; (3) heating the resulting mixture; , is characterized by comprising the steps of separating into two phases and recovering the polysulfide olefin in the organic phase. (4) Additionally, in some cases, treating the product obtained with basic compounds such as mineral bases. In the process of the invention, the starting olefins may contain 2 to 5 carbon atoms and may be used alone or in mixtures. Isobutylene is most often used. It is also possible to plan to use these olefins in the form of a mixture with a small proportion of olefins having 5 or more carbon atoms (for example 2-isobutylene). 1.5 to 2.5 mol of olefin, preferably 1.8 mol per mol of monochloro and/or dichloro sulfur.
It may be used in a proportion of ~2.2 moles. Generally, the olefin is introduced into liquid monochloro- and/or dichlorosulfur at a temperature of 20-80°C, especially 30-50°C. In step (2) of the process according to the invention, the halogenated hydrocarbon used together with the "adduct" obtained after step (1) is C ₁ -C ₁₂ (preferably C ₁ -
C ₈ ) straight-chain or branched alkyl, optionally substituted C ₅ -C ₁₂ (preferably C ₆ ) cycloalkyl or optionally substituted
It may also consist of a chloride, bromide or iodide of a _C6 to _C12 (preferably _C7 to _C8 ) arylalkyl. For operational reasons, halogenated hydrocarbons whose boiling points reach, for example, approximately 100-150° C. are considered particularly advantageous. The halogenated hydrocarbons used mainly consist of monohalides. Examples include, inter alia, methyl, ethyl, isopropyl, n-propyl, tert-butyl, isobutyl, n-
-butyl, tertiary amyl, isoamyl, n-amyl, n-hexyl, ethyl-2-hexyl, n-
Mention may be made of the octyl, cyclohexyl and benzyl chlorides, bromides and iodides and mixtures thereof. Isopropyl chloride, n-butyl chloride and n-butyl bromide, n-octyl chloride, cyclohexyl chloride or benzyl chloride are preferably used. The proportion of halogenated hydrocarbon used must be sufficient so that the properties of the final material are significantly improved. In general, this ratio is about 0.015 to 1.9 g atoms per 100 g of adduct, especially when the starting monoolefin is isobutylene, relative to the total number of gram atoms of halogen in the adduct plus halogenated hydrocarbon. Corresponds to the number of moles of halogenated hydrocarbon. Within the scope of the present invention, at least a portion of the monohalogenated hydrocarbons as defined above may be
It is possible to substitute at least one monohalogenated hydrocarbon compound which additionally has at least one functional group containing one or more heteroatoms (such as oxygen and/or nitrogen and/or sulfur). Among these functional monohalogenated hydrocarbon compounds, predominantly monochloro or monobromo compounds are used, which are preferably selected from among the following compounds: at least one alcohol group and in particular 2-chloro and 2-bromoethanol, chloro and bromopropanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, andecanol, dodecanol and chloro or bromobenzyl alcohol,
and aliphatic, cycloaliphatic or araliphatic halogenated monoalcohols containing, for example, 2 to 8 carbon atoms, such as chloro or bromophenylethyl alcohol, *for example 3-chloro or 3-bromo-1, halogenated polyols such as 2-propanediol (and corresponding epoxy derivatives, e.g. 1-chloro or 1-bromo-2,3-epoxypropane), * e.g. chloro- and bromo(poly)ethoxyethanol, (poly)ethoxypropanol ,
(Poly)propoxyethanol and (Poly)
monohalides, including halogenated (poly)oxyalkylene monoalcohols, such as propoxypropanol; monohalides, including at least one phenol group, such as chloro and bromophenols, which are unsubstituted or substituted, for example by an alkyl group; halides, - monohalides containing at least one carboxyl group, such as, for example, chloro- and bromoacetic acid, propionic acid, butyric acid, valeric acid, benzoic acid and succinic acid, - especially monohalides, such as, for example, chloroethylamine hydrochloride and chloro-N,N, hydrochloride. - monohalides containing at least one amine group of aliphatic, alicyclic or aromatic compounds, such as dimethyl, diethyl and dipropylethylamine, chloro and bromobenzylamine and chloro and bromophenolethylamine, for example chloro or bromophenolethylamine; Monohalides containing at least one amide group such as acetamide and propionamide; and also at least one thiol group such as chloro and bromomercaptobenzothiazole, chloro and bromophenyl mercaptan and chloro and bromobenzyl mercaptan. Monohalides including. Among the functional monohalides exhibiting multiple groups of various types, the following may be mentioned: Compounds with hydroxyl and carboxyl acids, such as 5-chlorosalicylic acid or 3-chloro-4-hydroxymandelic acid; Compounds with amine and carboxyl groups, such as 4-chlorophenylalanine; or Compounds with hydroxyl groups, such as 4-chlorophenylalanine. and compounds with amine groups. Without departing from the scope of the invention, these multi-functional monohalogenated hydrocarbon compounds may be correspondingly used together with and alone with non-functional halogenated hydrocarbons as defined above. . The expressions (1) halogenated hydrocarbons and monohalogenated hydrocarbon compounds will be used indiscriminately below to generally indicate the non-functional and functional compounds or mixtures thereof used. In step (2) of the process according to the invention, when at least one functional monohalide as defined above is used, at least one transfer catalyst of each phase, in particular a quaternary ammonium halide (e.g. It is advantageous to carry out the reaction of this step in the presence of trace amounts (for example 0.1 to 10% by weight) of tetrabutylammonium) or alkyl phosphonium halides or even "ether rings" or (kryptonates). The sulfur compounds used in step (2) are selected from sulfides, hydrosulfides and polysulfides of alkali metals (e.g. sodium or potassium), alkaline earth metals (e.g. magnesium or calcium) or aluminum. Most often, sodium sulfide, sodium hydrogensulfide (e.g. in the presence of caustic soda) and sodium polysulfide are used.
1 gram atom of halogen contained in the total of adduct + halogenated hydrocarbon (as defined above) for the total of adduct (as obtained after step (1)) + halogenated hydrocarbon (as defined above) The sulfur compound is used in a proportion of about 0.4 to 0.8 mol per sulfur compound. In some cases, the elemental sulfur used with the sulfur compound in step (2) may be present with the sulfur compound in a molar ratio of up to about 7/1. This corresponds to an inverse ratio that may be as small as about 0.14/1. When it is desired that the sulfur content of the final product is not too high (up to about 45-55% by weight), molar ratios of elemental sulfur to sulfur compounds of, for example, up to 4/1 are used. This ratio is most often
It is 0.4/1 to 3.3/1. In this case, the inverse ratio is at least about 0.25/1 and most often about 0.3/1 to 2.5/
It is 1. It is not necessary in this case for the proportion of monohalogenated hydrocarbons used to be very high. 1-40%
(calculated in grams of halogen to the total number of grams of halogen formed from the "adduct" and the monohalogenated hydrocarbon) is generally suitable. This ratio is particularly important when the starting monoolefin is isobutylene.
Approximately 0.015 ~ halogen per 100g of "Adduct"
Equivalent to 0.55 gram atom. Polysulfurized olefins are then obtained which can generally exhibit a sulfur content of about 45-55% by weight, and sometimes even more (about 60% by weight). 100
Its viscosity at °C varies depending on the sulfur content. The viscosity may be about 4-20 mm ² /s. Its halogen content (mainly chlorine) is generally about 1 by weight
% or less, most often around 0.6% by weight. These products are generally soluble in most mineral and synthetic oils in significant concentrations and some in all proportions. Products with the highest sulfur content may have more limited solubility in lubricating oils. However, this solubility is sufficient for some of the applications using these products (eg additives for metal working oils). When a higher sulfur content (approximately 60-65% by weight) is desired in the final product, e.g.
1, more specifically, a molar ratio of elemental sulfur to sulfur compounds from about 3.3/1 to 7/1 may be used, with an inverse ratio of about 0.14/1, more specifically about
It may be as weak as 0.14/1 to 0.3/1). At this time, monohalogenated hydrocarbons have a higher proportion;
For example, from 40 to 70% (expressed in gram atoms of halogen relative to the total number of gram atoms of halogen formed from the "adduct" and the monohalogenated hydrocarbon), more particularly from about 45 to 65%. These proportions correspond to about 0.55 to 1.9 gram atoms of halogen (more specifically about 0.7 to 1.5 gram atoms of halogen) per 100 g of "adduct", especially when the starting monoolefin is isobutylene. At this time, although it has an extremely high sulfur content (approximately 60-65% by weight compared to 1% or less chlorine content), it has a low viscosity (4-15% by weight at 100℃).
mm ² /s) and also in low viscosity mineral oils used in metal processing (such as cutting and forming), in concentrations sufficient to improve the extreme pressure properties of these oils. A soluble product can be obtained. In step (2), the sulfur compound is generally introduced (or formed) in water or preferably in a mixture of water and a light aliphatic monoalcohol (e.g. containing 1 to 4 carbon atoms). In some cases, elemental sulfur is introduced. As light aliphatic monoalcohols, mention may be made of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol and tert-butanol. Isopropanol is preferred. The water-alcohol mixture used may be, for example, 2 to 60% alcohol by weight relative to the weight of water.
(preferably 5 to 45%). In the medium thus constituted and placed under stirring (at 20-100° C.), the addition product from step (1) and the halogenated hydrocarbon are combined for a few minutes, e.g. Add in 10 minutes to 3 hours. In step (3), for example, heating for 3 to 10 hours (50
°C to reflux temperature). Optionally, treatment of the product obtained at the end of step (3) is carried out in step (4), for example with a basic compound of mineral base (such as caustic soda or caustic potash) in an aqueous solution. It's okay. The aqueous solution used may be, for example, caustic soda or potassium hydroxide at a concentration of 0.5 to 20% by weight. The reaction of step (2) of the method according to the invention and the subsequent treatments may be carried out continuously.
The operation is preferably carried out by a cocurrent and multistage contact (rather than countercurrent) reactant feeding process. This is advantageous with respect to the properties of the final product obtained. under slight overpressure (absolute pressure approximately 3 bar =
(Possible to operate up to 0.3MPa). Thereby, the heat of reaction and reaction rate can be increased without altering the properties of the final product. Such implementation is described in more detail in Example 43 and in conjunction with the accompanying figures. The product obtained by the method according to the invention is
It may be advantageously used as an extreme pressure additive for lubricating oils. The first application relates more particularly to oil formulations for gears (transmissions). Base oils may be mineral or synthetic. Synthetic oils, especially in the presence of Lewis acids,
Contains oligomers of olefins such as trimers, tetramers and pentamers of 1-decene obtained by oligomerization. Other α-olefins can of course also be used. For example C ₆ ~ C ₁₄
α-olefins and further mono- or dialkylbenzenes, further synthesized from mono- or polycarboxylic acids (such as sebacic acid, fatty acids, etc.) and monoalcohols and polyols (such as 2-ethylhexanol, trimethylolpropane, etc.) Alkylbenzenes such as esters may also be used. In this application, polysulfurized olefins can be used, in which relatively low sulfur proportions (sulfur compounds/elemental sulfur molar ratio e.g. 1.8/1 to 2.5/1) as well as higher sulfur proportions are used in the production. good. For reasons of solubility in the chosen lubricant, the value of the molar ratio of sulfur compounds/elemental sulfur is approximately 0.4/1 for additives that can be dissolved in mineral oils and approximately 0.4/1 for additives that can be dissolved in synthetic oils. It may be about 1.5/1 (or less) lower. At this time, the polysulfide olefin studied was
It may be added to lubricating oils in concentrations up to 0.5-7%. These additives may be used in combination with phosphorus-containing additives such as metallic dialkyl or diaryldithiophosphates, phosphites and organophosphates. Other conventional additives such as anti-oxidants, anti-corrosion agents, copper phosphate, anti-foam agents, friction reducing agents may be added in conventional proportions. A second application of the products produced according to the invention as extreme pressure additives for lubricants relates more particularly to oil formulations for metal processing (cutting, forming, etc.). This application is particularly advantageously used in products produced with the lowest molar ratios of sulfur compounds/elemental sulfur, for example from 0.14/1 to 0.3/1. These products, which are extremely sulfur-rich, can be surprisingly well soluble in mineral base oils useful in formulating lubricants (eg 100 Neutral Solvent) for metalworking. In this application, the concentration of additives used is generally 0.1-10% and preferably 0.5-5% by weight of the lubricating oil. In this application, other conventional additives such as chlorinated paraffin may be added, for example in proportions of 2 to 10% by weight of chlorine to the lubricating oil. The following examples illustrate the invention without limiting it. Examples 1, 2, 5, 7, 10, 12, 22,
24 and 27 are shown for comparison. Example 1 (Comparative) 3800 g (28.14 mol) of monochlorosulfuric acid S ₂ Cl ₂ was introduced into 10 reactors heated to 40-45°C,
It is then constantly stirred by a dip tube.
3560 g (68.54 mol) of isobutene in which 35.6 g of methanol is dissolved are introduced below the surface of the S ₂ Cl ₂ . The temperature of the reaction medium is maintained at 45-50° C. during the introduction of isobutene (3 hours). 7040 g of adduct, designated by the term "adduct", are thus obtained. In the second reactor of 1, 296 g of water, 60 g of flaky
% Na ₂ S 159.3 g (1.225 mol), finely ground sulfur 19.5 g (0.609 gram atom) and isopropanol 31 cm ³ are introduced sequentially (the molar ratio of Na ₂ S/S used in this test is 2 ). The mixture is heated to 80°C under stirring for one hour, then the temperature is returned to 45°C. 250 g of the addition product obtained above are then introduced into the constantly stirred aqueous medium. The introduction is
It takes 0.75 hours. The temperature of the reaction medium is 45-75
Gradually increased to ℃. The following mixture was heated to total reflux (88~
Heat at 95℃). After decanting, the lower aqueous phase is removed and 200 cm ³ of a 10% strength by weight aqueous caustic soda solution are added to the aqueous phase. The mixture is again brought to reflux for 6 hours. The organic phase recovered after decanting is washed three times with 200 cm ³ of water, dried at 100° C. under a vacuum of 2666 Pa for 1 hour and then filtered in the presence of diatomaceous earth. 189 g of an orange-yellow liquid are thus obtained. The properties of this liquid are as follows. S (wt%) = 46.2 Cl (wt%) = 0.37 Viscosity at 100°C (mm ² /s) = 12.0 Example 2 (Comparative) Under conditions exactly equal to those of Example 1, alkali polysulfide Addition product isobutene/in aqueous solution
250 g of S ₂ Cl ₂ are introduced over 0.2 hours. After reaction and work-up (carried out as described in Example 1), 192.5 g of an orange-yellow sticky product are recovered. The properties of this product are as follows. S (wt%) = 45.4 Cl (wt%) = 1.17 Viscosity at 100°C (mm ² /s) = 30.0 Example 3 At operating conditions exactly equal to those described in Example 1, 296 g of water, 60 % _Na2S 159.3g, Sulfur 19.5
g and 31 cm ³ of isopropanol are introduced successively (as before, the molar ratio Na ₂ S/S is 2). A mixture consisting of 225 g of the addition product of Example 1 S ₂ Cl ₂ /isobutene and 18.72 g (0.202 mol) of n-butyl chloride is then introduced into the constantly stirred aqueous medium over the course of 0.2 hours. After reaction, treatment with caustic soda, washing with water, drying and filtration, 182.1 g of an orange-yellow liquid are recovered. The properties of this liquid are as follows. S (wt%) = 45.7 Cl (wt%) = 1.08 Viscosity at 100°C (mm ² /s) = 14.1 Example 4 Same introduction time, same conditions of Na ₂ S, sulfur and isopropanol as in example 3 and experiment. (Na ₂ S/S
The molar ratio of is 2), and this time the addition product of Example 1
200g and n-butyl chloride 37.45g (0.405 mole)
It is carried out using a mixture consisting of. After treatment, 181.6 g of an orange-yellow liquid are obtained.
The properties of this liquid are as follows. S (wt%) = 45.0 Cl (wt%) = 0.68 Viscosity at 100°C (mm ² /s) = 5.7 Example 5 22.4 g of sulfur by operating conditions similar to Example 1
(in the present test, the molar ratio Na ₂ S/S is then 1.75). Next, 250 g of the addition product isobutene/S ₂ Cl ₂ was added to the aqueous solution of the alkali polysulfide.
will be installed over 2 hours. After reaction, treatment with caustic soda, washing with water,
After drying and filtration, 192 g of a sticky orange-yellow liquid is recovered. The properties of this liquid are as follows. S (wt %) = 47.1 Cl (wt %) = 0.92 Viscosity at 100°C (mm ² /s) = 19.2 Example 6 Experiments were carried out by varying the introduction time and the concentration of Na ₂ S, sulfur and isopropanol (Na ₂ S/S molar ratio of 1.75)
was carried out under the same conditions, this time using 200 g of the addition product of Example 1 and 37.45 g of n-butyl chloride (0.405 g).
mol) is used. After treatment, 190 g of an orange-yellow liquid are obtained. The properties of this liquid are as follows. S (wt%) = 45.8 Cl (wt%) = 0.6 Viscosity at 100°C (mm ² /s) = 4.7 Example 7 Using the same operating conditions as Example 1, using 26 g of sulfur (in this test, Na ₂ The molar ratio of S/S is then 1.5). 195 g of a very viscous product, orange-yellow after reaction and treatment.
is collected. The properties of this product are as follows. S (wt%) = 45.2 Cl (wt%) = 1.34 Viscosity at 100°C (mm ² /s) = 14.7 Example 8 The experiment of Example 7 was repeated, this time using the addition product isobutene/S ₂ Cl ₂ 237.5 g and n-butyl chloride 9.4g
(0.102 mol) and repeat under the same operating conditions. After reaction and work-up, 187 g of orange colored product are recovered. This product exhibits the following properties. S (wt%) = 46.8 Cl (wt%) = 0.95 Viscosity at 100°C (mm ² /s) = 14.7 Example 9 The experiment of Example 7 was repeated under the same operating conditions, this time using the addition product S ₂ Cl A mixture consisting of 200 g of ₂ /isobutene and 37.45 (0.405 mol) n-butyl chloride is used. 170 g of liquid product are obtained. The characteristics are as follows. S (wt%) = 46.4 Cl (wt%) = 0.60 Viscosity at 100°C (mm ² /s) = 4.2 Example 10 (Comparative) The experiment of Example 1 is repeated using 78.4 g of sulfur (in this test The molar ratio of Na ₂ S/S is 0.5). After reaction of 250 g of the addition product isobutene/S ₂ Cl ₂ and subsequent work-up, 212 g of an orange-yellow, very sticky product are recovered. This product exhibits the following characteristics: S (wt%) = 44.7 Cl (wt%) = 1.54 Viscosity at 100°C (mm ² /s) = 39.8 Example 11 The experiment of Example 10
The same conditions are repeated using a mixture consisting of 200 g of S ₂ Cl ₂ and 37.45 g (0.405 mol) of butyl chloride. After reaction and work-up, 202 g of product are recovered. The properties of the product are as follows. S (wt%) = 48.1 Cl (wt%) = 0.44 Viscosity at 100°C (mm ² /s) = 9.6 Example 12 (comparison) In the reactor of 1, 296 g of water, 60%
159.3 g of Na ₂ S and 98 g of sulfur are sequentially introduced (the Na ₂ S/S molar ratio used in this example is 0.4). After heating at 80° C. for 1 hour and then cooling to 45° C., 250 g of the addition product from Example 1 are added over a period of 1 hour. After 8 hours of reflux, the organic phase is decanted and treated as in Example 1. 230 g of a very sticky product are recovered.
The properties of the product are as follows. S (wt%) = 46.2 Cl (wt%) = 2.43 Viscosity at 100°C (mm ² /s) = 47.5 Example 13 The experiment of Example 12 was carried out using 187.5 g of adduct and 47.4 g (0.512 mol) of n-butyl chloride. Repeat with a mixture consisting of Products after reaction and processing
225g recovered. This product exhibits the following characteristics: S (wt%) = 52.2 Cl (wt%) = 0.74 Viscosity at 100°C (mm ² /s) = 14.2 Example 14 The experiment was conducted using 120.8 g of sulfur (in this example
The molar ratio of Na ₂ S/S is 0.32) and a mixture of 187.5 g of the addition product isobutene/S ₂ Cl ₂ and 47.4 g (0.512 mol) of n-butyl chloride under the same conditions as in Example 13. It can be done. After reaction and work-up, 253 g of product are obtained. The properties of this product are as follows. S (% by weight) = 58.6 Cl (% by weight) = 0.61 Viscosity at 100°C (mm ² /s) = 18.7 The properties of the products of Examples 1 to 14 are shown in the table. In particular, the solubility tests (results listed) evaluated the products of Examples 1 to 14 by viscosity grade.
This is done by mixing it into SAE90 lubricating oil at a concentration of 5% by weight. One is a mineral oil refined by a solvent, and the other is a synthetic oil (polyalphaolefin PAO).

【table】

[Table] Can be dissolved.
This 5% concentration is close to the concentration commonly used for automotive gear oil formulations. The measurement is -
After storage in a cold room at 5°C, it is carried out at 20°C.
In these tests, products that are only partially soluble at the concentrations studied are said to be insoluble. Example 15 The experiment of Example 4 is repeated by introducing in 0.75 hours a mixture of 200 g of the adduct isobutene/S ₂ Cl ₂ and 37.45 (0.405 mol) of n-butyl chloride into a solution of sodium polysulfide (Na ₂ S/S molar ratio = 2). After reaction and work-up, 187 g of product are recovered. The properties of this product are as follows. S (wt%) = 45.6 Cl (wt%) = 0.51 Viscosity at 100°C (mm ² /s) = 5.3 Example 16 The experiment of Example 15 was repeated using 37.45 g of n-butyl chloride.
(0.405 mol) is replaced with the same number of moles of n-butyl bromide (55.44 g) and repeated. After reaction and work-up under the same conditions, 185 g of product are obtained.
The properties of this product are as follows. S (wt%) = 45.4 Cl (wt%) = 0.68 Viscosity at 100°C (mm ² /s) = 5.5 Example 17 The experiment of Example 15 was repeated by adding 37.45 g of n-butyl chloride to the same number of moles of cyclohexyl chloride. (47.98g) and repeat. After reaction and treatment, the product
Obtain 187g. The properties of this product are as follows. S (wt%) = 45.2 Cl (wt%) = 0.54 Viscosity at 100°C (mm ² /s) = 4.5 Example 18 The experiment of Example 15 was repeated by adding 37.45 g of n-butyl chloride to the same number of moles of benzyl chloride. (51.21g) and repeat. After reaction and work-up, 189 g of product are obtained. The properties of this product are as follows. S (wt%) = 45.3 Cl (wt%) = 0.72 Viscosity at 100°C (mm ² /s) = 4.7 Example 19 The experiment of Example 15 was repeated by adding 37.45 g of n-butyl chloride to the same number of moles of octyl chloride. (60.15g) and repeat. After reaction and work-up, 194 g of product are obtained. The characteristics of this product are as follows. S (wt%) = 44.1 Cl (wt%) = 0.49 Viscosity at 100°C (mm ² /s) = 4.7 Example 20 The experiment of Example 15 was repeated by adding 37.45 g of n-butyl chloride to the same number of moles of isopropyl chloride. (31.77g) and repeat. After reaction and work-up, 179 g of product are obtained. The characteristics of this product are as follows. S (% by weight) = 45.9 Cl (% by weight) = 0.53 Viscosity at 100°C (mm ² /s) = 5.7 The properties of the products described in Examples 15-20 are summarized in the table below. In particular, solubility tests (results are listed) showed that the products of Examples 15-20 were -
This is carried out by incorporation at a concentration of 5% by weight into a synthetic lubricating oil of the polyalphaolefin type with a viscosity class SAE 90 at 5°C. In the table, RX indicates the halogenated hydrocarbon used and X indicates the halogen considered.

[Table] Example 21 Pressure-resistant stainless steel with two jackets for heating or cooling, a strong stirrer with opposed blades (turbine type), an intake for internal temperature, a pressure gauge, and a short tube connected to a compression measuring pump. 159.3 g (1.225 mol) of 60% Na ₂ S, sulfur in one steel reactor
19.5 g (0.609 gram atom), isopropanol 31
cm ³ and 296 g of water are introduced sequentially (used
The Na ₂ S/S molar ratio is 2). A mixture consisting of 174.7 g of the addition product S ₂ Cl ₂ /isobutene of Example 1 and 30.6 g (approximately 0.61 mol) of methyl chloride is introduced in 0.75 h into the constantly stirred aqueous solution of the polysulfide using the pump described above. . The mixture is heated at 105°C for 8 hours. A gradual decrease in pressure is observed over time. After the reactor is cooled to ambient temperature, the reactor is opened and the aqueous phase is removed. The organic product obtained is treated as in the previous examples with a 10% by weight caustic soda solution at around 95° C. for 6 hours, followed by washing with water, drying and filtration. 155 g of orange colored product are recovered. The characteristics of this product are as follows. S (wt%) = 46.5 Cl (wt%) = 0.5 Viscosity at 100°C (mm ² /s) = 5.2 Solubility at 5% by weight and -5°C In mineral oil: Soluble PAO: Soluble Example 22 (Comparative) In one reactor, 145 g of sulfur dichloride SCl ₂ (1.407
mol) and then 178 g (3.43 mol) of isobutane in which 1.78 g of methanol is dissolved are introduced below the surface of the SCl ₂ which is constantly stirred by a dip tube. The reaction temperature is maintained at 45-50 °C during the introduction of isobutane (0.5 h). 301.5 g of addition product are thus obtained. 60% of the flakes in the second 1 reactor
_159.3 g (1.225 mol) of Na2S, 39.2 g (1.225 g atom) of finely ground sulfur and 31 ^cm3 of isopropanol (used in this test) are introduced sequentially.
The Na ₂ S/S molar ratio is 1. ) The mixture is heated at 80°C for 1 hour and then returned to 45°C. 214.2 g of the addition product obtained above are then introduced into the constantly stirred medium. The installation will take place over a period of 0.5 hours. The temperature of the reaction medium is increased sequentially from 45 to 75°C. The mixture is then heated at total reflux (88-95° C.) for 6 hours under vigorous stirring. After decanting, the lower aqueous phase is removed and then 200 cm ³ of a 10% strength by weight aqueous sodium hydroxide solution are added to the organic phase. The mixture is 6
Transported by time reflux. After decanting, the recovered organic phase is washed three times with water. The organic phase is dried under a vacuum of 2666 Pa at 100° C. for 1 hour and filtered in the presence of diatomaceous earth. An orange-yellow, very viscous product 180 is thus obtained. The properties of this product are as follows. S (wt %) = 44.1 Cl (wt %) = 1.59 Viscosity at 100°C (mm ² /s) = 47.3 Example 23 Under exactly the same operating conditions as described in Example 22, sodium polysulfide aqueous solution (Na ₂ S/S
37.45 g (0.405 mol) of n-butyl chloride and 171.3 g of the addition product isobutane/SCl ₂ in
Introducing a mixture consisting of Installation takes place in 0.5 hours. After treatment, a thin orange-yellow liquid is obtained. The properties of this liquid are as follows. S (% by weight) = 45.8 Cl (% by weight) = 0.64 Viscosity at 100°C (mm ² /s) = 7.2 The properties of the products described in Examples 22 and 23 are shown in the table. As mentioned above, solubility tests were carried out by incorporating the products of Examples 22 and 23 into SAE 90 lubricating oils (mineral oils and synthetic oils of the PAO type) at a concentration of 5% by weight. It can be done.

[Table] * Comparative Example Example 24 (Comparative) In the reactor of 1, 162 g of an aqueous solution of SHNa 32% by weight, 74 g of a 50% aqueous solution of caustic soda, 79.65 g of isopropanol and finely ground sulfur were added.
14.8 g are introduced (SHNa/S molar ratio is 2 in this test). Stir for 5 minutes, add 99 cm ³ of water and then heat to 75°C. 250 g of the addition product isobutene/S ₂ Cl ₂ prepared in Example 1 are added to this aqueous solution of sodium polysulfide. The addition takes place over a period of 2 hours at a temperature of 75°C. The mixture is then heated at reflux for 4 hours, after which the isopropanol is distilled at 90° C. under normal pressure and then under a vacuum of 2666 Pa. After decanting, the organic phase is mixed with 125 ^cm3 of water and 100 cm3 of benzene.
Washed with cm ³ . Decant again and then wash the organic phase twice with the same amount of water and benzene.
Bring to reflux for 0.5 h, cool and decant. The recovered organic phase was heated at 100% to remove benzene.
Evaporated under vacuum at 2666Pa at °C. After filtration in the presence of diatomaceous earth, 201.1 g of an orange-yellow product are obtained. The properties of this product are as follows. S (wt %) = 48.6 Cl (wt %) = 0.75 Viscosity at 100°C (mm ² /s) = 6.1 Example 25 The experiment of Example 24 was repeated using the addition product S ₂ Cl ₂ /isobutene 237.5 g and chloride Repeat using a mixture consisting of 9.4 g (0.102 mol) of n-butyl. After reaction and work-up, 190 g of thin product are obtained. This product exhibits the following properties: S (wt%) = 47.4 Cl (wt%) = 0.62 Viscosity at 100°C (mm ² /s) = 5.7 Example 26 The experiment of Example 24 was repeated using the addition product isobutane.
200 g of S ₂ Cl ₂ and 37.45 g of n-butyl chloride (0.405
Repeat using a mixture consisting of mol). After reaction and work-up, 176.1 g of product are obtained. The properties of this product are as follows. S (wt%) = 46.8 Cl (wt%) = 0.59 Viscosity at 100°C (mm ² /s) = 4.3 Example 27 (Comparative) The experiment of Example 24 is repeated using 59.25 g of sulfur (main test) , the SHNa/S molar ratio is 0.5
). After reaction of 250 g of the addition product isobutene/S ₂ Cl ₂ and subsequent work-up, 253 g of an orange-yellow product are obtained. This product exhibits the following properties: S (wt %) = 55.4 Cl (wt %) = 0.93 Viscosity at 100°C (mm ² /s) = 14.1 Example 28 The experiment of Example 27 was repeated using the addition product S ₂ Cl ₂ /isobutane 200 g and chloride n -Butyl 37.45g (0.405)
Repeat with a mixture consisting of After reaction and work-up, 214 g of product are recovered. The properties of this product are as follows. S (% by weight) = 55.0 Cl (% by weight) = 0.54 Viscosity at 100°C (mm ² /s) = 8.0 The properties of the products described in Examples 24-28 are summarized in the table.

[Table] * Comparative Example As mentioned above, the solubility test was carried out by mixing the products of Examples 21 to 25 in SAE 90 oil (mineral oil and PAO type synthetic oil) at a concentration of 5% by weight. Let's do it. Example 29 In the reactor of 1, 214.4 g of a 32% aqueous solution by weight of SHNa, 74 g of a 50% aqueous solution of caustic soda, 78.4 g of finely ground sulfur and isopropanol
79.65g was introduced sequentially (in this test,
The molar ratio of SHNa/S is 0.5). Stir for 5 minutes, add ^99cm3 of water, heat to 80°C and then cool to 45°C. 200 g of the addition product isobutene/S ₂ Cl ₂ obtained in Example 1 are then added to the constantly stirred medium.
and 37.45 g (0.405 mol) of n-butyl chloride are introduced. The installation time is 0.75 hours. After 6 hours of reflux, it is decanted, the alcohol-hydrogen phase is separated off and the organic phase is treated with 200 cm ³ of 10% aqueous sodium hydroxide solution for 6 hours. After decanting, the organic phase is collected, washed three times with 200 cm ³ of water, dried under vacuum at 100° C. for 1 hour and then filtered in the presence of diatomaceous earth. 197 g of an orange-yellow product, soluble (20 DEG C. to -5 DEG C.) in a mineral SAE 90 oil at a minimum concentration of 5% by weight, are thus recovered. The properties of the product thus obtained are as follows. S (wt%) = 51.7 Cl (wt%) = 0.47 Viscosity at 100°C (mm ² /s) = 9.27 Example 30 The experiment of Example 11 was carried out using flaky 60% Na ₂ S159.3
g, water, 78.4 g of finely divided sulfur and 79.65 g of isopropanol (in this test the Na ₂ S/S molar ratio is 0.5) and the mixture is then heated to 75°C. The experiment was carried out according to the operating conditions of Example 24, with a mixture consisting of 200 g of the addition product isobutene/S ₂ Cl ₂ and 37.45 g (0.405 mol) of n-butyl chloride in the alkaline polysulfide solution thus obtained. This will be continued by introducing . The addition takes place for 2 hours. After reaction and processing, an orange-yellow product 195 is soluble in SAE 90 mineral oil (20°C to -5°C) at a minimum concentration of 5% by weight.
get g. The properties of the product thus obtained are as follows. S (% by weight) = 53.1 Cl (% by weight) = 0.54 Viscosity at 100°C (mm ² /s) = 8.92 Example 31 Determination of the corrosion effect of the products according to the invention Using some, containing 5% by weight of additive
From SAE90 mineral oil to ASTM standard D-130
(NF M07-015) conduct corrosion tests on copper thin pieces. The results obtained are summarized in the table. These results are expressed by ratings including numbers (1 to 4).
This number is followed by a letter that clarifies the subtle differences in the corrosion of the copper flakes.

【table】

[Table] Example 4,
Products rated below 3 or 3 (especially at 121° C.) are particularly used, such as products No. 8, 9 and 11. On the other hand, all products prepared according to the invention may be used in the formulation of metalworking oils. More preferably, products with high corrosion ratings, such as those of Examples 13, 26, and 28, may be used, especially for iron and its alloys. Example 32: Evaluation of the extreme pressure properties of additives according to the invention Tests are carried out to characterize the extreme pressure properties of the additives prepared in Examples 4, 9 and 11 in gear oil type formulations. A - In the first group of tests, the products of Examples 4, 9 and 11 were tested at a concentration of 3% by weight in SAE 90 mineral oil and tested according to ASTM D2782-
tested using a TIMKEN machine according to the test method described in 71.

【table】 ~
*1 Libre - 0.4536
These results very clearly show that the use of the additive according to the invention increases the seizure load of lubricated metal surfaces. B - In the second group of tests, the extreme pressure properties of these same additives were determined by ASTM
According to methods D2783 and ASTM D2266,
A concentration of 1.5% by weight in SAE90 oil was studied. The results obtained are summarized in the table.

TABLE These results show that by using the additive according to the invention the load-wear index and the bonding load of the balls increase very significantly. Example 33 In the reactor of 1, 296 g of water, 60% of flaky
159.3 g (1.225 mol) of Na ₂ S, 152.3 g (4.75 gram atoms) of finely divided sulfur and 31 cm ³ of isopropanol are introduced in sequence. used in this test
The Na ₂ S/S molar ratio is 0.258. The mixture is heated to 80°C under stirring for 1 hour and then cooled to 45°C. A mixture consisting of 125 g of the addition product obtained as described in Example 1 (i.e. 1.01 gram atoms of chlorine) and 93.4 n-butyl chloride (1.01 mol) is then introduced into the constantly stirred aqueous medium.
The installation will take 1.5 hours. The temperature of the reaction medium increases gradually from 45 to 75 °C. The mixture is then heated at 75°C for 6 hours and at total reflux (80-85°C) for 2 hours to complete the reaction. After decanting, the aqueous phase is removed and 200 cm ³ of a 4% strength by weight aqueous caustic soda solution are added to the organic phase. The mixture is again brought to reflux for 6 hours. After decanting, the recovered organic phase is washed three times with 200 cm ³ of water and dried for 1 hour at 100° C. under a vacuum of 2666 Pa. It is then filtered in the presence of diatomaceous earth. In this way, an orange-yellow liquid is produced.
276g obtained. The characteristics of this liquid are as follows. S (wt%) = 60.0 Cl (wt%) = 0.86 Viscosity at 100°C (mm ² /s) = 5.7 Example 34 The experiment of Example 33 was repeated using 159.3 g of 60% Na ₂ S.
(1.225 mol), 163.4 g (or 5.096 gram atoms) of sulfur (in this test the molar ratio of Na ₂ S/S is 0.24
) and the addition product S ₂ Cl ₂ /isobutylene
125 g and n-butyl chloride 93.4 g (1.01 mole)
Repeat with a mixture consisting of After treatment, 286.3 g of product are recovered. The properties of this product are as follows. S (wt%) = 61.7 Cl (wt%) = 0.9 Viscosity at 100°C (mm ² /s) = 6.2 Example 35 The experiment of Example 33 was repeated using 60% Na ₂ S 159.3 g (1.225 mol), sulfur 196.05g (6.115g atom) ( _Na2S /
The molar ratio of S is 0.2 in this test) and a mixture consisting of 93.65 g of addition product S ₂ Cl ₂ /isobutene and 116.8 g (1.263 mol) of n-butyl chloride. After treatment, 252.7 g of product are obtained. The properties of this product are as follows. S (wt%) = 63.0 Cl (wt%) = 0.54 Viscosity at 100°C (mm ² /s) = 5.23 The solubility of the additive prepared as described in Examples 33, 34 and 35 is: Measured at two temperatures on two mineral oils of different compositions. Namely Mineral Oil 100 Neutral Solvent Naphthenic Spindle Oil The results obtained are summarized in the following table.

【table】

[Table] Example 36 Evaluation of extreme pressure properties of additives Example 33 in a metal cutting oil type formulation using a four-bead machine according to the method of ASTM D2783.
Tests are conducted to characterize the extreme pressure properties of the additives prepared according to 34 and 35. The lubricating formulation studied consisted of a 100 neutral solvent oil containing 3% chlorine in the form of chlorine paraffin and 1% sulfur in the form of the sulfur adducts of Examples 33, 34 and 35. The results obtained are summarized in the table on the next page.

TABLE These results show that by using the additive according to the invention the load at the ball joint increases significantly. Example 37 159.3 g (1.225 mol) of 60% Na ₂ S, 22.4 g (0.7 gram atom) of bloom sulfur, 28.35 g of caustic soda in pellet form, 296 cm ³ of water and 3 g of tetrabutylammonium chloride are introduced into the reactor of Example 37 1. . (The Na ₂ S/S molar ratio used in this test was 1.75
) The mixture is heated to 80°C under stirring for 1 hour. The temperature is then returned to 45°C. This solution is
It is then transferred to a bromine-containing container that is externally heated to maintain a temperature of approximately 45°C. In a second reactor, 162.5 g of addition product S ₂ Cl ₂ /isobutane and 67 g of monochloroacetic acid (0.709
mole). The mixture is heated to 50-55 °C under stirring for homogenization. The heated solution of sodium polysulfide is introduced gradually over a period of 2 hours into the chlorine mixture, which is maintained at a reaction temperature of 55-60° C., via a heated bromine vessel. The mixture was then brought under reflux for 8 hours and the temperature
Lower the temperature to 75 °C and add 150 cm ³ of benzene. Stop stirring and decant. The aqueous phase containing excess sodium polysulfide and the sodium salt of polythiodiglycolic acid formed is removed. The organic phase is refluxed for 3 hours with a 10% strength by weight caustic soda solution under gentle stirring. Lower the temperature to 75℃ and then to facilitate decanting.
Add 10 g of NaCl and remove the aqueous phase. The recovered organic phase is treated with 120 cm ³ of an aqueous solution of HCl6N at 70° C. for 1 hour under strong stirring. Decant and separate the aqueous phase. The organic phase is 2 in 150 cm ³ of water.
Washed _twice , dried over _Na2SO4 , filtered and then evaporated under vacuum (2.7x at 100 °C)
10 ³ Pa). 125 g of an orange-yellow organic product are thus obtained. The acidity index (I _A ) of this product corresponds to a molecular weight of approximately 1650. Moreover, the infrared spectrum of the compound shows the presence of carbonyl groups. The properties of the carbonyl sulfur compound thus obtained are as follows. S (wt%) = 40.1 Cl (wt%) = 0.94 Viscosity at 100°C (mm ² /s) = 31.5 I _A = 34.0 Example 38 In the reactor of 1, 60% Na ₂ S 159.3 g, sulfur 22.4
g, 296 g of water, 31 cm ^{3 of} isopropyl alcohol and 3 g of tetrabutylammonium chloride are successively introduced. Heat the mixture at 80 °C for 1 hour without stirring,
Next, lower the temperature to 45℃. At this time, an aqueous mixture consisting of 162.5 g of the addition product S ₂ Cl ₂ /isobutene and 67 g (0.709 mol) of 1-chloro-2-propanol was maintained at around 78-80°C in this constantly stirred solution. Add over 2 hours. Then total reflux for 8 hours (90-95
℃). Stop stirring and decant at 75°C. The aqueous solution containing excess sodium polysulfide and polythiodipropylene glycol formed is removed. The organic phase is 200 cm ³ of a 10% aqueous solution of caustic soda by weight.
and at reflux for 3 hours (processed at approximately 95°C). Cool to 75 °C and add 100 ^cm3 of benzene;
Stop stirring and decant. The recovered organic phase was washed twice with 150 cm ³ of water and
Dry over Na ₂ SO ₄ , filter and evaporate at 100 °C under reduced pressure (2.7, 10 ³ Pa). 130 g of a dark yellow organic product are thus obtained. The hydroxyl index ( _IOH ) corresponds to a molecular weight of 603. Furthermore, the infrared spectrum of the compound shows the presence of hydroxyl groups. The properties of the hydroxyl sulfur compound thus obtained are as follows. S (wt%) = 40.7 Cl (wt%) = 0.01 Viscosity at 100°C (mm ² /s) = 5.2 I _OH = 93 Example 39 The experiment of Example 38 was repeated using the addition product S ₂ Cl ₂ /isobutene 162.5 and 2-chloroethanol 57.1g
Repeat with a mixture consisting of (0.709 mol). After treatment, 134 g of dark yellow organic product are recovered. The hydroxyl index ( _IOH ) of this product is approximately
Corresponds to a molecular weight of 1600. Furthermore, the infrared spectrum of the mixture shows the presence of hydroxyl groups. The properties of the hydroxyl sulfur compound thus obtained are as follows. S (wt%) = 41.6 Cl (wt%) = 0.7 Viscosity at 100°C (mm ² /s) = 7.72 I _OH = 35 Example 40 Addition product S ₂ Cl ₂ /isobutene in the reactor of 1
187.5 g and 65 g of 4-chlorophenol are introduced. The mixture is heated to 50-55 °C for homogenization. 159.3 g of Na ₂ S, 22.4 g of sulfur, 31 cm ³ of isopropanol, 296 g of water and tetrabutylammonium chloride are passed into a stirred reactor through a vessel containing bromine, which is heated externally to maintain the temperature below 45°C. is introduced while maintaining the reaction temperature at 55-60°C. The stirred mixture is then brought to reflux for 8 hours. After decanting and removing the aqueous phase, the organic phase was treated with 200 cm ^{3 of} 10% aqueous caustic soda solution and then with 82 cm ³ of HCl6N at 70 °C.
Processed in After decanting under reduced pressure, washing, drying, filtration and evaporation, 126 g of a tan organic product are recovered. The infrared spectrum of this product shows the presence of phenolic groups. The properties of the phenol-sulfur mixture thus obtained are as follows. S (wt %) = 38.2 Cl (wt %) = 0.95 Viscosity at 100°C (mm ² /s) = 13.6 I _OH = 23 Example 41 Addition product S ₂ Cl ₂ /isobutane 200 g, chloride n-
Butyl 18.5g and 4-chloromethyl-2,6-
Example 38 is repeated using a mixture consisting of 53.6 ditertiarybutylphenol. After 8 hours of reflux (85 DEG -90 DEG C.), treatment with caustic soda, washing, drying and filtration, 200 g of an orange-yellow product are recovered. The infrared spectrum of this product shows the presence of disturbed phenol groups. The properties of the phenol sulfur compound are as follows. S (wt%) = 37.4 Cl (wt%) = 0.75 Viscosity at 100°C (mm ² /s) = 7.1 In the reactor of Example 42 1, 60% Na ₂ S 144.8 g, sulfur 20.4
g, 222 cm ³ of water, 31 cm ³ of isopropanol and 3 g of tetrabutylammonium chloride are successively introduced.
The mixture is heated to 80° C. for 1 hour while stirring. The temperature is then returned to 45°C. At this time, a mixture consisting of 162.5 g of the addition product S ₂ Cl ₂ /isobutene and 65.5 g of 1-chloro-2,3-epoxypropane was added to this constantly stirred solution while maintaining the reaction heat at 50 to 55°C. Add over 2 hours. Then carry the mixture for 15 minutes at a temperature of reflux (94-96 ° C) and add 150 cm ³ of toluene. Stop heating and stirring and decant. The organic phase was then treated with 200 cm ³ of 10% caustic soda solution at reflux for 3 hours, washed twice with 200 cm ³ of water,
Dry over Na ₂ SO ₄ , filter and evaporate at 100° C. under a pressure of 2.7×10 ³ . 120g of the organic product that has become dark in this way
is obtained. The infrared spectrum of this product reveals the presence of hydroxyl groups. The properties of the hydroxysulfur compound thus obtained are as follows. S (wt%) = 41.4 Cl (wt%) = 0.8 Viscosity at 100°C (mm ² /s) = 16.3 I _OH = 76 Example 43 In this example, using the same reactant ratios as in Example 6, Operate continuously. For a description of this embodiment, please refer to the attached drawings. Flow of adduct S ₂ Cl ₂ /isobutane/n-BuCl halogen mixture 123 vol/h (line (1), pump (P1)) and 248 solution/h of aqueous alcohol solution of sodium polysulfide (line (2) , pump (P2)) are simultaneously sent to reactor R1, which is constantly stirred and maintained at 60-65 °C under an absolute pressure of 0.203 MPa. After an average residence time of 2 hours in R ₁ , the water stream of 371 vol/h is continuously stirred by the tilting line (3) and the same
It is led into a reactor (R ₂ ) maintained at 105° C. under an absolute pressure of 0.203 MPa. After an average residence time of 8 hours, the water stream is directed by the tilting line (4) towards the separator (S1) where it is
Phase decanting takes place at 80°C for 0.5 hours (absolute pressure 0.203 MPa). A flow of 371 vol/h of the upper sulfur organic phase is sent by line (5) to a “GROVE BACK-PRESSURE” type pressure reducing valve (G1), where it is reduced to a specified pressure (0.203 MPa) under normal pressure. It is sent to the reactor (R3). The lower aqueous phase of separator S ₁ is removed by line (6), pump (P3) and pressure reducing valve (G ₂ ) of the same type as G ₁ . The reactor ( _R3 ) maintained at 95-100 °C (atmospheric pressure) with constant stirring produces a sulfur-organic phase of 371
volume/h flow line (5) and 116 volumes/h flow of 10% caustic soda aqueous solution by weight (line (7), pump (P4))
simultaneously supplied by After an average contact time of 6 hours, 221 vol/h of the mixture flows by pouring (line (8), pump (P5)) into the separator (S ₂ ), where it is
Decantation is performed for 0.5 hour at 60°C. The upper 100 vol/h sulfur organic phase is led to the reactor (R ₄ ) by line (9) and pump (P6). Meanwhile, the spent caustic soda stream is removed from the bottom of the separator (S ₂ ). The constantly stirred reactor (R ₄ ) is simultaneously fed with a stream of 100 vol/h of sulfur organic phase and 115 vol/h of wash water originating from the separator (S ₂ ) (line (11), pump (P8)). After an average residence time of 0.5 hours at 60° C., the mixture is sent to a decanter (S ₃ ) by decanting through line (12);
Phase separation is then carried out at 60°C for 0.5 hours. The upper aqueous phase is sent to the mixer (M ₁ ) by tilting in line (13), where a 10% aqueous caustic soda solution is prepared with the feed of concentrated caustic soda in line (14) and the aid of water in line (15). Ru. A stream of 100 vol/h of the sulfur organic phase is taken off at the bottom of the separator (S ₃ ) (line (16), pump (P9)),
It is sent to a thin layer continuous evaporator (2.7×10 ³ Pa/100° C.), then to a filter and finally to a storage tank. The physicochemical properties of the additive thus obtained are as follows. S (wt%) = 46.1 Cl (wt%) = 0.52 Viscosity at 100°C (mm ² /s) = 6.1

[Brief explanation of the drawing]

The drawing is a flow sheet showing the flow of Example 43.

Claims (1)

[Claims] 1 (1) At least one compound selected from sulfur monochloride and sulfur dichloride containing 2 to 2 carbon atoms
reacting with at least one of the five monoolefins in a ratio of 1.5 to 2.5 moles of monoolefin per mole of sulfur monochloride and/or sulfur dichloride to form an addition product or adduct; (2) with said adduct; , _C1 - _C12 alkyl, _C5-
at least one halogenated hydrocarbon selected from chlorides, bromides and iodides of C ₁₂ cycloalkyl or substituted cycloalkyl, C ₆ to _{C 12} arylalkyl or substituted arylalkyl (the halogenated hydrocarbon selected from the group consisting of (the proportion corresponds to 1 to 70% of gram atoms of halogen relative to the total number of gram atoms of halogen formed from the adduct and the halogenated hydrocarbon);
from about 0.4 to 0.8 moles per gram atom of the total halogen formed from said adduct and said halogenated hydrocarbon, and from 0 to 7 gram atoms of elemental sulfur per mole of said sulfide compound. contact with at least one sulfur compound selected from sulfides, hydrogenated sulfides and polysulfides of alkali metals, ammonium or alkaline earth metals in a medium consisting of water or a mixture of water and an aliphatic monohydric alcohol. (3) heating the obtained mixture to separate it into two phases, and then recovering the polysulfide olefin in the organic phase. . 2. Process according to claim 1, characterized in that in step (1), isobutene or a mixture of isobutenes is used as aliphatic monoolefin together with a small proportion of diisobutene. 3 The halogenated hydrocarbon is methyl, ethyl,
Isopropyl, n-propyl, tert-butyl, isobutyl, n-butyl, tertiary amyl, isoamyl,
Process according to claim 1 or 2, characterized in that it is selected from chlorides, bromides and iodides of n-amyl, n-hexyl, 2-ethylhexyl, n-octyl, cyclohexyl and benzyl. 4 The halogenated hydrocarbon is at least partially
Claims 1 to 1 are characterized in that they consist of a monohalogenated hydrocarbon compound having at least one functional group selected from alcohols, phenols, carboxylic acids, amines, amides, and thiols functional groups. Any one of the three items
The method described in section. 5. Claims 1 to 4, wherein the sulfur compound is selected from sodium sulfide, sodium hydrogen sulfide, and sodium polysulfide.
The method described in any one of the following paragraphs. 6 The proportion of elemental sulfur per mole of sulfur compounds
6. Process according to any one of claims 1 to 5, characterized in that the amount is 0.4/1 to 7/1 gram atom. 7 In step (2), the adult and the halogenated hydrocarbon are placed in a medium containing the sulfur compound and optionally elemental sulfur and maintained at 20°C to 100°C for 10 minutes to 3 hours. 7. The method according to any one of claims 1 to 6, characterized in that in step (3), the mixture is heated from 50°C to reflux temperature for 3 to 10 hours. 8. The method according to any one of claims 1 to 7, further comprising a step (4) in which the product derived from step (3) is treated with a basic compound. Method. 9. Among claims 1 to 8, the operation is carried out continuously from step (2), and the reactants used in step (2) are brought into contact by a cocurrent and multistage contacting process. The method described in any one of the above. 10. The proportion of halogenated hydrocarbon used in step (2) is 2 to 40% gram atoms of halogen based on the total number of gram atoms of halogen consisting of the adult and the halogenated hydrocarbon. A method according to any one of claims 1 to 9, characterized in that: 11 The ratio of elemental sulfur used in step (2) is 0.4/1 to 3.3/1 per mole of sulfur compound.
11. The method according to claim 10, characterized in that the atom is a gram atom. 12. The proportion of the halogenated hydrocarbon used in step (2) is approximately 40 to 70% of the halogen gram atoms relative to the total number of halogen gram atoms consisting of the adult and halogenated hydrocarbon. A method according to any one of claims 1 to 9, characterized in that: 13 The ratio of elemental sulfur used in step (2) is 3.3/1 to 7/1 per mole of sulfur compound.
13. A method according to claim 12, characterized in that the atom is a gram atom. 14. The method according to any one of claims 1 to 13, characterized in that a polysulfurized olefin is obtained. 15. A polysulfide olefin having a sulfur content of up to about 45-60% by weight and a kinematic viscosity of 4-20 mm ² /s at 100° C. is obtained, according to claim 14. the method of. 16. Process according to claim 14, characterized in that a polysulfided olefin is obtained with a sulfur content of about 60-65% by weight and a kinematic viscosity at 100C of 4-15 ^mm2 /s. 17 As an additive for gear oil, the polysulfide olefin is added to mineral or synthetic lubricating oil by 0.5% by weight.
16. Process according to claim 15, characterized in that the polysulfurized olefin is obtained for use in a process in which it is added at a rate of ~7%. 18 As an oil additive for metal processing, the polysulfide olefin is added in an amount of about 0.1 to 10% by weight to the oil.
17. A method according to claim 15 or 16, characterized in that the polysulfurized olefin is obtained for use in a method of adding %.